U.S. patent application number 14/946822 was filed with the patent office on 2016-03-17 for laundry care compositions containing dyes.
The applicant listed for this patent is The Procter & Gamble Company. Invention is credited to Gregory Scot MIRACLE, Eduardo TORRES.
Application Number | 20160075977 14/946822 |
Document ID | / |
Family ID | 48048256 |
Filed Date | 2016-03-17 |
United States Patent
Application |
20160075977 |
Kind Code |
A1 |
MIRACLE; Gregory Scot ; et
al. |
March 17, 2016 |
LAUNDRY CARE COMPOSITIONS CONTAINING DYES
Abstract
This application relates to laundry care compositions comprising
carboxylate fabric shading dyes and methods of treating a textile
comprising such laundry care compositions.
Inventors: |
MIRACLE; Gregory Scot;
(Liberty Township, OH) ; TORRES; Eduardo; (Boiling
Springs, SC) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Procter & Gamble Company |
Cincinnati |
OH |
US |
|
|
Family ID: |
48048256 |
Appl. No.: |
14/946822 |
Filed: |
November 20, 2015 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
14489772 |
Sep 18, 2014 |
|
|
|
14946822 |
|
|
|
|
PCT/US2013/032953 |
Mar 19, 2013 |
|
|
|
14489772 |
|
|
|
|
61612539 |
Mar 19, 2012 |
|
|
|
Current U.S.
Class: |
8/137 ; 510/296;
510/320; 510/324 |
Current CPC
Class: |
C11D 3/42 20130101; C11D
17/042 20130101; C09B 29/0809 20130101; C11D 3/505 20130101; C09B
29/0802 20130101; C11D 3/0021 20130101; C11D 11/0017 20130101; C11D
17/045 20130101; C11D 3/40 20130101; C09B 29/0003 20130101; C11D
3/38627 20130101; C09B 29/0007 20130101 |
International
Class: |
C11D 3/42 20060101
C11D003/42; C11D 3/00 20060101 C11D003/00; C09B 29/08 20060101
C09B029/08; C11D 3/50 20060101 C11D003/50; C09B 29/01 20060101
C09B029/01; C11D 17/04 20060101 C11D017/04; C11D 3/386 20060101
C11D003/386 |
Claims
1. A laundry care composition comprising from 0.00001 wt % to 0.5
wt % carboxylate dye having the structure of Formula I:
D-L-CO.sub.2M Formula I wherein D is a dye moiety selected from
benzodifuranes, methines, triphenylmethanes, naphthalimides,
pyrazoles, naphthoquinones, anthraquinones and mono- and di-azo
dyes and mixtures thereof, L is an organic linking group, and in
the sequence of bonds starting from the carbonyl carbon of the
C(O)OM group and ending at the dye moiety, any
--(C.sub.a(O)--O.sub.b)-- groups are incorporated such that the
oxygen atom O.sub.b is encountered prior to the carbonyl carbon
C.sub.a; and M is any suitable counterion.
2. A laundry care composition according to claim 1 wherein the dye
is an anthraquinone or azo dye.
3. A laundry care composition according to claim 1 wherein the dye
is an azo dye.
4. A laundry care composition according to claim 1 wherein the
compound D-H, preferably has a maximum extinction coefficient
greater than about 1000 liter/mol/cm at the .lamda..sub.max in the
wavelength range from 400 nm to 750 nm in methanol solution.
5. A laundry care composition according to claim 1 wherein the
compound D-H has a maximum extinction coefficient from about 20,000
to about 100,000 liter/mol/cm at the .lamda..sub.max in the
wavelength range of about 560 nm to about 610 nm.
6. A laundry care composition according to claim 1 wherein group L
has a molecular weight from 14 to 1000 Daltons.
7. A laundry care composition according to claim 1 wherein group L
consists essentially only of C, H and optionally additionally O
and/or N.
8. A laundry care composition according to claim 1 wherein group L
is a C.sub.1-20 alkylene chain having optionally therein ether
(--O--) and/or ester and/or amide links, the chain being optionally
substituted with --OH, --CN, --NO.sub.2, --SO.sub.2CH.sub.3, --Cl,
--Br.
9. A laundry care composition according to claim 1 comprising a
laundry care adjunct.
10. A laundry care composition according to claim 1 comprising a
laundry care adjunct wherein the laundry care adjunct comprises a
first wash lipase.
11. A laundry care composition according to claim 1 wherein the
laundry care adjunct comprises a fluorescent agent selected from:
sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-djtriazole,
disodium 4,4'-bis{[(4-anilino-6-{N methyl-N-2 hydroxyethyl) amino
1,3,5-triazin-2-yl)]amino}stilbeno-2-2' disulfonate, disodium
4,4'-bis[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)amino]stilbene-2-2'di-
sulfonate, and disodium 4,4'-bis (2-sulfostyryl) biphenyl, in an
amount of from 0.005 to 2 wt % of the laundry care composition.
