Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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LAUNDRY CARE COMPOSITION COMPRISING A WHITENING AGENT
HAVING AN AZO-THIOPHENE OR TRIPHENYLMETHANE COLORANT MOIETY
AND A POLYOXYALKYLENE MOIETY
TECHNICAL FIELD
This invention relates to novel whitening agents for cellulosic substrates.
The whitening agents
are comprised of at least two components: at least one chromophore component
and at least one
polymeric component. Suitable chromophore components generally fluoresce blue,
red, violet,
or purple color when exposed to ultraviolet light, or they may absorb light to
reflect these same
shades. The whitening agents are further characterized by having a dispersion
component value
of the Hansen Solubility Parameter of less than or equal to about 17 MPa0'5.
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 blueing 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, table
linens, etc., may be
extended.
The present invention offers advantages over US Patents No. 4,137,243,
5,039,782 and US
Patent Application Publication No. 2005/0288206 as this invention takes
advantage of
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compounds having a Hansen Solubility Parameter of less than or equal to about
17 MPa0.5 and
which 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. These compounds
function ideally as
whitening agents for cellulosic substrates and may be incorporated into
laundry detergent
formulations for use by consumers during the laundering process.
SUMMARY OF INVENTION
This invention relates to novel whitening agents for cellulosic substrates.
The whitening agents
are comprised of at least two components: at least one chromophore component
and at least one
polymeric component. Suitable chromophore components generally fluoresce blue,
red, violet,
or purple color when exposed to ultraviolet light, or they may absorb light to
reflect these same
shades. The whitening agents are further characterized by having a dispersion
component value
of the Hansen Solubility Parameter of less than or equal to about 17 MPa05.
This invention 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.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a graphical representation of dispersion component values of the
Hansen Solubility
Parameter versus CIELab b* values for various whitening agents after 1 rinse
cycle.
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.
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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 terns "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.
The test methods disclosed in the Test Methods Section of the present
application should be used
to determine the respective values of the parameters of Applicants'
inventions.
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.
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. The
chromophore
constituent is characterized in that it emits or absorbs wavelength in the
range of blue, red, violet,
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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.
Examples of suitable polymeric constituents include polyoxyalkylene chains
having multiple
repeating units. Preferably the polymeric constituents include polyoxyalkylene
chains having
from 2 to about 20 repeating units, and more preferably from 2 to about 10 or
even from about 4
to about 6 repeating units. Non-limiting examples of polyoxyalkylene chains
include ethylene
oxide, propylene oxide, glycidol oxide, butylene oxide and mixtures thereof.
The whitening agent of the present invention may be characterized by the
following structure:
H N
3C /
/
/ \ H
= N H
N
S
N R1
N
H3C R2
H
Wherein R1 and R2 can independently be selected from:
a) [(CH2CR'HO)x(CH2CR"HO)yH]
wherein R' is selected from the group consisting of H, CH3, CH2O(CH2CH2O)ZH,
and
mixtures thereof; wherein R" is selected from the group consisting of H,
CH2O(CH2CH2O)ZH, and mixtures thereof; wherein x + y < 5; wherein y > 1; and
wherein z = 0 to 5;
b) Ri = alkyl, aryl or aryl alkyl and R2 = [(CH2CR'HO)X(CH2CR"HO)yH]
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wherein R' is selected from the group consisting of H, CH3, CH2O(CH2CH2O)ZH,
and
mixtures thereof; wherein R" is selected from the group consisting of H,
CH2O(CH2CH2O)ZH, and mixtures thereof; wherein x + y < 10; wherein y > 1; and
wherein z = 0 to 5;
5 c) R1= [CH2CH2(OR3)CH2OR4] and R2 = [CH2CH2(O R3)CH2O R41
wherein R3 is selected from the group consisting of H, (CH2CH2O)ZH, and
mixtures
thereof; and wherein z = 0 to 10;
wherein R4 is selected from the group consisting of (C1-C16)alkyl , aryl
groups, and
mixtures thereof; and
d) wherein R1 and R2 can independently be selected from the amino 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 1 to 10 alkylene oxide units.
A preferred whitening agent of the present invention may be characterized by
the following
structure:
CH3
/ \ H
H
N \
S N
N[(CH2CR'HO)x(CH2CR"HO)yH]2
CH3 H
wherein R' is selected from the group consisting of H, CH3, CH2O(CH2CH2O)ZH,
and mixtures
thereof; wherein R" is selected from the group consisting of H,
CH2O(CH2CH2O)ZH, and
mixtures thereof; wherein x + y < 5; wherein y > 1; and wherein z = 0 to 5.
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Another characteristic of the whitening agent of the present invention is its
affinity for cellulosic
material. Affinity may be determined quantitatively from using the dispersion
force component
of the Hansen Solubility Parameter. The Hansen Solubility Parameter is a three
component
measuring system that includes a dispersion force component ((5d), a hydrogen
bonding
component (8h), and a polar component ((Sp). The Hansen Solubility Parameter
"s" is derived
from the fact that the total cohesive energy, which is the energy required to
break all the cohesive
bonds, is the combination of the dispersion forces (d), the molecular dipole
forces (p), and the
hydrogen bonding forces (h) according to the following equation:
82 = 5d2+6 P 2 + 6h2. (1)
Dispersion forces are weak attractive forces between non-polar molecules. The
magnitude of
these forces depends on the polarizability of the molecule, and the dispersion
Hansen Solubility
Parameter, 8d, typically increases with increasing volume (and size) of the
molecule, all other
properties being roughly equal. The parameter "8P" increases with increasing
polarity of the
molecule.
