Note: Descriptions are shown in the official language in which they were submitted.
CA 02347809 2004-05-31
1
FABRIC CARE COMPOSITIONS
HAVING REDUCED FABRIC ABRASION
10 FIELD OF THE INVENTION
The present invention relates to fabric care compositions which provide fabric
enhancement benefits while reducing the damage to fabric from abrasion. The
Compositions of
the present invention comprise one or more fabric abrasion reducing polymers
as well as other
ingredients which provide a benefit to the consumer inter alia fabric
softening, anti-static, dye
fixation.
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.
CA 02347809 2004-05-31
2
SUMMARY OF THE INVENTION
The present invention meets the aforementioned needs in that it has been
surprisingly
discovered that pertain higher molecular weight polymers which comprise an
amide unit, an N-
oxide unit, or mixtures thereof, are useful for providing fabric abrasion
reduction. The polymers
of the present invention, herein described as "fabric abrasion reducing
polymers, when applied to
fabric provide a reduction in the amount of damage which is incurred by the
fabric. Surprisingly,
the fabric abrasion reducing polymers of the present invention comprise one or
more units which
in addition to fabric abrasion benefits, provides a dye transfer inhibition
benefit. Therefore, the
polymers of the present invention have a primary fabric abrasion benefit, and
preferably a dye
transfer inhibition benefit as well.
A first aspect of the present invention which relates 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 fabric abrasion reducing polymer, said fabric abrasion
reducing polymer comprising:
i) at least one monomeric unit comprising an amide moiety; and
ii) at least one monomeric unit comprising an N-oxide moiety;
b) the balance carriers and adjunct ingredients;
provided the molecular weight of said fabric abrasion reducing polymer is
greater than
100,000 daltons.
The present invention further 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 abrasion reducing polymer, said fabric abrasion
reducing polymer comprising:
i) at least one monomeric unit comprising an amide moiety; and
ii) at least one monomeric unit comprising an N-oxide moiety;
b) optionally from about I%, 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;
c) optionally less than about 15% by weight, of a principal solvent,
preferably said
principal solvent has a CIogP 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;
CA 02347809 2006-O1-06
3
e) optionally from about 0.01% to about SO% 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) optionally 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 5% by
weight, of an enzyme;
j) optionally from about 0.01% to about 8% by weight,
of a polyolefn emulsion or
suspension;
k) optionally from about 0.01 % to about 0.2% by
weight, of a stabilizer;
1) optionally from about 0.5% to about 5% by weight,
of a cationic surfactant;
m) optionally from about 0.01 % to about 50% by
weight, of one or more linear or
cyclic polyamines which provide bleach protection;
and
o) the balance carrier and adjunct ingredients;
provided
the molecular
weight of
said fabric
abrasion
inducing
polymer is
Beater than
100,000
daltons.
In another particular embodiment there is provided a fabric care composition
comprising: a) from 0.01 % to 20% by weight, of a fabric abrasion reducing
polymer,
said fabric abrasion polymer comprising at least one monomeric unit comprising
an
amide moiety; and b) the balance carriers and adjunct ingredients; wherein
the molecular weight of said fabric abrasion reducing polymer is greater than
100,000 daltons; and wherein said amide moiety is selected from the group
consisting
of: i) polyacrylamides and N-substituted polyacrylamides having the formula:
-I ~Q~i-CHa7n
~O
N(Rh
CA 02347809 2005-04-05
3a
wherein each R' is independently hydrogen, Ct-C6 alkyl, or both R' unit can
be taken together to form a ring comprising 4-6 carbon atoms;
ii) polymethacrylamides and N-substituted polymethacrylamides
having the general formula:
3
----~~_~2~0
C=CD
I
N(R
wherein each R' is independently hydrogen, C1-CG alkyl, or both R' units can
be taken together to form a ring comprising 4-6 carbon atoms; and iii)
mixtures thereof; wherein said composition further comprises from 0.001 %
to 50% by weight, of dye fixing agent, from 0.01 % to 50% weight of a
bleach protection polyamine selected from the group consisting of 1,4-bis-
(3-aminopropyl)piperazine, l,l-N-dimethyl-5-N'-methyl-9,9-N"-dimethyl
dipropylenetriamine, l,l-N-dimethyl-9,9-N"-dimethyl dipropylenetriamine,
N,N'-bis(3-aminopropyl)-1,3-propylenediamine, and mixtures thereof.
The present invention further relates to a composition suitable for use as a
pre-soak or rinse
composition comprising. a) from 3% to 4% by weight, of a polyvinylpyrrolidone
fabric abrasion
reducing polymer having a molecular w~;ight of 160,000 daitons; b) from 2% to
3% by weight, of a non
cellulose reactive dye fixative; c) from 15% to 20% by weight, l,4-Bis-(3-
aminopropyl)piperazine; d)
fmm 0.5 to 1.5% by weight, 2-Phosphonobutane-1,2,G-tricarboxylie acid; and e)
the balance carriers and
adjunct ingredients.
The present invention relates to compositions which are laundry detergent
composition, rinse-
added fabric conditioning compositions, and dryer-added fabric conditioning
compositions.
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 fabric abrasion reducing
polymer. 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.
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4
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to compositions which when applied to fabric,
reduce the
fabric wear and enhance the faabric appearance. These benefits are provided by
the surprising
discovery that certain polymers which comprise an amide or N-oxide functional
unit have fabric
abrasion reduction benefits. Surprisingly, it has also been discovered that
theses units also
provide a secondary benefit; dye transfer inhibition. Therefore the
compositions of the present
invention provide not only fabric damage amelioration but also fabric color
fidelity benefits.
The fabric care compositions of the present invention comprise one or more
fabric
abrasion reducing polymers as described herein. For the purposes of the
present invention the
term "fabric c;~re compositions"' is defined as "a composition which provides
care to the fabric
non-limiting examples of v~rhich include laundry detergent compositions, 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 describe the required elements 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".
The fabric abrasion reducing polymers useful in the present invention have the
formula:
~-P~D~ro-~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 defm<;d 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".
