FABRIC ENHANCEMENT COMPOSITIONS

COMPOSITIONS D'AMELIORATION DE L'ASPECT DES TEXTILES

English Abstract

The present invention relates to fabric enhancement compositions which provide
reduced fabric abrasion damage. The compositions of the present invention
comprise: a) from about 0.01% by weight, of a fabric enhancement system, said
fabric enhancement system comprising one or more modified polyamine compounds,
said modified polyamine compounds are selected from: i) (PA)w(T)x; ii)
(PA)w(L)z; iii) [(PA)w(T)x]y[L]z; and iv) mixtures thereof; wherein PA is a
grafted or non-grafted, modified or unmodified polyamine backbone unit, T is
an amide-forming polycarboxylic acid crosslinking unit, and L is a non-amide
forming crosslinking unit; provided that for compounds of type (i) and (iii)
the indices w and x have values such that the ratio of w to x is from 0.8:1 to
1.5:1; for compounds of type (ii) the indices w and z have values such that
said modified polyamine compound comprises from about 0.05 to about 2 parts by
weight of said L unit; for compounds of type (iii) the indices y and z have
values such that said modified polyamine compound comprises from about 0.05 to
about 2 parts by weight of said L unit; b) from about 1% to about 80% by
weight, of a fabric softening active; c) and the balance carriers and adjunct
ingredients.

French Abstract

L'invention concerne des compositions d'amélioration de l'aspect des textiles, permettant d'obtenir un endommagement réduit des textiles, consécutif à une certaine abrasion. Ces compositions comprennent: a) environ 0,01 % en poids d'un système d'amélioration de l'aspect des textiles, lequel comporte au moins un composé polyamine modifié, ce composé étant choisi dans le groupe constitué par: i) (PA)¿w?(T)¿x?; ii) (PA)¿w?(L)¿z?; iii) [(PA)¿w?(T)¿x?]¿y?[L]¿z?, ou iv) des mélange de ceux-ci, PA représentant une unité à squelette polyamine, modifiée ou non, greffée ou non, T représentant une unité de réticulation d'acide polycarboxylique formant un amide, et L représentant une unité de réticulation ne formant pas un amide, à condition que, d'une part, pour les composés des types (i) et (iii) les indices w et x possèdent des valeurs telles que le rapport w/x soit compris entre 0,8/1 et 1,5/1, et d'autre part, pour les composé du type (ii), les indices w et z possèdent des valeurs telles que le composé polyamine modifié comprenne entre environ 0,05 et environ 2 parties en poids de l'unité L; b) environ 1 à environ 80 % en poids d'un agent adoucissant de textiles et c) le solde étant constitué par des excipients et des ingrédients d'adjonction.

Claims

46
What is claimed is:
1. A fabric care composition comprising:
a) from 0.01% by weight, of a fabric enhancement system, said fabric
enhancement
system comprising one or more modified polyamine compounds, said modified
polyamine compounds are selected from:
i) (PA)w(T)x;
ii) (PA)w(L)z;
iii) [(PA)w(T)x]y[L]z; and
iv) mixtures thereof;
wherein PA is a grafted or non-grafted, modified or unmodified polyamine
backbone unit, T is an amide-forming polycarboxylic acid crosslinking unit,
and
L is a non-amide forming crosslinking unit; provided that for compounds of
type
(i) and (iii) the indices w and x have values such that the ratio of w to x is
from
0.8:1 to 1.5:1; for compounds of type (ii) the indices w and z have values
such
that said modified polyamine compound comprises from 0.05 to 2 parts by
weight of said L unit; for compounds of type (iii) the indices y and z have
values
such that said modified polyamine compound comprises from 0.05 to 2 parts by
weight of said L unit; and
b) the balance carriers and adjunct ingredients.
2. A composition according to Claim 1 wherein said PA polyamine backbone unit
comprises a polyamine which is grafted wherein said grafting agent is selected
from
aziridine, caprolactam, and mixtures thereof.
3. A composition according to either Claim 1 or 2 wherein said T unit has the
formula:
<IMG>
wherein R1 is methylene, phenylene, and mixtures thereof; R2 is -NH-; k is
from 2 to 8,
each j is independently 0 or 1.
4. A composition according to any of Claims 1-3 wherein said L unit is
selected from:
i) polyalkylene units having the formula:

47
~(CH2)n~
wherein n is from 1 to 50;
ii) epihalohydrin/polyalkylene units having the formula:
<IMG>
wherein n is from 1 to 50;
iii) polyalkyleneoxy comprising units having the formula:
<IMG>
wherein R1 is ethylene, R2 is 1,2-propylene, x is from 0 to 100 and y is from
0 to
100;
iv) polyhydroxy comprising units having the formula:
<IMG>
wherein the index t is at least 2and the index a is from 1 to 6;
v) polyalkyleneoxy/polyhydroxy comprising units having the formula;
<IMG>
wherein R1, R2, t, u, x, and y are the same as defined above, the indexes w
and z
are each independently from 1 to 50;
vi) units which comprise an aziridine unit having the formula:
<IMG>
wherein h is from 0 to 22; and
vii) mixtures thereof.

48
5. A composition according to any of Claims 1-4 wherein said polyamine
compound is
formed by the reaction of:
a) 1 part by weight, of a polyamidoamine obtained by condensation of 1 mole of
a
dicarboxylic acid with from 0.8 to 1.5 moles of a polyalkylene polyamine then
optionally reacting the obtained polyamidoamine condensation product with up
to 8 ethyleneimine units per basic nitrogen atom; and
b) further reacting the product obtained in (a) with from 0.05 to 2 parts by
weight,
of a reaction product of a polyalkylene oxide having from 8 to 100 alkylene
oxide units with epichlorohydrin at a temperature of from 20 °C to 100
°C.
6. A composition which provides reduced fabric abrasion, said composition
comprises:
a) from 0.01% by weight, of a polyamidoamine fabric abrasion reducing polymer
according to the present invention;
b) optionally from 0.01% by weight, of a fabric abrasion polymer comprising:
i) at least one monomeric unit comprising an amide moiety;
ii) at least one monomeric unit comprising an N-oxide moiety;
iii) and mixtures thereof;
c) optionally from 1% by weight, of a fabric softening active;
d) optionally less than 15% by weight, of a principal solvent;
e) optionally from 0.001% to 90% by weight, of one or more dye fixing agents;
g) optionally from 0.01% to 50% by weight, of one or more cellulose reactive
dye
fixing agents;
h) optionally from 0.01% to 15% by weight, of a chlorine scavenger:
i) optionally 0.005% to 1% by weight, of one or more crystal growth
inhibitors;
j) optionally from 1% to 12% by weight, of one or more liquid carriers;
k) optionally from 0.001% to 1% by weight, of an enzyme;
l) optionally from 0.01% to 8% by weight, of a polyolefin emulsion or
suspension;
m) optionally from 0.01% to 0.2% by weight, of a stabilizer;
n) optionally from 0.01 % by weight, of one or more linear or cyclic
polyamines
which provide bleach protection; and
o) the balance carrier and adjunct ingredients.
7. A pre-soak or rinse-added composition comprising:

49
a) from 0.01% by weight, of a fabric enhancement system, said fabric
enhancement
system comprising one or more modified polyamine compounds, said modified
polyamine compounds are selected from:
i) (PA)w(T)x:
ii) (PA)w(L)z;
iii) L(PA)w(T)x]y[L]z: and
iv) mixtures thereof;
wherein PA is a grafted or non-grafted, modified or unmodified polyamine
backbone unit, T is an amide-forming polycarboxylic acid crosslinking unit,
and
L is a non-amide forming crosslinking unit; provided that for compounds of
type
(i) and (iii) the indices w and x have values such that the ratio of w to x is
from
0.8:1 to 1.5:1; for compounds of type (ii) the indices w and z have values
such
that said modified polyamine compound comprises from 0.05 to 2 parts by
weight of said L unit; for compounds of type (iii) the indices y and z have
values
such that said modified polyamine compound comprises from 0.05 to 2 parts by
weight of said L unit;
b) from 1% to 80% by weight, of a fabric softening active: and
c) the balance carriers and adjunct ingredients.
8. A composition according to Claim 7 further comprising a dispersibility aid
system, said
system comprising:
i) 0.2% of ethoxylated cocoyl amine having an average of 10 ethoxy units; and
ii) 0.1% of ethoxylated cocoyl alcohol having an average of 10 ethoxy units.
9. A method for providing fabric with decreased abrasion damage comprising the
step of
contacting a fabric with a composition comprising:
a) from 0.01% by weight, of a fabric enhancement system, said fabric
enhancement
system comprising one or more modified polyamine compounds, said modified
polyamine compounds are selected from:
i) (PA)w(T)x:
ii) (PA)w(L)z;
iii) [(PA)w(T)x]y[L]z; and
iv) mixtures thereof;
wherein PA is a grafted or non-grafted, modified or unmodified polyamine
backbone unit, T is an amide-forming polycarboxylic acid crosslinking unit,
and

50
L is a non-amide forming crosslinking unit; provided that for compounds of
type
(i) and (iii) the indices w and x have values such that the ratio of w to x is
from
0.8:1 to 1.5:1; for compounds of type (ii) the indices w and z have values
such
that said modified polyamine compound comprises from 0.05 to 2 parts by
weight of said L unit; for compounds of type (iii) the indices y and z have
values
such that said modified polyamine compound comprises from 0.05 to 2 parts by
weight of said L unit;
b) from 1% to 80% by weight, of a fabric softening active; and
c) the balance carriers and adjunct ingredients.
10. A method according to Claim 9 wherein said composition further comprises:
d) optionally less than 15% by weight. of a principal solvent;
e) optionally from 0.001% to 90% by weight, of one or more dye fixing agents;
g) optionally from 0.01% to 50% by weight, of one or more cellulose reactive
dye
fixing agents;
h) optionally from 0.01% to 15% by weight, of a chlorine scavenger;
i) optionally 0.005% to 1% by weight, of one or more crystal growth
inhibitors;
j) optionally from 1% to 12% by weight, of one or more liquid carriers;
k) optionally from 0.001% to 1% by weight, of an enzyme;
l) optionally from 0.01% to 8% by weight, of a polyolefin emulsion or
suspension;
m) optionally from 0.01 % to 0.2% by weight, of a stabilizer;
n) optionally from 0.01% by weight, of one or more linear or cyclic; and
polyamines which provide bleach protection.

Description

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FABRIC ENHANCEMENT COMPOSITIONS
FIELD OF THE INVENTION
The present application relates to rinse-added fabric care compositions which
comprise
one or more crosslinked and/or grafted polyamines which provide enhanced
fabric appearance
benefits. The crosslinked and/or grafted polyamines of the present invention
which mitigate
fabric damage and improve fabric appearance may be combined with fabric
softener actives
compositions which mitigate fabric damage.
BACKGROUND OF THE INVENTION
The domestic treatment of fabric is a problem known in the art to the
formulator of laundry
compositions. Hence, It is well known that alternating cycles of using and
laundering fabrics and
textiles, such as articles of worn clothing and apparel, will inevitably
adversely affect the
appearance and integrity of the fabric and textile items so used and
laundered. Fabrics and
textiles simply wear out over time and with use. Laundering of fabrics and
textiles is necessary
to remove soils and stains which accumulate therein and thereon during
ordinary use. However;
the laundering operation itself, over many cycles, can accentuate and
contribute to the
deterioration of the integrity and the appearance of such fabrics and
textiles.
Deterioration of fabric integrity and appearance can manifest itself in
several ways.
Short fibers are dislodged from woven and knit fabric/textile structures by
the mechanical action
of laundering. These dislodged fibers may form lint, fuzz or "pills" which are
visible on the
surface of fabrics and diminish the appearance of newness of the fabric. Such
a problem of
fabric abrasion is even more acute after multiwash cycles.
'There exists a long felt need for compositions which provide fabric with
protection
against damage done due to fabric abrasion. In addition, there is a long felt
need to provide
compositions which provide a remedy for fabric abrasion damage.