Hansen Solubility Parameters are calculated at 25 C with ChemSW's Molecular
Modeling Pro
v.6.1.9 software package which uses an unpublished proprietary algorithm that
is based on values
published in the Handbook of Solubility Parameters and Other Parameters by
Allan F.M. Barton
(CRC Press, 1983) for solvents obtained experimentally by Hansen. All values
of the Hansen
Solubility Parameter reported herein are in units of MPa0.5 (square root of
megaPascals). Hansen
originally determined the solubility parameter of solvents for polymer
solutions. While Hansen
Solubility Parameter calculation has been applied successfully to a wide range
of applications
such as solubility of biological materials, characterization of pigments,
fillers and fibers, etc., it
has not heretofore been adapted to polymeric colorants.
Thus, for the effective whitening agents of the present invention, it is
preferable that the
dispersion force component of the Hansen Solubility Parameter, 8d, is less
than or equal to about
17, and more preferably less than or equal to about 15. It may also be
desirable that the
dispersion force component of the Hansen Solubility Parameter is from about 12
to about 17, and
more preferably from about 12 to about 15.
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While the affinity of the whitening agent to the cellulosic material appears
to correlate very well
with the Hansen Solubility Dispersion Component parameter, the invention is
not limited to the
use of 8d. Other molecular descriptors, which are directly or indirectly
related to bd such as, for
example, polarizability, radius of gyration, molecular volume, and Jurs
descriptors based on
partial atomic charges mapped on solvent-accessible surface area, were also
considered.
However, the goodness of fit of the univariate correlations of the affinity
with these descriptors
was not as good as with 8d.
Without being bound by theory, it is believed that the affinity of the
whitening agents for the
cellulose substrates may be ascribed to Van der Waals forces, the attractive
forces that exist
between electrically neutral molecules in close proximity to one another. It
is also postulated that
if the cellulose substrate is comprised of porous regions, the whitening
agent, or portions thereof,
may be physically trapped in the pores of the cellulose, depending on the size
of the molecule as
compared to the diameter of the pores. This physical entrapment may provide
some level of
durability to protect the whitening agent from being easily removed form the
cellulose substrate
upon exposure to washing or rinsing.
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 substrates using a variety of
application
techniques. For application to cellulose-containing textile substrates, the
whitening agent is
preferably included as an additive in laundry detergent. Thus, application to
the cellulose-
containing 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 detergent composition comprises a surfactant
in an amount
sufficient to provide desired cleaning properties.
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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 C<sub>10-16</sub> alkyl
benzene sulfonic
acids, preferably C<sub>11-14</sub> 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., C12,
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'--O--(C2I14O)õ--SO3M 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 C10-C18
alkyl, n is from about 1 to 15, and M is sodium, potassium, ammonium,
alkylammonium, or
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alkanolammonium. In more specific embodiments, R' is a C12-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 C8-C20 fatty
alcohols. Conventional
primary alkyl sulfate surfactants have the general formula: ROSO3-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) C11-C18 alkyl
benzene sulfonates (LAS); b) C10-C20 primary, branched-chain and random alkyl
sulfates (AS);
c) C10-C18 secondary (2,3) alkyl sulfates having formulae (I) and (II):
wherein M in formulae (I)
and (II) is hydrogen or a cation which provides charge neutrality, and all M
units, whether
associated with a surfactant or adjunct ingredient, can either be a hydrogen
atom or a cation
depending upon the form isolated by the artisan or the relative pH of the
system wherein the
compound is used, with non-limiting examples of preferred cations including
sodium, potassium,
ammonium, and mixtures thereof, and x is an integer of at least about 7,
preferably at least about
9, and y is an integer of at least 8, preferably at least about 9; d) C10-C18
alkyl alkoxy sulfates
(AE<sub>xS</sub>) wherein preferably x is from 1-30; e) C10-C18 alkyl alkoxy
carboxylates preferably
comprising 1-5 ethoxy units; f) 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).
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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.
5
Suitable nonionic surfactants for use herein include the alcohol alkoxylate
nonionic surfactants.
Alcohol alkoxylates are materials which correspond to the general formula:
R'(CmH2mO)õOH
wherein R' is a C8-C16 alkyl group, m is from 2 to 4, and n ranges from about
2 to 12. Preferably
R' is an alkyl group, which may be primary or secondary, that comprises from
about 9 to 15
10 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
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 trademarks
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(EO),(PO)y(BO)ZN(O)(CH2R')2.gH2O. 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 C12_14
alkyldimethyl amine
oxide.
Non-limiting examples of nonionic surfactants include: a) C12-Cis alkyl
ethoxylates, such as,
NEODOL nonionic surfactants from Shell; b) C6-C12 alkyl phenol alkoxylates
wherein the
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alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; c) C12-
C18 alcohol and C6-
C12 alkyl phenol condensates with ethylene oxide/propylene oxide block
polymers such as
Pluronic 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.
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.
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
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cocodimethyl amidopropyl betaine, C8 to C18 (preferably C12 to C18) amine
oxides and sulfo and
hydroxy betaines, such as N-alkyl-N,N-dimethylammino-1-propane sulfonate where
the alkyl
group can be C8 to C18, preferably C10 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 ampholytic surfactants.
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.
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Detergent compositions may also contain bleaching agents. Suitable bleaching
agents include,
for example, hydrogen peroxide sources, such as those described in detail in
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
TM
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.