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WO 00/26331 PCT/US99/24941
P backbones preferably comprise units having the formula:
--[C:RZ-CR2]- or -[(CR2)X L]-
wherein each R unit is independently hydrogen, C,-C,z alkyl, C6-C,2 aryl, and
D units as
described herein below; preferably C,-C4 alkyl.
5 Each L unit is independently selected from heteroatom-containing moieties,
non-limiting
examples of v~rhich are selected from the group consisting of:
R O O O O
-N- -O- --~O-C- -C-O- -O-C-O- -C
' ' ' ' ,
O O O O O
-S- -SI- -_IS-. -O-SI- -gl-O- -O-SI-O-
' ' II ' II ' II ' II
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:
Rq O O
II II
--1'd- -N- C- -C-N-
' I ' I
'
R3 R3
and mixtures thereof; wherein R' is hydrogen, C~-C,2 alkyl, C6-C,2 aryl, and
mixtures thereof. RZ
is C,-C,2 alkyl, C,-<:12 alkoxy, C~-C,2 aryloxy, and mixtures thereof;
preferably methyl and
methoxy. R3 is hydrogen C,-C;,2 alkyl, C6-C,2 aryl, and mixtures thereof;
preferably hydrogen or
C,-C4 alkyl, more preferably hydrogen. R4 is C,-C,2 alkyl, C6-C,z aryl, and
mixtures thereof.
The backbones of the: fabric abrasion reducing polymers of the present
invention
comprise one or more D units vrhich are units which comprise one or more units
which provide a
dye transfer inhibiting benefit. The D unit can be part of the backbone itself
as represented in the
general formula:
[-P(D)m ~n
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6
or the D unit may be incorporated into the backbone as a pendant group to a
backbone unit
having, for example, the formula:
-[CK-CRZ]- 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 any
optional dye transfer inhibition while providing a polymer which has fabric
abrasion reducing
properties. The molecular weight of the fabric abrasion reducing polymers of
the present
invention are from about 500, ;preferably from about 1,000, 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 polyv~inylpyrrolidone having the formula:
- [CH-CH2]n-
N
~~O
polyvinyloxazolidone having the formula:
_' [ i H-CH2]n-
N
~O
O
polyvinylmethyloxazolidone having the formula:
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7
-( i H-CH2~n-
N
~O
,/O
H3C
polyacrylamides and N-substituted polyacrylamides having the formula:
-( I H_CH2~n~
C=O
NCR )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
polyrnethacrylamides having the general formula:
-( i -CH2)n-
C=O
I
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:
_" ( I H_ CH2~n"
C=O O
I II
~-CH2-C-N(R~)2
wherein each R' is independently hydrogen, C,-C:6 alkyl, or both R' units can
be taken together to
form a ring comprising 4-6 carbon atoms; poly(N-methacrylylglycinamide) having
the formula:
-( i -CH2an-
C=O O
I
NH-CH2-C-N(R')2
wherein each R' is independently hydrogen, C,-C6 alkyl, or both R' units can
be taken together to
1 S form a ring comprising 4-6 carbon atoms; polyvinylurethanes having the
formula:
CA 02347809 2004-05-31
g
y i H-CH2Jn
O
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.
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-CH2-N]n'-'
C=O
CHzCH3
wherein the index n indicates the number of monomer residues present.
The fabric abrasion reducing polymers of the present invention can comprise
any mixture
of 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-
pyaolidones,
polyvinyloxazolidones, N,N-disubstituted polyacrylamides, and N,N-
disubstituted
I S polymethacrylamides. A detailed description of physico-chemical properties
of some of these
polymers are given in "Water-Soluble Synthetic Polymers: Properties and
Behavior", Philip
Molyneux, Vol. I, CRC Press, (1983) .
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
3ersey, and BASF
Corp., Parsippany, New Jersey, as a powder or aqueous solutions in several
viscosity grades,
designated as, e.g., K-12, K-15, K-25, and K-30. These K-values indicate the
viscosity average
molecular weight, as shown below:
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9
PVP viscosity averageK-12 K-15 K-25 K-30 K-60 K-90
molecular
weight (in thousands 2.5 10 24 40 160 360
of daltons)
PVP K-12, K-15, and K-30 are also available ex Polysciences, Inc. Warrington,
Pennsylvania,
PVP K-15, K-25, and K-30 and poly(2-ethyl-2-oxazoline) are available ex
Aldrich Chemical Co.,
Inc., Milwaukee, Wisconsin. PVP K30 (40,000) through to K90 (360,000) are also
commercially
available ex BASF under the trademark Luviskol or commercially available ex
ISP. Still higher
molecular PVP like PVP 1.3MM, commercially available ex Aldrich is also
suitable for use
herein. Yet further PVP-type of material suitable for use in the present
invention are
polyvinylpyrrolidone-co-dimethylaminoethylmethacrylate, commercially available
commercially
ex 1SP in a quaternised form under the trademark Gafquat~ or commercially
available ex
Aidrich Chemical Co. having a molecular weight of approximately I.OMM;
polyvinylpyrrolidone-co-vinyl acetate, available ex BASF under the trademark
Luviskol~,
available in vinylpyrrolidone:vinylacetate ratios of from 3:7 to 7:3.
Polymers ComprisingN-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
Ry ~ -R3
R2
wherein R', R2, and R' can be any hydrocarbyl unit (for the purposes of the
present invention the
term "hydrocarbyl" does not include hydrogen atom alone). The N-oxide unit may
be part of a
polymer, such as a polyamine, i.e., polyalkyleneamine backbone, or the N-oxide
may be part of a
pendant group attached to the polymer backbone. An example of a polymer which
comprises an
the N-oxide unit as a part of the polymer backbone is polyethyleneimine N-
oxide. Non-limiting
examples of groups which can comprise an N-oxide moiety include the N-oxides
of certain
heterocycles inter alia pyridine, pyrrole, imidazole, pyrazole, pyrazine,
pyrimidine, pyridazine,
piperidine, pyrrolidine, pyrrolidone, azolidine, morpholine. A preferred
polymer is poly(4-
vinylpyriding N-oxide, PVNO). In addition, the N-oxide unit may be pendant to
the ring, for
example, aniline oxide.