12. A laundry care composition according to claim 1 wherein the
laundry care adjunct comprises a dye transfer inhibitor selected
from the group consisting of: (a) polyvinylpyrrolidone polymers; or
(b) polyamine N-oxide polymers; or (c) copolymers of
N-vinylpyrrolidone and N-vinylimidazole; or (d)
polyvinyloxazolidones; or (e) polyvinylimidazoles; or (f) mixtures
thereof.
13. A laundry care composition according to claim 1, said laundry
care composition being a unit dose pouch.
14. A laundry care composition according to claim 1 said laundry
care composition being a multi-compartment unit dose product.
15. A laundry care composition according to claim 1 comprising,
based on total laundry care composition weight, a total of no more
than 15% water and from 10% to 70% of a water-miscible organic
solvent having a molecular weight of greater than 70 Daltons.
16. A laundry care composition according to claim 1 comprising,
based on total laundry care composition weight, a perfume
microcapsule comprising a core and a shell that encapsulates said
core, said perfume microcapsule having a D[4,3] average particle of
from about 0.01 microns to about 200 microns.
17. A method of treating a textile, the method comprising the steps
of (i) treating the textile with an aqueous solution comprising a
laundry care adjunct and from 1 ppb to 500 ppm of a carboxylate
dye; and (ii) rinsing and drying the textile, the dye comprising a
dye having a structure of Formula I: D-L-CO.sub.2M Formula I
wherein D is a dye moiety selected from benzodifuranes, methines,
triphenylmethanes, naphthalimides, pyrazoles, naphthoquinones,
anthraquinones and mono- and di-azo dyes and mixtures thereof; and
L is an organic linking group having a molecular weight from 14 to
1000 Daltons, and in the sequence of bonds starting from the
carbonyl carbon of the C(O)OM group and ending at the dye moiety,
any --(C.sub.a(O)--O.sub.b)-- groups are incorporated such that the
oxygen atom O.sub.b is encountered prior to the carbonyl carbon
C.sub.a; and M is any suitable counterion.
18. A method according to claim 17 wherein the L group is a
C.sub.1-20 alkylene chain having optionally therein ether (--O--)
and/or ester and/or amide links, the chain being optionally
substituted for example with --OH, --CN, --NO.sub.2,
--SO.sub.2CH.sub.3, --Cl, --Br.
19. A method according to claim 17 wherein the aqueous solution
comprises from 0.05 to 3 g/l of a surfactant.
Description
FIELD OF INVENTION
[0001] This invention relates to laundry care compositions
comprising fabric shading dyes and methods of treatment of fabrics
using such compositions.
BACKGROUND OF THE INVENTION
[0002] 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. To counteract this
unwanted effect, laundry detergent manufacturers incorporate
shading dyes into their products. The purpose of shading dyes is
typically to counteract the fading and yellowing of the textile
substrates by providing a blue-violet hue to the laundered fabrics,
reducing the visual impact of the yellowing. There are many
disclosures of shading dyes in detergents. However, formulating
detergent compositions with shading dyes is challenging: not only
do the compositions need to provide good product appearance, they
also need to deposit the shading dyes evenly onto fabrics during
the treatment step and provide consistent hue throughout the
product life-cycle.
SUMMARY OF THE INVENTION
[0003] This invention relates to a laundry care composition
comprising from 0.00001 wt % to 0.5 wt % carboxylate dye having the
structure of Formula I:
D-L-CO.sub.2M Formula I
wherein D is a dye moiety selected from benzodifuranes, methines,
triphenylmethanes, naphthalimides, pyrazoles, naphthoquinones,
anthraquinones and mono- and di-azo dyes and mixtures thereof, azo
dyes being particularly preferred, wherein the compound D-H,
preferably has a maximum extinction coefficient greater than about
1000 liter/mol/cm at the .lamda.max in the wavelength range from
400 nm to 750 nm in methanol solution, preferably a maximum
extinction coefficient from about 20,000 to about 100,000
liter/mol/cm at the .lamda.max in the wavelength range of about 540
nm to about 630 nm, and most preferably a maximum extinction
coefficient from about 20,000 to about 65,000 liter/mol/cm at the
.lamda.max in the wavelength range of about 560 nm to about 610 nm;
and L is an organic linking group preferably having a molecular
weight from 14 to 1000 Daltons or 14 to 600 or 28 to 300,
preferably consisting essentially only of C, H and optionally
additionally O and/or N, and in the sequence of bonds starting from
the carbonyl carbon of the C(O)OM group and ending at the dye
moiety, any --(C.sub.a(O)--O.sub.b)-- groups are incorporated such
that the oxygen atom O.sub.b is encountered prior to the carbonyl
carbon C.sub.a, preferably L is a C.sub.1-20 alkylene chain having
optionally therein ether (--O--) and/or ester and/or amide links,
the chain being optionally substituted for example with --OH, --CN,
--NO.sub.2, --SO.sub.2CH.sub.3, --Cl, --Br; and M is any suitable
counterion, typically hydrogen, sodium or potassium ion.
