FABRIC MAINTENANCE COMPOSITIONS COMPRISING CERTAIN CATIONICALLY CHARGED FABRIC MAINTENANCE POLYMERS

COMPOSITIONS D'ENTRETIEN DES TISSUS CONTENANT CERTAINS POLYMERES D'ENTRETIEN DES TISSUS CHARGES CATIONIQUEMENT

English Abstract

A composition providing die protection benefits to fabric comprising A) from
about
0.1% by weight, of a polymer, copolymer, or mixtures thereof, said polymer or
copolymer comprising one or more monomers having a cationic group and which is
capable of attenuating and/or abating the loss of fabric dye; and B) the
balance
carriers and adjunct ingredients.

French Abstract

On décrit une composition d'entretien pour tissus qui contient : A) au moins environ 0,1 % en poids d'un polymère, d'un copolymère ou de mélanges de ces derniers ; ce polymère ou ce copolymère comprenant un ou plusieurs monomères ayant un groupe cationique et étant capable d'atténuer et/ou de supprimer la perte des couleurs des tissus ; et B) pour le solde des matières de charge et d'appoint.

Claims

-47-


What is claimed is:

1. A composition providing dye protection benefits to fabric comprising:
A) from 0.05% by weight, of a polymer, copolymer, or mixtures thereof,
said polymer or copolymer comprising one or more units selected from
the group consisting of:
I) linear polymer units having the formula:
Image
wherein each R1 is independently
a) hydrogen;
b) C1-C4 alkyl;
c) substituted or unsubstituted phenyl;
d) substituted or unsubstituted benzyl;
e) carbocyclic;
f) heterocyclic;
g) or mixtures thereof;
each R2 is independently
a) hydrogen;
b) halogen


-48-


c) C1-C4 alkyl;
d) C1-C4 alkoxy;
e) substituted or unsubstituted phenyl;
f) substituted or unsubstituted benzyl;
g) carbocyclic;
h) heterocyclic;
i) or mixtures thereof;
each Z is independently
a) hydrogen;
b) hydroxyl;
c) halogen;
d) -(CH2)m R;
wherein R is:
i) hydrogen;
ii) hydroxyl
iii) halogen;
iv) nitrilo;
v) -OR3;
vi) -O(CH2)n N(R3)2;
vii) -O(CH2)n N+(R3)3X-;
viii) -OCO(CH2)n N(R3)2;


-49-


ix) -OCO(CH2)n N+(R3)3X-;
x) -NHCO(CH2)n N(R3)2;
xi) -NHCO(CH2)n N+(R3)3X-;
xii) -(CH2)n N(R3)2;
xiii) -(CH2)n N+(R3)3X-;
xiv) carbocyclic;
xv) heterocyclic;
xvi) nitrogen heterocycle quaternary ammonium;
xvii) nitrogen heterocycle N-oxide;
xviii) aromatic N-heterocyclic quaternary ammonium;
xix) aromatic N-heterocyclic N-oxide;
xx) -NHCHO;
xxi) or mixtures thereof;
each R3 is independently hydrogen, C1-C8 alkyl, C2-C8
hydroxyalkyl, or mixtures thereof; X is a water soluble anion;
the index n is from 0 to 6;
e) -(CH2)m COR'
wherein R' is
i) -OR3;
ii) -O(CH2)n N(R3)2;
iii) -O(CH2)n N+(R3)3X-;


-50-


iv) -NR3(CH2)n N(R3)2;
V) -NR3(CH2)n N+(R3)3X-;
vi) -(CH2)n N(R3)2;
vii) -(CH2)n N+(R3)3X-;
viii) or mixtures thereof;
each R3 is independently hydrogen, C1-C8 alkyl, C2-C8 hydroxyalkyl,
or mixtures thereof; X is a water soluble anion; the index n is from 0 to
6;
f) or mixtures thereof; the index m is from 0 to 6;
II) cyclic units derived from cyclically polymerizing monomers
having the formula:
Image
wherein each R4 is independently an olefin comprising unit
which propagates polymerization in addition to forming a
cyclic residue with an adjacent R4 unit; R5 is C1-C12 linear or
branched alkyl, benzyl, substituted benzyl, or mixtures thereof;
X is a water soluble anion; and
III) mixtures thereof; provided said polymer or co-polymer has a
net cationic charge;
B) a polyamine selected from the group consisting of N,N'-
bis(aminopropyl)-1,3-propylenediamine, N,N'-bis(hydroxyethyl)-N,N'-
bis[3-N,N-bis(hydroxyethyl)aminopropyl]-1,3-propylenediamine,
N,N'-bis(2-hydroxypropyl)-N,N'-bis[3-N,N-bis(2-


-51-


hydroxypropyl)aminopropyl]-1,3-propylenediamine, N,N'-bis(2-
hydroxybutyl)-N,N'-bis [3-N,N-bis(2-hydroxybutyl)aminopropyl]-1,3-
propylenediamine, 5-N-methyl dipropylenetriamine, 1,1-N-dimethyl-5-
N'-methyl-9,9-N"-dimethyl dipropylenetriamine, 1,1-N-dimethyl-9,9-
N"-dimethyl dipropylenetriamine, and mixtures thereof; and
C) the balance carriers and adjunct ingredients.
2. A composition according to Claim 1 comprising the co-polymer wherein each
R1 is hydrogen, C1-C4 alkyl, phenyl or mixtures thereof and R2 is hydrogen,
C1-C4 alkyl, or mixtures thereof.
3. A composition according to either Claim 1 or 2 comprising the co-polymer
wherein Z has the formula:
-(CH2)m COR
wherein each R is independently -O(CH2)n N(R3)2; -O(CH2)n N+(R3)3X-; -
(CH2)n N (R3)2;-(CH2)n N+(R3)3X-; and mixtures thereof, m is 0, n is from 2 to
4.
4. A composition according to any of Claims 1-3 wherein Z units having the
formula CONH2, -CO2(CH2)2N+(CH3)3Cl-, and mixtures thereof, wherein a
ratio of -CONH2 units to CO2(CH2)2N+(CH3)3Cl- units is from 9:1 to 1:9.
5. A composition according to any of Claims 1-4 wherein said composition
further comprises from 1% to 80% by weight, of a fabric softening active, said
fabric softener active comprises a quaternary ammonium compound having
the formula:
Image


-52-


an amine having the formula:
Image
and mixtures thereof; wherein each R is independently C1-C6 alkyl, C1-C6
hydroxyalkyl, benzyl, or mixtures thereof; R1 is C1-C22 alkyl, C3-C22 alkenyl,
or mixtures thereof; Q is a carbonyl containing moiety having the formula:
Image
wherein R2 is hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, or mixtures thereof;
R3 is hydrogen, C1-C4 alkyl, or mixtures thereof; X is an anion; m is from 1
to
3; n is from 1 to 4.
6. A composition according to any of Claims 1-5 further comprising a crystal
growth inhibitor 2-phosphonobutane-1,2,4-tricarboxylic acid and a dye fixing
agent dodecyl trimethylammonium chloride.
7. A composition for providing enhanced fabric protection to fabric, said
composition comprising:
a) from 0.05% by weight, of a polymer, copolymer, or mixtures thereof,
said polymer or copolymer comprising one or more units selected from
the group consisting of:


-53-


I) linear polymer units having the formula:
Image
wherein each R1 is independently
a) hydrogen;
b) C,-CQ alkyl;
c) substituted or unsubstituted phenyl;
d) substituted or unsubstituted benzyl;
e) carbocyclic;
f) heterocyclic;
g) and mixtures thereof;
each R2 is independently
a) hydrogen;
b) halogen;
c) C1-C4 alkyl;
d) C1-C4 alkoxy;
e) substituted or unsubstituted phenyl;
f) substituted or unsubstituted benzyl;
g) carbocyclic;


-54-


h) heterocyclic;
i) or mixtures thereof;
each Z is independently
a) hydrogen;
b) hydroxyl;
c) halogen;
d) -(CH2)m R;
wherein R is:
i) hydrogen;
ii) hydroxyl
iii) halogen;
iv) nitrilo;
v) -OR3;
vi) -O(CH2)n N(R3)2;
vii) -O(CH2)n N+(R3)3X-;
viii) -OCO(CH2)n N(R3)2;
ix) -OCO(CH2)n N+(R3)3X-;
x) -NHCO(CH2)n N(R3)2;
xi) -NHCO(CH2)n N+(R3)3X-;
xii) -(CH2)n N(R3)2;
xiii) -(CH2)n N+(R3)3X-;


-55-


xiv) carbocyclic;
xv) heterocyclic;
xvi) nitrogen heterocycle quaternary ammonium;
xvii) nitrogen heterocycle N-oxide;
xviii) aromatic N-heterocyclic quaternary ammonium;
xix) aromatic N-heterocyclic N-oxide;
xx) -NHCHO;
xxi) or mixtures thereof;
each R3 is independently hydrogen, C1-C8 alkyl, C2-C8
hydroxyalkyl, or mixtures thereof; X is a water soluble
anion; the index n is from 0 to 6
e) -(CH2)m COR'
wherein R' is
i) -OR3;
ii) -O(CH2)n N(R3)2;
iii) -O(CH2)n N+(R3)3X-;
iv) -NR3(CH2)n N(R3)2;
v) -NR3(CH2)n N+(R3)3X-;
vi) -(CH2)n N(R3)2;
vii) -(CH2)n N+(R3)3X-;
viii) or mixtures thereof;


