Note: Descriptions are shown in the official language in which they were submitted.
1 1
Case 15532-CA 1
NOVEL WHITENING AGENTS FOR CELLULOSIC SUBSTRATES
TECHNICAL FIELD
The present application relates to novel whitening agents for cellulosic
substrates. The whitening
agents are comprised of at least two constituents: at least one chromophore
constituent and at least
one polymeric constituent. Suitable chromophore components generally fluoresce
blue, red, violet,
or purple color when exposed to light, or they may absorb light to reflect
these same shades. These
whitening agents may be ideal for use in laundry care compositions including
but not limited to
liquid and/or powder laundry detergent formulations and rinse added fabric
softening (RAFS)
compositions.
BACKGROUND
.. The use of whitening agents, either optical brighteners or bluing agents,
in textile applications is
well known in the prior art. As textile substrates age, their color tends to
fade or yellow due to
exposure to light, air, soil, and natural degradation of the fibers that
comprise the substrates. Thus,
the purpose of whitening agents is generally to visually brighten these
textile substrates and
counteract the fading and yellowing of the substrates. Typically, whitening
agents may be found
.. in laundry detergents, fabric softeners, or rinse aids and are therefore
applied to textile substrates
during the laundering process. However, it is important that whitening agents
function to brighten
treated textile substrates without causing undesirable staining of the textile
substrates.
Cellulosic substrates, in particular, tend to exhibit a yellow hue after
exposure to light, air, and/or
soiling. This yellowness is often difficult to reverse by normal laundering
procedures. As a result,
there exists a need for improved whitening agents which are capable of
eliminating the yellowness
exhibited by ageing cellulosic substrates. By utilizing such improved
whitening agents, the life of
the textile substrates, such as clothing articles, bed and table linens,
towels, etc., may be extended.
.. The present whitening agent offers advantages over the prior art and emit
light with wavelengths
in the range of blue, red, violet, purple, or combinations thereof upon
exposure to ultraviolet light
(or, they absorb light to produce the same shades) in order to neutralize the
yellowness of cellulosic
substrates. The present compounds function ideally as whitening agents for
substrates comprised
of cellulose, polyester, nylon and mixtures thereof and may be incorporated
into laundry detergent
formulations for use by consumers during the laundering process.
CA 3042081 2019-05-02
Case I5532-CA 2
SUMMARY OF INVENTION
The present disclosure relates to laundry care compositions comprising a
laundry care ingredient
and a whitening agent. The whitening agent is an nonionic amphiphilic oxygen-
linked nonionic
dye selected from the group consisting of acridines, anthraquinones, azines,
azos, benzodifuranes,
benzodifuranones, carotenoids, coumarins, cyanines, diazahemicyanines,
diphenylmethanes,
fonnazans, hem icyanines, indigoids, methanes, naphthalimides,
naphthoquinones, nitros, nitrosos,
oxazines, phthalocyanines, pyrazoles, stilbenes, styryls, triarylmethanes,
triphenylmethanes,
xanthenes and mixtures thereof.
The present disclosure also relates to laundry care compositions including but
not limited to liquid
and/or powder laundry detergent formulations and rinse added fabric softening
(RAFS)
compositions that comprise such whitening agents.
DETAILED DESCRIPTION
As used herein, "cellulosic substrates" are intended to include any substrate
which comprises at
least a majority by weight of cellulose. Cellulose may be found in wood,
cotton, linen, jute, and
hemp. Cellulosic substrates may be in the form of powders, fibers, pulp and
articles formed from
powders, fibers and pulp. Cellulosic fibers, include, without limitation,
cotton, rayon (regenerated
cellulose), acetate (cellulose acetate), triacetate (cellulose triacetate),
and mixtures thereof.
Articles formed from cellulosic fibers include textile articles such as
fabrics. Articles formed from
pulp include paper.
As used herein, the term "laundry care composition" includes, unless otherwise
indicated, granular,
powder, liquid, gel, paste, bar form and/or flake type washing agents and/or
fabric treatment
compositions.
As used herein, the term "fabric treatment composition" includes, unless
otherwise indicated,
fabric softening compositions, fabric enhancing compositions, fabric
freshening compositions and
combinations there of. Such compositions may be, but need not be rinse added
compositions.
As used herein, the articles including "the", "a" and "an" when used in a
claim, are understood to
mean one or more of what is claimed or described.
As used herein, the terms "include", "includes" and "including" are meant to
be non-limiting.
As used herein, the term "non-ionic" refers to any of many organic compounds
devoid of cationic
or anionic substituents and thus lacking any ionic charge at a neutral pH.
As used herein, the term "amphiphilic" refers to any of many organic compounds
composed of
hydrophilic and hydrophobic portions. A compound is determined to be
amphiphilic for the
CA 3042081 2019-05-02
Case 15532-CA 3
purposes of the present invention when the compound partitions between
deionized water and
dodecane at 25 C such that the compound is predominantly in the water layer.
Amphiphilic
compounds are determined to be amphiphilic whitening agents if the amphiphilic
compound
qualifies as a shading dye according to the test methods disclosed herein.
Unless otherwise noted, all component or composition levels are in reference
to the active portion
of that component or composition, and are exclusive of impurities, for
example, residual solvents
or by-products, which may be present in commercially available sources of such
components or
compositions.
All percentages and ratios are calculated by weight unless otherwise
indicated. All percentages
and ratios are calculated based on the total composition unless otherwise
indicated.
It should be understood that every maximum numerical limitation given
throughout this
specification includes every lower numerical limitation, as if such lower
numerical limitations were
expressly written herein. Every minimum numerical limitation given throughout
this specification
will include every higher numerical limitation, as if such higher numerical
limitations were
expressly written herein. Every numerical range given throughout this
specification will include
every narrower numerical range that falls within such broader numerical range,
as if such narrower
numerical ranges were all expressly written herein.
All documents cited are, in relevant part, incorporated herein by reference;
the citation of any
document is not to be construed as an admission that it is prior art with
respect to the present
invention.
The whitening agents of the present invention may be dyes, pigments, or
polymeric
colorants comprising a chromophore constituent and a polymeric constituent
covalently bound to
one another. It will be understood by those skilled in the art that the
whitening agents are not two
separate molecules, one comprising a chromophore and the other comprising a
polymer, but rather
one molecule and that the chromophore constituent and the polymeric
constituent are distinct parts
of the same molecule. Moreover, the polymeric constituent is bound directly to
a oxygen atom on
the chromophore constituent. It will further be understood that inclusion of
the polymeric
constituent, as with all polymeric compounds, may produce a mixture of
molecules which
incorporate different quantities of monomeric units. For example, during a
typical ethoxylation
process the randomness of the ethylene oxide addition results in a mixture of
oligomers with
different degrees of ethoxylation. As a consequence of its ethylene oxide
number distribution,
which often follows a Poisson law, a commercial material contains substances
with somewhat
different properties. For example, in one aspect the product resulting from an
ethoxylation is not a
CA 3042081 2019-05-02
Case 15532-CA 4
single compound containing five (CH2CH20) units as a general structure may
suggest. Instead, the
product is a mixture of several homologs whose total of ethylene oxide units
may vary from about
2 to about 10. Industrially relevant processes will typically result in such
mixtures, which may
normally be used directly to provide the fabric shading dye, or less commonly
may undergo a
purification step.
The whitening agent chromophore constituent may be selected from acridines,
anthraquinones, azines, azos, benzodifuranes, benzodifuranones, carotenoids,
coumarins,
cyanines, diazahemicyanines, diphenylmethanes, formazans, hemicyanines,
indigoids, methanes,
naphthalimides, naphthoquinones, nitros, nitrosos, oxazines, phthalocyanines,
pyrazoles, stilbenes,
styryls, triarylmethanes, triphenylmethanes, xanthenes and mixtures thereof
Preferably, the
whitening agent is ananthraquinone or an azo dye, and even more preferably the
whitening agent
is an azo dye. The chromophore constituent is characterized in that it emits
or absorbs wavelength
to provide a color on substrates in the range of blue, red, violet, purple, or
combinations thereof
upon exposure to light. Preferably, the chromophore constituent exhibits an
absorbance spectrum
value from about 520 nanometers to about 640 nanometers in water, and more
preferably from
about 570 nanometers to about 610 nanometers in water. Preferably, the
chromophore constituent
exhibits an emission spectrum value from about 400 nanometers to about 480
nanometers in water.
The whitening agent of the present invention may be characterized by the
following
structure:
R50¨(C(R3)H)b R1
iN
(R4)a o'
Formula I
wherein each R4 is independently selected from the group consisting of alkyl,
oxyalkyl,
oxyaryl, sulfonamidoalkyl, sulfonamidoaryl, amidoalkyl, am idodialkyl,
amidoaryl,
amidodiaryl, halogen, thioalkyl, thioaryl, and -N=N-D, provided that at least
one of R4 is -
N=N-D and no more than three of R4 are -N=N-D, preferably no more than two R4
are -
N=N-D, and any -N=N-D groups are attached to the ring at a position marked in
Formula
1 as o, o', or p;
wherein the index a is an integer from 1 to 4; the index b is an integer from
0 to 1;
wherein each D is independently selected from an aromatic or heteroaromatic
group;
wherein the heteroatom of the heteroaromatic group is preferably N. 0 and S,
most
preferably N and S; preferably the heteroatom(s) of the heteroaromatic groups
is part of a
CA 3042081 2019-05-02
Case 15532-CA 5
five or six membered ring; preferably the heteroaromatic is a monocyclic six
of five
membered heterocyclic aromatic groups; preferably the heteroaromatic is
selected from
thiophene, thiazole, isothiazole, thiadiazole and pyridinyl; preferably all D
groups are the
same;
wherein RI and R2 are independently selected from the group consisting of H
and
unsubstituted or substituted CI to C12 alkyl chains, optionally the alkyl
chains comprise
ether (C-O-C), ester and/or amide links, optionally the alkyl chains are
substituted with -
Cl, -Br, -CN, -NO2, -S02CH3, -0R8 and mixtures thereof;
wherein R3 is selected from H and C1-C6 alkyl;
wherein R5 is selected from the group consisting of:
(a) RCH2CR'HO),(CH2CR"HO)yR8]
wherein R' is selected from the group consisting of H, CH3, CH20(CH2CH20)zR8,
and
mixtures thereof; wherein R" is selected from the group consisting of H,
CH20(CH2CH20),R8, and mixtures thereof; wherein said x (CH2CR'HO) groups and
said
y (CH2CR"HO) groups may be arranged in any order; wherein x + y < 20 or even <
10;
wherein y? 1; and wherein independently each z = 0 to 5;
(b) (CH2CH20)x(CH2C(OR)HCH20)y(CH2CH20)zR8, wherein each R is
independently selected from the group consisting of H, (CH2CH20)z,128, and
mixtures
thereof; wherein groups indicated by indices x, y and z may be arranged in any
order;
wherein x + y < 5; wherein y? 1; and wherein independently z = 0 to 10 and
each z' = 0
to 10;
(c) CH2CH(OR6)C1120R7
wherein R6 is selected from the group consisting of H, (CH2CH20),R8, and
mixtures
thereof; and wherein z = 0 to 20; wherein R7 is selected from the group
consisting of C1-
C16 alkyl , aryl groups, and mixtures thereof; and
(d) the hydroxy addition product of styrene oxide, glycidyl methyl ether,
isobutyl
glycidyl ether, isopropylglycidyl ether, t-butyl glycidyl ether, 2-
ethylhexylgycidyl ether,
and glycidylhexadecyl ether, followed by the addition of from Ito 20 alkylene
oxide units
terminating with an R8 group;
wherein each R8 is independently selected from H and -CH2CO2M wherein M is H
or a
suitable charge-balancing counterion; preferably no more than two R8 are non-
H, more
preferably no more than one R8 is non-H, most preferably all R8 are H.