[0004] In one aspect of the invention L may comprise formula 2:
##STR00001##
[0005] The present invention also comprises a method of treating a
textile, the method comprising the steps of (i) treating the
textile with an aqueous solution comprising a laundry care adjunct
and from 1 ppb to 500 ppm of a carboxylate dye; and (ii) rinsing
and drying the textile, the carboxylate dye comprising a dye having
a structure of Formula I above.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
[0006] As used herein, the term "alkoxy" is intended to include
C1-C8 alkoxy and alkoxy derivatives of polyols having repeating
units such as butylene oxide, glycidol oxide, ethylene oxide or
propylene oxide.
[0007] As used herein, unless otherwise specified, the terms
"alkyl" and "alkyl capped" are intended to include C1-C18 alkyl
groups, and in one aspect, C1-C6 alkyl groups.
[0008] As used herein, unless otherwise specified, the term "aryl"
is intended to include C3-C12 aryl groups.
[0009] As used herein, unless otherwise specified, the term
"arylalkyl" is intended to include C1-C18 alkyl groups and, in one
aspect, C1-C6 alkyl groups.
[0010] The terms "ethylene oxide," "propylene oxide" and "butylene
oxide" may be shown herein by their typical designation of "EO,"
"PO" and "BO," respectively.
[0011] As used herein, the term "laundry care composition"
includes, unless otherwise indicated, granular, powder, liquid,
gel, paste, unit dose, bar form and/or flake type washing agents
and/or fabric treatment compositions, including but not limited to
products for laundering fabrics, fabric softening compositions,
fabric enhancing compositions, fabric freshening compositions, and
other products for the care and maintenance of fabrics, and
combinations thereof. Such compositions may be pre-treatment
compositions for use prior to a washing step or may be rinse added
compositions, as well as cleaning auxiliaries, such as bleach
additives and/or "stain-stick" or pre-treat compositions or
substrate-laden products such as dryer added sheets.
[0012] As used herein, the term "detergent composition" is a
sub-set of laundry care composition and includes cleaning
compositions including but not limited to products for laundering
fabrics. Such compositions may be pre-treatment composition for use
prior to a washing step or may be rinse added compositions, as well
as cleaning auxiliaries, such as bleach additives and "stain-stick"
or pre-treat types.
[0013] 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.
[0014] As used herein, the term "maximum extinction coefficient" is
intended to describe the molar extinction coefficient at the
wavelength of maximum absorption (also referred to herein as the
maximum wavelength), in the range of 400 nanometers to 750
nanometers.
[0015] As used herein "average molecular weight" of the thiophene
azo carboxylate dyes is reported as an average molecular weight, as
determined by its molecular weight distribution: as a consequence
of their manufacturing process, the thiophene azo carboxylate dyes
disclosed herein may contain a distribution of repeating units in
their polymeric moiety.
[0016] 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.
[0017] As used herein, articles such as "a" and "an" when used in a
claim, are understood to mean one or more of what is claimed or
described.
[0018] As used herein, the terms "include/s" and "including" are
meant to be non-limiting.
[0019] As used herein, the term "solid" includes granular, powder,
bar and tablet product forms.
[0020] As used herein, the term "fluid" includes liquid, gel, paste
and gas product forms.
[0021] 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.
[0022] 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.
Dye
[0023] Suitable dyes are selected from the group comprising
carboxylate dyes having the structure of Formula I:
D-L-CO.sub.2M Formula I
wherein D is a dye moiety selected from benzodifuranes, methines,
triphenylmethanes, naphthalimides, pyrazoles, naphthoquinones,
anthraquinones and mono- and di-azo dyes and mixtures thereof, azo
dyes being particularly preferred, wherein the compound D-H,
preferably has a maximum extinction coefficient greater than about
1000 liter/mol/cm at the .lamda.max in the wavelength range from
400 nm to 750 nm in methanol solution, preferably a maximum
extinction coefficient from about 20,000 to about 100,000
liter/mol/cm at the .lamda.max in the wavelength range of about 540
nm to about 630 nm, and most preferably a maximum extinction
coefficient from about 20,000 to about 65,000 liter/mol/cm at the
.lamda.max in the wavelength range of about 560 nm to about 610 nm;
and L is an organic linking group preferably having a molecular
weight from 14 to 1000 Daltons or 14 to 600 or 28 to 300,
preferably consisting essentially only of C, H and optionally
additionally O and/or N, and in the sequence of bonds starting from
the carbonyl carbon of the C(O)OM group and ending at the dye
moiety, any --(C.sub.a(O)--O.sub.b)-- groups are incorporated such
that the oxygen atom O.sub.b is encountered prior to the carbonyl
carbon C.sub.a, preferably L is a C.sub.1-20 alkylene chain having
optionally therein ether (--O--) and/or ester and/or amide links,
the chain being optionally substituted for example with --OH, --CN,
--NO.sub.2, --SO.sub.2CH.sub.3, --Cl, --Br; and M is any suitable
counterion, typically hydrogen, sodium or potassium ion.
[0024] In one aspect of the invention L may comprise formula 2:
##STR00002##
As examples of L there may be mentioned ethylene, trimethylene,
tetraamethylene, hexamethylene, isopropylene, decamethylene,
hexadecamethylene and --(CH.sub.2CH.sub.2O).sub.n--CH.sub.2--,
where n is from 1 to 9.