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SUMMARY OF THE INVENTION
The present invention meets the aforementioned needs in that it has been
surprisingly
discovered that high molecular weight modified polyamine compounds, preferably
compounds
formed by the reaction of grafted or ungrafted and/or modified or unmodified
polyamines with a
crosslinking agent wherein said modified polyamine compounds have a molecular
weight of
from about 1,000 daltons, preferably from about 10,000 daltons to about 10
million daltons,
preferably to about 2.5 million daltons, are suitable for use in rinse-added
fabric care
compositions wherein said modified polyamines comprise a fabric enhancement
system which
provides fabric appearance benefits inter alia mitigation of fabric dye damage
via bleaching
agents, prevention of fabric mechanical damage.
A first aspect of the present invention relates to rinse-added fabric
enhancement or fabric
care compositions comprising:
a) from about 0.01 % by weight, of a fabric enhancement system, said fabric
enhancement system comprising one or more modified polyamine compounds,
said modified polyamine compounds are selected from:
i) (PA),~(T)~;
ii) (PA)W(L)Z~
iii) [(PA)W(T)~]Y[L]Z; and
iv) mixtures thereof;
wherein PA is a grafted or non-grafted, modified or unmodified polyamine
backbone unit, T is an amide-forming polycarboxylic acid crosslinking unit,
and
L is a non-amide forming crosslinking unit; provided that for compounds of
type
(i) and (iii) the indices w and x have values such that the ratio of w to x is
from
0.8 : 1 to 1.5 : 1; for compounds of type (ii) the indices w and z have values
such
that said modified polyamine compound comprises from about 0.05, preferably
from about 0.3 to 2 parts by weight of said L unit; for compounds of type
(iii) the
indices y and z have values such that said modified polyamine compound
comprises from about 0.05, preferably from about 0.3 to 2 parts by weight of
said L unit; and
b) the balance carriers and adjunct ingredients.
A second aspect of the present invention relates to fabric care compositions
comprising:
a) from about 0.01%, preferably from about 0.1% to about 20%, preferably to
about
10% by weight, of a modified polyamine compound according to the present
invention;

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3
b) optionally from about 0.01% by weight, of a fabric abrasion polymer
compnsmg:
i) at least one monomeric unit comprising an amide moiety;
ii) at least one monomeric unit comprising an N-oxide moiety;
iii) and mixtures thereof;
c) optionally from about 1%, preferably from about 10%, more preferably from
about 20% to about 80%, preferably to about 60%, more preferably to about 45%
by weight, of a fabric softening active;
d) optionally less than about 15% by weight, of a principal solvent,
preferably said
principal solvent has a ClogP of from about 0.15 to about l;
e) optionally from about 0.001 % to about 90% by weight, of one or more dye
fixing
agents;
g) optionally from about 0.01% to about SO% by weight, of one or more
cellulose
reactive dye fixing agents;
g) optionally from about 0.01% to about 15% by weight, of a chlorine
scavenger;
h) optionally about 0.005% to about 1 % by weight, of one or more crystal
growth
inhibitors;
i) optionally from about 1% to about 12% by weight, of one or more liquid
carriers;
j) optionally from about 0.001 % to about 1% by weight, of an enzyme;
k) optionally from about 0.01% to about 8% by weight, of a polyolefm emulsion
or
suspension;
1) optionally from about 0.01% to about 0.2% by weight, of a stabilizer;
m) optionally from about 0.01% by weight, of one or more linear or cyclic
polyamines which provide bleach protection; and
n) the balance carrier and adjunct ingredients.
The present invention also relates to a method for providing reduced fabric
abrasion to
fabric, said method comprising the step of contacting said fabric with a
composition which
comprises from about 0.01% by weight, of the herein described modified
polyamine fabric
enhancement system.
A further aspect of the present invention provides a method for enhancing the
color
fidelity of fabric while reducing the damage to fabric due to the interaction
of laundry adjunct
ingredients and damage due to mechanical wear. This method comprises the step
of contacting
an article of fabric with the compositions of the present invention in an
aqueous solution.

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The present invention further provides laundry pre-soak compositions which are
used to
pre-treat fabric which have not been previously treated with a composition of
the present
invention. The disclosed pre-treatment compositions provide fabric and fabric
color protection
though the wash to the treated articles.
These and other objects, features and advantages will become apparent to those
of
ordinary skill in the art from a reading of the following detailed description
and the appended
claims. All percentages, ratios and proportions herein are by weight, unless
otherwise specified.
All temperatures are in degrees Celsius (° C) unless otherwise
specified. All documents cited are
in relevant part, incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to fabric enhancement compositions which
comprise from
about 0.01 %, preferably from about 0.1 %, more preferably from 0.25%, most
preferably from
about 0.5% to about 20%, preferably to about 10%, more preferably to about 5%
by weight, of a
fabric enhancement system. Said fabric enhancement system is comprised of one
or more
modified polyamine compounds. The fabric care and/or fabric enhancement
compositions may
take any form, for example, solids (i.e., powders, granules, extrudates),
gels, thixotropic liquids,
liquids (i.e., dispersions, isotropic solutions), preferably the rinse-added
fabric conditioning
compositions take the form of liquid dispersions or isotropic liquids.
For the purposes of the present invention the terms "fabric enhancement" and
"fabric
care" are used interchangeable throughout the present specification and stand
equally well for
one another. Fabric enhancement/fabric care is achieved when the properties
inter alia color,
fiber integrity of the garment are conserved. An additional benefit realized
by the use of the
compositions of the present invention is a reversion of much of the damage
which has occurred
to fabric which has never been treated with the herein described fabric
enhancement
compositions.
Fabric Enhancement System
The fabric enhancement system of the present invention is comprised of one or
more
modified polyamines according to the present invention. The modified
polyamines of the present
invention which comprise the fabric enhancement system may be formulated as an
admixture
wherein a proportional amount of two or more compounds are combined to make up
the fabric
enhancement system. Alternatively, the formulator may adjust the reaction
conditions which
form the modified polyamines of the present invention in order to create an
admixture of suitable
ingredients inter alia an admixture of polyamine fragments and/or partially
crosslinked modified
polyamines. Whether a formulated admixture or a product by process is used, or
a mixture of

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both, the compounds which comprise the fabric enhancement compositions of the
present
invention have the formula:
i) (PA)W(T)X;
ii) (PA)W(L)Z;
5 iii) [(PA)W(T)x]Y[L]Z;
wherein PA is a grafted or non-grafted, modified or unmodified polyamine
backbone unit, T is an
amide-forming polycarboxylic acid crosslinking unit, and L is a non-amide
forming crosslinking
unit. For compounds of type (i) and (iii) the relative amounts of PA units and
T units which are
present are such that the molar ratio of PA units to T units is from 0.8 : 1
to 1.5 : 1. For
compounds of type (ii) the relative amounts of PA units and L units which are
present are such
that the (PA)W(L)Z comprises from about 0.05, preferably from about 0.3 to 2
parts by weight of
said L units. Therefore, 1 part of a grafted or non-grafted, modified or
unmodified polyamine
backbone unit may be combined with from about 0.05, preferably from about 0.3
parts by weight
of an L unit to about 2 parts by weight of an L unit to form a suitable
modified polyamine
compound. Likewise, for compounds of type (iii), crosslinked polyamines having
the formula
(PA)W(T)a may be combined with from about 0.05, preferably from about 0.3
parts by weight of
an L unit to about 2 parts by weight of an L unit to form a suitable modified
polyamine
compound having the formula [(PA)W(T)X]Y[L)Z.
Polvamine Backbone~PA units)
The modified polyamine compounds of the present invention comprise a Polyamine
Backbone, PA unit, which can be optionally, but preferably grafted. The
following are non-
limiting examples of suitable PA units according to the present invention.
Polyalkyleneimine
A preferred PA unit according to the present invention are polyalkyleneimines
and
polyalkyleneamines having the general formula:
H B
[HZN-R]W [N-R]X [N-R]y NH2
wherein R is C,-C,, linear alkylene, C3-C,~ branched alkylene, and mixtures
thereof; B
representing a continuation of the chain structure by branching. The indices
w, x, and y have
various values depending upon such factors as molecular weight and relative
degree of
branching. The polyalkyleneimines and polyalkyleneamines which comprise PA
units of the
present invention are divided into three categories based upon relative
molecular weight. The
terms polyalkyleneimine and polyalkyleneamine are used interchangeably
throughout the present

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6
specification and are taken to mean polyamines having the general formula
indicated above
regardless of method of preparation.
Low Molecular Wei hg t Polyalkyleneimines
For low molecular weight polyalkyleneimines having the formula:
S
H B
LHzN- R~ W LI'1- R~x L1'I- Ray ~z
R is CZ-C,, linear alkylene, C3-C,~ branched alkylene, and mixtures thereof;
preferably R is
ethylene, 1,3-propylene, and 1,6-hexylene, more preferred is ethylene. The
indices w, x, and y
are such that the molecular weight of said polyamines does not exceed about
600 daltons. For
example, for an entirely linear polyethyleneimine having a molecular weight of
about 600
daltons, the index w = 1, x = 13, and y = 0. For an entirely branched
polyethyleneimine having a
molecular weight of approximately 600 daltons, w = 8, x = 0 and y =7. (This
combination of
indices results in a material having an average molecular weight of about 646
daltons, which, for
the purposes of the present invention is a low molecular weight
polyalkyleneimine.) The index w
1 S typically has the value of y + 1. The simplest of the low molecular weight
polyamines of this
type is ethylene diamine which may be present up to about 10% by weight of the
PA unit
mixture. Non-limiting examples of low molecular weight polyalkyleneimine PA
units include
diethylene triamine, triethylene tetramine, tetraethylene pentamine,
dipropylene triamine,
tripropylene tetramine, and dihexamethylene triamine. PA units may be used as
crude products
or mixtures, and if desired by the formulator, these PA units may be used in
the presence of small
amounts of diamines as described herein above, wherein the amount of diamines,
inter alia,
ethylene diamine, hexamethylene diamine may be present up to about 10% by
weight, of the PA
unit mixture.
Medium Range Molecular Wei hg t Pol~yleneimines
2S For medium range molecular weight polyalkyleneimines having the formula:
H B
~HzN- R~ W L1'1- R~ X L1'1- Rly NHz
R is C~-C4 linear alkylene, C3-C4 branched alkylene, and mixtures thereof;
preferably R is
ethylene, 1,3-propylene, and mixtures thereof, more preferred is ethylene
wherein said
polyamines are polyethyleneimines (PEI's). The indices w, x, and y are such
that the molecular
weight of said polyamines is from about 600 daltons to about 50,000 daltons.
The indices w, x,
and y will indicate not only the molecular weight of the polyalkyleneimines
but also the degree
of branching present in the PA unit backbone.