N-oxide comprising polymers of the present invention will preferably have a
ration of N-
oxidized amine nitrogen to non-oxidized amine nitrogen of from about 1:0 to
about 1:2,
preferably to about 1;1, more preferably to about 3:1. The amount of N-oxide
units can be
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WO 00/26331 PCT/US99/24941
adjusted by the formulator. lror 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 thc: formulator may control the oxidation level of
the polymer during
preparation. 'fhe amine oxide unit of the polyamine N-oxides of the present
invention have a Pka
5 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.
10 Pol ~~r~ers 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 rruxed amide/N-oxide polymers. However, the resulting polymers
must retain the
water solubility requirements described herein above.
Molecular weight
For all the above described polymers of the invention, it is most preferred
that they have
a molecular weight in the range as described herein above. This range is
typically higher than the
range for polymers which render only dye transfer inhibition benefits alone.
Indeed, the higher
molecular weight of the abrasion reducing polymers provides for reduction of
fabric abrasion
which typically occurs subsequent to treatment, for example during garment
use, 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 poRymer 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 b~eated fabrics. It should be noted, however, that a similar
benefit may be predicted
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11
from the approach of increasing charge density while retaining a lower
molecular weight
material.
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 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 mi~;tures thereof;
b) optionally fron-i about 1 %, preferably from about 10%, more preferably
from
about 20% to abaut 80%, preferably to about 60%, more preferably to about 45%
by weight, of a fabric softening active;
c) optionally less than about 15% by weight, of a principal solvent,
preferably said
1 S principal solvent has a ClogP of from about 0.1 S 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 fram about 0.01% to about 15% by weight, of a chlorine
scavenger;
g) optionally 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 5% 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 0.5% to about 5% by weight, of a cationic surfactant;
m) from about 0.01 °ro by weight, of one or more linear or cyclic
polyamines which
provide bleach protection; and
o) the balance carrier and adjunct ingredients;
provided the molecular weight of said fabric abrasion reducing polymer is
greater than
100,000 daltons.
CA 02347809 2004-05-31
12
The following are non-limiting examples of ingredients which can be combined
with the
amide-containing, N-oxide-containing, and combination thereof polymers of the
present
invention.
Dve Fixine Aeents
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 "$xatives",' are well-lmown, 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
'1'M
suppliers. Representative examples include: CROSCOLOR PMF (3uly 1981, Code No.
7894)
TM
and CROSCOLOR NOFF (3anuary 1988, Code No. 8544) ex Crosfield; INDOSOL E-50
TM
(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
TM
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 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 DYe Fixing Agents
CA 02347809 2004-05-31
13
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
suitably combined with one or more dye fixatives described herein above in
order to comprise a
"dye fixative system".
The term "cellulose reactive dye firing 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 ReactivitYTest~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
I'M
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 %z
hour at 60°C, followed by a thorough rinsing of 4 times 200 ml of cold
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 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.
CA 02347809 2004-05-31
14
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, wea,
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.
I'M
Commercially available compounds among this class are Sandofix WE 56 ex
Clariant, Zetex E ex
TM
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 trademark of Indosol CR ex
Clariant. Still other most
preferred cellulosic reactive dye fixing agents are commercialized under the
trademark Rewin
DWR and Rewin WBS ex CHT R. Beitlich.
Chlorine Scavengers
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 the
cation 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:
UR)3R~Nl + 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,-C9 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.
CA 02347809 2004-05-31
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%,
5 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 Growth Inhibition Test (CGTT)
10 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 Claaract., Vol 3, 77-102, (1980), is
a
method which is suitable for evaluating compounds for their crystal growth
15 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 CGI
Volume of
base added
With CGI
TIME
t-lag
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.
Exemnlary Procedure
Combine in a suitable vessel, 2.1M KCI (35 mL), 0.0175M CaClz (50mL), O.O1M
KH2P04 (50mL), and de-ionized water (350mL). A standard pH electrode equipped
with a
CA 02347809 2004-05-31
16
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 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 HCl. 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'~M. 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 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 foams 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,
CA 02347809 2004-05-31
17
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 I,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-Rite~ ex BF Goodrich, Acrysol~ ex Rohm &
Haas,
Sokalan~ ex BASF, and Norasol~ 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 growth inhibitors include citrates, e.g., citric acid
and soluble
salts thereof (particularly sodium salt), 3,3-dicarboxy.ll-oxa-1,6-
hexanedioates and related
compounds further disclosed in U.S. 4,566,984 CS-C~" alkyl, CS-C2~, 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,
Organic Phosphonic 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 CZ diphosphonic
acid selected
from the group consisting of ethylene diphosphonic acid, a-hydroxy-2 phenyl
ethyl diphosphonic
acid, methylene diphosphonic acid, vinylidene-I,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-I,1-diphosphonic acid (HEDP). A preferred is
phosphonic acid
is 2-phosphonobutane-1,2,4-tricarboxylic acid available as BAYHIBTT AIvI~ ex
Bayer.
CA 02347809 2001-04-20
WO 00/26331 PCT/US99/24941
18
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) N~CH2)~ Q-R
3-mm
m~
quaternary ammonium compounds having the formula:
(R)4-m N-t (CHy Q- R~ X -
rn
- ,
and mixtures thereof, wherein each R is independently C1-C6 alkyl, C1-C6
hydroxyalkyl, benzyl,
and mixtures thereof; R1 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 t:he units having the formula:
O O RZ O O RZ
II II I II II I
--O-C- -C-O- , -N-C- , -C-N-
O
O R3 O O-C-Rl O
II I II I II
--O-C-O- y -CH-O-C- ~ -CH-CH2-O-C-
wherein R2 i;; hydrogen, CI-C4 alkyl, preferably hydrogen; R3 is C1-C4 alkyl,
preferably
hydrogen or methyl; preferably ~Q has the formula:
O O
II il
--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
CA 02347809 2001-04-20
WO 00/26331 PCT/US99/24941
I9
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
N (CH2)n-O-r R~ X _
4-m
m
wherein the unit having the formula:
O
-O-C-Rr
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 a.rt 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 source:. 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 ali,a 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
CA 02347809 2001-04-20
WO 00/26331 PCT/US99/24941
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 ac;yl groups can be from about 3%, preferably from about
5%, more
5 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 3:1, and more preferably from about 4:1 to
about 50:1, more
preferably about 20: l, however, the minimum being 1:1.