-56-


each R3 is independently hydrogen, C1-C8 alkyl, C2-C8
hydroxyalkyl, or mixtures thereof; X is a water soluble
anion; the index n is from 0 to 6;
f) or mixtures thereof; the index m is from 0 to 6;
II) cyclic units derived from cyclically polymerizing monomers
having the formula:
Image
wherein each R4 is independently an olefin comprising unit which
propagates polymerization in addition to forming a cyclic residue with
an adjacent R4 unit; R5 is C1-C12 linear or branched alkyl, benzyl,
substituted benzyl, or mixtures thereof; X is a water soluble anion; and
III) mixtures thereof; provided said polymer or co-polymer has a
net cationic charge;
b) from 0.01% to 50% by weight, of a polyamine, said
polyamine is selected from the group consisting of
N,N'-bis(aminopropyl)-1,3-propylenediamine;
N,N'bis(hydroxyethyl)-N,N'-bis[3-N,N-
bis(hydroxyethyl)aminopropyl]-1,3-propylenediamine;
N,N'-bis(2-hydroxypropyl)-N,N'-bis[3-N,N-bis(2-
hydroxypropyl)aminopropyl]-1,3-propylenediamine;
N,N'-bis(2-hydroxybutyl)-N,N'-bis[3-N,N-bis(2-
hydroxybutyl)aminopropyl]-1,3-propylenediamine; 5-
N-methyl dipropylenetriamine; 1,1-N-dimethyl-5-N'-
methyl-9,9-N"-dimethyl dipropylenetriamine; 1,1-N-
dimethyl-9,9-N"-dimethyl dipropylenetriamine; and
mixtures thereof;


-57-


c) from 0.005% to 1% by weight, of one or more crystal
growth inhibitors;
d) from 0.001% to 90% by weight, of one or more dye
fixing agents; and
e) the balance carriers and adjunct ingredients.
8. A composition providing dye protection benefits to fabric comprising:
a) from 0.05% by weight, of a copolymer having the formula:
Image
wherein Z1 has the formula:
Image
Z2 has the formula:
Image
x has the value of from 10 to 100,000; y has the value of from 10 to
100,000; the ratio of x to y is from 9:1 to 1:9;


-58-


b) the balance carriers and adjunct ingredients.
9. A composition providing dye protection benefits to fabric comprising:
A) from 0.05% by weight, of a polymer, copolymer, or mixtures
thereof, said polymer or copolymer comprising one or more
units selected from the group consisting of:
I) linear polymer units having the formula:
Image
wherein each R1 is independently
a) hydrogen;
b) C1-C4 alkyl;
c) substituted or unsubstituted phenyl;
d) substituted or unsubstituted benzyl;
e) carbocyclic;
f) heterocyclic;
g) or mixtures thereof;
each R2 is independently
a) hydrogen;
b) halogen


-59-


c) C1-C4 alkyl;
d) C1-C4 alkoxy;
e) substituted or unsubstituted phenyl;
f) substituted or unsubstituted benzyl;
g) carbocyclic;
h) heterocyclic;
i) or mixtures thereof;
each Z is independently
a) hydrogen;
b) hydroxyl;
c) halogen;
d) -(CH2)m R;
wherein R is:
i) hydrogen;
ii) hydroxyl;
iii) halogen;
iv) nitrilo;
v) -OR3;
vi) -O(CH2)n N(R3)2;
vii) -O(CH2)n N+(R3)3X-;
viii) -OCO(CH2)n N(R3)2;


-60-


ix) -OCO(CH2)n N+(R3)3X-;
x) -NHCO(CH2)n N(R3)2;
xi) -NHCO(CH2)n N+(R3)3X-;
xii) -(CH2)n N(R3)2;
xiii) -(CH2)n N+(R3)3X;
xiv) carbocyclic;
xv) heterocyclic;
xvi) nitrogen heterocycle quaternary ammonium;
xvii) nitrogen heterocycle N-oxide;
xviii) aromatic N-heterocyclic quaternary ammonium;
xix) aromatic N-heterocyclic N-oxide;
xx) -NHCHO;
xxi) or mixtures thereof;
each R3 is independently hydrogen, C1-C8 alkyl, C2-C8
hydroxyalkyl, or mixtures thereof; X is a water soluble
anion; the index n is from 0 to 6
e) -(CH2)m COR' wherein R' is
i) -OR3;
ii) -O(CH2)n N(R3)2;
iii) -O(CH2)n N+(R3)3X-;
iv) -NR3(CH2)n N(R3)2;


-61-


v) -NR3(CH2)n N+(R3)3X-;
vi) -(CH2)n N(R3)2;
vii) -(CH2)n N(R3)3X-,
viii) or mixtures thereof;
each R3 is independently hydrogen, C1-C8 alkyl, C2-C8
hydroxyalkyl, or mixtures thereof; X is a water soluble
anion; the index n is from 0 to 6;
f) or mixtures thereof; the index m is from 0 to 6;
II) cyclic units derived from cyclically polymerizing monomers having
the formula:
Image
wherein each R4 is independently an olefin comprising unit which propagates
polymerization in addition to forming a cyclic residue with an adjacent R4
unit; R5 is C1-C12 linear or branched alkyl, benzyl, substituted benzyl, or
mixtures thereof; X is a water soluble anion; and
III) mixtures thereof; provided said polymer or co-polymer has a net
cationic charge;
B) from 0.01% by weight, of a fabric abrasion reducing polymer,
said 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) or mixtures thereof;


-62-


C) optionally from 1% by weight, of a fabric softening active;
D) optionally less than 15% by weight, of a principal solvent, said
principal solvent has a ClogP of from 0.15 to 1;
E) optionally from 0.001% to 90% by weight, of one or more dye
fixing agents;
F) optionally from 0.01% to 50% by weight, of one or more
cellulose reactive dye fixing agents;
G) optionally from 0.01% to 15% by weight, of a chlorine
scavenger;
H) 0.005% to 1% by weight, of one or more crystal growth
inhibitors;
n optionally from 1% to 12% by weight, of one or more liquid
carriers;
J) optionally from 0.001% to 1% by weight, of an enzyme;
K) optionally from 0.01% to 8% by weight, of a polyolefin
emulsion or suspension;
L) optionally from 0.01% to 0.2% by weight, of a stabilizer;
M) optionally from 1% to 80% by weight, of a cationic surfactant;
N) 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.

Description

CA 02365282 2001-08-31
WO 00/56848 PCT/US00/08030
FABRIC MAINTENANCE COMPOSITIONS COMPRISING CERTAIN CATIONICALLY
CHARGED FABRIC MAINTENANCE POLYMERS
FIELD OF THE INVENTION
The present invention relates to fabric dye maintenance compositions which
comprise
one or more dye maintenance compounds which can be oligomers, polymers, co-
polymers, and
the like which comprise one or more monomers which results in the final dye
maintenance
compound having a net positive charge. Compositions comprising the dye
maintenance
polymers of this invention impart appearance and integrity benefits to fabrics
and textiles treated
with solutions formed from such compositions.
BACKGROUND OF THE INVENTION
It is, of course, 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.
Further, repeated
laundering of fabrics and textiles, especially with bleach-containing laundry
products, can
remove dye from fabrics and textiles and impart a faded, worn out appearance
as a result of
diminished color intensity, and in many cases, as a result of changes in hues
or shades of color.
Given the foregoing, there is clearly an ongoing need to identify materials
which could
be added to fabric treatment products, specifically to rinse added fabric
conditioners, pre-wash
spray on compositions, pre-soak compositions as well as after wash or between
wash malodor



WO 00/56848 CA 02365282 2001-08-31 PCT/US00/08030
2
control or fabric re-freshening compositions, materials which would associate
themselves with
the fibers of the fabrics and textiles thereby reducing, abating, or
minimizing the tendency of the
fabric/textiles to deteriorate in appearance. Any such fabric treatment/fabric
maintenance
composition additive material should, of course, be able to benefit fabric
appearance and
integrity without unduly interfering with the ability of the balance of
laundry products to perform
their intended function. The present invention is directed to the use of dye
maintenance polymers
in fabric treatment and fabric enhancement compositions which perform in this
desired manner.
SUMMARY OF THE INVENTION
The present invention meets the aforementioned need in that it has been
surprisingly
discovered that fabric which is treated, and subsequently re-treated with the
compositions of the
present invention, will resist normal fading and color loss without regard to
the circumstances,
inter alia, due to mechanical wear and abrasion. In addition, fabric which has
not been treated
can have the loss of fabric dye attenuated by adding the compositions of the
present invention to
the laundry cycle as an adjunct via pre-soak, rinse additive, etc. The
compositions of the present
invention can be added is any manner, inter alia, as part of a formulation or
as a separate
composition.
The first aspect of the present invention relates to compositions providing
dye protection
benefits to fabric comprising:
A) from about 0.05%, preferably for about 0.1%, more preferably from about
0.5%,
most preferably from about 1% to about 10%, preferably to about 7%, more
preferably to about 5% by weight, of a polymer, copolymer, or mixtures
thereof,
said polymer or copolymer comprising one or more units selected from the group
consisting of:
I) linear polymer units having the formula:
R1 R2
C-C
Rl Z
wherein each R' is independently
a) hydrogen;
b) C,-C4 alkyl;
c) substituted or unsubstituted phenyl;