[0025] In a preferred embodiment, the carboxylate dye comprises the
structure of Formula 3:
##STR00003##
wherein R is a C1-20, or C2-12 alkyl chain having optionally
therein ether (--O--) and/or ester and/or amide links, the chain
being optionally substituted for example with --OH, --CN,
--NO.sub.2, --SO.sub.2CH.sub.3, --Cl, --Br; R.sup.1 and R.sup.2 are
independently selected and may be hydrogen but are preferably each
independently selected from electron-withdrawing groups such as
--CN, --NO.sub.2, --SO.sub.2CH.sub.3, --Cl, --Br; Z is an
electron-withdrawing group preferably selected from cyano,
sulphamoyl, N:N-diethylsulphamoyl, N-ethylsulphamoyl,
trifluoromethyl, ethylsulphonyl, nitro, N-methylsulphamoyl, chloro,
bromo, most preferably Z is nitro; Y is hydrogen, lower (C1-4)
alkyl, halogen, --NHCOR, preferably H, CH3, --Cl; X is hydrogen,
lower (C1-4) alkoxy, and halogen, preferably H, methoxy, ethoxy and
--Cl.
[0026] As examples of lower (C.sub.1-4) alkyl and/or alkoxy (C1-4)
radicals there may be mentioned methyl, ethyl, n-propyl, and
n-butyl, ethoxy and methoxy. As examples of the optionally
substituted lower (C1-4) alkyl radicals represented by R there may
be mentioned hydroxy lower alkyl such as .beta.-hydroxyethyl, cyano
lower alkyl such as .beta.-cyanoethyl, lower alkoxy lower alkyl
such as .beta.-(methoxy- or ethoxy-)ethyl and -methoxypropyl, aryl
lower alkyl such as benzyl and .beta.-phenyl-ethyl, lower
alkoxycarbonyl lower alkyl such as .beta.-methoxycarbonylethyl, and
acyloxylower alkyls such as .beta.-acetoxyethyl.
[0027] The dye may comprise a dye of Formula 4 in which the Z, R,
X, Y and L groups are as defined above:
##STR00004##
[0028] In some aspects, dyes having carboxylic acid groups with a
pKa value below 4, or below 3, or even below 2, may be preferred as
carboxylic acid groups are well known to have potentially
deleterious interactions with multivalent metal ions such as, for
example, Ca.sup.2+, Mg.sup.2+, and Fe.sup.3+ among others, which
may be present in the wash or on fabrics. Without wishing to be
bound by theory, it is believed that dyes with carboxylic acid
groups having lower pKa values have decreased interaction with such
metal ions, leading to improved consistency in performance across
the wide range of wash conditions used by consumers.
[0029] In a preferred embodiment, the carboxylate dye comprises the
structure of Formula 5:
##STR00005##
wherein D is an aromatic or heteroaromatic group, preferably a
heteroaromatic group, even more preferably a thiophene group;
R.sub.1 is C.sub.1-C.sub.4 alkyl preferably methyl; R.sub.2 and
R.sub.3 are independently selected from the group consisting of
alkyl, alkyleneoxy, and polyalkyleneoxy moieties, preferably alkyl
and polyalkyleneoxy moieties, even more preferably at least one
R.sub.2 and R.sub.3 are polyalkyleneoxy moieties, most preferably
polyoxyethylene moieties, provided that at least one of R.sub.2 and
R.sub.3 comprises a carboxylic acid group, preferably one with a
pKa value below about 4, or even below about 3 or even below about
2.
[0030] In one aspect of the invention, the composition is in the
form of a single or multi-compartment unit dose laundry care
composition.
DYE SYNTHESIS EXAMPLES
Synthesis Example 1
##STR00006##
[0032] C.I. Disperse Violet 55 (also known as Disperse Red 65) is
converted to Dye 1 using the hydrolysis procedure disclosed in EP
2085434 A1, Example 11, followed by formation of the sodium salt
via treatment with NaH in THF (or treatment with Na2CO3 in water).
The product is isolated as the sodium salt.
Synthesis Example 2
##STR00007##
[0034] C. I. Disperse Blue 148 is converted to Dye 2 using the
hydrolysis procedure disclosed in EP 2085434 A1, Example 6. The
product is isolated as the sodium salt.
Synthesis Example 3
##STR00008##
[0036] C. I. Disperse Blue 85 is converted to Dye 3 using the
sequential alkylation and hydrolysis procedures disclosed in EP
2085434 A1, Examples 5 and 6, respectively. The product is isolated
as the sodium salt.
Synthesis Example 4
##STR00009##
[0038] C. I. Disperse Blue 106 is converted to Dye 4 using the
sequential alkylation and hydrolysis procedures disclosed in EP
2085434 A1, Examples 5 and 6, respectively. The product is isolated
as the sodium salt.
Synthesis Example 5
##STR00010##
[0040] C. I. Disperse Blue 12 is converted to Dye 5 using the
sequential alkylation and hydrolysis procedures disclosed in EP
2085434 A1, Examples 5 and 6, respectively. The product is isolated
as the sodium salt.