In one aspect. preferred D groups are selected from:
CA 3042081 2019-05-02
Case 15532-CA 6
Br CI
02N** 02N
NO2; NO2; ON
CN
* 02N *
NO2 Cl CN
NO2 CN
02N 11 * 02N * 02N 411 *
CN = CN ; CN . EtO2CS =NCS
..¨N
*
n
. . 02N Sand mixtures thereof.
In a preferred whitening agent of the present invention, the index a is from
about 1 to about
2; wherein R3 is H; wherein R5 is selected from the group consisting of:
(a) (CH2CRI-10)x(CH2CR"HO)yR8
wherein R' is selected from the group consisting of H, CH3, CH20(C1-
I2CH20),R8, and
mixtures thereof; wherein R" is selected from the group consisting of H,
CH20(CH2CH20),R8, and mixtures thereof; wherein said x (CH2CR'HO) groups and
said
y (CH2CR"HO) groups may be arranged in any order; wherein x + y < 20 or even <
10;
wherein y? 1; and wherein independently each z = 0 to 5; and
(b) (CH2CH20),e(CH2C(OR)HCH20)y(CH2CH20)z,R8, wherein each R is
independently selected from the group consisting of H, (CH2CH20),R8, and
mixtures
thereof; wherein groups indicated by indices x', y' and z' may be arranged in
any order;
wherein x' + y' < 5; wherein y'? 1; wherein z' = 0 to 10 and wherein
independently
each w' = 0 to 10;
wherein each R8 is independently selected from H and -C1-12CO2M wherein M is H
or a
suitable charge balancing counterion; preferably no more than two R8 are non-I-
1, more
preferably no more than one R8 is non-H, most preferably all R8 are H.
In another preferred whitening agent of the present invention, the index b =
0; wherein R5
is (CH2CR'110),,(CH2CR"HO)yR8; wherein R' is selected from the group
consisting of H, CH3,
CH20(CH2CH20),R8, and mixtures thereof; wherein R" is selected from the group
consisting of
H, CH20(CH2CH20)zR8, and mixtures thereof; wherein said x (CH2CR'HO) groups
and said y
(CH2CR"HO) groups may be arranged in any order; wherein x + y < 20; wherein y?
1; and
wherein independently each z = 0 to 10 ; wherein each R8 is independently
selected from H and -
CA 3042081 2019-05-02
Case 15532-CA 7
CH2CO2M wherein M is H or a suitable charge balancing counterion; preferably
no more than two
R8 are non-H, more preferably no more than one R8 is non-H, most preferably
all R8 are H.
One skilled in the art understands that the degree of ethoxylation modifies
the deposition
and removal properties of such dyes. When the overall ethoxylation number is
low, the dye may
deposit better than when the overall ethoxylation number is high. But the
lower ethoxylated dye
will also be less easily removed in subsequent washes and may tend to suffer
from more instances
of spot staining in the hands of the consumer where the neat product (e.g.,
liquid or granule) comes
into direct contact with fabrics for prolonged periods. Dyes with longer
ethoxylate chains will be
less prone to such staining, and will be easier to remove, but they will not
deposit to the fabric as
well from a wash solution, and so will require that more dye be added to the
formulation, which
impacts finished product aesthetics and cost of the final formulation. Dyes
are therefore selected
that provide the desired balance between these properties.
In one aspect a preferred whitening agent of the invention will have an R5
group that
comprises at least one divalent -(CH2CH20),- moiety where the index w is at
least 3, preferably at
least 4, more preferably at least 5, most preferably at least 6. Frequently,
the whitening agent of
the invention comprises mixtures of different oligomer lengths. In such an
instance, a preferred
whitening agent will have at least lOwt%, more preferably at least 25wt% or
50wt%, even more
preferably at least 75wt% or even 90wt% of the mixture comprising dyes
containing at least one
R5 group that comprises at least one (CH2CH20)R8 unit where the index w is at
least 3, preferably
at least 4, more preferably at least 5, most preferably at least 6. Without
being limited by theory, it
is believed that such whitening agents may have a desirable balance between
ability to deposit
from a wash solution and the risk of spot staining from the dye when the
detergent formulation in
neat or moderately diluted forms is in direct contact with fabric. One of
ordinary skill in the art can
determine the desired average number of monomeric units in the R5 group or
groups through
routine experimentation.
In one aspect, whitening agents suitable for use in the present invention
include, but are not
limited to, the following structures:
OR5
NR1R2
D-N Formula 11
=
CA 3042081 2019-05-02
Case 15532-CA 8
OR5
NRIR2
D-N
N=1\1
D ; Formula III
OR5
N = NRIR2
D-1\1. Formula IV
OR5
NR1R2
N=N
D = Formula V
OR5 D
N=1\1
NR1R2
DN Formula VI
=
R50
NRIR2
D-N
.\1 =
Formula VII
R50
N =NR1R2
D-N.
1\1=N
D ; Formula VIII
R50 N=N
N NRIR2
= D-N Formula IX
OR5
N 111 NR1R2
D-N Formula X
OR5
NRIR2
D-N
N =1\1
D ; Formilla XI
CA 3042081 2019-05-02
, 1
Case 15532-CA 9
OR5
N 411 NRIR2
D-N
R4 = Formula XII
'
OR5
. N NR1R2
D-N
R4 NN
D ; Formula XIII
and mixtures thereof, wherein each D, RI, R2, R4, and R5 are as defined above.
Compounds according to Formula XII that may be preferred whitening agents
include the
following structures, wherein R5 is as defined above:
Br o a / ___ CN
OR5 0-- OR5 0---/
02N 110 N /¨/ 02N 41 N
1\1 11 N 'N . N
NO2 NO2 \__\
HN 0 HN / 0--\
____________________________ 0¨ \¨CN
0 ; 0 =
,
Br
OR5 = OR5
02N 41 N HO
N 411 N --N N . NH
NO2 \--\ 0
HN 0---4 02N S I-1N OH
0 - 0
Br
OR5 Br
OR5
02N . N
1\1 . NH 02N 41 N /---Ph
\ N N
NO2
HN =o NO2
Ph
HN \--
/--0
0 0--/
/ = 0 =
, ,
Br Cl
OR5 OH OR5
N N NH
02N N / __ / 02N N
1\1
NO2 \
\ NO2 \
\
HN CN HN / 0---\
\--CN
O = o ; ,
,
CA 3042081 2019-05-02
II, I
Case 15532-CA 10
Br CI 0
OR5 OR5 /0 --
/K
02N N milk¨ /--- 02N N /
N V N 1\1 N
NO2 \_ CI \
HN FIN 04
0
0 ; 0 ;
NO2 NO2
OR5 OH OR5
02N 41 N = /---/ ON . N /¨
N N N = N\_4-- OH
\----\ CI
HN OH FIN OH
)i
0 = 0 -
NO2 NO2
OR5 OR5 //02N . N /---/
02N = N /
Br .i\I * N .N Ilik N
Br
=
HN \--1 HN
0 = 0 =
Br NO2
OR5
02N = N m_mi0R5/¨/CN 02N = N
N ir N .N = NH
NO2 \ s\ Br
HN FIN
0 . (::1 =
NO2 NO2
OR5 OR5 0 ¨
02N N
.N 11 NH 02N N
.I\1 1\1/ __ /
CI \____\ CI \
\
HN 0¨ HN 0-
0 = 0 =
, ,
Br NO2
OR5 OR5
02N N /-- 02N N
µI\I N 1\1 N H
NO2
\_ _____________________________ \ \ __
CI \
HN ,7¨O HN 0-
0 0 \ \
0¨ ; 0 =
,
I
CA 3042081 2019-05-02
Case 15532-CA 11
NO2
OR5 OR5
02N Cl
1\1 NH2 NH
Cl 02N
HN HN
CN
O 0 = =
OR5 0¨ Br OR5 0¨
Cl 02N N
02N **
NO2
N N
HN 0¨
CN p
;and
As will be appreciated by those skilled in the art unreacted starting
materials and additional
components resulting from minor side reactions will typically be present at
levels that are unlikely
to significantly impact the whitening agent's performance, as perceived by the
average
consumer. As will further be appreciated, when present at levels that may
impact the whitening
agent's performance, or the overall performance of a detergent formulation
containing the mixture,
as perceived by the average consumer, such additional components may be
removed or retained as
desired.
The Test Methods provided below can be used to determine if a dye, or a
mixture of dyes,
is a whitening agent for the purposes of the present invention.
Test Methods
1. Method for Determining
Deposition for a Dye
a.)
Unbrightened Multifiber Fabric Style 41 swatches (MFF4 I , 5cm x 10cm, average
weight 1.46g) serged with unbrightened thread are purchased from Testfabrics,
Inc. (West Pittston,
PA). MFF41 swatches are stripped prior to use by washing two full cycles in
AATCC heavy duty
liquid laundry detergent (HDL) nil brightener at 49 C and washing 3 additional
full cycles at 49 C
without detergent. Four replicate swatches are placed into each flask.
b.) A
sufficient volume of AATCC standard nil brightener HDL detergent solution is
prepared by dissolving the detergent in 0 gpg water at room temperature at a
concentration of I .55
g per liter.
c.)
A concentrated stock solution of dye is prepared in an appropriate solvent
selected
from dimethyl sulfoxide (DMSO), ethanol or 50:50 ethanol:water. Ethanol is
preferred. The dye
stock is added to a beaker containing 400mL detergent solution (prepared in
step I.b. above) in an
CA 3042081 2019-05-02
Case 15532-CA 12
amount sufficient to produce an aqueous solution absorbance at the kmax of 0.1
AU (+ 0.01AU) in
a cuvette of path length 1.0 cm. For a mixture of dyes, the sum of the aqueous
solution absorbance
at the
¨max of the individual dyes is 0.1 AU (+ 0.01AU) in a cuvette of path length
1.0 cm. Total
organic solvent concentration in a wash solution from the concentrated stock
solution is less than
0.5%. A 125mL aliquot of the wash solution is placed into 3 separate
disposable 250mL
Erlenmeyer flasks (Thermo Fisher Scientific, Rochester, NY). Solution hardness
is adjusted to
6gpg by addition of an appropriate volume of 10,000gpg Ca:Mg (3:1) hardness
stock solution
prepared in deionized water.
d.) Four MFF41 swatches are placed into each flask (which correlates to
approximately
a 25:1 liquor:fabric ratio), flasks are capped and manually shaken to wet the
swatches. Flasks are
placed onto a Model 75 wrist action shaker from Burrell Scientific, Inc.