T'he level of unsaturation contained within the tallow, canola, or other fatty
acyl unit
10 chain can be measured by the Iodine Value (N) of the corresponding fatty
acid, which in the
present case should preferably be in the range of from S to 100 with two
categories of compounds
being distinguished, having a N below or above 25.
Indeed, for compounds lhaving the formula:
(R)a-m N~CH~n-Q-RJ X
m
1 S derived from ti~llow 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
20 concentrations are needed. A i:urther 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 (N) of the parent fatty acid, said IV
is preferably from
about 10, more: preferably from about S0, 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" (N 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 prei:ered 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,
CA 02347809 2001-04-20
WO 00/26331 PCT/US99/24941
21
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 C1~ 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-etlryl)-N,N-dimethyl ammonium chloride;
N,N-di(canolyl-oxy-eth:yl)-N,N-dimethyl ammonium chloride;
N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl
sulfate;
N,N-di(canolyl-oxy-ethyl) N-methyl, N-(2-hydroxyethyl) ammonium methyl
sulfate;
N,N-di(tallowylamidoethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl
sulfate;
N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium chloride;
N,N-di(2-canolyloxyeth;ylcarbonyloxyethyl)-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-ta.llowyloxy-2-oxoethyl)-N-(tallowyl)-N,N-dimethyl ammonium chloride;
N-(2-canolyloxy-2-oxoethyl)-N-(canolyl)-N,N-dimethyl ammonium chloride;
1,2-dit<tllowyloxy-3-N,T1,N-trimethylammoniopropane chloride; and
1,2-dicanolyloxy-3-N,N,N-trimethylammoniopropane chloride;
and mi:Ktures 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)
CA 02347809 2004-05-31
22
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 al., issued
December 12, 1995; U.S. 5,417,868 Tumer 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.
Principal solvent
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.
Sorne 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
minmize 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
OdOT.
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 4o C and have the ability to fully recover their clarity if stored as
low as about 7o C.
The principal solvents according to the present invention are selected base
upon their
octanol/water partition coefficient (P). The octanollwater 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.
CA 02347809 2004-05-31
23
The IogP 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,
S 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). 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.,
Crippen's fragmentation method as disclosed in J. Chem. Inf. Comput. 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. - Chim. 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 1, preferably from about 0.15 to
about 0.64, more
preferably from about 0.25 to about 0.62, most preferably form 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 97103169
"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
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.
Hydrophobic Dispersant
CA 02347809 2004-05-31
24
A preferred composition of the present invention comprises from about 0. I %,
preferably
from about 5%, more preferably form about 10% to about 80%, preferably to
about SO%, more
preferably to about 25% by weight, of a hydrophobic polyamine dispersant
having the formula:
R1 B
~(R1~N-R1W (1'l-R)x~-RIYN~t)z
wherein R, R' and B are suitably described in U.S. 5,565,145 Watson et al.,
issued October 15,
1996 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 1, 1986; European Patent Application 111,965, Oh and Gosselink,
published June 27,
1984; European Patent Application 111,984, Gosselink, published June 27, 1984;
European
Patent Application 112,592, Gosselink, published July 4, 1984; U.S. 4,548,744,
Connor, issued
October 22, 1985; and U.S. 5,565,145 Watson et al., issued October 15, 1996.
However, any
suitable clay/soil dispersent or anti-redepostion agent can be used in the
laundry
compositions of the present invention.
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
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
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
CA 02347809 2001-04-20
WO 00/26331 PCT/US99/24941
2s
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
present invention to insure phase stability and prevent the diluted softener
composition from
S "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
level of electrolyte is also influenced by other factors inter 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
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 acaive, 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 a~f electrolyte
A wide variety of ioniz.able 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 t:he 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 plane 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, monohydrochl,oride and l,5-diammonium 2-methyl pentane
dihydrochloride.
CA 02347809 2004-05-31
26
Enzymes
The compositions and processes herein can optionally employ one or more
enzymes inter
olio lipases, proteases, cellulose, amylases, mannanases, xyloglucanases, and
peroxidases. A
preferred enzyme for use herein is cellulose enzyme. Cellulases usable for use
in the fabric
enhancement compositions of the present invention include both bacterial and
fungal types which
preferably exhibit an optimal performance at a pH of from 5 to 9.5. U.S.
4,435,307 Barbesgaard
et al., issued March 6, 1984, discloses suitable fungal cellulases ex
Humicola insolens or Humicola strain DSM1800 or a cellulose 212-producing
fungus belonging
to the genus Aeromonas, and cellulose enzymes extracted from the
hepatopanereas of a marine
mollusk, Dolabella Auricula Solander. Suitable cellulases are also disclosed
in GB-A-2.075.028;
GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME~ and
CELLUZYME~ (Novo) are especially useful. Other suitable cellulases are
also disclosed in WO 91/17243 to Novo, WO 96/34092, WO 96/34945 and EP-A-
0,739,982.
Compositions may comprise up to 5 mg by weight, more typically 0.01 mg to 3
mg, of active
enzyme per gram of the composition. Stated otherwise, the compositions herein
will typically
comprise from 0.001 %, preferably from 0.01 % to 5%, preferably to 1 % by
weight, of a
commercial enzyme preparation. In the particular cases where activity of the
enzyme preparation
can be defined otherwise such as with cellulases, corresponding activity units
are preferred (e.g.