Synthesis Example 6
##STR00011##
[0042] C. I. Disperse Blue 13 is converted to Dye 6 using the
sequential alkylation and hydrolysis procedures disclosed in EP
2085434 A1, Examples 5 and 6, respectively. The product is isolated
as the sodium salt.
Synthesis Example 7
##STR00012##
[0044] C. I. Disperse Blue 24 is converted to Dye 7 using the
sequential alkylation and hydrolysis procedures disclosed in EP
2085434 A1, Examples 5 and 6, respectively. The product is isolated
as the sodium salt.
Synthesis Example 8
##STR00013##
[0046] Dye 8' is prepared according to the procedure disclosed in
U.S. Pat. No. 3,793,305, Example 4, except that
N-(2-cyanoethyl)-N-hexyl-m-toluidine is used in place of
N-(2-cyanoethyl)-N-ethyl-m-toluidine. Dye 8' is converted to Dye 8
according to the procedure described in Example 1 above.
Synthesis Example 9
##STR00014##
[0048] Dye 9 is prepared according to the sequence described in
Example 8, except that N-(2-cyanoethyl)-N-decyl-m-toluidine is used
in place of N-(2-cyanoethyl)-N-ethyl-m-toluidine.
Synthesis Example 10
##STR00015##
[0050] Dye 10' is prepared according to the procedure disclosed in
the Journal of the Society of Dyers and Colourists, 1984, 100(10),
316-19, except that ethyl 3-[(N-hexyl-N-phenyl)amino]propionate is
used in place of N-Ethyl-N-2-(methoxycarbonyl)ethylaniline. Dye 10
is prepared from dye 10' using the hydrolysis procedure disclosed
in EP 2085434 A1, Example 6. The product is isolated as the sodium
salt.
Synthesis Example 11
##STR00016##
[0052] Dye 11 is prepared according to Example 1 of GB 1,428,395
using 3-[(N-hexyl-N-phenyl)amino]propionic acid in place of
N-ethyl-N-(-carboxyethyl)-m-toluidine.
Synthesis Example 12
##STR00017##
[0054] Dye 12 is prepared according to Example 2 of GB 1,428,395
using 3-[(N-hexyl-N-phenyl)amino]propionic acid in place of
N-ethyl-N-(-carboxyethyl)-m-toluidine.
Synthesis Example 13
##STR00018##
[0056] Dye 13' is prepared according to the procedures described in
WO 2011/17719 A2 using
15-(3-methylphenyl)-3,6,9,12-tetraoxa-15-azatetracosan-1-ol, which
is prepared according to the procedure disclosed in WO 2011/017719
A2 for the preparation of
15-(3-methylphenyl)-3,6,9,12-tetraoxa-15-azaheptadecan-1-ol, except
that N-ethyl-m-toluidine is replaced by N-octyl-m-toluidine. Dye
13' is converted to Dye 13 using the sequential alkylation and
hydrolysis procedures disclosed in EP 2085434 A1, Examples 5 and 6,
respectively. The product is isolated as the sodium salt.
[0057] The dye may be incorporated into the composition in the form
of a mixture of reaction products formed by the organic synthesis
route used: such a reaction mixture will typically comprise a
mixture of the dyes of formula I and often, in addition, reaction
products of side reactions and/or minor amounts of unreacted
starting materials. Although it may be preferred to remove
impurities other than the dyes as defined in formula I, it may not
be necessary, so the mixture of reaction products may be used
directly in a composition according to the invention.
[0058] Typically the dye or mixture of dyes of formula I will be
present in the composition in an amount from 0.00001 to 5 wt % of
the composition, more usually in an amount from 0.0001 to 1 wt % or
to 0.5 wt % of the composition.
[0059] Where the dye is first formed into a pre-mix, for example a
particle or concentrated liquid for incorporation into the
composition, the dye may be present at a level of from 0.001 or
even 0.01 or greater, up to an amount of 2 wt %, or 10 wt % based
on the weight of the pre-mix.
[0060] The compositions of the present invention typically
comprises in addition to the dye, one or more laundry care adjunct
materials.
Laundry Care Adjunct Materials
[0061] Suitable adjuncts may be, for example to assist or enhance
cleaning performance, for treatment of the substrate to be cleaned,
for example by softening or freshening, or to modify the aesthetics
of the composition as is the case with perfumes, colorants,
non-fabric-shading dyes or the like. Suitable adjunct materials
include, but are not limited to, surfactants, builders, chelating
agents, dye transfer inhibiting agents, dispersants, enzymes, and
enzyme stabilizers, catalytic materials, bleach activators,
hydrogen peroxide, sources of hydrogen peroxide, preformed
peracids, polymeric dispersing agents, clay soil
removal/anti-redeposition agents, brighteners, suds suppressors,
dyes, hueing dyes, perfumes, perfume delivery systems, structure
elasticizing agents, fabric softeners, carriers, hydrotropes,
processing aids, solvents, additional dyes and/or pigments, some of
which are discussed in more detail below. In addition to the
disclosure below, suitable examples of such other adjuncts and
levels of use are found in U.S. Pat. Nos. 5,576,282, 6,306,812 B1
and 6,326,348 B1 that are incorporated by reference.