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~h Molecular Wei hg t Pol~kyleneimines
For high molecular weight polyalkyleneimines having the formula:
H B
~H2N-R~w ~- R~x ~- R~y ~2
R is C~-C3 linear alkylene, preferably R is ethylene. The indices w, x, and y
are such that the
molecular weight of said polyamines is from about 50,000 daltons to about
1,000,000 (1 million)
daltons. The indices w, x, and y will indicate not only the molecular weight
of the
polyalkyleneimines but also the degree of branching present in the PA unit
backbone.
Co~olymeric Polyamines
Another example of a preferred PA unit according to the present invention are
the
polyvinyl amine homo-polymers or co-polymers having the formula:
~2
--EV CHZCH
m n
wherein V is a co-monomer, non-limiting examples of which include vinyl
amides, vinyl
pyrrolidone, vinyl imidazole, vinyl esters, vinyl alcohols, and mixtures
thereof all of which can
be taken together or in combination with polyvinyl amine to form suitable co-
polymerization
products suitable for use in the fabric enhancement systems of the present
invention. The indices
m and n are such that the copolymers comprise at least 10%, more preferably at
least about 30%
of units derived from vinyl amine and wherein further the molecular weight of
said copolymers if
from about 500 daltons, preferably from about 5,000 daltons to about 50,000
daltons, preferably
to about 20,000 daltons.
Polvamine Backbone Modifications
Optionally, but preferably, the PA units of the present invention are modified
either
before or after reaction with a T unit or L unit crosslinking agent. The two
preferred types of
modifications are grafting and capping.
Preferably the PA units of the present invention are grafted, that is the PA
unit is further
reacted with a reagent which elongates said PA unit chain, preferably by
reaction of the nitrogens
of the PA backbone unit with one or more equivalents of aziridine
(ethyleneimine), caprolactam,
and mixtures thereof. Grafting units, in contrast to the "capping" units
described herein below,
can further react on themselves to provide PA unit chain propagation. An
example of a preferred
grafted PA unit of the present invention has the formula:

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G B
[G2N- R] W LI'1- R] X Ll'1- R]y NG2
wherein R, B, w, x, and y are the same as defined herein above and G is
hydrogen or an extension
of the PA unit backbone by grafting. Non-limiting examples of preferred
grafting agents are
aziridine (ethyleneimine), caprolactam, and mixtures thereof. A preferred
grafting agent is
aziridine wherein the backbone is extended by units having the formula:
B~
I
-[CH2CHZNH]p[CHZCH2N]qCH2CH2NH2
wherein B' is a continuation by branching wherein the graft does not exceed
about 12 units,
preferably -CHzCH2NH2 and the value of the indices p + q have the value from
0, preferably from
about l, more preferably from about 2 to about 7, preferably to about 5.
Another preferred
grafting unit is caprolactam.
The PA units of the present invention can be grafted prior to or after
crosslinking with
one or more T units described herein below, preferably the grafting is
accomplished after
crosslinking with said T unit. This allows the formulator to take advantage of
the differential
reactivity between the primary and secondary amino units of the PA unit
backbone thereby
allowing the formulator to controllably link said PA units and to also control
the amount of
subsequent branching which results from the grafting step.
Another optional but preferred PA unit modification is the presence of
"capping" units.
For example, a PA unit is reacted with an amount of a monocarboxylic acid, non-
limiting
examples of which are C,-C2, linear or branched alkyl, preferably C,o-C,g
linear alkyl hater alia
lauric acid, myristic acid. The amount of capping unit which is reacted with
the PA unit is an
amount which is sufficient to achieve the desired properties of the formula.
However, the
amount of capping unit used is not sufficient to abate any further
crosslinking or grafting which
the formulator may choose to perform.
Crosslinkin~ Units
Amide-forming T Crosslinkin~ Units
T crosslinking units are preferably carbonyl comprising polyamido forming
units. The T
units are taken together with PA units to form crosslinked modified polyamine
compounds
having the formula (PA)w,(T)~ or [(PA)W(T)X]Y[L]Z.
A preferred embodiment of the present invention includes crosslinked PA units
wherein
a T unit provides crosslinking between two or more PA units to form a
(PA),~(T)X polyamido
crosslinked section. A preferred crosslinking T unit has the general formula:

CA 02359438 2001-07-25
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9
O O
-C-(RZ)~-(R~)k-(RZ)j C
wherein R' is methylene, phenylene, and mixtures thereof; preferably
methylene. The index k has
the value from 2 to about 8, preferably to about 4. Preferred values of k are
2, 3, and 4. RZ is -
S NH- thereby forming a urethane amide linkage when said R'- comprising T
units react with the
backbone nitrogens of the PA units. The value of the index j is independently
0 or 1. The
presence of R-' units can result, for example, from the use of diisocyanates
as crosslinking agents.
Non-limiting examples of dibasic acids which are used as a source for T units
in the above
formula include succinic acid, malefic acid, adipic acid, glutaric acid,
suberic acid, sebacic acid,
and terephthalic acid. However, the formulator is not limited to crosslinking
T units deriving
from dibasic acids, for example, tribasic crosslinking T units, inter alia,
citl-ate, may be used to
link the PA units of the present invention.
Examples of (PA)W(T),~ compounds according to the present invention are
obtained by
condensation of dicarboxylic acids irater alia succinic acid, malefic acid,
adipic acid, terephthalic
acid, with polyalkylene polyamines intef° alia diethylenetriamine,
triethylenetetramine,
dipropylenetriamine, tripropylenetetramine wherein the ratio of the
dicarboxylic acid to
polyalkyleneamine is from 1:0.8 to 1:1.5 moles, preferably a ratio of from I
:0.9 to 1:1.2 moles
wherein the resulting crosslinked material has a viscosity in a 50% by weight,
aqueous solution
of more than 100 centipoise at 25 °C.
Non-amide Forming L Crosslinking Units
Another preferred embodiment of the polyamines of the present invention are
(PA)",(T)c
units which are further crosslinked by L units to form polyamido amines having
the formula
[(PA)W(T)t]y,[L], or are reacted with PA units to form non-amide polyamines
having the formula
(PA)W(L)Z~
The L units of the present invention are any unit which suitably crosslinks PA
units or
(PA)",(T)~ units. Preferred L linking units comprise units which are derived
from the use of
epihalohydrins, preferably epichlorohydrin, as a crosslinking agent. The
epihalohydrins can be
used directly with the PA units or suitably combined with other crosslinking
adjuncts non-
limiting examples of which include alkyleneglycols, and polyalkylene
polyglycols itzter alia
ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol,
dipropylene glycol,
polypropylene glycol, butylene glycol, hexanediol-1,6-glycerol, oligoglycerol,
pentaerythrites,
polyols which are obtained by the reduction of carbohydrates (sorbitol,
mannitol),
monosaccharides, disaccharides, oligosaccharides, polysaccharides, polyvinyl
alcohols, and
mixtures thereof.

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For example, a suitable L unit is a dodecylene unit having the formula:
-(CHZ) 12-
wherein an equivalent of 1,12-dichlorododecane is reacted, for example, with a
suitable amount
5 of a PA unit to produce a polyamine which is crosslinked via dodecylene
units. For the purposes
of the present invention, L crosslinking units which comprise only carbon and
hydrogen are
considered to be "hydrocarbyl" L units. Preferred hydrocarbyl units are
polyalkylene units have
the formula:
10 -(CH2)n~
wherein n is from 1 to about 50.
Hydrocarbyl L units may be derived from hydrocarbons having two units which
are
capable of reacting with the nitrogen of the PA units. Non-limiting examples
of precursors
which result in the formation of hydrocarbyl L units include 1,6-
dibromohexane, 1,8-
ditosyloctane, and 1,14-dichlorotetradecane.
Further examples of preferred non-amide forming crosslinking L units are the
units
which derive from crosslinking units wherein epihalohydrin is used as the
connecting unit. For
example, 1,12-dihydroxydodecane is reacted with epichlorohydrin to form the
bis-epoxide non-
amide forming L unit precursor having the formula:
OI,-CH20-(CH2)IZ-OCH2--
O
which when reacted with one or more PA units or (PA)W(T)~ units results in an
L crosslinking
unit having the formula:
-CH2- i H-CH20-(CHZ)i2-OCHZ- i H-CH2-
OH OH
however, it is not necessary to pre-form and isolate the bis-epoxide, instead
the crosslinking unit
precursor may be formed in situ by reaction of 1,12-dihydroxydodecane or other
suitable
precursor unit with epihalohydrin in the presence of grafted or ungrafted PA
units or (PA)W(T)x
units.
Other crosslinking L units which utilize one or more epihalohydrin connecting
units
include polyalkyleneoxy L units having the formula:

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11
CH2- i H-CHZ-O(Rl0),~R20)y-CH2- i H-CH2-
OH OH
wherein R' is ethylene, Rz is 1,2-propylene, x is from 0 to 100 and y is from
0 to 100.
Another preferred unit which can comprise an L unit and which can be suitably
combined with
epihalohydrin connecting units include polyhydroxy units having the formula:
OH
-CH2- i H-CHZ-O(CHZ)t(CH)u0-CH2- i H-CH2-
OH OH
wherein the index t is from at least 2 to about 20 and the index a is from 1
to about 6. The
formulator may also combine units to form hybrid L crosslinking units, for
example, units having
the formula:
OH
-CHZ- i H-CH2 O(CHZ)t(CH)uO O(R1O)x(R2O)y CH2°CH-CHZ
OH W L yL off
wherein the indexes w and y are each independently from 1 to 50, z is units
are present in a
sufficient to suitably connect the polyhydroxy units and the polyalkyleneoxy
units into the
backbone without the formation of ether linkages.
The following is an example of an L linking group which comprises both a
polyalkyleneoxy and a polyhydroxy unit.
OH i HZOH
-CHZ i HCHZ-OCHZCH i HCHCHO-CHZ i HCHZ-O(CH2CH20)4-CHZ i HCH2
OH OH OH OH
A further example of a preferred crosslinking L units are units which
comprises at least
two aziridine groups as connecting groups, for example an L unit having the
formula:
O O
C N-CHZCHZ-NH-C-(CH2)0.~-C-NH-CHZCHZ-N
which can be used to link two (PA)W units, two (PA)";(T)X units, or mixtures
thereof.
The polyamines of the present invention may have varying final compositions,
for
example, (PA)",(T)" [(PA)W(T),]y,[L]Z, [(PA)]w,[L]Z, and mixtures thereof,
wherein each PA unit

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12
may be grafted or ungrafted. The indices w and x have values such that the
ratio of w to x is
from 0.8 : 1 to 1.5 : 1; y and z have values such that said polyamido compound
comprises from
about 0.05, preferably to about 0.3 to 2 parts by weight of said L unit. In
the cases wherein no
crosslinking takes place the indices w and y will be equal to 1 and x and z
will be equal to 0. In
the case wherein no crosslinking occurs using L units, the index y is equal to
1 and z is equal to
0. In the case wherein no crosslinking occurs using T units, the indices w and
y are equal to 1
and x is equal to 0.
An preferred embodiment of the present invention which comprises PA units, T
units,
and L units includes the reaction product of:
a) 1 part by weight, of a polyamine obtained by condensation of 1 mole of a
dicarboxylic acid with a polyalkylene polyamine (i.e., diethylenetriamine) to
the
extent wherein at least about 10% of the -NH backbone hydrogens are
unmodified by reaction with said dicarboxylic acid, then optionally reacting
the
obtained polyamine condensation product with up to 12 ethyleneimine units
(i.e.,
grafting of the backbone using aziridine) per basic nitrogen atom; and
b) further reacting the product obtained in (a) with from 0.05, preferably
from about
0.3 to about 2 parts by weight, of an L units, itzter alia the reaction
product of a
polyalkylene oxide having from 8 to 100 alkylene oxide units with
epichlorohydrin at a temperature of from about 20 °C to about 100
°C.
A preferred embodiment of the present invention are the water-soluble
condensation
products which can be obtained by the reaction of:
a) polyalkyleneimines and polyalkyleneimines grafted with ethyleneimines, and
mixtures thereof; with
b) at least bifunctional halogen-free cross-linking agents, said agents
selected from
the group consisting of:
i) ethylene carbonate, propylene carbonate, urea, and mixtures thereof;
ii) mono-carboxylic acids comprising one olefin moiety inter alia acrylic
acid, methacrylic acid, crotonic acid; and the esters, amides, and
anhydrides thereof; polycarboxylic acids inter alia oxalic acid, succinic
acid, tartaric acid, itaconic acid, malefic acid; and the esters, amides, and
anhydrides thereof;
iii) reaction products of polyetherdiamines, alkylenediamines, polyalkylene-
diamines, and mixtures thereof, with mono-carboxylic acids comprising
one olefin moiety wherein the resulting polyamine comprises a
functional units which is selected from the group consisting of at least