WO 00/56848 CA 02365282 2001-08-31 PCT/[1500/08~30
3
d) substituted or unsubstituted
benzyl;


e) carbocyclic;


f) heterocyclic;


g) and mixtures thereof;


eachRZ is independently


a) hydrogen;


b) halogen


c) C,-C4 alkyl;


d) C,-C4 alkoxy;


e) substituted or unsubstituted
phenyl;


f) substituted or unsubstituted
benzyl;


g) carbocyclic;


h) heterocyclic;


i) and mixtures thereof;


eachZ is independently


a) hydrogen;


b) hydroxyl;


c) halogen;


d) -(CHZ)mR;


wherein R is:


i) hydrogen;


ii) hydroxyl


iii) halogen;


iv) nitrilo;


v) -OR3;


vi) -O(CHZ)"N(R3)z;


vii) -O(CHZ)nN+(R3)3X-;


viii) -OCO(CHz)"N(R3)~;


ix) -OCO(CHZ)"N+(R3)3X-;


x) -NHCO(CHZ)"N(R3)z;


xi) -NHCO(CHZ)"N+(R3)3X
;


xii) -(CHZ)"N(R3)z;


xiii) -(CHZ)nN+(R3)3X-;





CA 02365282 2001-08-31
WO 00/56848 PCT/US00/08030
4
xiv) carbocyclic;
xv) heterocyclic;
xvi) nitrogen heterocycle quaternary ammonium;
xvii) nitrogen heterocycle N-oxide;
xviii) aromatic N-heterocyclic quaternary ammonium;
xix) aromatic N-heterocyclic N-oxide;
xx) -NHCHO;
xxi) or mixtures thereof;
each R3 is independently hydrogen, C,-C8 alkyl, CZ-C8
hydroxyalkyl, and mixtures thereof; X is a water soluble anion;
the index n is from 0 to 6
e) -(CHZ)",COR'


wherein
R' is


i) -OR3;


ii) -O(CHZ)"N(R3)z;


iii) -O(CHZ)"N+(R3)sX-;


iv) -NR3(CHZ)"1V(R3)z;


v) -NR3(CHz)"N+(R3)sX
;


vi) -(CHZ)"N(R3)2;


vii) -(CHZ)nN+(R3)3X
;


viii) or mixtures thereof;
each R3 is independently hydrogen, C,-Cg alkyl, CZ-C8 hydroxyalkyl, and
mixtures thereof; X is a water soluble anion; the index n is from 0 to 6;
f) and mixtures thereof;
the index m is from 0 to 6;
II) cyclic units derived from cyclically polymerizing monomers having the
formula:
X_
R4
R4-N~ Rs
Rs
wherein each R4 is independently an olefin comprising unit which is
capable of propagating polymerization in addition to forming a cyclic
residue with an adjacent R4 unit; R5 is C,-C,, linear or branched alkyl,


CA 02365282 2004-08-06
benzyl, substituted benzyl, and mixtures thereof: X is a water soluble
anion; and
III) mixtures thereof;
provided said polymer or co-polymer has a net cationic charge; and
B) the balance carriers and other adjunct ingredients.
Another aspect of the present invention is the combination a dye protection
composition
and a fabric appearance composition to form a system form providing enhanced
color and fabric
fiber benefits to fabric comprising clothing and apparel, said dye protection
system ,;omprising:
A) from about 1% by weight, of a polymer or co-polymer comprising dye
protection
composition as described herein above; and
B) from about 1 % by weight, of a fabric enhancement composition, said
composition providing one or more fabric enhancement benefits (fabric
enhancement component); and
C) the balance carriers and adjunct ingredients.
The present invention also relates to methods for preventing fading an loss of
color to
fabric comprising the step of contacting fabric with a composition according
to the present
invention or with a composition which comprises the components of the present
invention as a
color-care system.
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 (o C) unless otherwise specified.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to attenuation and/or abatement of fabric
appearance loss.
The compositions of the present invention comprise a cationic polymer or co-
polymer which acts
together with a low molecular weight fabric enhancement polyamine, fabric
softness agent
(crystal growth inhibitor) and dye fixing agent to provide protection to
fabric from appearance
loss which is primarily due to mechanical loss. Another aspect of the present
invention relates to
a composition which comprises a cationic polymer or co-polymer which acts
together with a low
molecular weight fabric enhancement polyamine, fabric softness agent
(quaternary ammonium
fabric softener active), dye fixing agent, and one further enhancement agent,
inter al:a, a
stabilizer, co-solvent. Yet another aspect of the present invention relates to
a composition which
comprises a cationic polymer or co-polymer which acts together with a low
molecular weight



WO 00/56848 CA 02365282 2001-08-31 pCT~S00/08030
6
fabric enhancement polyamine, fabric softness agent (crystal growth inhibitor)
and quaternary
ammonium fabric softness agent, and dye fixing agent. The normal abrasive
destruction of the
fabric surface removes the surface layers of fabric which are dyed. Especially
in the case of
cotton fabric, below this layer of dyed fabric is the less dyed, then non-dyed
fabric. As wears a
"washed looked" develops which is due to the abrasive destruction of fabric
and the subsequent
loss of the weakened fabric fiber in the laundry cycle.
It has been surprisingly discovered that the combination of elements which
comprise the
compositions of the present invention modify the surface of fabric, especially
cellulosic fabric
and ameliorate many of the conditions which enhance fabric fiber surface wear
and subsequent
loss. The compositions of the present invention also soften the fabric surface
making the fibers
less abrasive and thereby reducing the level of friction between the fabric
and surfaces in which
the garment comes into contact. This change in surface condition can nullify
many of the
conditions which contribute to fabric damage and hence attenuate, and in some
cases, abate
fabric damage and therefore the concomitant loss of color.
The compositions of the present invention can be used for a stand alone
treatment of
fabric wherein the compositions are added as ingredients to a compatible fully
formulated rinsed
additive, laundry additive or pre-soak all of which are used together with
fabric softeners,
laundry detergent compositions and the like. The compositions of the present
invention, either as
a stand alone treatment or as a system, are suitable for providing a method
for treating fabric and
subsequently attenuating or abating the loss of color due to mechanical
abrasion and removal of
the top layer of dyed fabric.
Alternatively, the compositions comprise a fabric color integrity system. The
systems of
the present invention are used as an initial treatment of fabric by the
manufacturer of either the
fabric from which apparel is made or the fully formed article of manufacture
(apparel).
However, if the fabric is not pre-treated by the manufacturer, suitable
protection is afforded to
the fabric wherein the consumer applies the system to fabric during
laundering. The systems of
the present invention can be used at any point during the lifetime of apparel
to abate the loss of
color from fabric.
The following is a detailed description of the essential elements of the
present invention.
Cationic Polymer or Co-polymer
Compositions and systems of the present invention comprise from about 0.05%,
preferably for about 0.1 %, more preferably from about 0.5%, most preferably
from about 1 % to
about 10%, preferably to about 7%, more preferably to about S% by weight, of a
polymer, co-
polymer, or mixture thereof, wherein said polymer or co-polymer comprises at
least one



CA 02365282 2001-08-31
WO 00/56848 PCT/US00/08030
7
cationically charged unit, inter alia, quaternary ammonium moiety or unit
which cari form a
cationic charge in situ, inter alia, primary amine moiety.
I) Linear Polymer Units
The polymers or co-polymers of the present invention can comprise one or more
linear
polymer units having the formula:
RI R2
C-C
R1 Z
wherein R', Rz, and Z are defined herein below. Preferably, the linear polymer
units are formed
from linearly polymerizing monomers. Linearly polymerizing monomers are
defined herein as
monomers which under standard polymerizing conditions result in a linear
polymer chain or
alternatively which linearly propagate polymerization. The linearly
polymerizing monomers of
the present invention have the formula:
R~ R2
i
C=C~
Rl~ Z .
however, those of skill in the art recognize that many useful linear monomer
units are introduced
indirectly, inter alia, vinyl amine units, vinyl alcohol units, and not by way
of linearly
polymerizing monomers. For example, vinyl acetate monomers once incorporated
into the
backbone are hydrolyzed to form vinyl alcohol units. For the purposes of the
present invention,
linear polymer units may be directly introduced, i.e. via linearly
polymerizing units, or indirectly,
i.e. via a precursor as in the case of vinyl alcohol cited herein above.
Each R' is independently hydrogen, C,-C4 alkyl, substituted or unsubstituted
phenyl,
substituted or unsubstituted benzyl, carbocyclic, heterocyclic, and mixtures
thereof. Preferably
R' is hydrogen, C,-CQ alkyl, phenyl, and mixtures thereof, more preferably
hydrogen and methyl.
Each RZ is independently hydrogen, halogen, C,-C4 alkyl, C,-C4 alkoxy,
substituted or
unsubstituted phenyl, substituted or unsubstituted benzyl, carbocyclic,
heterocyclic, and mixtures
thereof. Preferred R'' is hydrogen, C,-C4 alkyl, and mixtures thereof.
Each Z is independently hydrogen; hydroxyl; halogen; -(CHZ)mR, wherein R is
hydrogen,
hydroxyl, halogen, nitrilo, -OR3, -O(CHz)"N(R3)2, -O(CHz)"N+(R3)3X-, -
OCO(CHz)"N(R3)z, -
OCO(CHZ)nN+(R3)3x , -NHCO(CHZ)"N(R3)z, -NHCO(CHZ)~N+(R3)3X , -(CHZ)nN(R3)2, -
(CHZ)~Nt(R3)3X-, a non-aromatic nitrogen heterocycle comprising a quaternary
ammonium ion, a
non-aromatic nitrogen heterocycle comprising an N-oxide moiety, an aromatic
nitrogen