Additional Fabric Hueing Agents.
[0062] Although it is not preferred to incorporate additional
fabric shading dyes, in addition to the thiophene azo dye, the
composition may comprise one or more additional fabric hueing
agents. Fabric shading can be accomplished through application of
any suitable ingredient as known in the art. Preferred fabric
shading agents include fabric shading dyes, pigments and mixtures
thereof.
[0063] The additional fabric shading dye (sometimes referred to as
hueing, bluing or whitening agents) typically provides a blue or
violet shade to fabric. The additional fabric shading dye can be
used either alone or in combination to create a specific shade of
hueing and/or to shade different fabric types. This may be provided
for example by mixing a red and green-blue dye to yield a blue or
violet shade. The additional fabric shading dye may be selected
from any chemical class of dye as known in the art, including but
not limited to acridine, anthraquinone (including polycyclic
quinones), azine, azo (e.g., monoazo, disazo, trisazo, tetrakisazo,
polyazo), benzodifurane, benzodifuranone, carotenoid, coumarin,
cyanine, diazahemicyanine, diphenylmethane, formazan, hemicyanine,
indigoids, methane, naphthalimides, naphthoquinone, nitro, nitroso,
oxazine, phthalocyanine, pyrazoles, stilbene, styryl,
triarylmethane, triphenylmethane, xanthenes and mixtures
thereof.
[0064] Suitable additional fabric shading dyes include small
molecule dyes, polymeric dyes and dye-clay conjugates. Preferred
additional fabric shading dyes are selected from small molecule
dyes and polymeric dyes.
[0065] Small Molecule Dyes
[0066] Suitable small molecule dyes may be selected from the group
consisting of dyes falling into the Colour Index (C.I., Society of
Dyers and Colourists, Bradford, UK) classifications of Acid,
Direct, Basic, Reactive, Solvent or Disperse dyes. Preferably such
dyes can be classified as Blue, Violet, Red, Green or Black, and
provide the desired shade either alone or in combination with other
dyes or in combination with other adjunct ingredients. Reactive
dyes may contain small amounts of hydrolyzed dye as sourced, and in
detergent formulations or in the wash may undergo additional
hydrolysis. Such hydrolyzed dyes and mixtures may also serve as
suitable small molecule dyes.
[0067] In another aspect, suitable dyes include those selected from
the group consisting of dyes denoted by the Colour Index
designations such as Direct Violet 5, 7, 9, 11, 31, 35, 48, 51, 66,
and 99, Direct Blue 1, 71, 80 and 279, Acid Red 17, 73, 52, 88 and
150, Acid Violet 15, 17, 24, 43, 49 and 50, Acid Blue 15, 17, 25,
29, 40, 45, 48, 75, 80, 83, 90 and 113, Acid Black 1, Basic Violet
1, 3, 4, 10 and 35, Basic Blue 3, 16, 22, 47, 66, 75 and 159,
anthraquinone Disperse or Solvent dyes such as Solvent Violet 11,
13, 14, 15, 15, 26, 28, 29, 30, 31, 32, 33, 34, 26, 37, 38, 40, 41,
42, 45, 48, 59; Solvent Blue 11, 12, 13, 14, 15, 17, 18, 19, 20,
21, 22, 35, 36, 40, 41, 45, 59, 59:1, 63, 65, 68, 69, 78, 90;
Disperse Violet 1, 4, 8, 11, 11:1, 14, 15, 17, 22, 26, 27, 28, 29,
34, 35, 36, 38, 41, 44, 46, 47, 51, 56, 57, 59, 60, 61, 62, 64, 65,
67, 68, 70, 71, 72, 78, 79, 81, 83, 84, 85, 87, 89, 105; Disperse
Blue 2, 3, 3:2, 8, 9, 13, 13:1, 14, 16, 17, 18, 19, 22, 23, 24, 26,
27, 28, 31, 32, 34, 35, 40, 45, 52, 53, 54, 55, 56, 60, 61, 62, 64,
65, 68, 70, 72, 73, 76, 77, 80, 81, 83, 84, 86, 87, 89, 91, 93, 95,
97, 98, 103, 104, 105, 107, 108, 109, 11, 112, 113, 114, 115, 116,
117, 118, 119, 123, 126, 127, 131, 132, 134, 136, 140, 141, 144,
145, 147, 150, 151, 152, 153, 154, 155, 156, 158, 159, 160, 161,
162, 163, 164, 166, 167, 168, 169, 170, 176, 179, 180, 180:1, 181,
182, 184, 185, 190, 191, 192, 196, 197, 198, 199, 203, 204, 213,
214, 215, 216, 217, 218, 223, 226, 227, 228, 229, 230, 231, 232,
234, 235, 236, 237, 238, 239, 240, 241, 242, 243, 244, 245, 246,
247, 249, 252, 261, 262, 263, 271, 272, 273, 274, 275, 276, 277,
289, 282, 288, 289, 292, 293, 296, 297, 298, 299, 300, 302, 306,
307, 308, 309, 310, 311, 312, 314, 318, 320, 323, 325, 326, 327,
331, 332, 334, 347, 350, 359, 361, 363, 372, 377 and 379, azo
Disperse dyes such as Disperse Blue 10, 11, 12, 21, 30, 33, 36, 38,
42, 43, 44,47,79,79:1,79:2,79:3, 82, 85, 88, 90, 94, 96, 100, 101,
102, 106, 106:1, 121, 122, 124, 125, 128, 130, 133, 137, 138, 139,
142, 146, 148, 149, 165, 165:1, 165:2, 165:3, 171, 173, 174, 175,
177, 183, 187, 189, 193, 194, 200, 201, 202, 206, 207, 209, 210,
211, 212, 219, 220, 224, 225, 248, 252, 253, 254, 255, 256, 257,
258, 259, 260, 264, 265, 266, 267, 268, 269, 270, 278, 279, 281,