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13
two ethylenically unsaturated double bonds, carbonamide, carboxyl
group, ester group, and mixtures thereof;
iv) at least two aziridine group-containing reaction products of dicarboxylic
acid esters with ethyleneimine and mixtures of the cross-linking agents.
However, prior to reaction of (PA)W(T),~ units formed herein above, the
(PA),~(T)X
polyamine compound may be partially amidated ("capped" as described herein
above) by
treatment with a mono carboxylic acid or the esters of mono carboxylic acids.
The formulator
may vary the degree to which the backbone nitrogens are amidated according to
the desired
properties of the final Fabric Enhancement Polymer. Non-limiting examples of
suitable mono-
carboxylic acids include formic acid, acetic acid, propionic acid, benzoic
acid, salicylic acid,
lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, behenic
acid, and mixtures
thereof.
The high molecular weight modified polyamine condensation products of the
present
invention (also referred to herein as "resins") are preferably formed from the
reaction of one or
more grafted, cross-linked polyethyleneimines and one or more polyethylene
and/or
polypropylene glycol copolymers, wherein the resulting crosslinked modified
polyamines
(resins) have a final viscosity of more than or equal to 300 mPa-sec.,
preferably from 400 to
2,500 mPa-sec. when measured at 20° C in a 20% aqueous solution. The
modified polyamine
compounds of the present invention are suitably described in U.S. 3,642,572
Eadres et al., issued
February 15, 1972, U.S. 4,144,123 Scharf et al., issued March 13, 1979 and
U.S. 4,371,674
Hertel et al., issued February 1, 1983, NE 6,612,293, DT 1,946,471, DT 36386,
DT 733,973, DE
1,771,814, all of which are included herein by reference.
FABRIC CARE COMPOSITIONS
The present invention relates to fabric care compositions which comprise:
a) from about 0.01 %, preferably from about 0.1 % to about 20%, preferably to
about
10% by weight, of a fabric enhancement system according to the present
invention;
b) optionally from about 0.01% by weight, of a fabric abrasion polymer
comprising:
i) at least one monomeric unit comprising an amide moiety;
ii) at least one monomeric unit comprising an N-oxide moiety;
iii) and mixtures thereof;

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14
c) optionally from about 1%, preferably from about 10%, more preferably from
about 20% to about 80%, preferably to about 60%, more preferably to about 45%
by weight, of a fabric softening active;
d) optionally less than about 15% by weight, of a principal solvent,
preferably said
principal solvent has a ClogP of from about 0.15 to about 1;
e) optionally from about 0.001% to about 90% by weight, of one or more dye
fixing
agents;
g) optionally from about 0.01 % to about 50% by weight, of one or more
cellulose
reactive dye fixing agents;
h) optionally from about 0.01% to about 15% by weight, of a chlorine
scavenger;
i) optionally about 0.005% to about 1% by weight, of one or more crystal
growth
inhibitors;
j) optionally from about 1% to about 12% by weight, of one or more liquid
carriers;
k) optionally from about 0.001 % to about 1 % by weight, of an enzyme;
1) optionally from about 0.01% to about 8% by weight, of a polyolefin emulsion
or
suspension;
m) optionally from about 0.01 % to about 0.2% by weight, of a stabilizer;
n) optionally from about 0.01 % by weight, of one or more linear or cyclic
polyamines which provide bleach protection; and
o) the balance carrier and adjunct ingredients.
One aspect of the fabric enhancement systems of the present invention is the
combination
of the enhancement system and a cationic fabric softening active. A preferred
embodiment of the
present invention provides for rinse-added compositions which comprise:
a) from about 0.01 % by weight, of a fabric enhancement system, said fabric
enhancement system comprising one or more modified polyamine compounds,
said modified polyamine compounds are selected from:
i) (PA),~(T)X;
ii) (PA)W(L)Z~
iii) [(PA)W(T)a]Y[L]Z; and
iv) mixtures thereof;
wherein PA is a grafted or non-grafted, modified or unmodified polyamine
backbone unit, T is an amide-forming polycarboxylic acid crosslinking unit,
and
L is a non-amide forming crosslinking unit; provided that for compounds of
type
(i) and (iii) the indices w and x have values such that the ratio of w to x is
from

CA 02359438 2001-07-25
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0.8 : 1 to 1.5 : 1; for compounds of type (ii) the indices w and z have values
such
that said modified polyamine compound comprises from about 0.05, preferably
from about 0.3 to 2 parts by weight of said L unit; for compounds of type
(iii) the
indices y and z have values such that said modified polyamine compound
comprises from about 0.05, preferably from about 0.3 to 2 parts by weight of
said L unit;
b) an effective amount of a cationic fabric softener active as described
herein
below; and
c) the balance carriers and adjunct ingredients.
10 For the purposes of the present invention the term "effective amount" of a
fabric softener
active may vary depending upon the execution of the fabric softener
formulation. Certain
embodiments may comprise from 6% to about 9%, preferably about 8% by weight,
of a fabric
softener active, while isotropic liquid embodiments may comprise from about
28% to bout 45%
by weight of a cationic softener active. Other embodiments may comprise
amounts between the
15 two ranges.
The fabric care compositions of the present invention comprise one or more
modified
polyamine compounds as described herein. For the purposes of the present
invention the term
"fabric care compositions" is defined as "a composition which provides care to
the fabric non-
limiting examples of which include stand-alone compositions, detergent
additives, fabric
softening compositions inter alia rinse-added softening composition, dryer-
added softening
compositions". The compositions of the present invention provide an efficient
fabric abrasion
reduction. The term "efficient fabric abrasion reduction" is defined herein as
"fabric which has
been treated by the herein described compositions have an improved appearance
relative to
fabrics which have been un-treated by the herein disclosed compositions.
The following are non-limiting examples of ingredients which can be combined
with the
modified polyamine compounds of the present invention.
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 prefered reduced abrasion polymers of the present invention are water-
soluble
polymers. For the purposes of the present invention the term "water-soluble"
is defined as "a
polymer which when dissolved in water at a level of 0.2% by weight, or less,
at 25° C, forms a
clear, isotropic liquid".

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16
The fabric abrasion reducing polymers useful in the present invention have the
formula:
[-P~D)m ]n
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:
-[CRZ-CR2]- or -[(CR2)X L]-
wherein each R unit is independently hydrogen, C,-C,2 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:
i
R O O O O
-N- -O- -O-C- -C-O- -O-C-O- -C
> > > > >
O O O O O
S ' S ' II ' O II ' (I O ' O II O
O O O O
polysiloxane having the formula:
R2
O Si-O
R2
p
wherein the index p is from 1 to about 6; units which have dye transfer
inhibition activity:

CA 02359438 2001-07-25
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17
4
R O O
-N- -N-C- -C-N-
9 f
R3 R3
and mixtures thereof; wherein R' is hydrogen, C,-C,, alkyl, C6-C,, aryl, and
mixtures thereof. R'
is C,-C,Z alkyl, C,-C,2 alkoxy, C6-C,~ aryloxy, and mixtures thereof;
preferably methyl and
methoxy. R3 is hydrogen C,-C,~ alkyl, C~-C,~ aryl, and mixtures thereof;
preferably hydrogen or
S C,-C., alkyl, more preferably hydrogen. R4 is C,-C,~ 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)ni ]n
or the D unit may be incorporated into the backbone as a pendant group to a
backbone unit
having, for example, the formula:
- [ i R-CR2]- or - [( i R)X L]
D D
However, the number of D units depends upon the formulation. For example, the
number of D
units will be adjusted to provide water solubility of the polymer as well as
efficacy of 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, more preferably from about 100,000
most preferably
from 160,000 to about 6,000,000, preferably to about 2,000,000, more
preferably to about
1,000,000, yet more preferably to about 500,000, most preferably to about
360,000 daltons.
Therefore the value of the index n is selected to provide the indicated
molecular weight, and
providing for a water solubility of least 100 ppm, preferably at least about
300 ppm, and more
preferably at least about 1,000 ppm in water at ambient temperature which is
defined herein as
25°C.
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:

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18
-[ i H-CH2~n
N
~~O
polyvinyloxazolidone having the formula:
-[ i H-CH2~ri
N
~O
O
polyvinylmethyloxazolidone having the formula:
-[ i H-CHzln-
N
~O
O
H3C
polyacrylamides and N-substituted polyacrylamides having the formula:
-[ i H-CH2~n-
C=O
N(R)2
wherein each R' is independently hydrogen, C,-C~; 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 -CH2~ri
C=O
N(R)2
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:

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19
- (CH-CH2]ri
C=O O
NH-CH2-C-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; poly(N-methacrylylglycinamide) having
the formula:
~H3
-( i -CH2]n~
C=O O
~-CH2-C-N(R~)2
wherein each R' is independently hydrogen, C,-C~ alkyl, or both R' units can
be taken together to
form a ring comprising 4-6 carbon atoms; polyvinylurethanes having the
formula:
-[ i H-CH2]n
O
C=O
N(R~)z
wherein each R' is independently hydrogen, C,-C~, alkyl, or both R' units can
be taken together to
form a ring comprising 4-6 carbon atoms.
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:
-[CH2-CHZ-N]p
C=O
CH2CH3
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 dye 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,
polyvinyloxazolidones, N,N-disubstituted polyacrylamides, and N,N-
disubstituted
polymethacrylamides. A detailed description of physico-chemical properties of
some of these

CA 02359438 2001-07-25
WO 00/49122 PCT/US00/03933
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-attracting 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
10 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)
IS 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 1.3MM, commercially available ex Aldrich is also
suitable for use
20 herein. Yet further PVP-type of material suitable for use in the present
invention are
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 a ,
available in vinylpyrrolidone:vinylacetate ratios of from 3:7 to 7:3.
Polymers Comprising.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
RI- ~ -Rs
RZ

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21
wherein R', R'-, and R3 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 Pkd
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
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 amidelN-oxide polymers. However, the resulting
polymers must
retain the water solubility requirements described herein above.
Molecular wei r~ht
For all the above described fabric abrasion reducing 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

CA 02359438 2001-07-25
WO 00/49122 PCT/US00/03933
22
reduction of fabric abrasion which typically occurs subsequent to treatment,
for example during
garment use, especially in a later 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 rate of deposition onto the fabric surface and 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 inter
alia the attraction 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.
Dve Fixing A ents
The compositions of the present invention optionally comprise from about
0.001%,
preferably from about 0.5% to about 90%, preferably to about 50%, more
preferably to about
10%, most preferably to about 5% by weight, of one or more dye fixing agents.
Dye fixing agents, or "fixatives", are well-known, commercially available
materials
which are designed to improve the appearance of dyed fabrics by minimizing the
loss of dye
from fabrics due to washing. Not included within this deEnition are components
which can in
some embodiments serve as fabric softener actives.
Many dye fixing agents are cationic, and are based on quaternized nitrogen
compound or
on nitrogen compounds having a strong cationic charge which is formed in sitcc
under the
conditions of usage. Cationic fixatives a_re available under various trade
names from several
suppliers. Representative examples include: CROSCOLOR PMF (July 1981, Code No.
7894)
and CROSCOLOR NOFF (January 1988, Code No. 8544) ex Crosfield; INDOSOL E-50
(February 27, 1984, Ref. No. 6008.35.84; polyethyleneamine-based) ex Sandoz;
SANDOFIX
TPS, ex Sandoz, is a preferred dye fixative for use herein. Additional non-
limiting examples
include SANDOFIX SWE (a cationic resinous compound) ex Sandoz, REWIN SRF,
REWIN
SRF-O and REWIN DWR ex CHT-Beitlich GMBH; Tinofix~ ECO, Tinofix0 FRD and
SolfinO
ex Ciba-Geigy. A preferred dye fixing agent for use in the compositions of the
present invention
is CARTAFIX CB~ ex Clariant.
Other cationic dye fixing agents are described in "Afterneatments for
Improving the
Fastness of Dyes on Textile Fibres", Christopher C. Cook, Rev. Prog.
Coloration, Vol. XII,