CA 02365282 2001-08-31
WO 00/56848 PCT/US00/08030
8
containing heterocyclic wherein one or more or the nitrogen atoms is
quaternized; an aromatic
nitrogen containing heterocycle wherein at least one nitrogen is an N-oxide; -
NHCHO
(formamide), or mixtures thereof; wherein each R3 is independently hydrogen,
C,-C8 alkyl, CZ-C8
hydroxyalkyl, and mixtures thereof; X is a water soluble anion; the index n is
from 0 to 6;
carbocyclic, heterocyclic, or mixtures thereof; -(CHZ)mCOR' wherein R' is -
OR3, -
O(CHZ)nN(R3)z~ -O(CHZ)nN+(R3)3X ~ -~3(CHz)nN(R3)z~ -~3(CH2)nN+(R3)3X ~ -
(CH2)oN(R3)2~ -
(CH2)nN+(R3)3X-, or mixtures thereof, wherein R3, X, and n are the same as
defined herein above.
A preferred Z is -O(CHZ)"N+(R3)3X-, wherein the index n is 2 to 4. The index m
is from 0 to 6,
preferably 0 to 2, more preferably 0.
Non-limiting examples of linearly polymerizing monomers comprising a
heterocyclic Z
unit includes 1-vinyl-2-pyrrolidinone, 1-vinylimidazole, 2-vinyl-1,3-
dioxolane, 4-vinyl-1-
cyclohexenel,2-epoxide, and 2-vinylpyridine.
The polymers and co-polymers of the present invention comprise Z units which
have a
cationic charge or which result in a unit which forms a cationic charge in
situ. When the co-
polymers of the present invention comprise more than one Z unit, for example,
Z', ZZ,...Z° units,
at least about 1 % of the monomers which comprise the co-polymers will
comprise a cationic
unit. Preferred cationic units include -O(CHZ)~N+(R3)3X- and -(CHZ)"N+(R3)3X .
When the co-
polymers of the present invention are formed from two monomers, Z' and ZZ, the
ratio of Z' to Zz
is preferably from about 9:1 to about 1:9.
A non-limiting example of an indirect Z unit which can be made to form a
cationic
charge in situ is the -NHCHO unit, formamide. The formulator can prepare a
polymer or co-
polymer comprising formamide units some of which are subsequently hydrolyzed
to form vinyl
amine equivalents. For example the formulator may prepare a co-polymer having
the general
formula:
which comprises a formamide unit and then subsequently treat the co-polymer
such that some of
the formamide units are hydrolyzed to form a co-polymer comprising vinyl amine
units, said
polymer having the formula:



CA 02365282 2001-08-31
WO 00/56848 PCT/US00/08030
9
wherein Z may be a cationic unit comprising or non-cationic unit comprising
moiety and x' + x"
= x.
Another class of preferred linearly polymerizable monomers comprise
cationically
charged heteroaromatic Z units having the formula:
R1 Rz
\C=C~
Ri/
N~ +
6
R
an non-limiting example of which is 4-vinyl (N-alkyl)pyridine wherein R' and
RZ are each
hydrogen and R6 is methyl.
Another class of preferred linearly polymerizable monomers which comprises a
heterocyclic ring includes Z units comprising an N-oxide, for example, the N-
oxide having the
formula:
R' RZ
/C=C~
R
N
~O
a non-limiting example of which is 4-vinyl pyridine N-oxide.
N-alkyl vinylpyridine monomers and N-oxide vinylpyridine monomers can be
suitably
combined with other non aromatic monomers, inter alia, vinyl amine. However,
preferred
polymers of the present invention include co-polymers derived from a
combination of
quaternized, N-oxide, and nitrogen containing heteroaromatic monomers, non-
limiting examples
of which includes a copolymer of N-methyl vinyl pyridine and vinyl pyridine in
a ratio of 4:1; a
copolymer of N-methyl vinyl pyridine and vinyl pyridine in a ratio of 4:6; a
co-polymer of
poly(N-methyl vinyl pyridine) and vinyl pyridine N-oxide in a ratio of polymer
to monomer of
.. ,



CA 02365282 2001-08-31
WO 00/56848 PCT/US00/08030
4:1; poly(N-methyl vinyl pyridine) and vinyl pyridine N-oxide in a ratio of
polymer to monomer
of 4:6; and mixtures thereof.
A preferred linear co-polymer according to the present has the formula:
Zl~x~ 22 Jy
wherein Z' has the formula:
O NH2.
ZZ has the formula:
CH3 X
~/N~CH3
O O
CH3
wherein X is chlorine; x has the value of from about 10 to about 100,000; y
has the value of from
about 10 to about 100,000; the ratio of x to y is from 9:1 to 1:9. Co-polymers
of this type are
available as, e.g., Sedipur~ CF104 ex BASF.
As described herein above, some preferred polymer residues may be formed by
treatment
of the resulting polymer. For example, vinyl amine residues are preferably
introduced via
formamide monomers which are subsequently hydrolyzed to the free amino unit.
Also vinyl
alcohol units are obtained by hydrolysis of residues formed form vinyl acetate
monomers.
Likewise, acrylic acid residues may be esterified after polymerization, for
example, units having
the formula:
iH3 X_
O O/~N'CH3
CH3
may be more conveniently formed after the backbone has been formed by
polymerization with
acrylic acid or acrylic acid precursor monomers.
II) Cyclic Units Derived from Cyclically Polymerizing Monomers
The polymers or co-polymers of the present invention can comprise one or more
cyclic
polymer units which are derived from cyclically polymerizing monomers.
Cyclically
polymerizing monomers are defined herein as monomers which under standard
polymerizing



CA 02365282 2001-08-31
WO 00/56848 PCT/US00/08030
11
conditions result in a cyclic polymer residue as well as serving to linearly
propagate
polymerization. Preferred cyclically polymerizing monomers of the present
invention have the
formula:
R4 _
X
Ra-N~ Rs
Rs
wherein each R4 is independently an olefin comprising unit which is capable of
propagating
polymerization in addition to forming a cyclic residue with an adjacent R4
unit; RS is C,-C,z
linear or branched alkyl, benzyl, substituted benzyl, and mixtures thereof; X
is a water soluble
anion.
Non-limiting examples of R° units include allyl and alkyl substituted
allyl units.
Preferably the resulting cyclic residue is a six-member ring comprising a
quaternary nitrogen
atom.
RS is preferably C,-C4 alkyl, preferably methyl.
An example of a cyclically polymerizing monomer which results in a cyclic
polymer unit
is dimethyl diallyl ammonium having the formula:
N+
H3C CH3
which results in a polymer or co-polymer having units with the formula:
N+ X-
H3C CH3
wherein preferably the index z is from about 10 to about 50,000.
III) Mixtures thereof.
The polymers or co-polymers of the present invention must retain a net
cationic charge,
whether the charged is developed in situ, or whether the polymer or co-polymer
itself has a
formal positive charge. Preferably the polymer or co-polymer has at least 10%,
more preferably
at least about 25%, more preferably at least about 35%, most preferably at
least about 50% of the
residues comprise a cationic charge.



CA 02365282 2001-08-31
WO 00/56848 PCT/US00/08030
12
The polymers or co-polymers of the present invention can comprise mixtures of
linearly
and cyclically polymerizing monomers, for example the poly(dimethyldiallyl-
ammonium
chloride/acrylamide) co-polymer having the formula:
wherein Z', Z2, x, y, and z are the same as defined herein above and X is
chloride ion.
A particularly preferred embodiment of this invention is the composition
comprising a
polymer based on dimethyldiallylammonium chloride and a copolymer which is
based upon
acrylamide with a co-monomer selected from the group consisting of N, N
dialkylaminoalkyl(meth)acrylate, N, N dialkylaminoalkylacrylate, N,N
dialkylaminoalkylacrylamide, N,N dialkylaminoalkyl(meth)acrylamide, their
quaternized
derivatives and mixtures thereof.
Non-limiting examples of preferred polymers according to the present invention
include
dye maintenance copolymers comprising:
i) a first monomer selected from the group consisting of N, N
dialkylaminoalkyl(meth)acrylate, N, N dialkylaminoalkylacrylate, N,N
dialkylaminoalkylacrylamide, N,N dialkylaminoalkyl(meth)acrylamide, their
quaternized derivatives and mixtures thereof; and
ii) a second monomer selected from the group consisting of acrylic acid,
methacrylic acid, C,-C6 alkylmethacrylate, C,-C6 alkyl acrylate, C,-C8
hydroxyalkylacrylate, C,-C$ hydroxyalkylmethacrylate, acrylamide, C,-C,6 alkyl
acrylamide, C,-C,6 dialkylacrylamide, 2-acrylamido-2-methylpropane sulfonic
acid or its alkali salt, methacrylamide, C,-C,6 alkylmethacrylamide, C,-C,6
dialkylmethacrylamide, vinyl formamide, vinylacetamide, vinyl alcohol, C,-C8
vinylalkylether, vinyl pyridine, itaconic acid, vinyl acetate, vinyl
propionate,
vinyl butyrate and mixtures thereof;
wherein the copolymer comprises at least 25 mole % of the first monomer.
Non-limiting examples of co-polymers which are highly effective in the
embodiments of
the present invention include co-polymer of acrylamide/dimethylamino
ethylacrylate
methochloride (molar ratio 24:1, K-value 85); co-polymer of polyacrylamides:
acrylamide/dimethylamino ethylacrylate methochloride (molar ratio 9:1, K-value
70); co-