283, 284, 285, 286, 287, 290, 291, 294, 295, 301, 304, 313, 315,
316, 317:319, 321, 322, 324, 328, 330, 333, 335, 336, 337, 338,
339, 340, 341, 342, 343, 344, 345, 346, 351, 352, 353, 355, 356,
358, 360, 366, 367, 368, 369, 371, 373, 374, 375, 376 and 378,
Disperse Violet 2, 3, 5, 6, 7, 9, 10, 12, 3, 16, 24, 25,33,39, 42,
43, 45, 48, 49, 50, 53, 54, 55, 58, 60, 63, 66, 69, 75, 76, 77, 82,
86, 88, 91, 92, 93, 93:1, 94, 95, 96, 97, 98, 99, 100, 102, 104,
106 and 107. Preferably, small molecule dyes can be selected from
the group consisting of C. I. numbers Acid Violet 17, Acid Blue 80,
Acid Violet 50, Direct Blue 71, Direct Violet 51, Direct Blue 1,
Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113 or mixtures
thereof.
[0068] In another aspect suitable small molecule dyes include dyes
with CAS-No's 52583-54-7, 42783-06-2, 210758-04-6,
104366-25-8,122063-39-2,167940-11-6,52239-04-0,
105076-77-5,84425-43-4, and 87606-56-2, and non-azo dyes Disperse
Blue 250, 354, 364, Solvent Violet 8, Solvent blue 43, 57, Lumogen
F Blau 650, and Lumogen F Violet 570.
[0069] In another aspect suitable small molecule dyes include azo
dyes, preferably mono-azo dyes, covalently bound to phthalocyanine
moieties, preferably Al- and Si-phthalocyanine moieties, via an
organic linking moiety.
[0070] Polymeric Dyes
[0071] Suitable polymeric dyes include dyes selected from the group
consisting of polymers containing covalently bound (sometimes
referred to as conjugated) chromogens, (also known as dye-polymer
conjugates), for example polymers with chromogen monomers
co-polymerized into the backbone of the polymer and mixtures
thereof.
[0072] Polymeric dyes include: (a) Reactive dyes bound to water
soluble polyester polymers via at least one and preferably two free
OH groups on the water soluble polyester polymer. The water soluble
polyester polymers can be comprised of comonomers of a phenyl
dicarboxylate, an oxyalkyleneoxy and a polyoxyalkyleneoxy; (b)
Reactive dyes bound to polyamines which are polyalkylamines that
are generally linear or branched. The amines in the polymer may be
primary, secondary and/or tertiary. Polyethyleneimine in one aspect
is preferred. In another aspect, the polyamines are ethoxylated;
(c) Dye polymers having dye moieties carrying negatively charged
groups obtainable by copolymerization of an alkene bound to a dye
containing an anionic group and one or more further alkene
comonomers not bound to a dye moiety; (d) Dye polymers having dye
moieties carrying positively charged groups obtainable by
copolymerization of an alkene bound to a dye containing an cationic
group and one or more further alkene comonomers not bound to a dye
moiety; (e) Polymeric azo polyoxyalkylene dyes containing
carboxylate groups; in some aspects those having carboxylic acid
groups with a pKa value below 4, or below 3, or even below 2, may
be preferred as carboxylic acid groups are well known to have
potentially deleterious interactions with multivalent metal ions
such as, for example, Ca.sup.2+, Mg.sup.2+, Fe.sup.3+ among others,
which may be present in the wash or on fabrics, and those acids
with lower pKa values are believed to have less ability to interact
with such metal ions, leading to improved consistency in
performance across widely varying wash conditions; and (f) dye
polymer conjugates comprising at least one reactive dye and a
polymer comprising a moiety selected from the group consisting of a
hydroxyl moiety, a primary amine moiety, a secondary amine moiety,
a thiol moiety and combinations thereof; said polymers preferably
selected from the group consisting of polysaccharides, proteins,
polyalkyleneimines, polyamides, polyols, and silicones. In one
aspect, carboxymethyl cellulose (CMC) may be covalently bound to
one or more reactive blue, reactive violet or reactive red dye such
as CMC conjugated with C.I. Reactive Blue 19, sold by Megazyme,
Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product
code S-ACMC,
[0073] Other suitable polymeric dyes include polymeric dyes
selected from the group consisting of alkoxylated triphenyl-methane
polymeric colourants, alkoxylated carbocyclic and alkoxylated
heterocyclic azo colourants, including alkoxylated thiophene
polymeric colourants, and mixtures thereof. Preferred polymeric
dyes comprise the optionally substituted alkoxylated dyes, such as
alkoxylated triphenyl-methane polymeric colourants, alkoxylated
carbocyclic and alkoxylated heterocyclic azo colourants including
alkoxylated thiophene polymeric colourants, and mixtures thereof,
such as the fabric-substantive colorants sold under the name of
Liquitint.RTM. (Milliken, Spartanburg, S.C., USA).