CA 02359438 2001-07-25
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23
(1982). Dye fixing agents suitable for use in the present invention are
ammonium compounds
such as fatty acid-diamine condensates inter alia the hydrochloride, acetate,
metosulphate and
benzyl hydrochloride salts of diamine esters. Non-limiting examples include
oleyldiethyl
aminoethylamide, oleylmethyl diethylenediamine methosulphate,
monostearylethylene
S diaminotrimethylammonium methosulphate. In addition, the N-oxides of
tertiary amines;
derivatives of polymeric alkyldiamines, polyamine-cyanuric chloride
condensates, and aminated
glycerol dichlorohydrins are suitable for use as dye fixatives in the
compositions of the present
invention.
Cellulose Reactive Dve Fixing Aged
Another dye fixing agent suitable for use in the present invention are
cellulose reactive
dye fixing agents. The compositions of the present invention optionally
comprise from about
0.01%, preferably from about 0.05%, more preferably from about 0.5% to about
50%, preferably
to about 25%, more preferably to about 10% by weight, most preferably to about
5% by weight,
of one or more cellulose reactive dye fixing agents. The cellulose reactive
dye fixatives may be
1 S suitably combined with one or more dye fixatives described herein above in
order to comprise a
"dye fixative system".
The term "cellulose reactive dye fixing agent" is defined herein as "a dye
fixative agent
which reacts with the cellulose fibers upon application of heat or upon a heat
treatment either in
situ or by the formulator". The cellulose reactive dye fixing agents suitable
for use in the present
invention can be defined by the following test procedure.
Cellulose Reactivity Test (CRT)
Four pieces of fabric which are capable of bleeding their dye (e.g. 10 x 10 cm
of knitted
cotton dyed with Direct Red 80) are selected. Two swatches are used as a first
control and a
second control, respectively. The two remaining swatches are soaked for 20
minutes in an
aqueous solution containing 1% (w/w) of the cellulose reactive dye fixing
agent to be tested. The
swatches are removed and thoroughly dried. One of the treated swatches which
has been
thoroughly dried, is passed ten times through an ironing calender which is
adjusted to a "linen
fabric" temperature setting. The first control swatch is also passed ten times
through an ironing
calender on the same temperature setting.
All four swatches ( the two control swatches and the two treated swatches, one
of each
which has been treated by the ironing calender) are washed separately in
Launder-O-Meter pots
under typical conditions with a commercial detergent used at the recommended
dosage for '/2
hour at 60°C, followed by a thorough rinsing of 4 times 200 ml of cold
water and subsequently
line dried.

CA 02359438 2001-07-25
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24
Color fastness is then measured by comparing the DE values of a new untreated
swatch
with the four swatches which have undergone the testing. DE values, the
computed color
difference, is defined in ASTM D2244. In general, DE values relate to the
magnitude and
direction of the difference between two psychophysical color stimuli defined
by tristimulus
values, or by chromaticity coordinates and luminance factor, as computed by
means of a
specified set of color-difference equations defined in the CIE 1976 CIELAB
opponent-color
space, the Hunter opponent-color space, the Friele-Mac Adam-Chickering color
space or any
equivalent color space. For the purposes of the present invention, the lower
the DE value for a
sample, the closer the sample is to the un-tested sample and the greater the
color fastness benefit.
As the test relates to selection or a cellulose reactive dye fixing agent, if
the DE value for
the swatch treated in the ironing step has a value which is better than the
two control swatches,
the candidate is a cellulose reactive dye fixing agent for the purposes of the
invention.
Typically cellulose reactive dye fixing agents are compounds which contain a
cellulose
reactive moiety, non limiting examples of these compounds include halogeno-
triazines, vinyl
sulphones, epichlorhydrine derivatives, hydroxyethylene urea derivatives,
formaldehyde
condensation products, polycarboxylates, glyoxal and glutaraldehyde
derivatives, and mixtures
thereof. Further examples can be found in "Textile Processing and Properties",
Tyrone L. Vigo,
at page 120 to 121, Elsevier (1997), which discloses specific electrophilic
groups and their
corresponding cellulose affinity.
Preferred hydroxyethylene urea derivatives include
dimethyloldihydroxyethylene, urea,
and dimethyl urea glyoxal. Preferred formaldehyde condensation products
include the
condensation products derived from formaldehyde and a group selected from an
amino-group, an
imino-group, a phenol group, an urea group, a cyanamide group and an aromatic
group.
Commercially available compounds among this class are Sandofix WE 56 ex
Clariant, Zetex E
ex Zeneca and Levogen BF ex Bayer. Preferred polycarboxylates derivatives
include butane
tetracarboxilic acid derivatives, citric acid derivatives, polyacrylates and
derivatives thereof. A
most preferred cellulosic reactive dye fixing agents is one of the
hydroxyethylene urea
derivatives class commercialized under the tradename of Indosol CR ex
Clariant. Still other most
preferred cellulosic reactive dye fixing agents are commercialized under the
tradename Rewin
DWR and Rewin WBS ex CHT R. Beitlich.
Chlorine Scaven ers
The compositions of the present invention optionally comprise from about
0.01%,
preferably from about 0.02%, more preferably from about 0.25% to about 15%,
preferably to
about 10%, more preferably to about 5% by weight, of a chlorine scavenger. In
cases wherein

CA 02359438 2001-07-25
WO 00/49122 PCT/US00/03933
the canon portion and the anion portion of the non-polymeric scavenger each
react with chlorine,
the amount of scavenger can be adjusted to fit the needs of the formulator.
Suitable chlorine scavengers include ammonium salts having the formula:
5 L(R)3R11'l] + X -
wherein each R is independently hydrogen, C,-C4 alkyl, C,-C4 substituted
alkyl, and mixtures
thereof, preferably R is hydrogen or methyl, more preferably hydrogen. R' is
hydrogen C,-C9
alkyl, C,-C~ substituted alkyl, and mixtures thereof, preferably R is
hydrogen. X is a compatible
anion, non-limiting examples include chloride, bromide, citrate, sulfate;
preferably X is chloride.
10 Non-limiting examples of preferred chlorine scavengers includ ammonium
chloride,
ammonium sulfate, and mixtures thereof; preferably ammonium chloride.
Crystal Growth Inhibitor
The compositions of the present invention optionally comprise from about
0.005%,
preferably from about 0.5%, more preferably from about 0.1% to about 1%,
preferably to about
15 0.5%, more preferably to about 0.25%, most preferably to about 0.2% by
weight, of one or more
crystal growth inhibitors. The following "Crystal Growth Inhibition Test" is
used to determine
the suitability of a material for use as a crystal growth inhibitor.
Crystal Growth Inhibition Test (CGIT,~
The suitability of a material to serve as a crystal growth inhibitor according
to the present
20 invention can be determined by evaluating in vitro the growth rate of
certain inorganic micro-
crystals. The procedure of Nancollas et al., described in "Calcium Phosphate
Nucleation and
Growth in Solution", Prog. Crystal GrowtIZ Claaract., Vol 3, 77-102, (1980),
incorporated herein
by reference, is a method which is suitable for evaluating compounds for their
crystal growth
inhibition. The graph below serves as an example of a plot indicating the time
delay (t-lag) in
25 crystal formation afforded by a hypothetical crystal growth inhibitor.

CA 02359438 2001-07-25
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26
Volume of
base added
(mL)
t-lag
TIME
The observed t-lag provides a measure of the compound's efficiency with
respect to delaying the
growth of calcium phosphate crystal. The greater the t-lag, the more efficient
the crystal growth
inhibitor.
S Exemplary Procedure
Combine in a suitable vessel, 2.1M KCl (35 mL), 0.0175M CaClz (SOmL), O.OlM
KHZPO,~ (SOmL), and de-ionized water (350mL). A standard pH electrode equipped
with a
Standard Calomel Reference electrode is inserted and the temperature adjusted
to 37° C while
purging of the solution of oxygen. Once the temperature and pH are stabilized,
a solution of the
crystal growth inhibitor to be test is then added. A typical inhibitor test
concentration is 1 x 10-6
M. The solution is titrated to pH 7.4 with O.OSM KOH. The mixture is then
treated with 5 mL's
of a hydroxyapatite slurry. The hydroxyapatite slurry can be prepared by
digesting Bio-Gel
HTP hydroxyapatite powder (100 g) in 1 L of distilled water the pH of which is
adjusted to 2.5
by the addition of sufficient 6N HCl and subsequently heating the solution
until all of the
hydroxyapatite is dissolved (heating for several days may be necessary). The
temperature of the
solution is then maintained at about 22° C while the pH is adjusted to
12 by the addition of a
solution of 50% aqueous KOH. Once again the solution is heated and the
resulting slurry is
allowed to settle for two days before the supernatant is removed. 1.5 L of
distilled water is
added, the solution stirred, then after settling again for 2 days the
supernatant is removed. This
rinsing procedure is repeated six more time after which the pH of the solution
is adjusted to
neutrality using 2N HCI. The resulting slurry can be stored at 37°C for
eleven months.
Crystal growth inhibitors which are suitable for use in the present invention
have a t-lag
of at least 10 minutes, preferably at least 20 minutes, more preferably at
least 50 minutes, at a
concentration of 1 x 10-6M. Crystal growth inhibitors are differentiated from
chelating agents by

CA 02359438 2001-07-25
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27
the fact that crystal growth inhibitors have a low binding affinity of heavy
metal ions, i.e.,
copper. For example, crystal growth inhibitors have an affinity for copper
ions in a solution of
0.1 ionic strength when measured at 25° C, of less than 15, preferably
less than 12.
The preferred crystal growth inhibitors of the present invention are selected
from the
group consisting of carboxylic compounds, organic diphosphonic acids, and
mixtures thereof.
The following are non-limiting examples of preferred crystal growth
inhibitors.
Carboxylic Compounds
Non-limiting examples of carboxylic compounds which serve as crystal growth
inhibitors include glycolic acid, phytic acid, polycarboxylic acids, polymers
and co-polymers of
carboxylic acids and polycarboxylic acids, and mixtures thereof. The
inhibitors may be in the
acid or salt form. Preferably the polycarboxylic acids comprise materials
having at least two
carboxylic acid radicals which are separated by not more than two carbon atoms
(e.g., methylene
units). The preferred salt forms include alkali metals; lithium, sodium, and
potassium; and
alkanolammonium. The polycarboxylates suitable for use in the present
invention are further
disclosed in U.S. 3,128,287, U.S. 3,635,830, U.S. 4,663,071, U.S. 3,923,679;
U.S. 3,835,163;
U.S. 4,158,635; U.S. 4,120,874 and U.S. 4,102,903, each of which is included
herein by
reference.
Further suitable polycarboxylates include ether hydroxypolycarboxylates,
polyacrylate
polymers, copolymers of malefic anhydride and the ethylene ether or vinyl
methyl ethers of
acrylic acid. Copolymers of 1,3,5-trihydroxybenzene, 2, 4, 6-trisulphonic
acid, and
carboxymethyloxysuccinic acid are also useful. Alkali metal salts of
polyacetic acids, for
example, ethylenediamine tetraacetic acid and nitrilotriacetic acid, and the
alkali metal salts of
polycarboxylates, for example, mellitic acid, succinic acid, oxydisuccinic
acid, polymaleic acid,
benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, are suitable
for use in the
present invention as crystal growth inhibitors.
The polymers and copolymers which are useful as crystal growth inhibitors have
a
molecular weight which is preferably greater than about 500 daltons to about
100,000 daltons,
more preferably to about 50,000 daltons.
Examples of commercially available materials for use as crystal growth
inhibitors
include, polyacrylate polymers Good-RiteO ex BF Goodrich, Acrysol~ ex Rohm &
Haas,
Sokalan0 ex BASF, and Norasol0 ex Norso Haas. Preferred are the Norasol0
polyacrylate
polymers, more preferred are Norasol~ 410N (MW 10,000) and Norasol0 440N (MW
4000)
which is an amino phosphonic acid modified polyacrylate polymer, and also more
preferred is
the acid form of this modified polymer sold as Norasol0 QR 784 (MW 4000) ex
Norso-Haas.