CA 02365282 2001-08-31
WO 00/56848 PCT/L1S00/08030
13
polymer of acrylamide/dimethylamino ethylacrylate methochloride (molar ratio
9:1, K-value 60);
co-polymer of acrylamide/dimethylamino ethylacrylate methochloride (molar
ratio 49:1, K-value
60); and co-polymer of acrylamide/dimethylamino ethylacrylate methochloride
(molar ratio 24/1,
K-value 85).
CARE SYSTEMS
The present invention also relates to systems for providing enhanced care to
fabric. The
care systems according to the present invention comprise a composition
providing dye protection
benefits to fabric in combination with a separately added composition which
provides a fabric
enhancement benefit, said system comprising:
a) from about 0.05%, preferably for about 0.1%, more preferably from about
0.5%,
most preferably from about 1% to about 10%, preferably to about 7%, more
preferably to about 5% by weight, of a polymer or co-polymer comprising dye
protection composition as described herein;
b) from about 0.01%, preferably from about 0.1% to about 20%, preferably to
about
10% by weight, of a fabric abrasion reducing polymer, said 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 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 quaternary ammonium fabric softening active, an amine derived
therefrom, and mixtures thereof;
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;
optionally from about 0.01% to about 50% 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) 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;



CA 02365282 2001-08-31
WO 00/56848 PCT/US00/08030
14
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 1% to about 80% by weight, of a cationic surfactant;
n) 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.
A non-limiting example of a preferred system according to the present
invention
comprises:
a) from about 0.05%, preferably from about 0.1%, more preferably from about
0.5%, most preferably from about 1% to about 10%, preferably to about 7%,
more preferably to about 5% by weight, of a polymer or co-polymer comprising
dye protection composition as described herein;
b) from about 0.01% to about 50% by weight, of a polyamine, said polyamine is
selected from the group consisting of N,N'-bis(aminopropyl)-1,3-
propylenediamine; N,N'-bis(hydroxyethyl)-N,N'-bis[3-N,N-
bis(hydroxyethyl)aminopropyl]-1,3-propylenediamine; N,N'-bis(2-
hydroxypropyl)-N,N'-bis[3-N,N-bis(2-hydroxypropyl)aminopropyl]-1,3-
propylenediamine; N,N'-bis(2-hydroxybutyl)-N,N'-bis[3-N,N-bis(2-
hydroxybutyl)aminopropyl]-1,3-propylenediamine; 5-N-methyl
dipropylenetriamine; l,l-N-dimethyl-5-N'-methyl-9,9-N"-dimethyl
dipropylenetriamine; 1,1-N-dimethyl-9,9-N"-dimethyl dipropylenetriamine; and
mixtures thereof;
c) from about 0.005% to about 1% by weight, of one or more crystal growth
inhibitors;
d) from about 0.001 % to about 90% by weight, of one or more dye fixing
agents;
and
e) the balance carriers and adjunct ingredients.
Another preferred system according to the present invention comprises:
a) from about 0.05%, preferably from about 0.1%, more preferably from about
0.5%, most preferably from about 1% to about 5%, preferably to about 3% by
weight, of a polymer or co-polymer comprising dye protection composition as
described herein;



CA 02365282 2001-08-31
WO 00/56848 PCT/US00/08030
b) 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 quaternary ammonium fabric softening active, an amine derived therefrom, and
mixtures thereof;
c) from about 0.01% to about 50% by weight, of a low molecular polyamine, said
polyamine is selected from the group consisting of N,N'-bis(aminopropyl)-1,3-
propylenediamine; N,N'-bis(hydroxyethyl)-N,N'-bis[3-N,N-
bis(hydroxyethyl)aminopropyl]-1,3-propylenediamine; N,N'-bis(2-
hydroxypropyl)-N,N'-bis[3-N,N-bis(2-hydroxypropyl)aminopropyl]-1,3-
propylenediamine; N,N'-bis(2-hydroxybutyl)-N,N'-bis[3-N,N-bis(2-
hydroxybutyl)aminopropyl]-1,3-propylenediamine; 5-N-methyl
dipropylenetriamine; 1,1-N-dimethyl-5-N'-methyl-9,9-N"-dimethyl
dipropylenetriamine; 1,1-N-dimethyl-9,9-N"-dimethyl dipropylenetriamine; and
mixtures thereof;
d) from about 0.005% to about 1% by weight, of one or more crystal growth
inhibitors; and
e) the balance carriers and adjunct ingredients.
Low Molecular Weight Polyamines
The compositions of the present invention comprise from about 0.01%,
preferably from
about 0.75%, more preferably from 2%, to about 50%, preferably to about 35%,
more preferably
to about 20%, most preferably to about 15% by weight, of the herein described
low molecular
weight polyamines. In general, the polyamines are either linear polyamines or
cyclic
polyamines.
Linear Polyamines
The enhanced fabric appearance compositions of the present invention may
comprise one
or more polyalkyleneimines which have backbones comprising CZ-C6 alkylene
units, however,
the backbones must comprise at least one C3-C6 alkylene unit, preferably the
linear polyamines
have each backbone unit comprising a C3-C6 alkylene unit.
The polyamines of the present invention have the formula:
R2
(R1)ZN-R-[N-R]n N(R~)2
wherein each R is independently CZ-C6 linear alkylene, C3-C6 branched
alkylene, and mixtures
thereof; preferably the backbone is a mixture of ethylene, 1,3-propylene, 1,3-
propylene, 1,4



CA 02365282 2001-08-31
WO 00/56848 PCT/US00/08030
16
butylene, 1,6-hexylene, more preferably a mixture of ethylene and 1,3-
propylene, most
preferably the backbone comprises only 1,3-propylene units.
R' is hydrogen; C,-C,2 alkyl, preferably C,-Cg alkyl, more preferably C,-C4
alkyl;
alkyleneoxy having the formula:
-~3~)W R4
wherein R3 is CZ C6 linear alkylene, C3-C6 branched alkylene, or mixtures
thereof; preferably
ethylene, mixtures of ethylene and 1,2-propylene, 1,2-butylene, preferably
ethylene, 1,2-
propylene. R4 is hydrogen, C,-C6 alkyl, or mixtures thereof; preferably
hydrogen or methyl, more
preferably hydrogen. The index m is from 1 to 4, however, the value of m is
predicated on the
desired fabric enhancement benefit sought by the formulator. For example, the
level of bleach
protection varies over the value of m. Also, the dye fixation properties of
the substantially linear
polyamines are maximized when the alkyleneoxy unit is absent, i.e., R' and RZ
are hydrogen. R'
is also acyl having the formula:
O
-C~ Rs
wherein RS is C,-C2~ linear or branched alkyl, C3-C22 linear or branched
alkenyl, or mixtures
thereof; preferably RS is a hydrocarbyl moiety which sufficiently provides
increased fabric
lubricity, more preferably C6-C,Z alkyl; hydroxy alkyl having the formula:
(CHZ)y(CHOH)ZH
wherein the index y is from 1 to 5, z is from 1 to 3, provided y + z is less
than or equal to 6 and
the -(CHOH)- unit is not directly attached to a nitrogen atom. Non-limiting
examples of hydroxy
alkyl units include 2-hydroxy alkyl, for example, -CHZCHOHCH3, -
CHZCHOHCHZCHZCHZCH3.
Two R' units can be taken together to form a 5-7 member ring, i.e.,
piperidine, morpholine. An
example of a backbone wherein two R' units are taken together to form a ring
has the formula:
R2 R2 ~ O
(Rl)2N~~/ N~~/ N~~/ NJ
The present invention also includes mixtures of the herein described R' units.
RZ is hydrogen, R', -RN(R'),, and mixtures thereof. The integer n has the
value from 1 or
6; preferably from 1 to 4, more preferably 1 or 3.



CA 02365282 2001-08-31
WO 00/56848 PCT/US00/08030
17
Most prefered linear polyamine has a backbone wherein R is 1,3-propylene and n
is
equal to 2, N,N'-bis(3-aminopropyl)-1,3-propylenediamine (TPTA). This
preferred backbone
can then be substituted or left unsubstituted in a manner which affords the
formulator the
maximal fabric benefit and compatibility of the low molecular weight amine
with the particular
embodiment. As a non-limiting example, when R' and RZ are each equal to
hydrogen, dye
fixative properties, in certain liquid fabric care embodiments, even in the
presence of bleach, are
maximal. Also when R' and RZ are not equal to hydrogen, bleach scavenging
benefits are
enhanced.
Those of ordinary skill in the art will recognize that depending upon the
synthetic
procedure used to prepare the polypropyleneamine backbones, varying amounts of
both the linear
and branched materials will be present in the final product admixture. The
preferred backbones
of the linear polyamines of the present invention comprise at least one 1,3-
propylene unit,
preferably at least two 1,3-propylene units.
For the purposes of the present invention, when a backbone nitrogen is
referred to as
"unmodified" the nitrogen contains only hydrogen atoms. "Modified" polyamines
have one or
more alkyleneoxy units as described herein above. Preferred substituents are
methyl, 2-
hydroxyethyl, 2-hydroxypropyl, 1,2-propyleneoxy, 2-hydroxybutyl, and mixtures
thereof, more
preferably methyl and 2-hydroxypropyl.
For certain formulations, polyamines which comprise alkylated polyamines are
preferred, for example, tetramethyl dipropylenetriamine (1,1-N-dimethyl-9,9-N"-
dimethyl
dipropylenetriamine) having the formula:
H
(H3C)ZN~~ N~~ N(CH3)2
the permethylated dipropylenetriamine (1,1-N-dimethyl-5-N'-methyl-9,9-N"-
dimethyl
dipropylenetriamine) having the formula:
i H3
(H3C)2N ~~ N ~~ N(CH3)2
and the mono-methylated dipropylenetriamine (5-N'-methyl dipropylenetriamine)
having the
formula:
CH3
H2N~~N~~NH2