CEVU or cellulose Equivalent Viscosity Units). For instance, the compositions
of the present
invention can contain cellulose enzymes at a level equivalent to an activity
from 0.5 to 1000
CEVUlgram of composition. Cellulose enzyme preparations used for the purpose
of formulating
the compositions of this invention typically have an activity comprised
between 1,000 and 10,000
CEVU/gram in liquid form, around 1,000 CEW/gram in solid fornl.
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 olio 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) O,uaternar~ Ammonium Compounds
CA 02347809 2001-04-20
WO 00/26331 PCTNS99/24941
27
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
S wherein R1, 1~2, R3, and R4 are each independently C1-C22 alkyl, C3-C22
alkenyl, RS-Q-
(CH2)m-, whe;rein R~ is C 1-C;z2 alkyl, and mixtures thereof, m is from 1 to
about 6; X is an
anion.
Preferably R1 is C6-C,o2 alkyl, C6-C22 alkenyl, and mixtures thereof, more
preferably
C 11-C I g alkyl., C I 1-C 1 g alken;yl, and mixtures thereof; R2, R3, and R4
are each preferably C 1-
C4 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
iriglyceride selected from the group consisting of tallow, partially
hydrogenated tallow, lard,
partially hydrogenated lard, vel;etable 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~ j H3
O Cl + CH 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, bronude, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures
thereof, more
preferably chloride and methyl sulfate.
ii) Polyvinyl Amines
CA 02347809 2001-04-20
WO 00/26331 PCT/US99/24941
28
A preferred embodiment of the present invention contains at least about 0.2%,
preferably
from about 0.2% to about 5%, nnore preferably from about 0.2% to about 2% by
weight, of one or
more polyvinyl amines having t:he formula
CH2-CH
NH2
wherein y is ;from about 3 to about 10,000, preferably from about 10 to about
5,000, more
preferably fronn about 20 to about 500. Polyvinyl amines suitable for use in
the present invention
are available from BASF.
Optionally, one or more of the polyvinyl amine backbone -NH2 unit hydrogens
can be
substituted by an alkyleneoxy unit having the formula:
-(Rl O)xR2
wherein Rl 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
'-(CHzCHO)-(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-):?Ox-. 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 den;>ity. 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 S% by
weight, of a cationic charge booster having the formula:
CA 02347809 2001-04-20
WO 00/26331 PCT/US99/24941
29
R1 Rl
+I I+ _
R2-N-R- N-R2 2
X
R1 ~1
wherein R is substituted or unsubstituted C2-C12 alkylene, substituted or
unsubstituted C2-C12
hydroxyalkylene; each R1 is independently CI-C4 alkyl, each R2 is
independently CI-C22 alkyl,
C3-C22 alkenyl, RS-Q-(CH2)m-, wherein RS is CI-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.
Preferably R is ethylene; R1 is methyl or ethyl, more preferably methyl; at
least one R2 is
preferably CI-(:4 alkyl, more preferably methyl. Preferably at least one R2 is
Cl l-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 2:' 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, com 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:
3 CI CH3
nN~/N_CH3
C1 CH CH3
where
in RI is methyl, one R2 units is methyl and the other R2 unit is R5-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
2$ 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
CA 02347809 2004-05-31
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 preferred, for ensuring stability
under extreme
conditions when particular softener active levels are used. The surfactant
concentration aids are
5 typically selected from the group consisting of (1) single long chain alkyl
cationic surfactants; (2)
nonionic surfactants; (3) amine oxides; (4) fatty acids; and (5) mixtures
thereof. These aids are
described in U.S. Patent No. 5,545,340.
Preferred dispersibility aids are GENAM1NE~ and GENAPOL~ ex Clariant. When PVP
10 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~.
15 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
composition. These materials can either be added as part of the active
softener raw material,
e.g., the mono-long chain alkyl cationic surfactant andlor the fatty acid
which are reactants used
20 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.
Soil Release A.,gents
Particular to the embodiments of the rinse-added fabric softeners according to
the present
25 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.
Any polymeric soil release agent Irnown to those skilled in the art can
optionally be
employed in the compositions and processes of this invention. Polymeric soil
release agents are
30 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
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.
CA 02347809 2004-05-31
31
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%.
The following 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.
4,976,879 Maldonado et al. issued December 11, 1990; U.S. 4,968,451 Scheibel
et al., issued
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 Basadw, 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 .
Bleach Protection Polyamines
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 IS% to
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:
R~
(Rt~N-R-~N-R~n N(Rt)2
wherein R is 1,2-propylene, 1,3 propylene, and mixtures thereof; preferably
1,3-propylene.
Each R~ is independently hydrogen, methyl, ethyl, or an alkyleneoxy unit
having the formula:
_(R30)_ R4
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WO 00/26331 PCT/US99/24941
32
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. P:' may comprise any mixture of alkyleneoxy
units. RZ is hydrogen,
R', -RN(R')2, and mixtures thereof preferably at least one RZ is hydrogen when
n is equal to 2.
The integer n its I or 2. For "pe~ralkylated" amines each R' and RZ will be
independently selected
from methyl or ethyl.
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). For certain formulations, polyamines which comprise
alkylated
polyamines are preferred, for example, tetramethyl dipropylenetriamine,
permethylated
dipropylenetriamine, mono-methylated dipropylenetriamine.
Cyclic Amines
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')z, 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.
Each :Et' is independently hydrogen, C,-CZ alkyl, or an alkyleneoxy unit
having the
formula:
(R3U)_ Ra
wherein R3 is ethylene, 1,2-propylene, 1,2-butylene, or mixtures thereof;
preferably R' is ethylene
or 1,2-propylene, more preferably I,2-propylene. R4 is hydrogen, C,-C4 alkyl,
and mixtures
thereof; preferably hydrogen. R.' may comprise any mixture of alkyleneoxy
units.
Preferred polyamines o~E'the present invention have the formula:
(R-~)2N-(CHZ)k- L-(CH2)k-N~~)2
wherein the indices k each have the same value and each R' is the same unit.