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
0.010, 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
CA 02673239 2011-02-03
14
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 diaminc
(TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-
chlorobenzoylcaprolactam,
benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS),
phenyl
benzoate (PhBz), decanoyloxybenzenesulphonate (C10-OBS), benzoylvalerolactam
(BZVL),
octanoyloxybenzenesulphonate (Cg-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 OB S 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 C12-OBS); 10-
undecenoyloxybenzenesulfonate
(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 et al.; 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 a].; and U.S. Patent No. 4,412,934 to Chung et al.
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.
CA 02673239 2011-02-03
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
5 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.
10 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-nonanamidocaproyl)oxybenzenesulfonate, (6-
decanamidocaproyl)
oxybenzenesulfonate 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 C6144 ring to which
is fused in the 1,2-
positions a moiety --C(O)OC(RI)=N-.
Nitriles, such as acetonitriles and/or ammonium nitriles 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.
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.
CA 02673239 2011-02-03
16
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.).
(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. If a 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.
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-O)3(I,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, MnIIh(u-O)1(u-
OAc)2(1,4,7-
trimethyl-1,4,7-triazacyclononane)2(C104)9, Mn1V4(u-O)6(1,4,7-
triazacyclononane)4(C104)4,
MnifIMntV4(u-O)1(u-OAc)2-(1,4,7-trimethyl-1,4,7-triazacyclononane)2(C104)3,
MnIV(1,4,7-
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17
trimethyl-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. Inorg. Bioinorg. Mech.,
(1983), 2, pages 1-94.
The most preferred cobalt catalyst useful herein are cobalt pentaamine acetate
salts having the
formula [Co(NH3)5OAc] Ty, wherein "OAc" represents an acetate moiety and "Ty"
is an anion,
and especially cobalt pentaamine acetate chloride, [Co(NH3)5OAc]C12; as well
as
[Co(NH3)5OAc](OAc)2; [Co(NH3)5OAc](PF6)2; [Co(NH3)5OAc](SO4); [Co-
(NH3)5OAc](BF4)2; and [Co(NH3)5OAc](NO3)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);
Inorg. Chem., 21,
2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-
176 (1960); and
Journal of Physical Chemistry, 56, 22-25 (1952).
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).
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WO 2008/087497 PCT/IB2007/050192
18
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-dimethyl-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-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2]hexadecaneManganese(II)
Hexafluorophosphate
Diaquo-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)
Hexafluorophosphate
Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(III) Hexafluorophosphate
Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2]hexadecaneManganese(II)
Tetrafluoroborate
Dichloro-5,12-dimethyl-1,5,8,12 tetraazabicyclo[6.6.2]hexadecane
Manganese(III) Hexafluorophosphate
Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo [6.6.2]hexadecaneManganese(III)
Hexafluorophosphate
Dichloro-5,12-di-n-butyl-1,5,8,12-tetraaza bicyclo[6.6.2]hexadecane
Manganese(II)
Dichloro-5,12-dibenzyl-1,5, 8,12-tetraazabicyclo
[6.6.2]hexadecaneManganese(II)
Dichloro-5-n-butyl-12-methyl-1,5, 8,12-tetraaza-bicyclo[6.6.2]hexadecane
Manganese(II)
Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane
Manganese(II)
Dichloro-5-n-butyl-12-methyl-1,5, 8,12-tetraaza-bicyclo[6.6.2]hexadecane
Manganese(II).
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
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WO 2008/087497 PCT/IB2007/050192
19
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
~p+
R2
Y N , R4
R3
[I]
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.
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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
5 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
10 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.
15 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.
20 One class of suitable organic peroxycarboxylic acids have the general
formula:
O
II
Y-R-C-O-OH
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(O)OH or -C(O)OOH.
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
11
Y-(CH2)n C-O-OH
CA 02673239 2011-02-03
21
wherein Y can be, for example, H, CH3, CH2C1, C(O)OH, or C(O)OOH; and n is an
integer from 0 to 20. When the organic peroxycarboxylic acid is aromatic, the
unsubstituted
peracid has the general formula:
IO1
Y-C6-C-O-OH
wherein Y can he, for example, hydrogen, alkyl, alkylhalogen, halogen, C(O)OH
or
C(O)OOH.
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. monononylainide 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-nonylarnino-6-
oxoperoxycaproic acid as
described in U.S. Patent No. 4,634,551 to Burns et al. Persulfate compounds
such as for example
TM
OXONE, manufactured commercially by E.I. DuPont de Nemours of Wilmington, DE
can also
CA 02673239 2011-02-03
22
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.
(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 Publication
0537381 published March 17, 1999.
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.
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.
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23
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 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-II+ 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,
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WO 2008/087497 PCT/IB2007/050192
24
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 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.
CA 02673239 2011-02-03
Fabric Care Compositions / Rinse Added Fabric Softening Compositions
In another specific embodiment, the whitening agents of the present invention
may he included in
a fabric care composition. The fabric care composition may be comprised of at
least one
5 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 WO 2006/041954 published April 20, 2006. 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
10 composition may comprise from 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.