CA 02365282 2001-08-31
WO 00/56848 PCT/US00/08030
18
Cyclic Amines
The enhanced fabric appearance compositions of the present invention may
comprise one
or more cyclic polyalkyleneamines wherein at least one of the ring nitrogens
is substituted with
at least one C3-C6 alkyleneimine unit.
The low molecular weight 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;
for example, 1,4-piperazine. R is hydrogen, -(CHZ)kN(R')2, and mixtures
thereof, wherein at least
one cyclic polyamine R unit is a -(CHZ)kN(R')2 unit; preferably both R units
are -(CHZ)kN(R')2;
wherein each index k independently has the value from 3 to 12, preferably k is
3. Preferably the
backbone of the cyclic amines including R units is 250 daltons or less. Most
preferred backbone
ring is 1,4-piperazine.
R' is hydrogen; C,-C,2 alkyl, preferably C,-C8 alkyl, more preferably C,-C4
alkyl, most
preferably methyl; alkyleneoxy having the formula:
(Rs0)m R4
wherein R3 is CZ-C6 linear alkylene, C3-C6 branched alkylene, or mixtures
thereof; preferably
ethylene, mixtures of ethylene and 1,2-propylene, 1,2-butylene, preferably
ethylene, 1,2-
propylene. R4 is hydrogen, C,-C6 alkyl, or mixtures thereof; preferably
hydrogen or methyl, more
preferably hydrogen. The index m is from 1 to 4, however, the value of m is
predicated on the
desired fabric enhancement benefit sought by the formulator. For example, the
level of bleach
protection varies over the value of m. R' is also acyl having the formula:
O
-C-Rs
wherein R5 is C,-CZZ linear or branched alkyl, C3-CZ~ linear or branched
alkenyl, or mixtures
thereof; preferably RS is a hydrocarbyl moiety which sufficiently provides
increased fabric
lubricity, more preferably C6-C,2 alkyl; hydroxy alkyl having the formula:
-(CHZ)y(CHOH)ZH
wherein the index y is from 1 to 5, z is from 1 to 3, provided y + z is less
than or equal to 6 and
the -(CHOH)- unit is not directly attached to a nitrogen atom. Non-limiting
examples of hydroxy



CA 02365282 2001-08-31
WO 00/56848 PCT/C1S00/08030
19
alkyl units include 2-hydroxy alkyl, for example, -CHZCHOHCH3, -
CHZCHOHCHZCHZCHZCH3.
Two R' units can be taken together to form a 5-7 member ring, i.e.,
piperidine, morpholine.
Preferably the backbone of the cyclic amines of the present invention comprise
a N,N'-
bis-substituted 1,4-piperazine ring having the formula:
R~R~ R~R~
R-N N-R
R~~'~ R~
R~ R'
wherein each R' is independently hydrogen, C,-C4 alkyl, C,-C4 hydroxyalkyl, C,-
C4 aminoalkyl,
or two R' units of the same carbon atom are bonded to oxygen thus forming a
carbonyl group
(C=O) wherein the carbon atom is a ring atom, and mixture thereof. Examples of
carbonyl
containing rings which comprise L units are 1,4-diketopiperizines.
Preferably the backbones of the polyamines of the present invention, prior to
modification, have
the formula:
H2N-(CHz)3- ~ (CHz)3-~2
wherein each R unit is -(CHz)3NHz.
However, the cyclic units may be substituted on only one ring nitrogen as in
the case
wherein one R unit is hydrogen, and the other R unit is -(CHz)kNHz, for
example, the piperazine
having the formula:
H- ~ -(CHz)3-~z
The backbones of the cyclic polyamines of the present invention preferably
comprise at
least one 1,3-propylene unit, more preferably at least two 1,3-propylene
units.
For the purposes of the present invention, when a backbone nitrogen is
referred to as
"unmodified" the nitrogen contains only hydrogen atoms. "Modified" polyamines
have one or
more substituent units as described herein above. Preferably when the backbone
units are
modified all of the nitrogens are modified. Preferred alkyleneoxy substituents
are ethyleneoxy,
1,2-propyleneoxy, and mixtures thereof, more preferably 1,2-propyleneoxy.
Crystal Growth Inhibitor


CA 02365282 2004-08-06
20
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
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 Crrowth Inhibition Test 4CGIT)
The suitability of a material to serve as a crystal growth inhibitor according
to the present
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 Growth Charact., Vol 3, 77-102, (1980),
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
crystal formation afforded by a hypothetical crystal growth inhibitor.
Without CGT
Volume of
base added
) With CGI
t-lag
TIIiIE
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.
Exemplary Procedure
Combine in a suitable vessel, 2,IM KCl (35 mL), O.OI75M CaCI, (50mL), O.O1M
KHZPO4 (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-~


CA 02365282 2004-08-06
21
M. The solution is titrated to pH 7.4 with 0.05M 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 IOM. Crystal growth inhibitors are differentiated form
chelating agents by
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 I5, preferably
less than 12.
The prefer-ed 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. 4,102,90' .A preferred crystal grow-th
inhibitor
comprises 2-phosphonobutane 1.,2,4-tricarboaylic acid.
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


CA 02365282 2004-08-06
22
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-Rite~ ex BF Goodrich, Acrysol~ ex Rohm &
Haas,
Sokalan~ ex BASF, and Norasol0 ex Norso Haas. Preferred are the Norasol~
polyacrylate
polymers, more preferred are Norasol~ 410N (MW 10,000) and Norasol~ 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 Norasol~ QR 784 (MW 4000) ex
Norso-Haas.
Polycarboxylate crystal growrth 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 C<;-C20 alkyl,
CS-C20 alkenyl succinic acid and salts thereof, of which dodeeenyl 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,
panic D.iphosphonic Acids
Organic diphosphonic acid are also suitable for use as crystal growth
inhibitors. For the purposes
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,-C4 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-
dihydro~;yethane-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).
Dyc Fixing Agents
The compositions of the present invention optionally comprise from about 0.001
°a,,
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.


CA 02365282 2004-08-06
23
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 definition 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 situ
under the
conditions of usage. Cationic fixatives are 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, Tinofix~ FRD and
Solfin~
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 "Aftertreatments for
Improving the
Fastness of Dyes on Textile Fibres", Christopher C. Cook, Rev. Prog.
Coloration, Vol. XII,
(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
diaminotrimethylammonium methosulphate. In addition, the N-oxides of tertiary
amines;
derivatives of polymeric allcyldiamines, polyamine-cyanuric chloride
condensates, and aminated
glycerol dichlorohydrins are suitable for use as dye fixatives in the
compositions of the present
invention. A most preferred dye fixing agent comprises dodecyl
trimethylammonium chloride.
Cellulose Reactive Dve Fixing,Agents
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
SO°,io, 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
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


CA 02365282 2004-08-06
24
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 lalitted
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 i:o 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
TM
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 cola
water and subsequently
line dried.
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 beriveen 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-
triazincs, vinyl
sulphones, epichlorhydrine derivatives, hydroxyethylene urea derivatives.
formaldehyde
condensation products, polycarboxylates, glyoxal and giutaraldehyde
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.


CA 02365282 2004-08-06
25
Preferred hydroxyethylene urea derivatives include
dimethyloldihydroxyethylene, urca, 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, Zet X~ ex
~'eneca and
TM
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
celIulosic reaciive dye fixing agents are commercialized under the tradename
Rewin DWR and
Rewin V4BS cx CHT R. Beitlich.
ADJUNCT INGREDIENTS
The compositions of the present invention may also optionally comprise one or
more
adjunct ingredients. Non-limiting examples of adjunct ingredients are selected
from the group
consisting of fabric softener actives, electrolytes, stabilizers, low
molecular weight water soluble
solvents including principal solvents, chelating agents, cationic charge
boosters, dispersibility
aids, soil release agents, nonionic fabric softening agents, concentration
aid, perfume,
preservatives, colorants, optical brighteners, opacifiers, fabric care agents,
anti-shrinkage agents,
anti-wrinkle agents, fabric crisping agents, spotting agents, germicides,
fungicides, anti-corrosion
agents, antifoam agents, and mixtures thereof,
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 from
which cationic fabric softener actives are derived having the formula:
(R)N~CHz)n-Q-a~
3-m
quaternary ammonium compounds having the formula:


CA 02365282 2005-08-29
26
~R)4-m N~~~-Q-R~ X _
m
~ ,
and mixtures thereof, wherein each R is independently C1-C6 alkyl, C~-C6
hydroxyalkyl, benzyl,
and mixtures thereof; R1 is preferably C~-Czz linear alkyl, Cl -C22 branched
alkyl, C3 -CZz
linear alkenyl, C3-Czz branched alkenyl, and mixtures thereof; Q is a carbonyl
moiety
independently selected from the units having the formula:
O O R2 O O R2
II II I II II I
-O-C- , -C-O- , -N=C- ; -C-N-
. O
R3 O O-C-R' O
I 11 I I1
-O-C-O- _ -CH-O-C- T -CH-CIiz-O-C
wherein Rz is hydrogen, C,-C4 alkyl, C~-C4 hydroxyalkyl, preferably hydrogen;
R; is C,-C4 alkyl, preferably hydrogen or methyl; preferably Q has the
formula:
O
Il II
-o-C- or -NH-c-
h is a softener compatible anion; preferably the anion of a strong acid, for
example, chloride,
bromide, methylsulfate; ethylsulfate, sulfate; nitrate and mixtures thereof,
mare 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
OR)4_m N (CHz)n-O-C-R1
m
wherein the unit having the formula:



WO ~~/56848 CA 02365282 2001-08-31 pCT/[1500/08030
27
O
-O-C-R'
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 inter 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
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
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
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
preferably from about 10% to about 30%, preferably to about 25%, more
preferably to about
18%. As stated herein above cis and traps isomers can be used, preferably with
a cisltrans ratio
is of from 1:1, preferably at least 3: l, 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
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.