Preferably the backbone of the cyclic amines of the present invention comprise
a N,N'-
bis-substituted 1,4-piperazine ring having the formula:
CA 02347809 2001-04-20
WO 00/26331 PCT/US99124941
33
Rs Rs Rs Rs
R-N N-R
Rs,-~ Rs
Rs Rs
wherein each RS is independently hydrogen, C,-C4 alkyl, C~-C4 hydroxyalkyl, C~-
C4 aminoalkyl,
or two RS 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 rinf;s which comprise L units are 1,4-diketopiperizines.
A preferred backbone of the chlorine scavenging polyamines of the present
invention, prior to
modification, has the formula:
H2N~(CH2)3- ~ (CH2)3"~2
wherein each R unit is -(CHz)32JHz and each RS unit is hydrogen.
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)xNHz, for
example, the piperazine
having the fonnula:
H- ~ -(CH2)3-NHZ
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.
Cationic Surfactants
The fabric enhancerner~t compositions of the present invention may optionally
comprise
from about 0.'.i%, preferably from about 1% to about 10%, preferably to about
5% by weight, of
one or more cationic nitrogen containing compound, preferably a cationic
surfactant having the
formula:
R-N(RI)31 X
~JC
wherein R is C,o-C,B alkyl, each R' is independently C1-C4 alkyl, X is a water
soluble anion;
preferably R is Clz-C,4, preferably R' is methyl. Preferred X is halogen, more
preferably
CA 02347809 2004-05-31
34
chlorine. Non-limiting examples of preferred cationic nitrogen compounds are
N,N-dimethyl-(2-
hydroxyethyl)-N-dodecyl ammonium bromide, N,N-dimethyl-(2-hydroxyethyl)-N-
tetradecyi
ammonium bromide. Suitable cationic nitrogen compounds are available ex Akzo
under the
tradenames Ethomeen T/15~, Secomine TA15~, and Ethoduomeen T/20~.
METHOD OF USE
The present invention further relates to a method for providing protection and
enhancement of fabric, said method comprising the step of contacting a fabric
with a 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;
ii) and mixtures thereof;
b) optionally one or more fabric enhancement ingredients; and
c) the balance carriers;
provided the molecular weight of said fabric abrasion reducing polymer is
greater than 100,000
daltons.
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.
TABLEI
weight
Ingredients 1 2 3 4 5 6 ?
Polymer' 10.0 7.5 15.0 10.0 ?.5 5.0 5.0
Dye fixative -- 5.0 2.5 2.5 2.5 -- 1.0
2
CA 02347809 2004-05-31
Polyalkyleneimine-- -- 15.0 -- -- -- 10.0
3
Polyalkyleneimine-- -- -- 10.0 -- -- --
4
Polyamine -- -- -- -- 25.0 -- --
5
Fabric softener-- -- -- -- -- 15.0 --
6
Bayhibit AM' 1.0 I.0 0.2 1.0 1.0 -- I.0
NH4C1 -- -- -- 0.2 0.2 -- 0.5
MgClz __ _ __ __ __ __ 4.0
SRP-2 8 -- -- -- -- 0.5 -- 1.0
Optical brightener- -- -- - - - 0.2
9
Water & minorsbalancebalancebalancebalancebalancebalancebalance
1. Fabric abrasion reducing polymer polyvinylpyrrolidone K90 available ex BASF
under the
trademark Luviskol K90°°.
2. Dye fixing agent ex Clariant under the tradename Cartafix CB~.
3. PEI 1200 E4 according to U.S. 5,565,145 Watson et al., issued October 15,
1996.
5 4. PEI 1200 E 1 according to U.S. 5,565,145 Watson et al., issued October
15, 1996.
5. N,N-bis(3-aminopropyl)-1,3-propylenediamine.
6. Di-(tallowyl-oxy-ethyl) dimethyl ammonium chloride.
7. 2-Phosphonobutane-1,2,4-tricarboxylic acid ex Bayer.
8. Diethoxylated poly(1,2-propyleneterephthalate) short block polymer.
10 9. Disodium 4,4'-bis(2-sulphostyryl)biphenyl.
TABLE II
weight
Ingredients 8 9 10 11 12 13 14
Polymer' 10.0 7.5 15.0 10.0 7.5 5.0 5.0
Dye fixative -- 5.0 2.5 2.5 2.5 2.5 2.5
Z
Polyalkyleneimine'-- -- 15.0 -- 10.0 -- --
Polyalkyleneimine-- -- -- 5.0 -- -- --
Polyamine -- -- -- -- 15.0 10.0 20.0
5
Bayhibit AM 1.0 1.0 0.2 1.0 I .0 0.5 1.0
6
NHaCI -- - -- 0.2 0.2 -- 0.2
Water & minorsbalancebalancebalancebalancebalancebalancebalance
1. Fabric abrasion reducing polymer polyvinylpyrrolidone K60 available ex BASF
under the
trademark Luviskol K60~.
CA 02347809 2001-04-20
WO 00/26331 PCT/US99/Z4941
36
2. Dye fixing agent ex Clariant under the tradename Cartafix CB~.
3. PEI 1200 E4 according to U.S. 5,565,145 Watson et al., issued October 15,
1996.
4. PEI 1200 I?1 according to U.S. 5,565,145 Watson et al., issued October 15,
1996.
5. N,N-bis(3-aminopropyl)-1,3-propylenediamine.
6. 2-Phosphonobutane-1,2,4-tricarboxylic acid ex Bayer.
TABLE III
weight
Ingredients 15 16 17 18 19 20 21
Polymer ' 10.0 7.5 5.0 10.0 7.5 5.0 5.0
Dye fixative -- 5.0 2.5 2. 2. -- 2.5
Z S S
Polyalkyleneimine'-- -- 15.0 -- -- -- --
Polyamine 4 -- -- -- 1 S.0 -- -- --
Polyamine 5 -- -- -- -- 15.0 10.0 25.0
Bayhibit AM 1.0 1.0 0.5 1.0 1.0 -- 1.0
6
NH4C1 -- -- -- 0.2 0.2 -- 0.2
Water & minorsbalancebalancebalancebalancebalancebalancebalance
1. Fabric abrasion reducing polymer polyvinylpyrrolidone-co-dimethylaminoethyl-
methacrylate
ex Aldrich.