15 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,
20 but not limited to, as a monoalkyquaternary ammonium compound, a diarnido
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
25 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 - Nf - [(CH2)n - Y - R1111} X
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26
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 -O-(O)C-, -C(O)-O-, -NR-
C(O)-, or -C(O)-
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 -O-(O)C- or -NR-C(O) -, is C12-C22, preferably C14-C20,
with each R1
being a hydrocarbyl, or substituted hydrocarbyl group; it is acceptable for R1
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 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(+) - Rlm] A-
CA 02673239 2011-02-03
27
wherein each m is 2 or 3, each R I 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 H 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 conunercially available
dialkylenedimethylammonium salts usable in the present invention are di-
hydrogenated tallow
dimethyl ammonium chloride and ditallowdimethyl ammonium chloride available
from Degussa
under the trade marks AdogenU 442 and AdogenU 470 respectively. In one
embodiment, the
FSA comprises other actives in addition to 1)TFMAC. 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 tri ethan olamine 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,
CA 02673239 2011-02-03
28
dehydrogenated-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 marks Varisoft 110 and Varisoft 222). An example of an amide-ester
containing
compound is N-[3-(stearoylamino)propyl]-N-[2-(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 the composition as is the case with perfumes,
colorants, dyes or the like.
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 removallanti-redeposition agents, brighteners,
suds suppressors, dyes,
additional perfume and perfume delivery systems, structure elasticizing
agents, fabric softeners,
CA 02673239 2011-02-03
29
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 BI and 6,326,348 B1.
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 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
ethylenedianiine
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
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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, hemicellulases, peroxidases, proteases, cellulases, xylanases,
lipases,
phospholipases, esterases, cutinases, pectinases, keratanases, reductases,
oxidases,
phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,
pentosanases, malanases, B-
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 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
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31
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.
Examples
'The following examples are provided to further illustrate the novel whitening
agents of the
present invention; however, the scope of the claims should not be limited by
the preferred
_5 embodiments set forth but should be given the broadest interpretation
consistent with the
description as a whole. All parts and percents given in these examples are by
weight unless
otherwise indicated. All values of the Hansen Solubility Parameter reported
herein are in
units of MPa05.
Sample Preparation and Test Methods
A. Sample Preparation
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32
Each sample is prepared by adding 0.5 grains of whitening agent (0.1% based on
weight of the
cellulosic substrate) to a solution containing 3 grams of powdered laundry
detergent (AATCC
powder laundry detergent) and 500mL of room temperature water. Each colorant
loading is
corrected for absorbance to assure equal amount of color units. The
formulation is then
combined with 50 grams of cellulose powder (available from Aldrich) and the
mixture is agitated
for 10 minutes. The mixture is then filtered to separate the cellulose
particles from the liquid,
and the cellulose particles are allowed to air dry. Both the cellulose
particles and the liquid are
measured for color using a Gretag Macbeth Color Eye 7000A spectrophotometer,
as described
previously.
The cellulose particles are then placed in a container containing 500 mL of
tap water and agitated
for 10 minutes. The mixture is filtered to separate the cellulose particles
from the liquid, and the
cellulose particles are again allowed to air dry. Both the cellulose particles
and the liquid are
TM
again measured for color using the Gretag Macbeth Color Eye 7000A
spectrophotometer. A
Control Sample is also prepared that contained untreated cellulose particles
(no whitening agent
added).
The whitening agents shown in Tables IA and lB are prepared as described
herein and tested for
various parameters. All violet colorants are synthesized according to the
procedure disclosed in
US Patent No. 4,912,203 to Kluger et al. Note also that ethylene oxide,
propylene oxide and
butylenes oxide are shown below by their typical designation of "EO," "PO" and
"B0,"
respectively. The average length and composition of the polymeric components
of the whitening
agents in fables IA and lB is obtained from the formula: (Block 1 + Block 2 +
Block
3)/(number of chains). For example, the average structure for Violet
thiophene_5E0 consists of
a thiophene chromophore with 2 chains on the nitrogen, one equal to 3E0 and
one equal to 2E0.
Chain caps are present on all polymeric components.
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Table 1A - Identification of Inventive Whitening Agents
Example Sample Bloc # of
No. Identification Block 1 Block 2 k 3 Chain Chain caps
s
Example 1 Violet 3 EO - - 2 OH
thiophene_3EO
Example 2 Violet 5 EO - - 2 OH
thiophene_5EO
Example 3 Violet
thiophene_10EO 10 EO 2 OH
Example 4 Violet
thiophene_2EO_6PO 2 EO 6 PO 2 OH
Example 5 Violet
thiophene_5EO_5PO 5 EO 5 PO 2 OH
Violet
Example 6 thiophene_2EO_13P 2 EO 13 PO - 2 OH
0
Violet thiophene
Example 7 2EO 14PO 8EO 2 EO 14 PO 8 EO 2 OH
Violet
Example 8 thiophene_10EO_14P 10 EO 14 PO - 2 OH
0
Violet
Example 9 thiophene_10EO_8B 10 EO 8 BO - 2 OH
0
Violet
thiophene_5E0_OO0 COCHZCHRCOO
Example 10 5 EO - 2 H
H2CHROOOH_RC8H
R=C8H17
17
Violet
Example 11 thiophene_5EO_OOO 5EO - - 2 COCH3
H3
Example 12 Violet (CH2CHOH - 2 OH
thiophene glycidol CH2OH)2
Violet (CH2CHOH
Example 13 thiophene_glycidol_5 5 EO - 2 OH
EO (a) CH2O-)2
[CH2CHOH
Example 14 thiophene Violet CH2N+(CH3 - - 2 -N+(CH3)3
)3]2
Example 15 Triphenylmethane (10 EO)2 - - 4 OH
11 _lOEO
Example 16 Triphenylmethane (30 EO)2 - - 4 OH
30EO
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Example 17 Triphenylmethane_2 (2EO)2 (2 PO)2 - 4 OH
EO_2PO
(a) EO groups are added to the terminal OH group.