WO 00/56848 CA 02365282 2001-08-31 PCT/[JS00/08030
28
Indeed, for compounds having the formula:
(R)4_m N-j-(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 C 17 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;


CA 02365282 2004-08-06
29
N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl
sulfate;
N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl
sulfate;
N,N-di(tallowylamidoethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl
sulfate;
N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium chloride;
N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium chloride;
N-(2-tallowoyloxy-2-ethyl)-N-(2-tailowyloxy-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 1, 1997; U.S. 5,622,925 de Buzzaccarini et
al., issued April 22,
1997; U.S. 5,545,350 Baker et al., issued August 13, 1996; U.S. 5,474.690 Wahl
et czl., issued
December 12, 1995; U.S. 5,417,868 Tumer et al., issued January 27, 1994; U.S.
4,661,269 T'rinh
et al., issued April 28, 1987; U.S. 4,439,335 Burns, issued March 27, I984;
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.



WO 00/56848 CA 02365282 2001-08-31 pCT/US00/08030
METHOD OF USE
The present invention further relates to methods for utilizing the systems and
compositions of the present invention to abate and/or attenuate the loss of
fabric color. One
method according to the present invention comprises the step of contacting
fabric which has been
manufactured at a point wherein the fabric has not been worn or used, with a
composition
comprising:
A) from about 0.05%, preferably for about 0.1%, more preferably from about
0.5%,
most preferably from about 1 % to about 10%, preferably to about 7%, more
preferably to about 5% by weight, of a polymer, copolymer, or mixtures
thereof,
said polymer or copolymer comprising one or more units selected from the group
consisting of:
I) linear polymer units having the formula:
Rl R2
C-C
R1 Z
wherein
each
R'
is
independently


a) hydrogen;


b) C,-C4 alkyl;


c) substituted or unsubstituted
phenyl;


d) substituted or unsubstituted
benzyl;


e) carbocyclic;


f) heterocyclic;


g) and mixtures thereof;


eachR' is independently


a) hydrogen;


b) halogen


c) C,-C4 alkyl;


d) C,-C4 alkoxy;


e) substituted or unsubstituted
phenyl;


f] substituted or unsubstituted
benzyl;


g) carbocyclic;





WO 00/56848 CA 02365282 2001-08-31 pCT/j1S00/08030
31
h) heterocyclic;
i) and mixtures thereof;
each Z is independently
a) hydrogen;
b) hydroxyl;
c) halogen;
d) -(CHZ)mR;
wherein R is:
i) hydrogen;
ii) hydroxyl
iii) halogen;
iv) nitrilo;
v) -OR3;
vi) -O(CHZ)"N(R3)z;
vii) -O(CHZ)"N+(R3)sX ;
viii) -OCO(CHZ)"N(R3)2;
ix) -OCO(CHz)"N+(R3)3X-;
x) -NHCO(CHz)"N(R3)z;
xi) -NHCO(CHZ)"N+(R3)3X-;
xii) -(CHZ)"N(R3)z;
xiii) -(CHZ)nN+(R3)3X ;
xiv) carbocyclic;
xv) heterocyclic;
xvi) nitrogen heterocycle quaternary ammonium;
xvii) nitrogen heterocycle N-oxide;
xviii) aromatic N-heterocyclic quaternary ammonium;
xix) aromatic N-heterocyclic N-oxide;
xx) -NHCHO;
xxi) or mixtures thereof;
each R3 is independently hydrogen, C,-C8 alkyl, CZ-C8
hydroxyalkyl, and mixtures thereof; X is a water soluble anion;
the index n is from 0 to 6
e) -(CHZ)mCOR'



CA 02365282 2001-08-31
WO 00/56848 PCT/US00/08030
32
wherein
R'
is


i) -OR3;


ii)-O(CHZ)"N(R3)z;


iii)-O(CHZ)nN+(R3)3X-;


iv)-NR3(CH2)"N(R3)z;


v) -NR3(CHz)nN+(R3)3X
;


vi) -(CHz)nN(R3)z;
vii) -(CHZ)nN+(R3)3X ;
viii) or mixtures thereof;
each R3 is independently hydrogen, C,-C8 alkyl, CZ-C8
hydroxyalkyl, and mixtures thereof; X is a water soluble anion;
the index n is from 0 to 6;
f) and mixtures thereof;
the index m is from 0 to 6;
II) cyclic units derived from cyclically polymerizing monomers having the
formula:
Ra _
X
Ra-N~ Rs
Rs
wherein each R4 is independently an olefin comprising unit which is
capable of propagating polymerization in addition to forming a cyclic
residue with an adjacent R4 unit; RS is C,-C,Z linear or branched alkyl,
benzyl, substituted benzyl, and mixtures thereof; X is a water soluble
anion; and
III) mixtures thereof;
provided said polymer or co-polymer has a net cationic charge;
B) from about 50% by weight, of a fabric enhancement component, said
composition comprising:
a) from about 0.01 %, preferably from about 0.1 % to about 20%, preferably
to about 10% by weight, of a fabric abrasion reducing polymer, said
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;



CA 02365282 2001-08-31
WO 00/56848 PCT/US00/08030
33
iii) and mixtures thereof;
b) 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 quaternary ammonium fabric softening
active, an amine derived therefrom, and mixtures thereof;
c) 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;
d) optionally from about 0.001% to about 90% by weight, of one or more
dye fixing agents;
e) optionally from about 0.01 % to about 50% by weight, of one or more
cellulose reactive dye fixing agents;
f) optionally from about 0.01% to about 15% by weight, of a chlorine
scavenger;
g) about 0.005% to about 1% by weight, of one or more crystal growth
inhibitors;
h) optionally from about 1 % to about 12% by weight, of one or more liquid
carriers;
i) optionally from about 0.001 % to about 1 % by weight, of an enzyme;
j) optionally from about 0.01% to about 8% by weight, of a polyolefin
emulsion or suspension;
k) optionally from about 0.01% to about 0.2% by weight, of a stabilizer;
1) optionally from about 1 % to about 80% by weight, of a cationic
surfactant;
m) 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.
A preferred fabric enhancement component according to the present invention
comprises:
B) from about 0.01% to about SO% by weight, of a polyamine, said polyamine is
selected from the group consisting of N,N'-bis(aminopropyl)-1,3-
propylenediamine; N,N'-bis(hydroxyethyl)-N,N'-bis[3-N,N-
bis(hydroxyethyl)aminopropyl]-1,3-propylenediamine; N,N'-bis(2-
hydroxypropyl)-N,N'-bis[3-N,N-bis(2-hydroxypropyl)aminopropyl]-1,3-
propylenediamine; N,N'-bis(2-hydroxybutyl)-N,N'-bis[3-N,N-bis(2-



CA 02365282 2001-08-31
WO 00/56848 PCT/US00/08030
34
hydroxybutyl)aminopropyl]-1,3-propylenediamine; 5-N-methyl
dipropylenetriamine; 1,1-N-dimethyl-5-N'-methyl-9,9-N"-dimethyl
dipropylenetriamine; 1,1-N-dimethyl-9,9-N"-dimethyl dipropylenetriamine; and
mixtures thereof;
C) from about 0.005% to about 1% by weight, of one or more crystal growth
inhibitors;
D) from about 0.001 % to about 90% by weight, of one or more dye fixing
agents;
and
E) the balance carriers and adjunct ingredients.
A preferred usage regime consists of the pre-treating the garment, or the
fabric from
which it is derived, with a composition according to the present invention.
'This pre-treatment
can be carned out by the manufacturer of the garment, or by the consumer. The
pre-treatment
can conveniently be carried out by the consumer during the pre-treatment or
primary wash cycle
of the domestic washing machine. In conjunction with the pre-treatment step
the consumer may
also use a co-composition as described herein which can suitably be added to
the rinse cycle of
the washing process. The co-composition can be optionally used every time that
the garment is
laundered. The compositions of the invention can be used to re-apply a pre-
treatment to the
garment on a periodic basis. The frequency of pre-applying the compositions of
the present
invention can be varied depending on the degree of color protection desired by
the consumer. A
typical re-application may commence after every 3 or 4 washing cycles to
maintain a good level
of color protection.
The following are non-limiting examples of the compositions of the present
invention.
Table I
Weight
Ingredients 1 Z 3 4