(Pittsburg, PA) and agitated
on the highest setting of 10 (390 oscillations per minute with an arc of 14.6
). After 12 minutes,
the wash solution is removed by vacuum aspiration, 125mL of Ogpg water is
added for a rinse,
hardness of the rinse water is adjusted to 6gpg as noted above, and the flasks
agitated for 4
additional minutes. Rinse solution is removed by vacuum aspiration and
swatches are spun in a
Mini Countertop Spin Dryer (The Laundry Alternative Inc., Nashua, NH) for 5
minutes, after
which they are allowed to air dry in the dark.
e.) L*, a*, and b* values for the 2 most consumer relevant fabric types,
cotton and
polyester, are measured on the dry swatches using a LabScan XE reflectance
spectrophotometer
(HunterLabs, Reston, VA; D65 illumination, 10 observer, UV light excluded).
The L*, a*, and
b* values of the 12 swatches (3 flasks each containing 4 swatches) are
averaged and the hueing
deposition (1-1D) of the dye is calculated for each fabric type using the
following equation:
HD = DE* = ((L*, _ L*02 + (a*c _ a*02 (b*c _ b*02)1/2
wherein the subscripts c and s respectively refer to the control, i.e., the
fabric washed in detergent
with no dye, and the fabric washed in detergent containing dye, or a mixture
of dyes, according to
the method described above. The HD for any consumer relevant fabric, such as
nylon, can be
determined in the same manner.
II. Method for Determining Relative Hue Angle (vs. Nil Dye Control)
a) The a* and b* values of the 12 swatches from each solution were averaged
and the
following formulas used to determine Aa* and Ab*:
Aa* = a*c - a*s and Ab* = b*c - b*s
CA 3042081 2019-05-02
Case 15532-CA 13
wherein the subscripts c and s respectively refer to the fabric washed in
detergent
with no dye and the fabric washed in detergent containing dye, or mixture of
dyes,
according to the method described in I. above.
b.)
If the absolute value of both Aa* and Ab* <0.25, no Relative Hue Angle (RHA)
was calculated. If the absolute value of either Aa* or Ab* were > 0.25, the
RHA
was determined using one of the following formulas:
When Ab* > 0, RHA = ATAN2(Aa*,Ab*)
When Ab* <0, RHA = 360 + ATAN2(Aa*,Ab*)
III. Method to Determine if a Dye is a Whitening Agent
A dye, or mixture of dyes, is considered a whitening agent (also known as a
hueing dye)
for the purposes of the present invention if (a) either the HDcotton or the
HDpolyester is greater than or
equal to 2.0 DE* units or preferably greater than or equal to 3.0, or 4.0 or
even 5.0, according to
the formula above, and (b) the relative hue angle (see Method III. below) on
the fabric that meets
the DE* criterion in (a) is within 240 to 345, more preferably 260 to 325,
even more preferably
270 to 310. If the value of HD for both fabric types is less than 2.0 DE*
units, or if the relative hue
angle is not within the prescribed range on each fabric for which the DE*
meets the criteria the dye
is not a shading dye for the purposes of the present invention.
The whitening agent's described in the present specification may be
incorporated into a
laundry care composition including but not limited to laundry detergents and
fabric care
compositions. Such compositions comprise one or more of said whitening agents
and a laundry
care ingredient. The whitening agent may be added to cellulose and other
substrates using a variety
of application techniques. For application to cellulose-containing and other
textile substrates, the
whitening agent is preferably included as an additive in laundry detergent.
Thus, application to the
textile substrate actually occurs when a consumer adds laundry detergent to a
washing machine.
Similarly, RAFS compositions are typically added in the rinse cycle, which is
after the detergent
solution has been used and replaced with the rinsing solution in typical
laundering processes. For
application to cellulosic paper substrates, the whitening agent may be added
to the paper pulp
mixture prior to formation of the final paper product.
The laundry care compositions including laundry detergents may be in solid or
liquid form,
including a gel form. The laundry care compositions including laundry
detergents may also be in
CA 3042081 2019-05-02
Case 15532-CA 14
a unit dose pouch. The laundry detergent composition comprises a surfactant in
an amount
sufficient to provide desired cleaning properties.
The whitening agent may be present in the laundry detergent composition in an
amount from about
0.0001% to about 10% by weight of the composition, more preferably from about
0.0001% to
about 5% by weight of the composition, and even more preferably from about
0.0001% to about
1% by weight of the composition.
The laundry detergent composition comprises a surfactant in an amount
sufficient to provide
desired cleaning properties. In one embodiment, the laundry detergent
composition comprises, by
weight, from about 5% to about 90% of the surfactant, and more specifically
from about 5% to
about 70% of the surfactant, and even more specifically from about 5% to about
40%. The
surfactant may comprise anionic, nonionic, cationic, zwitterionic and/or
amphoteric surfactants. In
a more specific embodiment, the detergent composition comprises anionic
surfactant, nonionic
surfactant, or mixtures thereof.
Suitable anionic surfactants useful herein can comprise any of the
conventional anionic surfactant
types typically used in liquid detergent products. These include the alkyl
benzene sulfonic acids
and their salts as well as alkoxylated or non-alkoxylated alkyl sulfate
materials.
Exemplary anionic surfactants are the alkali metal salts of C1o_16 alkyl
benzene sulfonic acids,
preferably CI 1-14 alkyl benzene sulfonic acids. Preferably the alkyl group is
linear and such linear
alkyl benzene sulfonates are known as "LAS". Alkyl benzene sulfonates, and
particularly LAS, are
well known in the art. Such surfactants and their preparation are described
for example in U.S. Pat.
Nos. 2,220,099 and 2,477,383. Especially preferred are the sodium and
potassium linear straight
chain alkylbenzene sulfonates in which the average number of carbon atoms in
the alkyl group is
from about 11 to 14. Sodium C11-C14, e.g., Cu, LAS is a specific example of
such surfactants.
Another exemplary type of anionic surfactant comprises ethoxylated alkyl
sulfate surfactants.
Such materials, also known as alkyl ether sulfates or alkyl polyethoxylate
sulfates, are those which
correspond to the formula: R'--0--(C2H40)n--S03M wherein R' is a C8-C20 alkyl
group, n is from
about 1 to 20, and M is a salt-forming cation. In a specific embodiment, R' is
Cio-Ci8 alkyl, n is
from about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or
CA 3042081 2019-05-02
11,
Case 15532-CA 15
alkanolammonium. In more specific embodiments, R' is a Cu-C16, n is from about
1 to 6 and M is
sodium.
The alkyl ether sulfates will generally be used in the form of mixtures
comprising varying R' chain
lengths and varying degrees of ethoxylation. Frequently such mixtures will
inevitably also contain
some non-ethoxylated alkyl sulfate materials, i.e., surfactants of the above
ethoxylated alkyl sulfate
formula wherein n=0. Non-ethoxylated alkyl sulfates may also be added
separately to the
compositions of this invention and used as or in any anionic surfactant
component which may be
present. Specific examples of non-alkoxylated, e.g., non-ethoxylated, alkyl
ether sulfate
surfactants are those produced by the sulfation of higher Cs-C20 fatty
alcohols. Conventional
primary alkyl sulfate surfactants have the general formula: ROS03-M+ wherein R
is typically a
linear C8-C20 hydrocarbyl group, which may be straight chain or branched
chain, and M is a water-
solubilizing cation. In specific embodiments, R is a C10-C15 alkyl, and M is
alkali metal, more
specifically R is C12-C14 and M is sodium.
Specific, non-limiting examples of anionic surfactants useful herein include:
a) CI 1-C18 alkyl
benzene sulfonates (LAS); b) C10-C20 primary, branched-chain and random alkyl
sulfates (AS); c)
Cio-C1 8 secondary (2,3) alkyl sulfates; d) Cm-CB alkyl alkoxy sulfates
(AE,,S) wherein preferably
x is from 1-30; e) Cm-Cis alkyl alkoxy carboxylates preferably comprising 1-5
ethoxy units; 0
mid-chain branched alkyl sulfates as discussed in U.S. Pat. No. 6,020,303 and
U.S. Pat. No.
6,060,443; g) mid-chain branched alkyl alkoxy sulfates as discussed in U.S.
Pat. No. 6,008,181
and U.S. Pat. No. 6,020,303; h) modified alkylbenzene sulfonate (MLAS) as
discussed in WO
99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO
99/07656, WO 00/23549, and WO 00/23548; i) methyl ester sulfonate (MES); and
j) alpha-olefin
sulfonate (AOS).
Suitable nonionic surfactants useful herein can comprise any of the
conventional nonionic
surfactant types typically used in liquid detergent products. These include
alkoxylated fatty
alcohols and amine oxide surfactants. Preferred for use in the liquid
detergent products herein are
those nonionic surfactants which are normally liquid.
Suitable nonionic surfactants for use herein include the alcohol alkoxylate
nonionic surfactants.
Alcohol alkoxylates are materials which correspond to the general formula:
RI(Cm1-12m0)601-1
wherein 121 is a C8-C16 alkyl group, m is from 2 to 4, and n ranges from about
2 to 12. Preferably
CA 3042081 2019-05-02
Case 15532-CA 16
RI is an alkyl group, which may be primary or secondary, that comprises from
about 9 to 15 carbon
atoms, more preferably from about 10 to 14 carbon atoms. In one embodiment,
the alkoxylated
fatty alcohols will also be ethoxylated materials that contain from about 2 to
12 ethylene oxide
moieties per molecule, more preferably from about 3 to 10 or even from about 7
to 9 ethylene oxide
moieties per molecule.
The alkoxylated fatty alcohol materials useful in the liquid detergent
compositions herein will
frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about
3 to 17. More
preferably, the HLB of this material will range from about 6 to 15, most
preferably from about 8
to 15. Alkoxylated fatty alcohol nonionic surfactants have been marketed under
the tradenames
Neodol and Dobanol by the Shell Chemical Company.
Another suitable type of nonionic surfactant useful herein comprises the amine
oxide surfactants.
Amine oxides are materials which are often referred to in the art as "semi-
polar" nonionics. Amine
oxides have the formula: R(E0)x(PO)y(B0)zN(0)(CH2R')2.qH20. In this formula, R
is a relatively
long-chain hydrocarbyl moiety which can be saturated or unsaturated, linear or
branched, and can
contain from 8 to 20, preferably from 10 to 16 carbon atoms, and is more
preferably C12-C16
primary alkyl. R' is a short-chain moiety, preferably selected from hydrogen,
methyl and --
CH2OH. When x+y+z is different from 0, EO is ethyleneoxy, PO is propyleneneoxy
and BO is
butyleneoxy. Amine oxide surfactants are illustrated by Cl2-14 alkyldimethyl
amine oxide.