Table 1B - Identification of Inventive Whitening Agents
Example Sample Alky/ar Block Block # of Chain
No. Identification yl Block 1 2 3 Chain caps
Thiophene Violet
Example (CH2CHOHCH
18 N-Ethyl, N- CH2CH3 20H) 2 OH
glycidyl
Example Thiophene Violet CH2CH3 5EO 1 OH
19 N-Ethyl, 5EO
(CH2CH(O-
Example Violet thiophene )CH2OC(CH3)3)
20 N,N-Bisglycidyl - 2 5EO - 2 OH
t-butyl ether 5 EO
Violet thiophene (CH2CH(O
Example N,N-Bisglycidyl )CH2OC9 13 SEO 2 OH
21 do/tetradecyl
ether 5 ethoxylate Hi8 26CH3)2
Violet thiophene
N,N-Bisglycidyl (CH2CH(O-
Example 22 isopropyl ether 5 )CH2OCH(C2H6 - - 2 OH
ethoxylate ))2
Violet thiophene (CH2CH(O-
Example N,N-Bisglycidyl _ )CH2OCH2CH2 - - 2 OH
23 n-butyl ether 5 CH2
ethoxylated CH3)2
Example Violet thiophene CH2C6H
N-Benzyl, 5- 5EO - - 1 OH
24 Ethoxylate 5
Violet thiophene
Example N-Ethyl, N-t- CH2CH3 CH2CH(O- 5EO 1 OH
25 butyl-glycidyl )CH2OC(CH3)3
ether 5 ethoxylate
(a) EO groups are added to the terminal OH group.
B. Calculation of Whiteness: CIELab b* and Ganz and CIE Whiteness Index
Whiteness Index ("WP") is a qualifying assessment of color that is calculated
by a formula which
includes three components of color measurement - hue, saturation, and
lightness - which is then
indexed to a standard white value. Several whiteness formulas can be used to
measure whiteness
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on cellulose based substrates. Two common formulas are the Ganz Whiteness
Index and CIE
Whiteness. Ganz Whiteness Index is expressed by the formula: WI = (D*Y) +
(P*x) + (Q*y) +
C, where Y, x and y are colorimetric values and D, P, Q and C are formula
parameters. CIE
Whiteness is expressed by the formula: WI = Y- (800*x) - (1700*y) + 813.7,
where Y, x and y
5 are colorimetric values. Further information is available in the publication
of Rolf Griesser,
Ciba-Geigy Ltd, "Whiteness and Tint", June 1993.
The surface color of an article may be quantified using a series of
measurements - L*, a*, and b*
- generated by measuring the samples using a spectrophotometer. The equipment
used for this
10 test is a Gretag Macbeth Color Eye 7000A spectrophotometer. The software
program used is
"Color imatch." "L" is a measure of the amount of white or black in a sample;
higher "L" values
indicate a lighter colored sample. A measure of the amount of red or green in
a sample is
determined by "a*" values. A measure of the amount of blue or yellow in a
sample is determined
by "b*" values; lower (more negative) b* values indicate more blue on a
sample.
Yet another measurement of the relative color of a substrate is DE CMC. DE CMC
is a measure
of the overall color difference for all uniform color spaces, where DE CMC
represents the
magnitude of difference between a color and a reference (in this case, a pure
white standard).
The higher the DE CMC value, the more pronounced the difference in color. In
other words,
smaller DE CMC values represent colors that are closer to white. The Gretag
Macbeth Color
Eye 7000A Spectrophotometer calculates DE CMC values based on wavelength and
reflectance
data for each sample.
C. Calculation of Molecular Properties
The average structure of each inventive whitening agent is drawn with Material
Studio molecular
modeling software (available from Accelrys, Inc.). Each structure's geometry
is optimized by
minimizing its energy with the Forcite module using the semi-empirical
Universal forcefield and
the Qeq charge assignment system. The N=N bond of the diazo colorants are
calculated at
-1.270-1.275 Angstroms compared to the average N=N bond distance of 1.25
Angstroms. These
values are slightly shorter that those reported by Liu Jun-na et al., i.e., -
1.3 angstroms, which are
calculated for diphenyl diazo dyes with Gaussian 98 software package and the
B3LYP/6-311G
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method (Liu Jun-na, Chen Zhi-rong, and Yuan Shen-feng, Journal of Zhejiang
University
Science, 6B(6), 2005, pp. 584-589).
After the geometry optimization of all structures, a variety of descriptors
are calculated.
Descriptors can be categorized in the following categories: 1. Structural, 2.
Functional, 3.
Energetic, 4. Topological, 5. Spatial, and 6. Thermodynamic.
All descriptors are calculated with the QSAR module of Material Studio
software, except for the
total number of EO groups and PO groups on the chromophore, the Hansen
solubility parameter
(Solubility-parameter), and the Hydrophile-Lipophile Balance number (MW_HLB).
The latter
two parameters are calculated with ChemSW's Molecular Modeling Pro software.
Descriptors
are screened as potential predictors of affinity of the whitening agent to the
cellulosic substrate.
Table 2 summarizes some of the test parameters that are used to characterize
the whitening
agents of the present invention.