Cationic dye fixative ' 2.4 -- 4.0 --


Polymer 2 -- 2.4 -- 1.4


Polyamine 3 8.0 8.0 -- 6.0


Anti-scaling agent 4 0.75 -- -- 1.0


Anti-scaling agent 5 -- 1.0 0.75 --


Cationic surfactant 6 1.0 2.0 3.5 1.0


Polymer' -- 5.0 1.0 --


Polymer 8 1.0 -_ __ 1.0


Polymer 9 5.0 -- 4.0 5.0




CA 02365282 2004-08-06
35
Perfume 0.15 0.1 0.4 0.25


Water balancebalancebalancebalance


1, Dye fixing agent ex Clariant under the tradename Cartafix CB
2. Polydimethyl-diallyl ammonium chloride
3. N'-(3-(dimethylamino)propyl)-N,N-dimethylpropane-1,3-diamine
4. Hydroxyethanediphosphonate
5. BayhibiTtMAM ex Bayer
6. Armosott 12W ex Akzo-Nobel
TM
7. Polyvinylpyrrolidone K85 available ex BASF as Luviskol K85.
8. Polyvinylpyrrolidone K15 available ex BASF as Luviskol K15
9. Canonically modified polyacryiamides: acrylamide/dimethylamino
ethylacrylate
methochloride (molar ratio 24/1, K-value 8S).
Table II
Weight
Ingredients 5 6 7 8


Cationic dye fixative ' 4.0 2.4 2.0 2.5


Polyamine Z 3.0 -- -- 1.5


Polyamine' -- 15..0 12.0 6.0


Polymer' 1.0 -- -- 1.0


Anti-scaling agent 5 0.75 1.0 0.75 1.0


Cationic surfactant ~ 2.0 0.5 3.0 2.5


Polymer' 1.0 -- -- 1.0


Polymer a -- 1.0 1.0 1.0
~
'


Polymer y __ -_ 2.0 ~ 5.0


Polymer' S.0 3.5 3.0 --


Perfume 0.1 0.10 0.40 ' 0.25
S


Water balancebalancebalancebalance


1. Dye fixing agent ex Clariant under the tradename c:artatix Lts
TM
2. Lupasol SK ex BASF.
3. 1,4-bis(3-aminopropyl)piperizine.
4. Imidazole/epichlorohydrin co-polymer.
5. Hydroxyethanediphosphonate.
6. Armosoft 12W ex Akzo-Nobel.



CA 02365282 2001-08-31
WO 00/56848 PCT/LTS00/08030
36
7. Polyvinylpyrrolidone K85 available ex BASF as Luviskol K85.
8. Polyvinylpyrrolidone K15 available ex BASF as Luviskol K15
9. Cationically modified polyacrylamides: acrylamide/dimethylamino
ethylacrylate
methochloride (molar ratio 24:1, K-value 85).
10. Canonically modified polyacrylamides: acrylamide/dimethylamino
ethylacrylate
methochloride (molar ratio 9:1, K-value 70).
Table III
Weight
Ingredients 9 10 11 12


Cationic dye fixative ' 2.4 2.0 4.0 5.0


Polyamine 2 -- 10.0 -- 15.0


Polyamine 3 8.0 -- 12.0 --


Anti-scaling agent 4 0.75 -- -- 1.0


Anti-scaling agent 5 -- 1.0 0.75 --


Cationic surfactant 6 2.0 1.5 3.5 4.0


Polymer' -- __ 1.0 -_


Polymer 8 1.0 1.0 -- 1.0


Polymer 9 -- 3.5 3.0 --


Polymer' S.0 -- 3.0 5.0


Perfume 0.15 0.10 0.40 0.25


Water balance balancebalance balance


1. Dye fixing agent ex C;lamant under the tranename ~anamx ~,D
2. Permethylated dipropylenetriamine.
3. N'-(3-(dimethylamino)propyl)-N,N-dimethylpropane-1,3-diamine.
4. Hydroxyethanediphosphonate.
5. Bayhibit AM ex Bayer.
6. Armosoft 12W ex Akzo-Nobel.
7. Polyvinylpyrrolidone K85 available ex BASF as Luviskol K85.
8. Polyvinylpyrrolidone K15 available ex BASF as Luviskol K15
9. Cationically modified polyacrylamides: acrylamide/dimethylamino
ethylacrylate
methochloride (molar ratio 9:1, K-value 60).
10. Cationically modified polyacrylamides: acrylamide/dimethylamino
ethylacrylate
methochloride (molar ratio 49:1, K-value 60).



CA 02365282 2001-08-31
WO 00/56848 PCT/LTS00/08030
37
The following are non-limiting examples of clear, colorless isotropic liquid
embodiments
of the present invention.
Table IV
Weight
Ingredients 13 14 15 16


Fabric softener active ' 30.0 30.0 45.0 45.0


Ethanol Z 2.5 2.5 3.7 3.7


Hexylene glycol 3 2.7 2.7 4.0 4.0


Hexylene glycol 4 6.0 6.0 -- 10.0


Principal solvent 5 -- -- 10.0 --


Nonionic surfactant 6 4.5 4.5 -- --


Nonionic surfactant' -- -- 2.6 2.6


Polymer 8 1.0 1.0 -- 1.0


Polymer 9 -- 3.5 3.0 --


Polymer' 5.0 -- 3.0 5.0


CaCl2 -- -- 0.75 0.75


MgCl2 1.5 1.5 -- --


Chelant ' ' -- 0.2 -- --


Chelant '2 -- -- 0.2 0.2


Ammonium chloride 0.1 0.1 -- --


Perfume 2.5 2.5 2.5 2.5


Water balancebalance balancebalance


1. N,N-di(canoyloxyethyl)-N-Z-hydroxyetriyl-N-metny ammonium merry sumave
avamamc
from Witco.
2. Ethanol is present from the manufacturing process of the quaternary fabric
softener active.
3. Hexylene glycol is present from the manufacturing process of the quaternary
fabric softener
active.
4. Added hexylene glycol.
5. 2,2,4-Trimethyl-1,3-pentanediol (TMPD).
6. C9-C" alkyl E8 alcohol available as Neodol~ 91-8 ex Shell.
7. C"-C,5 alkyl E9 alcohol available as Tergitol~ 1559 ex Union Carbide.
8. Polyvinylpyrrolidone K15 available ex BASF as Luviskol K15
9. Cationically modified polyacrylamides: acrylamide/dimethylamino
ethylaerylate
methochloride (molar ratio 9:1, K-value 60).



WO 00/56848 CA 02365282 2001-08-31 pCT~s00/08030
38
10. Cationically modified polyacrylamides: acrylamide/dimethylamino
ethylacrylate
methochloride (molar ratio 49:1, K-value 60).
11. Diethylene triamine pentaacetate.
12. Tetrakis-(2-hydroxypropyl)ethylenediamine.
Table V
Weight
Ingredients 17 18 19 20


Fabric softener active ' 30.0 -- -- 45.0


Fabric softener active Z -- 28.5 -- --


Fabric softener active 3 -- -- 30.0 --


Ethanol4 2.5 2.5 3.7 3.7


Hexylene glycol5 2.7 2.7 4.0 4.0


Hexylene glycol 6 6.0 6.0 -- --


Principal solvent' -- -- 10.0 10.0


Nonionic surfactant $ 4.5 4.5 -- --


Nonionic surfactant 9 -- -- 2.6 2.6


Low molecular weight polyamine1.0 1.1 -- --
'


Low molecular weight polyamine-- -- l .l --
"


Low molecular weight polyamine-- -- -- 1.1
'2


Polymer'3 1.0 1.0 -- 1.0


Polymer'4 -- 3.5 3.0 --


Polymer's 5.0 -- 3.0 5.0


CaCl2 -- -- 0.75 0.75


MgCl2 1.5 1.5 -- --


Chelant'6 -- 0.2 -- --


Chelant " -- -- 0.2 0.2


Ammonium chloride 0.1 0.1 -- --


Perfume 2.5 2.5 2.5 2.5


Water balance balance balancebalance


1. N,N-di(canoyloxyethyl)-N-2-hydroxyethyl-N-methyl ammoW um methyl suitate
avaname ex
Witco.
2. N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride.



CA 02365282 2001-08-31
WO 00/56848 PCT/US00/08030
39
3. N,N-di(canoyloxyethyl)-N-2-hydroxyethyl-N-methyl ammonium chloride.
4. Ethanol is present from the manufacturing process of the quaternary fabric
softener active.
5. Hexylene glycol is present from the manufacturing process of the quaternary
fabric softener
active.
6. Added hexylene glycol.
7. 2,2,4-Trimethyl-1,3-pentanediol (TMPD).
8. C9-C" alkyl E8 alcohol available as Neodol~ 91-8 ex Shell.
9. C"-C,5 alkyl E9 alcohol available as Tergitol~ 15S9 ex Union Carbide.
10. 1,1-N-dimethyl-5-N'-methyl-9,9-N"-dimethyl dipropylenetriamine.
11. 1,1-N-dimethyl-9,9-N"-dimethyl dipropylenetriamine.
12. 1,1-N-dihydroxyethyl-7-N'-hydroxyethyl-13,13-N"-dihydroxyethyl
dihexylenetriamine
(penta-N-hydroxyethyl dihexylenetriamine).
13. Sedipur~ CF803 ex BASF.
14. Sedipur~ CF104 ex BASF.
15. Cationically modified polyacrylamides: acrylamide/dimethylamino
ethylacrylate
methochloride (molar ratio 49:1, K-value 60).
16. Diethylene triamine pentaacetate.
17. Tetrakis-(2-hydroxypropyl)ethylenediamine