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28
Polycarboxylate crystal growth inhibitors include citrates, e.g., citric acid
and soluble
salts thereof (particularly sodium salt), 3,3-dicarboxy-4-oxa-1,6-
hexanedioates and related
compounds further disclosed in U.S. 4,566,984 incorporated herein by
reference, CS-C20 alkyl,
CS-C20 alkenyl succinic acid and salts thereof, of which dodecenyl succinate,
lauryl succinate,
myristyl succinate, palmityl succinate, 2-dodecenylsuccinate, 2-pentadecenyl
succinate, are non-
limiting examples. Other suitable polycarboxylates are disclosed in U.S.
4,144,226, U.S.
3,308,067 and U.S. 3,723,322, all of which are incorporated herein by
reference.
Organic Phosphonic Acids
Organic diphosphonic acid are also suitable for use as crystal growth
inhibitors. For the proposes
of the present invention the term "organic diphosphonic acid" is defined as
"an organo-
diphosphonic acid or salt which does not comprise a nitrogen atom". Preferred
organic
diphosphonic acids include C,-C~ diphosphonic acid, preferably C, diphosphonic
acid selected
from the group consisting of ethylene diphosphonic acid, a-hydroxy-2 phenyl
ethyl diphosphonic
acid, methylene diphosphonic acid, vinylidene-1,1-diphosphonic acid , 1,2-
dihydroxyethane-1,1-
diphosphonic acid, hydroxy-ethane 1,1 diphosphonic acid, the salts thereof,
and mixtures thereof.
More preferred is hydroxyethane-1,1-diphosphonic acid (HEDP).
A more preferred phosphonic acid I 2-phosphonobutane-1,2,4-tricarboxylic acid
(PBTC)
available as Bayhibit~ AM ex Bayer.
Fabric Softening Actives
The compositions of the present invention optionally comprise at least about
1%,
preferably from about 10%, more preferably from about 20% to about 80%, more
preferably to
about 60%, most preferably to about 45% by weight, of the composition of one
or more fabric
softener actives.
The preferred fabric softening actives according to the present invention are
amines
having the formula:
(R)3_m N-f (CH2)p Q-R
m
quaternary ammonium compounds having the formula:
(R)4_m N-r(CHZ)p Q-R' I X
--~~ m

CA 02359438 2001-07-25
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29
and mixtures thereof, wherein each R is independently C1-C6 alkyl, Cl-C6
hydroxyalkyl, benzyl,
and mixtures thereof; Rl is preferably C11-C22 linear alkyl, C11-C22 branched
alkyl, C11-C22
linear alkenyl, C11-C22 branched alkenyl, and mixtures thereof; Q is a
carbonyl moiety
independently selected from the units having the formula:
O O R2 O O RZ
-O-C° ~ -C-O- ~ -N-C- ~ -C-N-
O
O R3 O O-C-R' O
-O-C-O- , -CH-O-C- , -CH-CH2-O-C-
wherein R2 is hydrogen, Cl-C4 alkyl, preferably hydrogen; R3 is Cl-C4 alkyl,
preferably
hydrogen or methyl; preferably Q has the formula:
O O
-O-C- or -NH-C-.
X is a softener compatible anion, preferably the anion of a strong acid, for
example, chloride,
bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures thereof,
more preferably
chloride and methyl sulfate. The anion can also, but less preferably, carry a
double charge, in
which case X(-) represents half a group. The index m has a value of from 1 to
3; the index n has
a value of from 1 to 4, preferably 2 or 3, more preferably 2.
One embodiment of the present invention provides for amines and quaternized
amines
having two or more different values for the index n per molecule, for example,
a softener active
prepared from the starting amine methyl(3-aminopropyl)(2-hydroxyethyl)amine.
More preferred softener actives according to the present invention have the
formula:
O
(R) N (CHZ)ri O-C-R1 X -
4-m
m
wherein the unit having the formula:
O
-O-C-R'

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WO 00/49122 PCT/US00/03933
is a fatty acyl moiety. Suitable fatty acyl moieties for use in the softener
actives of the present
invention are derived from sources of triglycerides including tallow,
vegetable oils and/or
partially hydrogenated vegetable oils including hater alia canola oil,
safflower oil, peanut oil,
sunflower oil, corn oil, soybean oil, tall oil, rice bran oil. Yet more
preferred are the Diester
Quaternary Ammonium Compounds (DEQA's) wherein the index m is equal to 2.
The formulator, depending upon the desired physical and performance properties
of the
final fabric softener active, can choose any of the above mentioned sources of
fatty acyl moieties,
or alternatively, the formulator can mix sources of triglyceride to form a
"customized blend".
However, those skilled in the art of fats and oils recognize that the fatty
acyl composition may
10 vary, as in the case of vegetable oil, from crop to crop, or from variety
of vegetable oil source to
variety of vegetable oil source. DEQA's which are prepared using fatty acids
derived from
natural sources are preferred.
A preferred embodiment of the present invention provides softener actives
comprising
R1 units which have at least about 3%, preferably at least about 5%, more
preferably at least
15 about 10%, most preferably at least about 15% C11-C22 alkenyl, including
polyalkenyl
(polyunsaturated) units inter alia oleic, linoleic, linolenic.
For the purposes of the present invention the term "mixed chain fatty acyl
units" is
defined as "a mixture of fatty acyl units comprising alkyl and alkenyl chains
having from 10
carbons to 22 carbon atoms including the carbonyl carbon atom, and in the case
of alkenyl
20 chains, from one to three double bonds, preferably all double bonds in the
cis configuration".
With regard to the R1 units of the present invention, it is preferred that at
least a substantial
percentage of the fatty acyl groups are unsaturated, e.g., from about 25%,
preferably from about
50% to about 70%, preferably to about 65%. The total level of fabric softening
active containing
polyunsaturated fatty acyl groups can be from about 3%, preferably from about
5%, more
25 preferably from about 10% to about 30%, preferably to about 25%, more
preferably to about
18%. As stated herein above cis and trams isomers can be used, preferably with
a cisltrans ratio
is of from 1:1, preferably at least 3:1, and more preferably from about 4:1 to
about 50:1, more
preferably about 20:1, however, the minimum being 1:1.
The level of unsaturation contained within the tallow, canola, or other fatty
acyl unit
30 chain can be measured by the Iodine Value (IV) of the corresponding fatty
acid, which in the
present case should preferably be in the range of from 5 to 100 with two
categories of compounds
being distinguished, having a IV below or above 25.
Indeed, for compounds having the formula:

CA 02359438 2001-07-25
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31
(R)4-m N~CH2)p Q-R~ X
m
derived from tallow fatty acids, when the Iodine Value is from 5 to 25,
preferably 15 to 20, it has
been found that a cisltrans isomer weight ratio greater than about 30/70,
preferably greater than
about 50/50 and more preferably greater than about 70/30 provides optimal
concentrability.
For compounds of this type made from tallow fatty acids having a Iodine Value
of above
25, the ratio of cis to traps isomers has been found to be less critical
unless very high
concentrations are needed. A further preferred embodiment of the present
invention comprises
DEQA's wherein the average Iodine Value for R1 is approximately 45.
The R1 units suitable for use in the isotropic liquids present invention can
be further
characterized in that the Iodine Value (IV) of the parent fatty acid, said IV
is preferably from
about 10, more preferably from about 50, most preferably from about 70, to a
value of about 140,
preferably to about 130, more preferably to about 115. However, formulators,
depending upon
which embodiment of the present invention they choose to execute, may wish to
add an amount
of fatty acyl units which have Iodine Values outside the range listed herein
above. For example,
"hardened stock" (IV less than or equal to about 10) may be combined with the
source of fatty
acid admixture to adjust the properties of the final softener active.
A prefered source of fatty acyl units, especially fatty acyl units having
branching, for
example, "Guerbet branching", methyl, ethyl, etc. units substituted along the
primary alkyl chain,
synthetic sources of fatty acyl units are also suitable. For example, the
formulator may with to
add one or more fatty acyl units having a methyl branch at a "non-naturally
occuring" position,
for example, at the third carbon of a C17 chain. What is meant herein by the
term "non-naturally
occuring" is "acyl units whihc are not found in significant (greater than
about 0.1%) quantities is
common fats and oils which serve as feedstocks for the source of triglycerides
described herein."
If the desired branched chain fatty acyl unit is unavailable from readily
available natural
feedstocks, therefore, synthetic fatty acid can be suitably admixed with other
synthetic materials
or with other natural triglyceride derived sources of acyl units.
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;

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32
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;
S 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-dimethyl 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.
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-
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; and mixtures thereof.
Additional fabric softening agents useful herein are described in U.S.
5,643,865
Mermelstein et al., issued July l, 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
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.
Principal solvent

CA 02359438 2001-07-25
WO 00/49122 PCT/US00/03933
33
The compositions of the present invention, preferably the isotropic liquid
embodiments
thereof, may also optionally comprise a principal solvent. The level of
principal solvent present
in the compositions of the present invention is typically less than about 95%,
preferably less than
about 50%, more preferably less than about 25%, most preferably less than
about 15% by weight.
Some embodiments of isotropic liquid embodiments of the present invention may
comprise no
principal solvent but may substitute instead a suitable nonionic surfactant.
The principal solvents of the present invention are primarily used to obtain
liquid
compositions having sufficient clarity and viscosity. Principal solvents must
also be selected to
rninmize solvent odor impact in the composition. For example, isopropyl
alcohol is not an
effective principal solvent in that it does not serve to produce a composition
having suitable
viscosity. Isopropanol also fails as a suitable principal solvent because it
has a relatively strong
odor.
Principal solvents are also selected for their ability to provide stable
compositions at low
temperatures, preferably compositions comprising suitable principal solvents
are clear down to
about 4° C and have the ability to fully recover their clarity if
stored as low as about 7° C.
The principal solvents according to the present invention are selected base
upon their
octanol/water partition coefficient (P). The octanol/water partition
coefficient is a measure of the
ratio of the concentrations of a particular principal solvent in octanol and
water at equilibrium.
The partition coefficients are conveniently expressed and reported as their
logarithm to the base
10; loge.
The loge of many principal solvent species has been reported; for example, the
Ponmona92 database, available from Daylight Chemical Information Systems,
Inc.(Daylight
CIS), contains many, along with citations to the original literature.
However, the loge values are most conveniently calculated by the "CLOGP"
program,
also available from Daylight CIS. This program also lists experimental loge
values when they
are available in the Pomona92 database. The "calculated loge" (ClogP) is
determined by the
fragment approach of Hansch and Leo ( cf., A. Leo, in Comprehensive Medicinal
Chemistry,
Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A. Ransden, Eds., p.
295, Pergamon
Press, 1990, incorporated herein by reference). The fragment approach is based
on the chemical
structure of each HR species, and takes into account the numbers and types of
atoms, the atom
connectivity, and chemical bonding. ClogP values are the most reliable and
widely used
estimates for octanol water partitioning. It will be understood by those
skilled in the art that
experimental log P values could also be used. Experimental log P values
represent a less
preferred embodiment of the invention. Where experimental log P values are
used, the one hour
log P values are preferred. Other methods that can be used to compute ClogP
include, e.g.,