Table 2 - Summary of Test Parameters
Descriptor Symbol Test Name Definition
s2 = S2dispersion + S2 polar + S 2
H-bonding
Hansen Solubility Hansen total (Hildebrand) sum of solubility components for
dispersion,
parameter, 6 solubility polarity, and hydrogen bonding forces,
respectively
FPSA1 Fractional Positive Sum of the solvent-accessible surface area of
(Jurs descriptor) Surface Area all positively-charged atoms divided by total
molecular solvent-accessible surface area
RPSA Relative Polar Surface Total polar surface area divided by total
(Jurs descriptor) Area molecular solvent-accessible surface area
Parameter characterizing (Emi rig / Emi ) 0 5 , where mi = mass of
Radius of Gyration the size of any shape element i, ri = distance of element
from center
of mass
Magnitude of dipole
Dipole Moment moment from spatial Eq; r; , where qi = partial atomic charge,
r; _
Magnitude distance
descriptor set
relative tendency of the electron cloud of a
Polarizability Sum of atomic molecule to be distorted from its normal
polarizabilities shape by the presence of a nearby ion or
dipole
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Test Results
Test 1: Whiteness Test As Determined by CIELab b* Values
and the Ganz Whiteness Index
Examples 1 through 17 are tested for whiteness to determine CIELab b* values
and Ganz
Whiteness Index ("Ganz WI") values. Test results are provided in Table 3.
Lower (more
negative) CIELab b* values and higher positive Ganz WI values indicate that
more blueing, or
whitening effect, is exhibited by the treated cellulose particles.
Table 3 - Test Results For Whiteness as Determined by
CIELab b* Values and the Ganz Whiteness Index
Sample CIELab b* Ganz Whiteness
Color Value Index Value
Post Rinse 1 Post Rinse 1
Control 2.66 54.34
Example 1 -7.57 144.11
Example 2 -9.28 162.21
Example 3 -5.34 118.09
Example 4 -6.58 135.30
Example 5 -4.12 107.80
Example 6 -3.49 102.93
Example 7 -4.57 113.82
Example 8 -3.19 101.29
Example 9 -3.58 102.75
Example 10 -5.76 127.03
Example 11 -4.48 112.85
Example 12 -9.37 162.00
Example 13 -5.94 126.34
Example 14 -5.36 119.92
Example 15 -5.46 125.44
Example 16 -3.69 107.50
Example 17 -6.51 135.99
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The test results indicate that Example 2, which contained 5 ethylene oxide
repeating units, and
Example 12, which contained a glycidol unit, performed the best under these
test conditions. The
data reveals a relatively linear correlation between CIELab b* color values
and the Ganz WI
values. A linear regression fit for all of the data points has a regression
value of R2 = 0.988.
Test 2: Measurement of CIELab b* Values
and the Dispersion Component Values of Hansen Solubility Parameter
Examples 1 through 17 are tested to determine CIELab b* values and the
dispersion component
values of the Hansen Solubility Parameter. Note that Examples 1 through 14
contain a violet
thiophene chromophore, while Examples 15 through 17 contain triphenylmethane
colorants.
Examples 18 through 25 are tested to determine the dispersion component value
of the Hansen
Solubility Parameter only.
Test results are provided in Table 4. Larger negative CIELab b* values
indicate that more
blueing, or whitening effect, is exhibited by the treated cellulose particles.
"N/A" indicates that
data are not available.
Table 4 - Measured CIELab b* Values and Dispersion Component Values of
Hansen Solubility Parameter
Dispersion Component
Sample CIELab b* Value of Hansen
Color Value Solubility Parameter
(MPa 's)
Post Rinse 1 Post Rinse 1
Control 2.66 25.4
Example 1 -7.57 14.9
Example 2 -9.28 14.8
Example 3 -5.34 16.6
Example 4 -6.58 17.9
Example 5 -4.12 18.4
Example 6 -3.49 18.5
Example 7 -4.57 18.2
Example 8 -3.19 19.1
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Example 9 -3.58 18.6
Example 10 -5.76 18.5
Example 11 -4.48 19.6
Example 12 -9.37 14.1
Example 13 -5.94 12.7
Example 14 -5.36 16.8
Example 15 -5.46 16.8
Example 16 -3.69 19.5
Example 17 -6.51 18.5
Example 18 N/A 16.3
Example 19 N/A 16.7
Example 20 N/A 15.8
Example 21 N/A 16.6
Example 22 N/A 16.0
Example 23 N/A 16.2
Example 24 N/A 17.0
Example 25 N/A 16.4
The test results reveal a relatively linear correlation between the blueing
parameter, CIELab b*,
and the dispersion component value of the Hansen Solubility Parameter. The
color value b*
decreases (i.e. blueing performance increases) linearly as 6d decreases.
A linear regression fit for all of the data points and has a regression value
of R2 = 0.763. The
regression line has the following equation:
b_blueing = 0.9704 * 6d - 22.468 (2)
Test 3: Prediction of CIELab b* Values
Based on the Dispersion Component Values of Hansen Solubility Parameter
Examples 1 - 10 and 15 - 17 are first used to train a model based on the
dispersion component
value of the Hansen Solubility Parameter. The CIELab b* value is calculated
for these Examples
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using Equation 3, as shown below, which utilizes the dispersion component
value obtained after
1 rinse cycle:
b_blueing = 1.0014* 6d - 23.02 (3)
5
This equation is very similar to Equation 2, which is derived using all of the
Examples. The
model represented by Equation 3 is validated with test compounds in Examples
11 - 14.
Equation 3 is used to generate predictions for the CIELab b* value of
molecules in Examples 11
- 14 (test molecules) before these molecules are synthesized and tested for
whitening efficiency.
10 The predicted CIELab b* values obtained from Equation 3 are compared to the
measured values
previously obtained from the Gretag Macbeth Color Eye 7000A spectrophotometer.
The percent
difference between measured b* color values and predicted b* color values is
also determined.