2. Dye fixing agent ex Clariant under the tradenarne Cartafix CB~.
3. PEI 1200 E4 according to U.S. 5,565,145 Watson et al., issued October 15,
1996.
4. N,N-bis(3-aminopropyl)-1,3-propylenediamine.
S. 1,4-Bis(3-aminopropyl)piperazine.
6. 2-Phospho:nobutane-1,2,4-tricarboxylic acid ex Bayer.
TABLE IV
weight
Ingredients 22 23 24 25 26
_-_.
Polymer' $.() 1.0 __ __ __
Polymer ' -- -- 0.5 2.0 --
Polymer 3 -- -- -- -- 2.5
Softener active 2.ti 18.0 19.0 -- --
4
Tallow alcohol. -- 1.0 -- -- --
E25
Fatty acid ' 0.3 1.0 -- -- --
Hydrochloric 0.02 0.02 0.02 -- --
acid
CA 02347809 2004-05-31
37
PEG 4000 - 0.6 0.6 - --
Perfume 1.0 1.0 1.0 0.1 0.1
Silicone antifoam0.01 0.01 0.01 - --
Polyalkyleneamine3.0 3.0 -- 15.0 --
6
Polyamine ' -- -- 5.0 - 10.0
Dye fixative 1.0 -- 5.0 - 10.0
8
Dye fixative -- 3.0 -- 5.0 -
9
HEDP ~ 0.2 __ __ 0.4 __
CaCl2 (ppm) -- 600 1200 -- --
Dye (ppm) 10 50 50 -- --
Water & Minors balance balance balance balancebalance
1. Fabric abrasion reducing polymer polyvinylpyrrolidone K90 available ex BASF
under the
trademark Luviskol K90~.
2. Fabric abrasion reducing polymer polyvinylpyrrolidone K60 available ex BASF
under the
trademark Luviskol K60~.
3. Fabric abrasion reducing polymer polyvinylpyrrolidone-co-dimethylaminoethyl-
methacrylate
ex Aldrich.
4. Di-(tallowyl-oxy-ethyl) dimethyl ammonium chloride.
5. Tallow fatty acid having an Iodine Value of 18.
6. PEI 1200 E4 according to U.S. 5,565,145 Watson et al., issued October 15,
1996.
7. N,N-bis(3-aminopropyl)-1,3-propylenediamine.
8. Cellulose reactive dye fixing agent ex Clariant under the trademark Indosol
CR~.
9. Cellulose reactive dye fixing agent ex CHT R. Beitlich under the trademark
Rewin WBS~.
10. 1,1-hydroxyethane diphosphonic acid.
TABLE V
weight
Ingredients 27 28 29 30
Polymer' S.0 1.0 2.0 1.0
Softener active-- -- -- 15.0
2
Softener active'2.6 19.0 -- --
Tallow alcohol 0.3 -- -- --
E25
Fatty acid 0.3 -- -- --
Hydrochloric 0.02 0.02 -- 0.02
acid
CA 02347809 2004-05-31
38
PEG 4000 -- 0.6 -- 0.6
Perfume 1.0 1,0 0.1 1.0
Silicone antifoam0.01 0.01 -- 0.01
Polyalkyleneamine3.0 3.0 10.0 3.0
Dye fixative 1.0 3.0 10.0 1.0
6
Dye fixative' 2.0 -- -- 2.0
CaClz (ppm) -- 600 -- 600
Dye (ppm) 10 50 -- 50
Water & Minors balancebalancebalancebalance
1. Fabric abrasion reducing polymer poiyvinylpyrrolidone K90 available ex
BASF under the trademark Luviskol K90~.
2. Ditallow dimethylammonium chloride.
3. Di-(tallowyl-oxy-ethyl) dimethyl ammonium chloride.
S 4. Tallow fatty acid having an Iodine Value of 18.
5. PEI 1200 E4 according to U.S.~ 5,565,145 Watson et al., issued October 15,
1996.
6. Cellulose reactive dye fixing agent ex Clariant under the trademark lndosol
CR°°.
7. Cellulose reactive dye fixing agent ex CHT R. Beitlich under the trademark
Rewin WBS~.
The following are non-limiting examples of the compositions of the present
invention
which are suitable for delivery via a substrate dryer sheet.
TABLE VI
weight
Ingredients 31 32 33 34 35 36
Polymer' 20.0 30.0 10.0 5.0 7.5 15.0
Softener active40.0 25.0 -- -- -- --
2
Softener active-- -- 20.0 - -- -
3
Softener active- -- -- 20.0 12.0 60.0
Softener active30.0 30.0 20.0 30.0 20.0 --
5
Glycosperse -- -- 10.0 -- -- --
S-20 6
Glycerol monostearate-- -- -- 20.0 10.0 --
Clay 4.0 4.0 3.0 4.0 4.0 --
CA 02347809 2004-05-31
39
Perfume 0.7 1.1 0.7 1.6 2.6 1.4
Polyalkyleneimine'-- S.0 -- -- -- --
Polyalkyleneimine-- -- 4.0 2.2 -- --
a
Polyalkyleneimine2.0 -- -- - 5.0 7.0
9
Dye fixative 2.0 5.0 4.0 2.2 5.0 3.0
'
HEDP " 0.2 -- 0.5 -- - 0.7
Glycolic acid -- 0.2 - 0.2 -- --
Polycarboxylic -- 0.2 -- -- 0.4 -
'2
Stearic acid balancebalancebalancebalancebalancebalance
1. Fabric abrasion reducing polymer polyvinylpyrrolidone K60 available ex BASF
under the
trademark Luviskol K60~.
2. Di-(oleyloxyethyl) dimethyl ammonium methylsulfate.
3. Di-(soft-tallowyl-oxy-ethyl) hydroxyethyl methyl ammonium methylsulfate.
4. Ditallow dimethyl ammonium methylsulfate.
5. 1:2 ratio of stearyl dimethyl amine: triple-pressed stearic acid.