CA 02359438 2001-07-25
WO 00/49122 PCT/US00/03933
34
Crippen's fragmentation method as disclosed in J. Chern. Inf. Cornput. Sci.,
27a,21 (1987);
Viswanadhan's fragmentation method as disclosed in J. Chem. Inf. Comput. Sci.,
29, 163 (1989);
and Broto's method as disclosed in Eur°. J. Med. Chem. - Chirn. Theor.,
19, 71 (1984).
The principal solvents suitable for use in the present invention are selected
from those
having a ClogP of from about 0.15 to about l, preferably from about 0.15 to
about 0.64, more
preferably from about 0.25 to about 0.62, most preferably from about 0.4 to
about 0.6.
Preferably the principal solvent is at least to some degree an asymmetric
molecule, preferably
having a melting, or solidification point which allows the principal solvent
to be liquid at or near
room temperature. Low molecular weight principal solvents may be desirable for
some
embodiments. More preferred molecules are highly asymmetrical.
A further description of principal solvents suitable for use in the isotropic
liquid
compositions of the present invention are thoroughly described in WO 97/03169
"Concentrated,
Stable Fabric Softening Composition", published January 30, 1997 and assigned
to the Procter &
Gamble Co.; WO 97/03170 "Concentrated, Water Dispersible, Stable, Fabric
Softening
1$ Composition", published January 30, 1997 and assigned to the Procter &
Gamble Co.; and WO
97/34972 "Fabric Softening Compound/Composition", published September 25, 1997
and
assigned to the Procter & Gamble Co. all included herein by reference.
Hydrophobic Dispersant
A preferred composition of the present invention comprises from about 0.1 %,
preferably
from about 5%, more preferably from about 10% to about 80%, preferably to
about 50%, more
preferably to about 25% by weight, of a hydrophobic polyamine dispersant
having the formula:
R1 B
L(R')2N-RAW h'1- R~X LI'1- Rly N(R1)z
wherein R, R' and B are suitably described in U.S. 5,565,145 Watson et al.,
issued October 15,
1996 incorporated herein by reference, and w, x, and y have values which
provide for a backbone
prior to substitution of preferably at least about 1200 daltons, more
preferably 1800 daltons.
R' units are preferably alkyleneoxy units having the formula:
-(CH2CHR'O)m(CH2CH20)nH
wherein R' is methyl or ethyl, m and n are preferably from about 0 to about
50, provided the
average value of alkoxylation provided by m + n is at least about 0.5.
A further description of polyamine dispersants suitable for use in the present
invention is
found in U.S. 4,891,160 Vander Meer, issued January 2, 1990; U.S.4,597,898,
Vander Meer,
issued July l, 1986; European Patent Application 111,965, Oh and Gosselink,
published June 27,
1984; European Patent Application 111,984, Gosselink, published June 27, 1984;
European

CA 02359438 2001-07-25
WO 00/49122 PCT/US00/03933
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. However, any suitable clay/soil dispersent or
anti-redepostion
agent can be used in the laundry compositions of the present invention.
5 Electrolyte
The fabric softening embodiments of the compositions of the present invention,
especially clear, isotropic liquid fabric softening compositions, may also
optionally, but
preferably comprise, one or more electrolytes for control of phase stability,
viscosity, and/or
clarity. For example, the presence of certain electrolytes inter alia calcium
chloride, magnesium
10 chloride may be key to insuring initial product clarity and low viscosity,
or may affect the
dilution viscosity of liquid embodiments, especially isotropic liquid
embodiments. Not wishing
to be limited by theory, but only wishing to provide an example of a
circumstance wherein the
formulator must insure proper dilution viscosity, includes the following
example. Isotropic or
non-isotropic liquid fabric softener compositions can be introduced into the
rinse phase of
15 laundry operations via an article of manufacture designed to dispense a
measured amount of said
composition. Typically the article of manufacture is a dispenser which
delivers the softener
active only during the rinse cycle. These dispensers are typically designed to
allow an amount of
water equal to the volume of softener composition to enter into the dispenser
to insure complete
delivery of the softener composition. An electrolyte may be added to the
compositions of the
20 present invention to insure phase stability and prevent the diluted
softener composition from
"gelling out" or from undergoing an undesirable or unacceptable viscosity
increase. Prevention
of gelling or formation of a "swelled", high viscosity solution insures
thorough delivery of the
softener composition.
However, those skilled in the art of fabric softener compositions will
recognize that the
25 level of electrolyte is also influenced by other factors i~zter alia the
type of fabric softener active,
the amount of principal solvent, and the level and type of nonionic
surfactant. For example,
triethanol amine derived ester quaternary amines suitable for use as softener
actives according to
the present invention are typically manufactured in such a way as to yield a
distribution of mono-
di-, and tri- esterified quaternary ammonium compounds and amine precursors.
Therefore, as in
30 this example, the variability in the distribution of mono-, di-, and tri-
esters and amines may
predicate a different level of electrolyte. Therefore, the formulator must
consider all of the
ingredients, namely, softener active, nonionic surfactant, and in the case of
isotropic liquids, the
principal solvent type and level, as well as level and identity of adjunct
ingredients before
selecting the type and/or level of electrolyte

CA 02359438 2001-07-25
WO 00/49122 PCT/US00/03933
36
A wide variety of ionizable salts can be used. Examples of suitable salts are
the halides
of the Group IA and IIA metals of the Periodic Table of the elements, e.g.,
calcium chloride,
sodium chloride, potassium bromide, and lithium chloride. The ionizable salts
are particularly
useful during the process of mixing the ingredients to make the compositions
herein, and later to
obtain the desired viscosity. The amount of ionizable salts used depends on
the amount of active
ingredients used in the compositions and can be adjusted according to the
desires of the
formulator. Typical levels of salts used to control the composition viscosity
are from about 20 to
about 10,000 parts per million (ppm), preferably from about 20 to about 5,000
ppm, of the
composition.
Alkylene polyammonium salts can be incorporated into the composition to give
viscosity
control in addition to or in place of the water-soluble, ionizable salts
above, In addition, these
agents can act as scavengers, forming ion pairs with anionic detergent carried
over from the main
wash, in the rinse, and on the fabrics, and can improve softness performance.
These agents can
stabilized the viscosity over a broader range of temperature, especially at
low temperatures,
compared to the inorganic electrolytes. Specific examples of alkylene
polyammonium salts
include L-lysine, monohydrochloride and 1,5-diammonium 2-methyl pentane
dihydrochloride.
Cationic Charge Boosters
The compositions or the present invention may optionally comprise one or more
cationic
charge boosters, especially to the rinse-added fabric softening embodiments of
the present
invention. Typically, ethanol is used to prepare many of the below listed
ingredients and is
therefore a source of solvent into the final product formulation. The
formulator is not limited to
ethanol, but instead can add other solvents inter alia hexyleneglycol to aid
in formulation of the
final composition. This is especially true in clear, translucent, isotropic
compositions.
The preferred cationic charge boosters of the present invention are described
herein
below.
i) Quaternary Ammonium Compounds
An optional composition of the present invention comprises at least about
0.2%,
preferably from about 0.2% to about 10%, more preferably from about 0.2% to
about 5% by
weight, of a cationic charge booster having the formula:
R2
R1-N+ R3 X _
R4

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37
wherein R1, R2, R3, and R4 are each independently C1-C22 alkyl, C3-C22
alkenyl, RS-Q-
(CH2)m , wherein RS is C1-C22 alkyl, and mixtures thereof, m is from 1 to
about 6; X is an
anion.
Preferably R1 is C6-C22 alkyl, Cb-C22 alkenyl, and mixtures thereof, more
preferably
C 11-C 1 g alkyl, C 11-C 1 g alkenyl, and mixtures thereof; R2, R3, and R4 are
each preferably C 1-
Cq. alkyl, more preferably each R2, R3, and R4 are methyl.
The formulator may similarly choose R1 to be a RS-Q-(CH2)m- moiety wherein RS
is an
alkyl or alkenyl moiety having from 1 to 22 carbon atoms, preferably the alkyl
or alkenyl moiety
when taken together with the Q unit is an acyl unit derived preferably derived
from a source of
triglyceride selected from the group consisting of tallow, partially
hydrogenated tallow, lard,
partially hydrogenated lard, vegetable oils and/or partially hydrogenated
vegetable oils, such as,
canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil,
tall oil, rice bran oil, etc.
and mixtures thereof.
An example of a fabric softener cationic booster comprising a RS-Q-(CH2)m-
moiety has
the formula:
O i H3
~ +N-CH3
O CH3
wherein RS-Q- is an oleoyl units and m is equal to 2.
X is a softener compatible anion, preferably the anion of a strong acid, for
example,
chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures
thereof, more
preferably chloride and methyl sulfate.
ii) Polyvinyl Amines
A preferred embodiment of the present invention contains at least about 0.2%,
preferably
from about 0.2% to about 5%, more preferably from about 0.2% to about 2% by
weight, of one
or more polyvinyl amines having the formula
CH2-CH
NH2
wherein y is from about 3 to about 10,000, preferably from about 10 to about
5,000, more
preferably from about 20 to about 500. Polyvinyl amines suitable for use in
the present invention
are available from BASF.

CA 02359438 2001-07-25
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38
Optionally, one or more of the polyvinyl amine backbone -NH2 unit hydrogens
can be
substituted by an alkyleneoxy unit having the formula:
-~1 O)xR2
wherein R1 is C2-C4 alkylene, R2 is hydrogen, C1-C4 alkyl, and mixtures
thereof; x is from 1 to
50. In one embodiment or the present invention the polyvinyl amine is reacted
first with a
substrate which places a 2-propyleneoxy unit directly on the nitrogen followed
by reaction of one
or more moles of ethylene oxide to form a unit having the general formula:
CH3
-~CH2CH0)-(CH2CH20)xH
wherein x has the value of from 1 to about 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.
iii) Poly-Quaternary Ammonium Compounds
A preferred composition of the present invention comprises at least about
0.2%,
preferably from about 0.2% to about 10%, more preferably from about 0.2% to
about 5% by
weight, of a cationic charge booster having the formula:
R1 Rl
+I I+ _
R2-N-R-N-R2 2 X
Rl R1
wherein R is substituted or unsubstituted C2-C12 alkylene, substituted or
unsubstituted C2-C12
hydroxyalkylene; each R1 is independently C1-C4 alkyl, each R2 is
independently C1-C22 alkyl,
C3-C22 alkenyl, RS-Q-(CH2)m-, wherein RS is C1-C22 alkyl, C3-C22 alkenyl, and
mixtures
thereof; m is from 1 to about 6; Q is a carbonyl unit as defined hereinabove;
and mixtures
thereof; X is an anion.

CA 02359438 2001-07-25
WO 00/49122 PCT/US00/03933
39
Preferably R is ethylene; R1 is methyl or ethyl, more preferably methyl; at
least one R2
is preferably C1-C4 alkyl, more preferably methyl. Preferably at least one R2
is CI I-C22 alkyl,
C11-C22 alkenyl, and mixtures thereof.
The formulator may similarly choose R2 to be a RS-Q-(CH2)m moiety wherein RS
is an
alkyl moiety having from 1 to 22 carbon atoms, preferably the alkyl moiety
when taken together
with the Q unit is an acyl unit derived preferably derived from a source of
triglyceride selected
from the group consisting of tallow, partially hydrogenated tallow, lard,
partially hydrogenated
lard, vegetable oils and/or partially hydrogenated vegetable oils, such as,
canola oil, safflower
oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran
oil, etc. and mixtures
thereof.
An example of a fabric softener cationic booster comprising a RS-Q-(CH2)m-
moiety has
the formula:
Cl CH3
n CHj~/N-CH3
Cl +CH CH3
3
where
1 S in R1 is methyl, one R2 units is methyl and the other R2 unit is RS-Q-
(CH2)m-wherein RS-Q- is
an oleoyl unit and m is equal to 2.
X is a softener compatible anion, preferably the anion of a strong acid, for
example,
chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures
thereof, more
preferably chloride and methyl sulfate.
Dispersibility Aids
Relatively concentrated compositions containing both saturated and unsaturated
diester
quaternary ammonium compounds can be prepared that are stable without the
addition of
concentration aids. However, the compositions of the present invention may
require organic
and/or inorganic concentration aids to go to even higher concentrations and/or
to meet higher
stability standards depending on the other ingredients. These concentration
aids which typically
can be viscosity modifiers may be needed, or prefen-ed, for ensuring stability
under extreme
conditions when particular softener active levels are used. The surfactant
concentration aids are
typically selected from the group consisting of (I) single long chain alkyl
cationic surfactants; (2)
nonionic surfactants; (3) amine oxides; (4) fatty acids; and (5) mixtures
thereof. These aids are
described in P&G Copending Application Serial No. 08/461,207, filed June 5,
1995, Wahl et al.,
specifically on page 14, line 12 to page 20, line 12, which is herein
incorporated by reference.