Non-limiting examples of nonionic surfactants include: a) Cu-Cis alkyl
ethoxylates, such as,
NEODOLO nonionic surfactants from Shell; b) Co-C12 alkyl phenol alkoxylates
wherein the
alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; c) Cu-C
8 alcohol and C6-
.. Cu alkyl phenol condensates with ethylene oxide/propylene oxide block
polymers such as
Pluronice from BASF; d) C14-C22 mid-chain branched alcohols, BA, as discussed
in U.S. Pat. No.
6,150,322; e) C14-C22 mid-chain branched alkyl alkoxylates, BAEx, wherein x if
from 1-30, as
discussed in U.S. Pat. No. 6,153,577, U.S. Pat. No. 6,020,303 and U.S. Pat.
No. 6,093,856; f)
Alkylpolysaccharides as discussed in U.S. Pat. No. 4,565,647 to Llenado,
issued Jan. 26, 1986;
specifically alkylpolyglycosides as discussed in U.S. Pat. No. 4,483,780 and
U.S. Pat. No.
4,483,779; g) Polyhydroxy fatty acid amides as discussed in U.S. Pat. No.
5,332,528. WO
92/06162, WO 93/19146, WO 93/19038, and WO 94/09099; and h) ether capped
poly(oxyalkylated) alcohol surfactants as discussed in U.S. Pat. No. 6,482,994
and WO 01/42408.
CA 3042081 2019-05-02
Case 15532-CA 17
In the laundry detergent compositions herein, the detersive surfactant
component may comprise
combinations of anionic and nonionic surfactant materials. When this is the
case, the weight ratio
of anionic to nonionic will typically range from 10:90 to 90:10, more
typically from 30:70 to 70:30.
In general compositions with increasing weight ratios favoring nonionic
surfactants may lead to
increased deposition of the inventive whitening agents in a wash. Such factors
must always be
carefully weighed over against any risk elements that may also increase in
these formulations. The
ordinarily-skilled artisan is well aware of such factors and formulates
accordingly.
Cationic surfactants are well known in the art and non-limiting examples of
these include
.. quaternary ammonium surfactants, which can have up to 26 carbon atoms.
Additional examples
include a) alkoxylate quaternary ammonium (AQA) surfactants as discussed in
U.S. Pat. No.
6,136,769; b) dimethyl hydroxyethyl quaternary ammonium as discussed in U.S.
Pat. No.
6,004,922; c) polyamine cationic surfactants as discussed in WO 98/35002, WO
98/35003, WO
98/35004, WO 98/35005, and WO 98/35006; d) cationic ester surfactants as
discussed in U.S. Pat.
Nos. 4,228,042, 4,239,660 4,260,529 and U.S. Pat. No. 6,022,844; and e) amino
surfactants as
discussed in U.S. Pat. No. 6,221,825 and WO 00/47708, specifically amido
propyldimethyl amine
(APA).
Non-limiting examples of zwitterionic surfactants include derivatives of
secondary and tertiary
amines, derivatives of heterocyclic secondary and tertiary amines, or
derivatives of quaternary
ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S.
Pat. No.
3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38
through column 22, line
48, for examples of zwitterionic surfactants; betaine, including alkyl
dimethyl betaine and
cocodimethyl amidopropyl betaine, C8 to CI8 (preferably Cu to CH) amine oxides
and sulfo and
hydroxy betaines, such as N-alkyl-N,N-dimethylammino-1 -propane sulfonate
where the alkyl
group can be Cs to CI8, preferably Cpo to C14.
Non-limiting examples of ampholytic surfactants include aliphatic derivatives
of secondary or
tertiary amines, or aliphatic derivatives of heterocyclic secondary and
tertiary amines in which the
aliphatic radical can be straight- or branched-chain. One of the aliphatic
substituents comprises at
least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms,
and at least one
comprises an anionic water-solubilizing group, e.g. carboxy, sulfonate,
sulfate. See U.S. Pat. No.
3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column 19, lines 18-35,
for examples of
am pholytic surfactants.
CA 3042081 2019-05-02
Case 15532-CA 18
As noted, the compositions may be in the form of a solid, either in tablet or
particulate form,
including, but not limited to particles, flakes, or the like, or the
compositions may be in the form
of a liquid. The liquid detergent compositions comprise an aqueous, non-
surface active liquid
carrier. Generally, the amount of the aqueous, non-surface active liquid
carrier employed in the
compositions herein will be effective to solubilize, suspend or disperse the
composition
components. For example, the compositions may comprise, by weight, from about
5% to about
90%, more specifically from about 10% to about 70%, and even more specifically
from about 20%
to about 70% of the aqueous, non-surface active liquid carrier.
The most cost effective type of aqueous, non-surface active liquid carrier is,
of course, water itself.
Accordingly, the aqueous, non-surface active liquid carrier component will
generally be mostly, if
not completely, comprised of water. While other types of water-miscible
liquids, such alkanols,
diols, other polyols, ethers, amines, and the like, have been conventionally
been added to liquid
detergent compositions as co-solvents or stabilizers, for purposes of the
present invention, the
utilization of such water-miscible liquids should be minimized to hold down
composition cost.
Accordingly, the aqueous liquid carrier component of the liquid detergent
products herein will
generally comprise water present in concentrations ranging from about 5% to
about 90%, more
preferably from about 20% to about 70%, by weight of the composition.
Detergent compositions may also contain bleaching agents. Suitable bleaching
agents include, for
example, hydrogen peroxide sources, such as those described in detail in the
herein incorporated
Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley &
Sons), Vol. 4,
pp. 271-300 "Bleaching Agents (Survey)." These hydrogen peroxide sources
include the various
forms of sodium perborate and sodium percarbonate, including various coated
and modified forms
of these compounds.
The preferred source of hydrogen peroxide used herein can be any convenient
source, including
hydrogen peroxide itself. For example, perborate, e.g., sodium perborate (any
hydrate but
preferably the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or
equivalent percarbonate
salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium
peroxide can be used
herein. Also useful are sources of available oxygen such as persulfate bleach
(e.g., OXONE,
manufactured by DuPont). Sodium perborate monohydrate and sodium percarbonate
are
particularly preferred. Mixtures of any convenient hydrogen peroxide sources
can also be used.
CA 3042081 2019-05-02
Case 15532-CA 19
A suitable percarbonate bleach comprises dry particles having an average
particle size in the range
from about 500 micrometers to about 1,000 micrometers, not more than about 10%
by weight of
said particles being smaller than about 200 micrometers and not more than
about 10% by weight
of said particles being larger than about 1,250 micrometers. Optionally, the
percarbonate can be
coated with a silicate, borate or water-soluble surfactants. Percarbonate is
available from various
commercial sources such as FMC, Solvay and Tokai Denka.
Compositions of the present invention may also comprise as the bleaching agent
a chlorine-type
bleaching material. Such agents are well known in the art, and include for
example sodium
dichloroisocyanurate ("NaDCC"). However, chlorine-type bleaches are less
preferred for
compositions which comprise enzymes.
(a) Bleach Activators - Preferably, the peroxygen bleach component in the
composition is
formulated with an activator (peracid precursor). The activator is present at
levels of from about
0.01%, preferably from about 0.5%, more preferably from about 1% to about 15%,
preferably to
about 10%, more preferably to about 8%, by weight of the composition. A bleach
activator as used
herein is any compound which, when used in conjunction with a hydrogen
peroxide, source leads
to the in situ production of the peracid corresponding to the bleach
activator. Various non-limiting
.. examples of activators are disclosed in U.S. Patent Nos. 5,576,282;
4,915,854 and 4,412,934. See
also U.S. Patent No. 4,634,551 for other typical bleaches and activators
useful herein.
Preferred activators are selected from the group consisting of tetraacetyl
ethylene diamine (TAED),
benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam,
3 -ch lorobenzoylcaprolactam,
benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS),
phenyl
benzoate (PhBz), decanoyloxybenzenesulphonate (C10-OBS), benzoylvalerolactam
(BZVL),
octanoyloxybenzenesulphonate (C8-OBS), perhydrolyzable esters and mixtures
thereof, most
preferably benzoylcaprolactam and benzoylvalerolactam. Particularly preferred
bleach activators
in the pH range from about 8 to about 11 are those selected having an OBS or
VL leaving group.
Preferred hydrophobic bleach activators include, but are not limited to,
nonanoyloxybenzene-
sulphonate (NOBS): 4-[N-(nonanoyl) amino hexanoyloxy]-benzene sulfonate sodium
salt
(NACA-OBS), an example of which is described in U.S. Patent No. 5,523,434;
dodecanoyloxybenzenesulphonate (LOBS or C [ 2-OBS); 10-
undecenoyloxybenzenesulfonate
CA 3042081 2019-05-02
Case 15532-CA 20
(UDOBS or C11-OBS with unsaturation in the 10 position); and
decanoyloxybenzoic acid
(DOBA).
Preferred bleach activators are those described in U.S. Patent No. 5,998,350
to Burns et al.; U.S.
Patent No. 5,698,504 to Christie et al.; U.S. Patent No. 5,695,679 to Christie
et al.; U.S. Patent No.
5,686,401 to Willey etal.; U.S. Patent No. 5,686,014 to Hartshorn et al.; U.S.
Patent No. 5,405,412
to Willey et al.; U.S. Patent No. 5,405,413 to Willey et al.; U.S. Patent No.
5,130,045 to Mitchel
et al.; and U.S. Patent No. 4,412,934 to Chung et al., and copending Patent
Application Serial No.
08/064,564, all of which are incorporated herein by reference.
The mole ratio of peroxygen source (as AvO) to bleach activator in the present
invention generally
ranges from at least 1:1, preferably from about 20:1, more preferably from
about 10:1 to about 1:1,
preferably to about 3:1.
Quaternary substituted bleach activators may also be included. The present
laundry compositions
preferably comprise a quaternary substituted bleach activator (QSBA) or a
quaternary substituted
peracid (QSP, preferably a quaternary substituted percarboxylic acid or a
quaternary substituted
peroxyimidic acid); more preferably, the former. Preferred QSBA structures are
further described
in U.S. Patent No. 5,686,015 to Willey et al.; U.S. Patent No. 5,654,421 to
Taylor et al.; U.S. Patent
No. 5,460,747 to Gosselink et al.; U.S. Patent No. 5,584,888 to Miracle et
al.; U.S. Patent No.
5,578,136 to Taylor et al.; all of which are incorporated herein by reference.
Highly preferred bleach activators useful herein are amide-substituted as
described in U.S. Patent
Nos. 5,698,504; 5,695,679; and 5,686,014, each of which are cited herein
above. Preferred
examples of such bleach activators include: (6-octanamidocaproyl)
oxybenzenesulfonate, (6-
nonanam idocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)
oxybenzenesuIfonate and
mixtures thereof.