Dispersion component values and predicted CIELab b* values are also determined
for
15 Comparative Examples 1 and 2. Comparative Example 1 is a blue polymeric
anthraquinone dye
disclosed in Example III of USPN 4,127,243 to Farmer. Comparative Example 2 is
Basic Violet
3, as disclosed in Table 2 of US Patent Application Publication No.
2005/0288206 to Sadlowski
et al.
20 Test results are provided in Table 5 and Figure 1. "N/A" indicates that
data are not available.
Table 5 - Predicted CIELab b* Values Based on Dispersion Component Values of
Hansen Solubility Parameter After Post Rinse 1
Dispersion Measured Difference Between
Component Value of Predicted Predicted and
Example No. Hansen Solubility CIELab b* CIValu b Measured CIELab
Parameter Value Value b* Values (%)
(MPa 's)
Control 25.4 N/A 2.66 N/A
Example 1 14.9 -8.1 -7.57 6.6
Example 2 14.8 -8.2 -9.28 -13.2
Example 3 16.6 -6.4 -5.34 17.0
Example 4 17.9 -5.1 -6.58 -29.9
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Example 5 18.4 -4.6 -4.12 10.6
Example 6 18.5 -4.5 -3.49 22.2
Example 7 18.2 -4.8 -4.57 5.0
Example 8 19.1 -3.8 -3.19 16.4
Example 9 18.6 -4.4 -3.58 19.3
Example 10 18.5 -4.5 -5.76 -27.6
Example 11 19.6 -4.3 -4.48 -3.8
Example 12 14.1 -8.9 -9.37 -4.9
Example 13 12.7 -8.7 -8.25 5.2
Example 14 16.8 -6.2 -5.32 14.4
Example 15 16.8 -6.2 -5.46 12.3
Example 16 19.5 -3.5 -3.69 -4.7
Example 17 18.5 -4.4 -6.51 -46.4
Comparative 21.3
-1.7 N/A N/A
Example 1
Comparative 19.5
-3.5 N/A N/A
Example 2
Example 11 (Violet thiophene_5EO_OOCH3) and Example 12 (Violet
thiophene_glycidol) are
synthesized and tested to verify that the model can explain the effects of the
functionality of the
polymeric chain end caps. Example 12 has four hydroxyl groups, while whitening
agents with
EO or PO end groups have only 2 hydroxyl groups. Example 11 has roughly the
same size as
Example 12, but the acetate caps are less polar than the OH groups.
Figure 1 provides a graphical representation of the data. The phrase "violet
thiophene" is shown
as "violet" and "triphenylmethane" is shown as "TPM" on Figure 1. The data
points represent
the measured CIELab b* color values. The solid line represents Equation 3,
which is the
predicted data. The linear correlation between color value b* and 6d suggests
that the smaller the
molecule the stronger the deposition on the cellulose powder. The size of the
whitening agent
compound may influence its ability to access and diffuse into the pores of the
cellulose powder.
In addition, whitening agents having a more polar cap on the chains of the
molecule, or those
whitening agents having a greater number of polar end groups, exhibited
greater blueing efficacy.
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The calculations also show that triphenylmethane-containing whitening agents
are preferred
whitening agents.
Exemplary Detergent Formulations
Formulations la - 11: Liquid Detergent Formulations
Tables 6A and 6B provide examples of liquid detergent formulations which
include at least one
whitening agent of the present invention. The formulations are shown in Table
6A as
Formulations 1 a through 1f and in Table 6B as Formulations 1 g through 11.
Table 6A - Liquid Detergent Formulations Comp ising the Inventive Whitenin A
ent
Ingredient la lb 1c 1d le If
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
DTPA' 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%
Example 15 table 1 0.001% 0.0005%
Example 2 table 1 0.013% 0.005% 0.003% 0.001%
water balance balance balance balance balance balance
100.0% 100.0% 100.0% 100.0% 100.0% 100.0%
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Table 6B - Liquid Detergent Formulations Comprising the
Inventive Whitening Agent
Ingredient 1 1h 1i 1' 1k 11
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% 1.7%
Amylase 0.2% 0.2% 0.2% 0.6%
Lipase 0.2% 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
DTPA' 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%
Example 15 table 1 0.01% 0.005%
Example 2 table 1 0.01% 0.02% 0.003% 0.012%
opacifier9 0.5%
Water balance balance balance balance balance balance
100.0% 100.0% 100.0% 100.0% 100.0% 100.0%
Footnotes for Formulations la-1:
1 diethylenetriaminepentaacetic acid, sodium salt
2 diethylenetriaminepentakismethylenephosphonic acid, sodium salt
3 ethylenediaminetetraacetic acid, sodium salt
4 a non-tinting dyes used to adjust formula color
5 compact formula, packaged as a unitized dose in polyvinyl alcohol film
6 alkoxylated anthraquinone colorant with hueing efficiency >10 and wash
removability 30-85%
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7 alkoxylated thiophene colorant with hueing efficiency >10 and wash
removability 30-85%
9 alkoxylated triphenylmethane colorant with hueing efficiency >10 and wash
removability 30-
85% TM
9 Acusol OP301
Formulations 2a - 2e: Granular Detergent Formulations
Table 7 provides examples of granular detergent formulations which include at
least one
whitening agent of the present invention. The formulations are shown in Table
7 as Formulations
2a through 2e.