CA 02359438 2001-07-25
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Preferred dispersibility aids are GENAMINE~ and GENAPOL~ ex Clariant. When PVP
is present in the compositions of the present invention, a preferred
embodiment comprises both a
cocoyl ethoxylated amine and a cocoyl ethoxylated alcohol, wherein the
ethoxylation is
approximately 10, each of which are available as GENAMINE~' and GENAPOL~'. A
preferred
example of the use of this admixture is a composition which compries, for
example, 0.2%
GENAMINE~' and 0.1 % GENAPOL~.
When said dispersibility aids are present, the total level is from 0.1%,
preferably from
0.3%, more preferably from 3%, even more preferably from 4%, and most
preferably from 5% to
25%, preferably to 17%, more preferably to 15%, most preferably to 13% by
weight, of the
10 composition. These materials can either be added as part of the active
softener raw material,
e.g., the mono-long chain alkyl cationic surfactant and/or the fatty acid
which are reactants used
to form the fabric softener active as discussed hereinbefore, or added as a
separate component.
The total level of dispersibility aid includes any amount that may be present
as part of the
softener active.
15 Soil Release Agents
Particular to the embodiments of the rinse-added fabric softeners according to
the present
invention, certain soil release agents provide not only the below described
soil release properties
but are added for their suitability in maintaining proper viscosity,
especially in the dispersed
phase, non-isotropic compositions.
20 Any polymeric soil release agent known to those skilled in the art can
optionally be
employed in the compositions and processes of this invention. Polymeric soil
release agents are
characterized by having both hydrophilic segments, to hydrophilize the surface
of hydrophobic
fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon
hydrophobic
fibers and remain adhered thereto through completion of the rinsing cycle and,
thus, serve as an
25 anchor for the hydrophilic segments. This can enable stains occurring
subsequent to treatment
with the soil release agent to be more easily cleaned in later washing
procedures.
If utilized, soil release agents will generally comprise from about 0.01 % to
about 10.0%,
by weight, of the detergent compositions herein, typically from about 0.1% to
about 5%,
preferably from about 0.2% to about 3.0%.
30 The following, all included herein by reference, describe soil release
polymers suitable
for us in the present invention. U.S. 5,728,671 Rohrbaugh et al., issued March
17, 1998; U.S.
5,691,298 Gosselink et al., issued November 25, 1997; U.S. 5,599,782 Pan et
al., issued February
4, 1997; U.S. 5,415,807 Gosselink et al., issued May 16, 1995; U.S. 5,182,043
Morrall et al.,
issued January 26, 1993; U.S. 4,956,447 Gosselink et al., issued September 11,
1990; U.S.
35 4,976,879 Maldonado et al. issued December 1 l, 1990; U.S. 4,968,451
Scheibel et al., issued

CA 02359438 2001-07-25
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41
November 6, 1990; U.S. 4,925,577 Borcher, Sr. et al., issued May 15, 1990;
U.S. 4,861,512
Gosselink, issued August 29, 1989; U.S. 4,877,896 Maldonado et al., issued
October 31, 1989;
U.S. 4,721,580 Gosselink issued January 26, 1988; U.S. Patent 4,702,857
Gosselink, issued
October 27, 1987; U.S. 4,711,730 Gosselink et al., issued December 8, 1987;
U.S. 4,000,093
Nicol et al., issued December 28, 1976; U.S. 3,959,230 Hayes, issued May 25,
1976; U.S.
3,893,929 Basadur, issued July 8, 1975; and European Patent Application 0 219
048, published
April 22, 1987 by Kud et al.
Further suitable soil release agents are described in U.S. 4,201,824 Voilland
et al.; U.S.
4,240,918 Lagasse et al.; U.S. 4,525,524 Tung et al.; U.S. 4,579,681 Ruppert
et al.; U.S.
4,220,918; U.S. 4,787,989; EP 279,134 A, 1988 to Rhone-Poulenc Chemie; EP
457,205 A to
BASF (1991); and DE 2,335,044 to Unilever N.V., 1974; all incorporated herein
by reference.
Bleach Protection Polvamines
The compositions of the present invention optionally comprise from about
0.01%,
preferably from about 0.75%, more preferably from 10%, most preferably from
about 15% to
1 S about 50%, preferably to about 35%, more preferably to about 30%, most
preferably to about 5%
by weight, of one or more linear or cyclic polyamines which provide bleach
protection.
Linear Polyamines
The bleach protection polyamines of the present invention have the formula:
R2
(R~)zN-R-~N-R~n N(R1)2
wherein R is 1,2-propylene, 1,3-propylene, and mixtures thereof; preferably
1,3-propylene. R'
is hydrogen or an alkyleneoxy unit having the formula:
(Rs0)_ R4
wherein R3 is ethylene, 1,2-propylene, 1,2-butylene, or mixtures thereof;
preferably R3 is
ethylene or 1,2-propylene, more preferably 1,2-propylene. R4 is hydrogen, C,-
C4 alkyl, and
mixtures thereof; preferably hydrogen. R' may comprise any mixture of
alkyleneoxy units. R-' is
hydrogen, R', -RN(R')2, and mixtures thereof; preferably at least one R= is
hydrogen when n is
equal to 2. The integer n is 1 or 2.
A prefered bleach protection linear polyamine has a backbone wherein R is 1,3-
propylene, RZ is hydrogen, or alkoxy, and n is equal to 2 is N,N'-bis(3-
aminopropyl)-1,3-
propylenediamine (TPTA).
Cyclic Amines

CA 02359438 2001-07-25
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42
The bleach protection cyclic polyamines of the present invention comprise
polyamine
backbones having the formula:
R-L-R
wherein L is a linking unit, said linking unit comprising a ring having at
least 2 nitrogen atoms; R
is hydrogen, -(CHz)kN(R')2, and mixtures thereof; wherein each index k
independently has the
value from 2 to 4, preferably 3. Preferably the backbone of the cyclic amines
including R units is
200 daltons or less.
R' is hydrogen or an alkyleneoxy unit having the formula:
- (R3~)- R4
wherein R~ is ethylene, 1,2-propylene, 1,2-butylene, or mixtures thereof;
preferably R3 is
ethylene or 1,2-propylene, more preferably 1,2-propylene. R~ is hydrogen, C,-
C4 alkyl, and
mixtures thereof; preferably hydrogen. R' may comprise any mixture of
alkyleneoxy units.
Examples of preferred optional polyamines of the present invention have the
formula:
(R~)ZN-(CH2)k~ L-(CH2)k-N(R~)2
wherein the indices k each have the same value and each R' is the same unit.
It has been surprisingly found that bleach protection is enhanced when the
backbone
nitrogens are substituted with one or more modiEcations which comprise an
alkyleneoxy unit
having the general formula:
R
CH2CH0-
wherein said unit is R3 as defined herein above.
METHOD OF USE
The present invention also relates to a method for enhancing the fabric
integrity if7ter alia
dye fidelity while reducing the damage to fabric due to the interaction of
laundry adjunct
ingredients and damage due to mechanical wear. The method includes the step of
contacting
fabric with an aqueous solution containing a least 50 ppm, preferably at least
about 100 ppm,
more preferably at least about 200 ppm, said composition comprising:

CA 02359438 2001-07-25
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43
a) from about 0.01% by weight, of a fabric enhancement system, said fabric
enhancement system comprising one or more modified polyamine compounds,
said modified polyamine compounds are selected from:
i) (PA),~(T)X;
ii) (PA)W(L)Z;
iii) [(PA)~,,(T)~]Y[L]Z; and
iv) mixtures thereof;
wherein PA is a grafted or non-grafted, modified or unmodified polyamine
backbone unit, T is an amide forming polycarboxylic acid crosslinking unit,
and
L is a non-amide forming crosslinking unit; provided that for compounds of
type
(i) and (iii) the indices w and x have values such that the ratio of w to x is
from
0.8 : 1 to 1.5 : 1; for compounds of type (ii) the indices w and z have values
such
that said modified polyamine compound comprises from about 0.05, preferably
from about 0.3 to 2 parts by weight of said L unit; for compounds of type
(iii) the
indices y and z have values such that said modified polyamine compound
comprises from about 0.05, preferably from about 0.3 to 2 parts by weight of
said L unit; and
b) the balance carriers and adjunct ingredients.
For the purposes of the present invention the term "contacting" is defined as
"intimate
contact of a fabric with an aqueous solution of the hereinabove described
composition which
comprises a fabric abrasion reducing polymer." Contacting typically occurs by
soaking,
washing, rinsing, spraying the composition onto fabric, but can also include
contact of a substrate
inter alia a material onto which the composition has been absorbed, with the
fabric. Laundering
is a preferred process. Temperatures for laundering can take place at a
variety of temperatures,
however, laundering typically occurs at a temperature less than about
30° C, preferably from
about 5° C to about 25° C.
The following are non-limiting examples of liquid rinse-added compositions of
the
present invention which comprise the polyamidoamine compounds which provide
fabric integrity
benefits.
The following is an example of a composition which comprises a cationic fabric
softener
active in combination with the fabric enhancement system of the present
invention.
TABLEI
weight

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44
Ingredients 1 2 3 4 5
Polymer ' 3.0 -- 1.0 -- 15.0
Polymer z -- 3.0 -- 1.0 --
Polymer 3 3.5 -- -- 1.0 --
Softener active -- 2.5 19.0 24.0 --
4
Dye fixative 2.2 2.4 -- 1.0 --
Bayhibit AM 6 1.0 1.0 -- -- 2.0
SRP-2 -- -- 0.5 0.25 --
NH4C1 -- 0.2 0.2 0.2 --
Water & Minors balance balance balance balance balance
1. Lupasol'~ SK ex BASF.
2. Lupasol~' SKA ex BASF.
3. Luviskol~' K90 ex BASF.
4. Di-(tallowyl-oxy-ethyl) dimethyl ammonium chloride.
5 5. Dye fixing agent ex Clariant under the tradename Cartafix CBS.
6. 2-Phosphonobutane-1,2,4-tricarboxylic acid ex Bayer.
The following is a composition which comprises the fabric enhancement system
of the
present invention.
TABLE II
weight
Ingredients 6 7 8 9 10
Polymer' 3.0 -- 1.0 -- 15.0
Polymer Z -- 3.0 -- 1.0 --
Polymer 3 3.5 -- -- 1.0 --
Dye fixative 2.2 2.4 -- 1.0 --
''
Bayhibit AM 5 1.0 1.0 -- -- 2.0
SRP-2 -- -- 0.5 0.25 --
NH4C1 -- 0.2 0.2 0.2 --
Water & Minors balance balance balance balance balance
1. Lupasol~' SK ex BASF.
2. Lupasol~ SKA ex BASF.
3. Luviskol~ K90 ex BASF.

CA 02359438 2001-07-25
WO 00/49122 PCT/US00/03933
4. Dye fixing agent ex Clariant under the tradename Cartafix CB~.
5. 2-Phosphonobutane-1,2,4-tricarboxylic acid ex Bayer.
TABLE II
5 weight
Ingredients 11 12
Polymer ' 1.0 --
Polymer 2 -- 1.0
Polymer 3 3.5 2.5
Fabric integrity10.0 --
agent4
Dispersant 4 -- 10.0
Dye fixative 2.2 2.4
5
Bayhibit AM 6 1.0 1.0
Water & Minors balance balance
1. Lupasol~' SK ex BASF.
2. Lupasol'~ SKA ex BASF.
3. Luviskol~ K90 ex BASF.
4. N,N'-bis(3-aminopropyl)-1,4-piperazine.
10 S. PEI 1800 E7
6. Dye fixing agent ex Clariant under the tradename Cartafix CBS.
7. 2-Phosphonobutane-1,2,4-tricarboxylic acid ex Bayer.