Other useful activators are disclosed in U.S. Patent Nos. 5,698,504;
5,695,679; and 5,686,014,
each of which is cited herein above, and in U.S. Patent No. 4,966,723 to Hodge
et al. These
activators include benzoxazin-type activators, such as a C6H4 ring to which is
fused in the 1,2-
positions a moiety --C(0)0C(R1)=N-.
CA 3042081 2019-05-02
Case 15532-CA 21
Nitriles, such as acetonitri les and/or ammonium nitri les and other
quaternary nitrogen containing
nitriles, are another class of activators that are useful herein. Non-limiting
examples of such
nitrile bleach activators are described in U.S. Patent Nos. 6,133,216;
3,986,972; 6,063,750;
6,017,464; 5,958,289; 5,877,315; 5,741,437; 5,739,327; 5,004,558; and in EP
Nos. 790 244, 775
127, 1 017 773, 1 017 776; and in WO 99/14302, WO 99/14296, W096/40661, all of
which are
incorporated herein by reference.
Depending on the activator and precise application, good bleaching results can
be obtained from
bleaching systems having an in-use pH of from about 6 to about 13, and
preferably from about
9.0 to about 10.5. Typically, for example, activators with electron-
withdrawing moieties are
used for near-neutral or sub-neutral pH ranges. Alkalis and buffering agents
can be used to secure
such pH.
Acyl lactam activators, as described in U.S. Patent Nos. 5,698,504; 5,695,679
and 5,686,014, each
of which is cited herein above, are very useful herein, especially the acyl
caprolactams (see for
example WO 94-28102 A) and acyl valerolactams (see U.S. Patent No. 5,503,639
to Willey et al.
incorporated herein by reference).
(b) Organic Peroxides, especially Diacyl Peroxides - These are extensively
illustrated in Kirk
Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons,
1982 at pages 27-
90 and especially at pages 63-72, all incorporated herein by reference. Ifa
diacyl peroxide is used,
it will preferably be one which exerts minimal adverse impact on fabric care,
including color care.
(c) Metal-Containing Bleach Catalysts - The compositions and methods of the
present invention
can also optionally include metal-containing bleach catalysts, preferably
manganese and cobalt-
containing bleach catalysts.
One type of metal-containing bleach catalyst is a catalyst system comprising a
transition metal
cation of defined bleach catalytic activity (such as copper, iron, titanium,
ruthenium tungsten,
molybdenum, or manganese cations), an auxiliary metal cation having little or
no bleach catalytic
activity (such as zinc or aluminum cations), and a sequestrate having defined
stability constants
for the catalytic and auxiliary metal cations, particularly
ethylenediaminetetraacetic acid,
ethylenediaminetetra (methylenephosphonic acid) and water-soluble salts
thereof. Such catalysts
are disclosed in U.S. Patent No. 4,430,243 to Bragg.
CA 3042081 2019-05-02
Case 15532-CA 22
Manganese Metal Complexes - If desired, the compositions herein can be
catalyzed by means of a
manganese compound. Such compounds and levels of use are well known in the art
and include,
for example, the manganese-based catalysts disclosed in U.S. Patent Nos.
5,576,282; 5,246,621;
5,244,594; 5,194,416; and 5,114,606; and European Pat. App. Pub. Nos. 549,271
Al; 549,272 Al;
544,440 A2; and 544,490 Al. Preferred examples of these catalysts include
MnIV2(u-0)3(1,4,7-
trimethy1-1,4,7-triazacyclononane)2(PF6)2,
mnIII2(u-0)1(u-OAc)2(1,4,7-trimethy1-1,4,7-
triazacyclononane)2(C104)2, MniV4(u-0)6(1,4,7-triazacyclononane)4(C104)4,
0)1(u-OAc)2_(1,4,7-trimethy1-1,4,7-triazacyclononane)2(C104)3, MnIV(1,4,7-
trimethy1-1,4,7-
triazacyclononane)- (OCH3)3(PF6), and mixtures thereof. Other metal-based
bleach catalysts
include those disclosed in U.S. Patent Nos. 4,430,243 and 5,114,611. The use
of manganese with
various complex ligands to enhance bleaching is also reported in the
following: U.S. Patent Nos.
4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161;
and 5,227,084.
Cobalt Metal Complexes - Cobalt bleach catalysts useful herein are known, and
are described, for
example, in U.S. Patent Nos. 5,597,936; 5,595,967; and 5,703,030; and M. L.
Tobe, "Base
Hydrolysis of Transition-Metal Complexes", Adv. lnorg. Bioinorg. Mech.,
(1983), 2, pages 1-94.
The most preferred cobalt catalyst useful herein are cobalt pentaamine acetate
salts having the
formula [Co(NH3)50Ac] Ty, wherein "OAc" represents an acetate moiety and "Ty"
is an anion,
and especially cobalt pentaamine acetate chloride, [Co(NH3)50Ac]C12; as well
as
[Co(NH3)50Ac](0Ac)2; [Co(NH3)50Acj(PF6)2; [Co(NH3)50A0SO4);
[Co-
(N1-13)50Ac](BF4)2; and [Co(NH3)50A0NO3)2 (herein "PAC").
These cobalt catalysts are readily prepared by known procedures, such as
taught for example in
U.S. Patent Nos. 6,302,921; 6,287,580; 6,140,294; 5,597,936; 5,595,967; and
5,703,030; in the
Tobe article and the references cited therein; and in U.S. Patent No.
4,810,410; J. Chem. Ed.
(1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic
Compounds, W.L. Jolly
(Prentice-Hall; 1970), pp. 461-3; Inorg. Chem., 18, 1497-1502 (1979); lnorg.
Chem., 21, 2881-
2885 (1982); lnorg. Chem., 18, 2023-2025 (1979); lnorg. Synthesis, 173-176
(1960); and Journal
of Physical Chemistry, 56, 22-25 ( I 952).
CA 3042081 2019-05-02
Case 15532-CA 23
Transition Metal Complexes of Macropolycyclic Rigid Ligands - Compositions
herein may also
suitably include as bleach catalyst a transition metal complex of a
macropolycyclic rigid ligand.
The amount used is a catalytically effective amount, suitably about 1 ppb or
more, for example up
to about 99.9%, more typically about 0.001 ppm or more, preferably from about
0.05 ppm to about
.. 500 ppm (wherein "ppb" denotes parts per billion by weight and "ppm"
denotes parts per million
by weight).
Transition-metal bleach catalysts of Macrocyclic Rigid Ligands which are
suitable for use in the
invention compositions can in general include known compounds where they
conform with the
definition herein, as well as, more preferably, any of a large number of novel
compounds expressly
designed for the present laundry or laundry uses, and are non-limitingly
illustrated by any of the
following:
Dichloro-5,12-dimethy1-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Diaquo-5,12-dimethy1-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)
Hexafluorophosphate
Diaquo-5,12-diethy1-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)
Hexafluorophosphate
Aquo-hydroxy-5,12-dimethy1-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(III) Hexafluorophosphate
Diaquo-5,12-dimethy1-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(11)
Tetrafluoroborate
Dichloro-5,12-dimethy1-1,5,8,12 tetraazabicyclo[6.6.2]hexadecane
Manganese(111) Hexafluorophosphate
Dichloro-5,12-diethy1-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(111)
Hexafluorophosphate
Dichloro-5,12-di-n-buty1-1,5,8,12-tetraaza bicyclo[6.6.2]hexadecane
Manganese(II)
Dichloro-5,12-dibenzyl- L5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(I1)
Dichloro-5-n-butyl-12-methy1-1,5,8,12-tetraaza-bicyclo[6.6.21hexadecane
Manganese(II)
Diehl oro-5-n-octy1-12-methy1-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane
Manganese(11)
Dichloro-5-n-butyl-12-methy1-1,5,8,12-tetraaza-bicyclo[6.6.2Thexadecane
CA 3042081 2019-05-02
Case 15532-CA 24
Manganese(I1).
As a practical matter, and not by way of limitation, the compositions and
methods herein can be
adjusted to provide on the order of at least one part per hundred million of
the active bleach catalyst
species in the composition comprising a lipophilic fluid and a bleach system,
and will preferably
provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05
ppm to about 10
ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the bleach
catalyst species in the
composition comprising a lipophilic fluid and a bleach system.
(d) Bleach Boosting Compounds - The compositions herein may comprise one or
more bleach
boosting compounds. Bleach boosting compounds provide increased bleaching
effectiveness in
lower temperature applications. The bleach boosters act in conjunction with
conventional
peroxygen bleaching sources to provide increased bleaching effectiveness. This
is normally
accomplished through in situ formation of an active oxygen transfer agent such
as a dioxirane, an
oxaziridine, or an oxaziridinium. Alternatively, preformed dioxiranes,
oxaziridines and
oxaziridiniums may be used.
Among suitable bleach boosting compounds for use in accordance with the
present invention are
cationic imines, zwitterionic imines, anionic imines and/or polyionic imines
having a net charge
of from about +3 to about -3, and mixtures thereof. These imine bleach
boosting compounds of
the present invention include those of the general structure:
R1
e
R2 N
R4
R3
[1]
where R1 - R4 may be a hydrogen or an unsubstituted or substituted radical
selected from
the group consisting of phenyl, aryl, heterocyclic ring, alkyl and cycloalkyl
radicals.
Among preferred bleach boosting compounds are zwitterionic bleach boosters,
which are
described in U.S. Patent Nos. 5,576,282 and 5,718,614. Other bleach boosting
compounds include
cationic bleach boosters described in U.S. Patent Nos. 5,360,569; 5,442,066;
5,478,357; 5,370,826;
5,482,515; 5,550,256; and WO 95/13351, WO 95/13352, and WO 95/13353.
CA 3042081 2019-05-02
Case 15532-CA 25
Peroxygen sources are well-known in the art and the peroxygen source employed
in the present
invention may comprise any of these well known sources, including peroxygen
compounds as well
as compounds, which under consumer use conditions, provide an effective amount
of peroxygen
in situ. The peroxygen source may include a hydrogen peroxide source, the in
situ formation of a
peracid anion through the reaction of a hydrogen peroxide source and a bleach
activator, preformed
peracid compounds or mixtures of suitable peroxygen sources. Of course, one of
ordinary skill in
the art will recognize that other sources of peroxygen may be employed without
departing from
the scope of the invention. The bleach boosting compounds, when present, are
preferably
.. employed in conjunction with a peroxygen source in the bleaching systems of
the present
invention.
(e) Preformed Peracids - Also suitable as bleaching agents are preformed
peracids. The preformed
peracid compound as used herein is any convenient compound which is stable and
which under
consumer use conditions provides an effective amount of peracid or peracid
anion. The preformed
peracid compound may be selected from the group consisting of percarboxylic
acids and salts,
percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric
acids and salts, and
mixtures thereof. Examples of these compounds are described in U.S. Patent No.