Table 7 - Granular Detergent Formulations Comprising the
Inventive 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/o 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%
Example 15 table 1 0.004% 0.02%
Example 2 table 1 0.006% 0.002% 0.004%
water and miscellaneous balance balance balance balance balance
100.0% 100.0% 100.0% 100.0% 100.0%
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Exemplary Fabric Care Compositions
Formulations 3a - 3d: Liquid Fabric Care Compositions
Table 8 provides examples of liquid fabric care compositions which include at
least one
5 whitening agent of the present invention. The compositions are shown in
Table 8 as
Formulations 3a through 3d.
Table 8 - Liquid Fabric Care Compositions
Comprising the Inventive 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%
erfume 1.45% 1.45% 1.45% 1.45%
Phase Stabilizing Polymer' 0.21% 0.21% 0.21% 0.21%
Calcium Chloride 0.147% 0.147% 0.147% 0.147%
TPA d 0.007%, 0.007% 0.007% 0.007%
Preservative 5 ppm 5 ppm 5 ppm 5 ppm
Antifoam f 0.015% 0.015% 0.015% 0.015%
Example I of Table 1 30 ppm 15 ppm
Example 2 of Table 1 30 ppm
Example 3 of Table 1 30 ppm 15 ppm
TinopalTM CBS-XI 0.2 0.2 0.2 0.2
EthoquadTM C/25b 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 %
eionized Water Balance Balance Balance Balance
a N,N-di(tallowoyloxyethyl)-N,N-dimethylanunonium chloride.
b 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
col.15, lines 1-5, wherein each X is methyl, each n is 40, u is 4, each R1 is
essentially 1,4-
phenylene moieties, each R2 is essentially ethylene, 1,2-propylene moieties,
or mixtures
thereof.
d Diethylenetriaminepentaacetic acid.
KATHON CG available from Rohm and Haas Co.
f Silicone antifoam agent available from Dow Corning Corp. under the trade
name DC2310.
Disodium 4,4'-bis-(2-sulfostyryl) biphenyl, available from Ciba Specialty
Chemicals.
h Cocomethyl ethoxylated [15] ammonium chloride, available from Akzo Nobel.
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Accordingly, the present invention provides a whitening agent for cellulosic
substrates
comprising at least one chromophore component that comprises a thiophene or
triphenylmethane
colorant and at least one polymeric component; wherein the whitening agent
possesses a
dispersion component value of the Hansen Solubility Parameter of less than or
equal to about 17
MPa0-5. A laundry detergent containing such a whitening agent is also
contemplated herein.
The whitening agent of the present invention includes a whitening agent for
cellulosic substrates
comprising at least one chromophore component that comprises a thiophene
colorant and at least
one polymeric component wherein the whitening agent is characterized by the
following
structure:
H N
3C /
/
/ \ H
= N H
N
S
N R1
N
H3C R2
H
Wherein R1 and R2 can independently be selected from:
a) [(CH2CR'HO),,(CH2CR"HO)yH]
wherein R' is selected from the group consisting of H, CH3, CH2O(CH2CH2O)ZH,
and
mixtures thereof; wherein R" is selected from the group consisting of H,
CH2O(CH2CH2O)ZH, and mixtures thereof; wherein x + y < 5; wherein y > 1; and
wherein z = 0 to 5;
b) Ri = alkyl, aryl or aryl alkyl and R2 = [(CH2CR'HO)x(CH2CR"HO)yH]
wherein R' is selected from the group consisting of H, CH3, CH2O(CH2CH2O)ZH,
and
mixtures thereof; wherein R" is selected from the group consisting of H,
CH2O(CH2CH2O)ZH, and mixtures thereof; wherein x + y < 10; wherein y > 1; and
wherein z = 0 to 5;
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c) R1= [CH2CH2(OR3)CH2OR4] and R2 = [CH2CH2(O R3)CH2O R41
wherein R3 is selected from the group consisting of H, (CH2CH2O)ZH, and
mixtures
thereof; and wherein z = 0 to 10;
wherein R4 is selected from the group consisting of (C1-C16)alkyl , aryl
groups, and
mixtures thereof; and
d) wherein R1 and R2 can independently be selected from the amino 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 1 to 10 alkylene oxide units.
A potentially preferred whitening agent of the present invention includes a
whitening agent for
cellulosic substrates comprising at least one chromophore component that
comprises a thiophene
colorant and at least one polymeric component wherein the whitening agent is
characterized by
the following structure:
CH3
/ \ H
N N H
S N
N[(CH2CR'HO)x(CH2CR"HO)yH]2
CH3 H
wherein R' is selected from the group consisting of H, CH3, CH2O(CH2CH2O)ZH,
and mixtures
thereof; wherein R" is selected from the group consisting of H,
CH2O(CH2CH2O)ZH, and
mixtures thereof; wherein x + y < 5; wherein y > 1; and wherein z = 0 to 5.
Additionally, the present invention provides a whitening agent characterized
by a CIELab b*
color value ("b") and a dispersion component value of the Hansen Solubility
Parameter ("8d"),
wherein "b" and " 8d" exhibit an approximately linear correlation with each
other according to the
CA 02673239 2011-09-28
48
following equation: b = 1.00(8d) - 23. A laundry detergent containing such a
whitening agent is
also contemplated herein.
Thus, it is believed to be an advantage of the present invention to employ the
predictive model to
aid in the selection of chromophore-containing compounds ideally suited as
whitening agents.
Test results provided herein tend to indicate that deposition of the whitening
agent on the
cellulose powder may be controlled, at least in part, by the size of the
whitening agent compound
and by its chain cap functionality. Test results also suggest that larger
molecules may be too
bulky to diffuse into the pores of the cellulose powder which may decrease the
whitening effect
after multiple washing and/or rinsing cycles.