6. Polyethoxylated sorbitan monostearate ex Lonza.
7. PE1 1800 E1 according to U.S. 5,565,145 Watson et al., issued October 15,
1996.
8. PEI 1200 E4 according to U.S. 5,565,145 Watson et al., issued October 15,
1996.
9. PEI 1800 E4 according to U.S. 5,565,145 Watson et al., issued October 15,
1996.
10. Cellulose reactive dye fixing agent ex Clariant under the trademark
Indosol CR~.
11. 1,1-Hydroxyethane diphosphonic acid.
12. Polycarboxylic compound ex BASF under the trademark Sokalan CP 10~.
The following are non-limiting examples of pre-soak fabric conditioning and/or
fabric
enhancement compositions according to the present invention which can also be
suitably used in
the laundry rinse cycle. The following provide fabric abrasion protection for
fabric treated with
said compositions.
TABLE VII
weight
Ingredients 37 38 39
Polymer ' 3.5 3.5 3.5
Dye fixative 2.3 2.4 2.5
2
Polyamine 3 15.0 17.5 20.0
Bayhibit AM i .0 1.0 1.0
CA 02347809 2004-05-31
Water & minors balance balance balance
1. Fabric abrasion reducing polymer polyvinylpyrrolidone K90 available ex
BASF under the trademark Luviskol K90~.
2. Dye fixative ex Clariant under the trademark Cartafix CB's.
3. 1,4-Bis-(3-aminopropyl)piperazine.
5 4. (trade mark) 2-Phosphonobutane-1,2,4-tricarboxylic acid ex Bayer.
TABLE VIII
weight
Ingredients 40 41 42
Polymer' 3.5 3.5 3.5
Dye fixative ' 2.3 2.4 2.5
Polyamine 3 15.0 17.5 20.0
Bayhibit AM 4 1.0 1.0 1.0
C,2-C14 Dimethyl Hydroxyethyl5.0 5.0 5.0
Quaternary
Ammonium Chloride
Fabric softener active ' 2.5 2.5 2.5
~'M
Genamine CI00 0.33 0.33 0.33
Water & minors balance balance balance
1. Fabric abrasion reducing polymer polyvinylpyrrolidone K90 available ex BASF
under the trademark Luviskol K90~.
10 2. Dye fixative ex Clariant under the trademark Cartafix CB~.
3. 1,4-Bis-(3-aminopropyl)piperazine.
4. 2-Phosphonobutane-1,2,4-tricarboxylic acid ex Bayer.
5. Di-(canoloyl-oxy-ethyl) hydroxyethyl methyl ammonium methylsulfate.
Table IX
15 Weight
Ingredients 43 44 45 46
Polymer' - 7.5 3.5 3.5
Dye fixative Z 2.5 5.0 2.4 2.4
Polyamine' -- 5.0 10.0 --
Polyamine 4 -- -- -- 10.0
Bayhibit ' 1.0 1.0 I .0 1.0
Water balancebalancebalancebalance
CA 02347809 2004-05-31
41
1. Polyvinylpyrrolidone K85 available ex BASF as Luviskol~ K85.
2. Dye fixing agent ex Clariant under the trademark Cartafix CB~.
3. 1,1-N-dimethyl-9,9-N"-dimethyl dipropylenetriamine.
4. 1,1-N-dimethyl-5-N'-methyl-9,9-N"-dimethyl dipropylenetriamine.
S. 2-Phosphonobutane-1,2,4-tricarboxylic acid ex Bayer.
Table X
Weight
Ingredients 47 48 49 50
Polymer' 3.5 3.5 2.0 --
Dye fixative z 2.4 2.4 1.0 2.5
Polyamine ' 15.0 17.0 S.0 7.0
Fabric softener 4 -- -- 10.0 --
Bayhibit 5 1.0 1.0 0.2 1.0
Water balancebalancebalancebalance
1. Polyvinylpyrrolidone K85 available ex BASF as Luviskol~' K85.
2. Dye fixing agent ex Clariant under the trademark Cartafix CB~.
3. N,N'-bis(3-aminopropyl)-1,4-piperazine.
4. Di (tallowyloxyethyl)dimethyl ammonium chloride.
5. 2-Phosphonobutane-1,2,4-tricarboxylic acid ex Bayer.
Table XI
Weight
Ingredients 51 52 53 54
Polymer' 4.5 4.5 3.5 3.5
Dye fixative ' 2.4 2.4 2.4 2.4
Polyamine' 7.0 8.0 -- --
Polyamine' -- -- 15.0 --
Polyamine S - - -- 15.0
Bayhibit 6 1.0 1.0 1.0 1.0
Water balancebalance balancebalance
1. Polyvinylpyrrolidone K85 available ex BASF as Luviskol~' K85.
2. Dye fixing agent ex Clariant under the trademark Cartafix CBS'.
3. 1,1-N-dimethyl-9,9-N"-dimethyl dipropylenetriamine.
4. 1,1-N-dimethyl-5-N'-methyl-9,9-N"~imethyl dipropylenetriamine.
CA 02347809 2004-05-31
42
5. N,N'-bis(3-aminopropyl)-1,4-piperazine.
6. 2-Phosphonobutane-1,2,4-tricarboxylic acid ex Bayer.
Table XII
Weight °l°
Ingredients 55 56 57 58
Polymer ' 4.5 4.5 3.5 3.5
Dye fixative ' 2.4 2.4 2.4 2.0
Polyamine' -- -- 17.0 25.0
Polyamine '' 20.0 25.0 - --
Bayhibit' 1.0 1.0 I.0 0.2
Water balancebalancebalance balance
1. Polyvinylpyrrolidone K85 available ex BASF as Luviskol K85.
2. Dye fixing agent ex Clariant under the trademark Cartafix CBS.
3. N.N'-bis(3-aminopropyl)-1,4-piperazine.
4. 1.1-N-dimethyl-5-N'-methyl-9,9-N"-dimethyi dipropylenetriamine.
5. 2-Phosphonobutane-1,2.4-tricarboxylic acid ex Bayer.