5,576,282 to
Miracle et al.
One class of suitable organic peroxycarboxylic acids have the general formula:
0
Y¨R¨C-0-0H
wherein R is an alkylene or substituted alkylene group containing from 1 to
about 22 carbon
atoms or a phenylene or substituted phenylene group, and Y is hydrogen,
halogen, alkyl, aryl, -
C(0)0H or -C(0)00H.
Organic peroxyacids suitable for use in the present invention can contain
either one or two peroxy
groups and can be either aliphatic or aromatic. When the organic
peroxycarboxylic acid is
aliphatic, the unsubstituted peracid has the general formula:
0
Y¨(CH2)n¨C-0-0H
CA 3042081 2019-05-02
Case 15532-CA 26
wherein Y can be, for example, H, CH3, CH2C1, C(0)0H, or C(0)00H; and n is an
integer
from 0 to 20. When the organic peroxycarboxylic acid is aromatic, the
unsubstituted peracid has
the general formula:
0
ti
Y¨C6H4¨C-0-0H
wherein Y can be, for example, hydrogen, alkyl, alkylhalogen, halogen, C(0)0H
or
C(0)0011.
Typical monoperoxy acids useful herein include alkyl and aryl peroxyacids such
as:
(i) peroxybenzoic acid and ring-substituted peroxybenzoic acid, e.g. peroxy-
a-
naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate), and o-
carboxybenzamidoperoxyhexanoic acid (sodium salt);
(ii) aliphatic, substituted aliphatic and arylalkyl monoperoxy acids, e.g.
peroxylauric
acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N,N-(3-
octylsuccinoyl)aminoperoxycaproic acid (SAPA) and N,N-
phthaloylaminoperoxycaproic
acid (PAP);
(iii) amidoperoxyacids, e.g. monononylamide of either peroxysuccinic acid
(NAPSA)
or of peroxyadipic acid (NAPAA).
Typical diperoxyacids useful herein include alkyl diperoxyacids and
aryldiperoxyacids, such as:
(i) 1,12-diperoxydodecanedioic acid;
(ii) 1,9-diperoxyazelaic acid;
(iii) diperoxybrassylic acid; diperoxysebacic acid and diperoxyisophthalic
acid;
(iv) 2-decyldiperoxybutane-1,4-dioic acid;
(v) 4,4'-sulfonylbisperoxybenzoic acid.
Such bleaching agents are disclosed in U.S. Patent Nos. 4,483,781 to Hartman
and 4,634,551 to
Burns et al.; European Patent Application 0,133,354 to Banks et al.; and U.S.
Patent No. 4,412,934
to Chung et al. Sources also include 6-nonylamino-6-oxoperoxycaproic acid as
described in U.S.
Patent No. 4,634,551 to Burns et al. Persulfate compounds such as for example
OXONE,
manufactured commercially by E.I. DuPont de Nemours of Wilmington, DE can also
be employed
as a suitable source of peroxymonosulfuric acid. PAP is disclosed in, for
example, U.S. Patent
Nos. 5,487,818; 5,310,934; 5,246,620; 5,279,757 and 5,132,431.
CA 3042081 2019-05-02
Case 15532-CA 27
(f) Photobleaches - Suitable photobleaches for use in the treating
compositions of the present
invention include, but are not limited to, the photobleaches described in U.S.
Patent Nos. 4,217,105
and 5,916,481.
(g) Enzyme Bleaching - Enzymatic systems may be used as bleaching agents. The
hydrogen
peroxide may also be present by adding an enzymatic system (i.e. an enzyme and
a substrate
therefore) which is capable of generating hydrogen peroxide at the beginning
or during the washing
and/or rinsing process. Such enzymatic systems are disclosed in EP Patent
Application 91202655.6
filed October 9, 1991.
The present invention compositions and methods may utilize alternative bleach
systems such as
ozone, chlorine dioxide and the like. Bleaching with ozone may be accomplished
by introducing
ozone-containing gas having ozone content from about 20 to about 300 g/m3 into
the solution that
is to contact the fabrics. The gas:liquid ratio in the solution should be
maintained from about 1:2.5
to about 1:6. U.S. Patent No. 5,346, 588 describes a process for the
utilization of ozone as an
alternative to conventional bleach systems and is herein incorporated by
reference.
The detergent compositions of the present invention may also include any
number of additional
optional ingredients. These include conventional laundry detergent composition
components such
as non-tinting dyes, detersive builders, enzymes, enzyme stabilizers (such as
propylene glycol,
boric acid and/or borax), suds suppressors, soil suspending agents, soil
release agents, other fabric
care benefit agents, pH adjusting agents, chelating agents, smectite clays,
solvents, hydrotropes
and phase stabilizers, structuring agents, dye transfer inhibiting agents,
opacifying agents, optical
brighteners, perfumes and coloring agents. The various optional detergent
composition ingredients,
if present in the compositions herein, should be utilized at concentrations
conventionally employed
to bring about their desired contribution to the composition or the laundering
operation.
Frequently, the total amount of such optional detergent composition
ingredients can range from
about 0.01% to about 50%, more preferably from about 0.1% to about 30%, by
weight of the
composition.
The liquid detergent compositions are in the form of an aqueous solution or
uniform dispersion or
suspension of surfactant, whitening agent, and certain optional other
ingredients, some of which
may normally be in solid form, that have been combined with the normally
liquid components of
the composition, such as the liquid alcohol ethoxylate nonionic, the aqueous
liquid carrier, and any
'Ir
CA 3042081 2019-05-02
Case 15532-CA 28
other normally liquid optional ingredients. Such a solution, dispersion or
suspension will be
acceptably phase stable and will typically have a viscosity which ranges from
about 100 to 600
cps, more preferably from about 150 to 400 cps. For purposes of this
invention, viscosity is
measured with a Brookfield LVDV-I1+ viscometer apparatus using a #21 spindle.
The liquid detergent compositions herein can be prepared by combining the
components thereof in
any convenient order and by mixing, e.g., agitating, the resulting component
combination to form
a phase stable liquid detergent composition. In a preferred process for
preparing such compositions,
a liquid matrix is formed containing at least a major proportion, and
preferably substantially all, of
the liquid components, e.g., nonionic surfactant, the non-surface active
liquid carriers and other
optional liquid components, with the liquid components being thoroughly
admixed by imparting
shear agitation to this liquid combination. For example, rapid stirring with a
mechanical stirrer
may usefully be employed. While shear agitation is maintained, substantially
all of any anionic
surfactants and the solid form ingredients can be added. Agitation of the
mixture is continued, and
if necessary, can be increased at this point to form a solution or a uniform
dispersion of insoluble
solid phase particulates within the liquid phase. After some or all of the
solid-form materials have
been added to this agitated mixture, particles of any enzyme material to be
included, e.g., enzyme
prills, are incorporated. As a variation of the composition preparation
procedure hereinbefore
described, one or more of the solid components may be added to the agitated
mixture as a solution
or slurry of particles premixed with a minor portion of one or more of the
liquid components. After
addition of all of the composition components, agitation of the mixture is
continued for a period of
time sufficient to form compositions having the requisite viscosity and phase
stability
characteristics. Frequently this will involve agitation for a period of from
about 30 to 60 minutes.
In an alternate embodiment for forming the liquid detergent compositions, the
whitening agent is
first combined with one or more liquid components to form a whitening agent
premix, and this
whitening agent premix is added to a composition formulation containing a
substantial portion, for
example more than 50% by weight, more specifically, more than 70% by weight,
and yet more
specifically, more than 90% by weight, of the balance of components of the
laundry detergent
composition. For example, in the methodology described above, both the
whitening agent premix
and the enzyme component are added at a final stage of component additions. In
a further
embodiment, the whitening agent is encapsulated prior to addition to the
detergent composition,
the encapsulated whitening agent is suspended in a structured liquid, and the
suspension is added
CA 3042081 2019-05-02
Case 15532-CA 29
to a composition formulation containing a substantial portion of the balance
of components of the
laundry detergent composition.
As noted previously, the detergent compositions may be in a solid form.
Suitable solid forms
include tablets and particulate forms, for example, granular particles or
flakes. Various techniques
for forming detergent compositions in such solid forms are well known in the
art and may be used
herein. In one embodiment, for example when the composition is in the form of
a granular particle,
the whitening agent is provided in particulate form, optionally including
additional but not all
components of the laundry detergent composition. The whitening agent
particulate is combined
with one or more additional particulates containing a balance of components of
the laundry
detergent composition. Further, the whitening agent, optionally including
additional but not all
components of the laundry detergent composition, may be provided in an
encapsulated form, and
the whitening agent encapsulate is combined with particulates containing a
substantial balance of
components of the laundry detergent composition.
The compositions of this invention, prepared as hereinbefore described, can be
used to form
aqueous washing solutions for use in the laundering of fabrics. Generally, an
effective amount of
such compositions is added to water, preferably in a conventional fabric
laundering automatic
washing machine, to form such aqueous laundering solutions. The aqueous
washing solution so
formed is then contacted, preferably under agitation, with the fabrics to be
laundered therewith.
An effective amount of the liquid detergent compositions herein added to water
to form aqueous
laundering solutions can comprise amounts sufficient to form from about 500 to
7,000 ppm of
composition in aqueous washing solution. More preferably, from about 1,000 to
3,000 ppm of the
detergent compositions herein will be provided in aqueous washing solution.
Fabric Care Compositions / Rinse Added Fabric Softening Compositions
In another specific embodiment, the whitening agents of the present invention
may be included in
a fabric care composition. The fabric care composition may be comprised of at
least one whitening
agent and a rinse added fabric softening composition ("RAFS;" also known as
rinse added fabric
conditioning compositions). Examples of typical rinse added softening
compositions can be found
in U.S. Provisional Patent Application Serial No. 60/687582 filed on October
8, 2004. The rinse
added fabric softening compositions of the present invention may comprise (a)
fabric softening
active and (b) a thiazolium dye. The rinse added fabric softening composition
may comprise from
CA 3042081 2019-05-02
Case 15532-CA 30
about 1% to about 90% by weight of the FSA, more preferably from about 5% to
about 50% by
weight of the FSA. The whitening agent may be present in the rinse added
fabric softening
composition in an amount from about 0.5 ppb to about 50 ppm, more preferably
from about 0.5
ppm to about 30 ppm.
In one embodiment of the invention, the fabric softening active (hereinafter
"FSA") is a quaternary
ammonium compound suitable for softening fabric in a rinse step. In one
embodiment, the FSA is
formed from a reaction product of a fatty acid and an aminoalcohol obtaining
mixtures of mono-,
di-, and, in one embodiment, triester compounds. In another embodiment, the
FSA comprises one
or more softener quaternary ammonium compounds such, but not limited to, as a
monoalkyquaternary ammonium compound, a diamido quaternary compound and a
diester
quaternary ammonium compound, or a combination thereof.
In one aspect of the invention, the FSA comprises a diester quaternary
ammonium (hereinafter
"DQA") compound composition. In certain embodiments of the present invention,
the DQA
compounds compositions also encompasses a description of diamido FSAs and FSAs
with mixed
amido and ester linkages as well as the aforementioned diester linkages, all
herein referred to as
DQA.
A first type of DQA ("DQA (1)") suitable as a FSA in the present CFSC includes
a compound
comprising the formula:
{R4_m - N - [(CH2)n - Y - R1]m} )(-
wherein each R substituent is either hydrogen, a short chain C1-C6, preferably
C1-C3 alkyl
or hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl,
hydroxyethyl, and the like,
poly (C2_3 alkoxy), preferably polyethoxy, group, benzyl, or mixtures thereof;
each m is 2 or 3;
each n is from 1 to about 4, preferably 2; each Y is -0-(0)C-, -C(0)-0-, -NR-
C(0)-, or -C(0)-
NR- and it is acceptable for each Y to be the same or different; the sum of
carbons in each R1,
plus one when Y is -0-(0)C- or -NR-C(0) -, is C12-C22, preferably C14-C20,
with each RI being
a hydrocarbyl, or substituted hydrocarbyl group; it is acceptable for R' to be
unsaturated or
saturated and branched or linear and preferably it is linear; it is acceptable
for each R1 to be the
same or different and preferably these are the same; and X- can be any
softener-compatible anion,
preferably, chloride, bromide, methylsulfate, ethylsulfate, sulfate,
phosphate, and nitrate, more
preferably chloride or methyl sulfate. Preferred DQA compounds are typically
made by reacting
CA 3042081 2019-05-02
Case 15532-CA 31
alkanolamines such as MDEA (methyldiethanolamine) and TEA (triethanolamine)
with fatty acids.
Some materials that typically result from such reactions include N,N-di(acyl-
oxyethyl)-N,N-
dimethylammonium chloride or N,N-di(acyl-oxyethyl)-N,N-
methylhydroxyethylammonium
methylsulfate wherein the acyl group is derived from animal fats, unsaturated,
and polyunsaturated,
fatty acids, e.g., tallow, hardended tallow, oleic acid, and/or partially
hydrogenated fatty acids,
derived from vegetable oils and/or partially hydrogenated vegetable oils, such
as, canola oil,
safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil,
rice bran oil, palm oil, etc.
Non-limiting examples of suitable fatty acids are listed in US Patent No.
5,759,990 at column 4,
lines 45-66. In one embodiment, the FSA comprises other actives in addition to
DQA (1) or DQA.
In yet another embodiment, the FSA comprises only DQA (1) or DQA and is free
or essentially
free of any other quaternary ammonium compounds or other actives. In yet
another embodiment,
the FSA comprises the precursor amine that is used to produce the DQA.
In another aspect of the invention, the FSA comprises a compound, identified
as DTTMAC
comprising the formula:
[R4_m - N(-) - Rim] A-
wherein each m is 2 or 3, each Ri is a C6-C22, preferably C14-C20, but no more
than one
being less than about C12 and then the other is at least about 16,
hydrocarbyl, or substituted
hydrocarbyl substituent, preferably C10-C20 alkyl or alkenyl (unsaturated
alkyl, including
polyunsaturated alkyl, also referred to sometimes as "alkylene"), most
preferably C12-C18 alkyl
or alkenyl, and branch or unbranched. In one embodiment, the Iodine Value (IV)
of the FSA is
from about 1 to 70; each R is 1-1 or a short chain C1-C6, preferably C1-C3
alkyl or hydroxyalkyl
group, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, and the
like, benzyl, or (R2 0)2_
4H where each R2 is a C1_6 alkylene group; and A- is a softener compatible
anion, preferably,
chloride, bromide, methylsulfate, ethylsulfate, sulfate, phosphate, or
nitrate; more preferably
chloride or methyl sulfate.
Examples of these FSAs include dialkydimethylammonium salts and
dialkylenedimethylammonium salts such as ditallowdimethylammonium and
ditallowdimethylammonium methylsulfate. Examples of commercially available
dialkylenedimethylammonium salts usable in the present invention are di-
hydrogenated tallow
CA 3042081 2019-05-02
Case 15532-CA 32
dimethyl ammonium chloride and ditallowdimethyl ammonium chloride available
from Degussa
under the trade names Adogen 442 and Adogen 470 respectively. In one
embodiment, the FSA
comprises other actives in addition to DTTMAC. In yet another embodiment, the
FSA comprises
only compounds of the DTTMAC and is free or essentially free of any other
quaternary ammonium
compounds or other actives.
In one embodiment, the FSA comprises an FSA described in U.S. Pat. Pub. No.
2004/0204337 Al,
published Oct. 14, 2004 to Corona et al., from paragraphs 30 ¨ 79. In another
embodiment, the
FSA is one described in U.S. Pat. Pub. No. 2004/0229769 Al, published Nov. 18,
2005, to Smith
et al., on paragraphs 26 ¨ 31; or U.S. Pat. No. 6,494,920, at column 1, line
51 et seq. detailing an
"esterquat" or a quaternized fatty acid triethanolamine ester salt.
In one embodiment, the FSA is chosen from at least one of the following:
ditallowoyloxyethyl
dimethyl ammonium chloride, dihydrogenated-tallowoyloxyethyl dimethyl ammonium
chloride,
ditallow dimethyl ammonium chloride, ditallowoyloxyethyl dimethyl ammonium
methyl sulfate,
dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, dihydrogenated-
tallowoyloxyethyl dimethyl ammonium chloride, or combinations thereof.
In one embodiment, the FSA may also include amide containing compound
compositions.
Examples of diamide comprising compounds may include but not limited to methyl-
bis(tallowamidoethyl)-2-hydroxyethylammonium methyl sulfate (available from
Degussa under
the trade names Varisoft 110 and Varisoft 222). An example of an amide-ester
containing
compound is N43-(stearoylamino)propy1]-N42-(stearoyloxy)ethoxy)ethyl)]-N-
methylamine.
Another specific embodiment of the invention provides for a rinse added fabric
softening
composition further comprising a cationic starch. Cationic starches are
disclosed in US
2004/0204337 Al. In one embodiment, the rinse added fabric softening
composition comprises
from about 0.1% to about 7% of cationic starch by weight of the fabric
softening composition. In
one embodiment, the cationic starch is HCP401 from National Starch.
Suitable Laundry Care Ingredients
While not essential for the purposes of the present invention, the non-
limiting list of laundry
care ingredients illustrated hereinafter are suitable for use in the laundry
care compositions and
may be desirably incorporated in certain embodiments of the invention, for
example to assist or
enhance performance, for treatment of the substrate to be cleaned, or to
modify the aesthetics of
CA 3042081 2019-05-02
Case 15532-CA 33
the composition as is the case with perfumes, colorants, dyes or the like. For
example, to obtain
other aesthetic colors in a detergent, the present dyes may be mixed with
additional dyes or
colorants, such as with a blue triphenylmethane dye. It is understood that
such ingredients are in
addition to the components that were previously listed for any particular
embodiment. The total
amount of such adjuncts may range from about 0.1% to about 50%, or even from
about 1% to
about 30%, by weight of the laundry care composition.
The precise nature of these additional components, and levels of incorporation
thereof, will
depend on the physical form of the composition and the nature of the operation
for which it is to
be used. Suitable laundry care ingredients include, but are not limited to,
polymers, for example
cationic polymers, surfactants, builders, chelating agents, dye transfer
inhibiting agents,
dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach
activators, polymeric
dispersing agents, clay soil removal/anti-redeposition agents, brighteners,
suds suppressors, dyes,
additional perfume and perfume delivery systems, structure elasticizing
agents, fabric softeners,
carriers, hydrotropes, processing aids and/or pigments. In addition to the
disclosure below, suitable
examples of such other adjuncts and levels of use are found in U.S. Patent
Nos. 5,576,282,
6,306,812 B1 and 6,326,348 B1 that are incorporated by reference.
As stated, the laundry care ingredients are not essential to Applicants'
laundry care
compositions. Thus, certain embodiments of Applicants' compositions do not
contain one or more
of the following adjuncts materials: bleach activators, surfactants, builders,
chelating agents, dye
.. transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers,
catalytic metal complexes,
polymeric dispersing agents, clay and soil removal/anti-redeposition agents,
brighteners, suds
suppressors, dyes, additional perfumes and perfume delivery systems, structure
elasticizing agents,
fabric softeners, carriers, hydrotropes, processing aids and/or pigments.
However, when one or
more adjuncts are present, such one or more adjuncts may be present as
detailed below:
Surfactants - The compositions according to the present invention can comprise
a surfactant
or surfactant system wherein the surfactant can be selected from nonionic
and/or anionic and/or
cationic surfactants and/or ampholytic and/or zwitterionic and/or semi-polar
nonionic surfactants.
The surfactant is typically present at a level of from about 0.1%, from about
1%, or even from
about 5% by weight of the cleaning compositions to about 99.9%, to about 80%,
to about 35%, or
even to about 30% by weight of the cleaning compositions.
Builders - The compositions of the present invention can comprise one or more
detergent
builders or builder systems. When present, the compositions will typically
comprise at least about
1% builder, or from about 5% or 10% to about 80%, 50%, or even 30% by weight,
of said builder.
Builders include, but are not limited to, the alkali metal, ammonium and
alkanolammonium salts
CA 3042081 2019-05-02
Case 15532-CA 34
of polyphosphates, alkali metal silicates, alkaline earth and alkali metal
carbonates, aluminosilicate
builders polycarboxylate compounds. ether hydroxypolycarboxylates, copolymers
of maleic
anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-
trisulphonic acid,
and carboxymethyl-oxysuccinic acid, the various alkali metal, ammonium and
substituted
ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid
and nitrilotriacetic
acid, as well as polycarboxylates such as mellitic acid, succinic acid,
oxydisuccinic acid,
polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic
acid, and soluble
salts thereof.
Chelating Agents - The compositions herein may also optionally contain one or
more
copper, iron and/or manganese chelating agents. If utilized, chelating agents
will generally
comprise from about 0.1% by weight of the compositions herein to about 15%, or
even from about
3.0% to about 15% by weight of the compositions herein.
Dye Transfer Inhibiting Agents - The compositions of the present invention may
also
include one or more dye transfer inhibiting agents. Suitable polymeric dye
transfer inhibiting
agents include, but are not limited to, polyvinylpyrrolidone polymers,
polyamine N-oxide
polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinyloxazolidones and
polyvinylimidazoles or mixtures thereof. When present in the compositions
herein, the dye transfer
inhibiting agents are present at levels from about 0.0001%, from about 0.01%,
from about 0.05%
by weight of the cleaning compositions to about 10%, about 2%, or even about
1% by weight of
the cleaning compositions.
Dispersants - The compositions of the present invention can also contain
dispersants.
Suitable water-soluble organic materials are the homo- or co-polymeric acids
or their salts, in
which the polycarboxylic acid may comprise at least two carboxyl radicals
separated from each
other by not more than two carbon atoms.
Enzymes - The compositions can comprise one or more detergent enzymes which
provide
cleaning performance and/or fabric care benefits. Examples of suitable enzymes
include, but are
not
limited to, hem icellulases, peroxidases, proteases, cellulases, xylanases,
lipases,
phospholipases, esterases, cut inases, pectinases,
keratanases, reductases, oxidases,
phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,
pentosanases, malanases, 13-
glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and
amylases, or mixtures
thereof. A typical combination is a cocktail of conventional applicable
enzymes like protease,
lipase, cutinase and/or cellulase in conjunction with amylase.
Enzyme Stabilizers - Enzymes for use in compositions, for example, detergents
can be
stabilized by various techniques. The enzymes employed herein can be
stabilized by the presence
CA 3042081 2019-05-02
Case 15532-CA 35
of water-soluble sources of calcium and/or magnesium ions in the finished
compositions that
provide such ions to the enzymes.
Catalytic Metal Complexes ¨ Applicants' compositions may include catalytic
metal
complexes. One type of metal-containing bleach catalyst is a catalyst system
comprising a
transition metal cation of defined bleach catalytic activity, such as copper,
iron, titanium,
ruthenium, tungsten, molybdenum, or manganese cations, an auxiliary metal
cation having little or
no bleach catalytic activity, such as zinc or aluminum cations, and a
sequestrate having defined
stability constants for the catalytic and auxiliary metal cations,
particularly
ethylenediaminetetraacetic acid, ethylenediaminetetra (methyl-enephosphonic
acid) and water-
soluble salts thereof. Such catalysts are disclosed in U.S. patent 4,430,243.
If desired, the compositions herein can be catalyzed by means of a manganese
compound.
Such compounds and levels of use are well known in the art and include, for
example, the
manganese-based catalysts disclosed in U.S. patent 5,576,282.
Cobalt bleach catalysts useful herein are known, and are described, for
example, in U.S.
patents 5,597,936 and 5,595,967. Such cobalt catalysts are readily prepared by
known procedures,
such as taught for example in U.S. patents 5,597,936, and 5,595,967.
Compositions herein may also suitably include a transition metal complex of a
macropolycyclic rigid ligand - abbreviated as "MRL". As a practical matter,
and not by way of
limitation, the compositions and cleaning processes herein can be adjusted to
provide on the order
of at least one part per hundred million of the benefit agent MRL species in
the aqueous washing
medium, and may provide from about 0.005 ppm to about 25 ppm, from about 0.05
ppm to about
10 ppm, or even from about 0.1 ppm to about 5 ppm, of the MRL in the wash
liquor.
Preferred transition-metals in the instant transition-metal bleach catalyst
include
manganese, iron and chromium. Preferred MRL's herein are a special type of
ultra-rigid ligand
that is cross-bridged such as 5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexa-
decane.
Suitable transition metal MRLs are readily prepared by known procedures, such
as taught
for example in WO 00/32601, and U.S. patent 6,225,464.
Exemplary Detergent Formulations
Table 1 provides examples of liquid detergent formulations which include at
least one whitening
agent of the present invention.
CA 3042081 2019-05-02
Case 15532-CA 36
Table 1 - Liquid Detergent Formulations Comprising the Present Whitening Agent
Ingredient la lb lc id le if 4
wt % wt % wt % wt % wt % wt %
sodium alkyl ether sulfate 14.4% 14.4% 9.2% 5.4%
linear alkylbenzene sulfonic
4.4% 4.4% 12.2% 5.7% 1.3% 22.0%
acid
alkyl ethoxylate 2.2% 2.2% 8.8% 8.1% 3.4%
18.0%
amine oxide 0.7% 0.7% 1.5%
citric acid 2.0% 2.0% 3.4% 1.9% 1.0%
1.6%
fatty acid 3.0% 3.0% 8.3% 16.0%
protease 1.0% 1.0% 0.7% 1.0% 2.5%
amylase 0.2% 0.2% 0.2% 0.3%
lipase 0.2%
borax 1.5% 1.5% 2.4% 2.9%
calcium and sodium formate 0.2% 0.2%
formic acid 1.1%
amine ethoxylate polymers 1.8% 1.8% 2.1% 3.2%
sodium polyacrylate 0.2%
sodium polyacrylate
0.6%
copolymer
DTPAI 0.1% 0.1% 0.9%
DTPMP2 0.3%
EDTA3 0.1%
fluorescent whitening agent 0.15% 0.15% 0.2% 0.12% 0.12%
0.2%
ethanol 2.5% 2.5% 1.4% 1.5%
propanediol 6.6% 6.6% 4.9% 4.0% 15.7%
sorbitol 4.0%
ethanolamine 1.5% 1.5% 0.8% 0.1% 11.0%
sodium hydroxide 3.0% 3.0% 4.9% 1.9% 1.0%
sodium cumene sulfonate 2.0%
silicone suds suppressor 0.01%
perfume 0.3% 0.3% 0.7% 0.3% 0.4%
0.6%
Whitening Agent 0.013% 0.001% 0.005% 0.003% 0.0005% 0.001%
water balance balance balance balance balance balance
100.0% 100.0% 100.0% 100.0% 100.0% 100.0%
'Ir
CA 3042081 2019-05-02
Case 15532-CA 37
diethylenetriaminepentaacetic acid, sodium salt
2 diethylenetriaminepentakismethylenephosphonic acid, sodium salt
3 ethylenediaminetetraacetic acid, sodium salt
4 a compact formula, packaged as a unitized dose in polyvinyl alcohol film
Granular Detergent Formulations
Table 2 provides examples of granular detergent formulations which include at
least one whitening
agent of the present invention.
Table 2 - Granular Detergent Formulations Comprising the
Present Whitening Agent
Ingredient 2a 2b 2c 2d 2e
wt% wt% wt% wt% wt
Na linear alkylbenzene sulfonate 3.4% 3.3% 11.0% 3.4%
3.3%
Na alkylsulfate 4.0% 4.1% 4.0%
4.1%
Na alkyl sulfate (branched) 9.4% 9.6% 9.4%
9.6%
alkyl ethoxylate 3.5%
type A zeolite 37.4% 35.4% 26.8%
37.4% 35.4%
sodium carbonate 22.3% 22.5% 35.9%
22.3% 22.5%
sodium sulfate 1.0% 18.8% 1.0%
sodium silicate 2.2%
protease 0.1% 0.2% 0.1%
0.2%
sodium polyacrylate 1.0% 1.2% 0.7% 1.0%
1.2%
carboxymethylcellulose 0.1%
PEG 600 0.5%
0.5%
PEG 4000 2.2%
2.2%
DTPA 0.7% 0.6%
0.7% 0.6%
fluorescent whitening agent 0.1% 0.1% 0.1% 0.1%
0.1%
sodium percarbonate 5.0%
5.0%
sodium nonanoyloxybenzenesulfonate 5.3%
5.3%
silicone suds suppressor 0.02% 0.02% 0.02%
0.02%
perfume 0.3% 0.3% 0.2% 0.3%
0.3%
Whitening Agent 0.004% 0.006% 0.002% 0.004%
0.02%
water and miscellaneous balance balance balance balance
balance
100.0% 100.0% 100.0% 100.0% 100.0%
Exemplary Fabric Care Compositions
Table 3 provides examples of liquid fabric care compositions which include at
least one whitening
agent of the present invention.
CA 3042081 2019-05-02
Case 15532-CA 38
Table 3 ¨ Liquid Fabric Care Compositions
Comprising the Present Whitening Agent
Ingredients 3a 3b 3c 3d
Fabric Softening Active a 13.70% 13.70% 13.70% 13.70%
Ethanol 2.14% 2.14% 2.14% 2.14%
Cationic Starch b 2.17% 2.17% 2.17% 2.17%
Perfume 1.45% 1.45% 1.45% 1.45%
Phase Stabilizing Polymer C 0.21% 0.21% 0.21% 0.21%
Calcium Chloride 0.147% 0.147% 0.147% 0.147%
DTPA d 0.007% 0.007% 0.007% 0.007%
Preservative e 5 ppm 5 ppm 5 ppm 5 ppm
Antifoam f 0.015% 0.015% 0.015% 0.015%
Whitening Agent 30 ppm 30ppm 30ppm 15 ppm
Tinopal CBS-X g 0.2 0.2 0.2 0.2
Ethoquad C/25 h 0.26 0.26 0.26 0.26
Ammonium Chloride 0.1% 0.1% 0.1% 0.1%
Hydrochloric Acid 0.012 % 0.012 % 0.012 % 0.012 %
Deionized Water Balance Balance Balance Balance
a N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride.
h Cationic starch based on common maize starch or potato starch, containing
25% to 95% amylose
and a degree of substitution of from 0.02 to 0.09, and having a viscosity
measured as Water
Fluidity having a value from 50 to 84.
c Copolymer of ethylene oxide and terephthalate having the formula described
in US 5,574,179 at
co1.15, lines 1-5, wherein each X is methyl, each n is 40, u is 4, each RI is
essentially 1,4-
phenylene moieties, each R2 is essentially ethylene, 1,2-propylene moieties,
or mixtures thereof.
d Diethylenetriaminepentaacetic acid.
e KATHON CG available from Rohm and Haas Co.
f Silicone antifoam agent available from Dow Corning Corp. under the trade
name DC2310.
g Disodium 4,4'-bis-(2-sulfostyryl) biphenyl, available from Ciba Specialty
Chemicals.
h Cocomethyl ethoxylated [15] ammonium chloride, available from Akzo Nobel.
The dimensions and values disclosed herein are not to be understood as being
strictly limited to
the exact numerical values recited. Instead, unless otherwise specified, each
such dimension is
intended to mean both the recited value and a functionally equivalent range
surrounding that value.
For example, a dimension disclosed as "40 mm" is intended to mean "about 40
mm."
Every document cited herein, including any cross referenced or related patent
or application and
any patent application or patent to which this application claims priority or
benefit thereof. is
CA 3042081 2019-05-02
Case 15532-CA 39
hereby incorporated herein by reference in its entirety unless expressly
excluded or otherwise
limited. The citation of any document is not an admission that it is prior art
with respect to any
invention disclosed or claimed herein or that it alone, or in any combination
with any other
reference or references, teaches, suggests or discloses any such invention.
Further, to the extent
that any meaning or definition of a term in this document conflicts with any
meaning or definition
of the same term in a document incorporated by reference, the meaning or
definition assigned to
that term in this document shall govern.
While particular embodiments of the present invention have been illustrated
and described, it
would be obvious to those skilled in the art that various other changes and
modifications can be
made without departing from the spirit and scope of the invention. It is
therefore intended to cover
in the appended claims all such changes and modifications that are within the
scope of this
invention.
CA 3042081 2019-05-02