[0074] Suitable polymeric bluing agents are illustrated below. As
with all such alkoxylated compounds, the organic synthesis may
produce a mixture of molecules having different degrees of
alkoxylation During a typical ethoxylation process, for example,
the randomness of the ethylene oxide addition results in a mixture
of oligomers with different degrees of ethoxylation. As a
consequence of its ethylene oxide number distribution, which often
follows a Poisson law, a commercial material contains substances
with somewhat different properties. For example, in one aspect the
product resulting from an ethoxylation is not a single compound
containing five (CH.sub.2CH.sub.2O) units as the general structure
(Formula A, with x+y=5) may suggest. Instead, the product is a
mixture of several homologs whose total of ethylene oxide units
varies from about 2 to about 10. Industrially relevant processes
will typically result in such mixtures, which may normally be used
directly to provide the fabric shading dye, or less commonly may
undergo a purification step.
[0075] Preferably, the fabric shading dye may have the
structure:
##STR00019##
wherein the index values x and y are independently selected from 1
to 10. In some aspects, the average degree of ethoxylation, x+y,
sometimes also referred to as the average number of ethoxylate
groups, is from about 3 to about 12, preferably from about 4 to
about 8. In some embodiments the average degree of ethoxylation,
x+y, can be from about 5 to about 6. The range of ethoxylation
present in the mixture varies depending on the average number of
ethoxylates incorporated. Typical distributions for ethoxylation of
toluidine with either 5 or 8 ethoxylates are shown in Table II on
page 42 in the Journal of Chromatography A 1989, volume 462, pp.
39-47. The whitening agents are synthesized according to the
procedures disclosed in U.S. Pat. No. 4,912,203 to Kluger et al.; a
primary aromatic amine is reacted with an appropriate amount of
ethylene oxide, according to procedures well known in the art. The
polyethyleneoxy substituted m-toluidine useful in the preparation
of the colorant can be prepared by a number of well known methods.
It is preferred, however, that the polyethyleneoxy groups be
introduced into the m-toluidine molecule by reaction of the
m-toluidine with ethylene oxide. Generally the reaction proceeds in
two steps, the first being the formation of the corresponding
N,N-dihydroxyethyl substituted m-toluidine. In some aspects, no
catalyst is utilized in this first step (for example as disclosed
at Column 4, lines 16-25 of U.S. Pat. No. 3,927,044 to Foster et
al.). The dihydroxyethyl substituted m-toluidine is then reacted
with additional ethylene oxide in the presence of a catalyst such
as sodium (described in Preparation II of U.S. Pat. No. 3,157,633
to Kuhn), or it may be reacted with additional ethylene oxide in
the presence of sodium or potassium hydroxide (described in Example
5 of U.S. Pat. No. 5,071,440 to Hines et al.). The amount of
ethylene oxide added to the reaction mixture determines the number
of ethyleneoxy groups which ultimately attach to the nitrogen atom.
In some aspects, it may be advantageous to dissolve the whitening
agent in a solvent which may be protic or aprotic. Typically for
ease of handling and formulation such whitening agents may be
dissolved in polar protic solvents such as, for example, a low
molecular weight polyethyleneglycol such as PEG200. In some
aspects, an excess of a polyethyleneoxy substituted coupler, such
as a m-toluidine coupler, may be employed in the formation of the
whitening agent and remain as a component in the final colorant
mixture. In certain aspects, the presence of excess coupler or
diluting solvent may confer advantageous properties to a mixture in
which it is incorporated such as the raw material, a pre-mix, a
finished product or even the wash solution prepared from the
finished product.
[0076] The fabric shading dye may preferably have the following
structure:
##STR00020##
wherein x+1 is an integer representing the approximate average
degree of ethoxylation, and the index x is an integer from 0 to 19.
More preferably from 1 to 9, even more preferably from 1 to 5.
[0077] In one aspect, a fabric shading mixture comprises a fabric
shading agent having the structure:
##STR00021##
and one or more additional components that may be unreacted
starting materials or components formed as a result of the
synthetic method employed in obtaining said bluing agent, as will
be appreciated by those skilled in the art. Such unreacted starting
materials and additional components may be selected from the group
consisting of:
##STR00022## ##STR00023##
[0078] Wherein: [0079] R.sub.1 is C.sub.1-C.sub.4 alkyl preferably
methyl; [0080] R2 and R3 are independently selected from the group
consisting of alkyl, alkyleneoxy, and polyalkyleneoxy moieties,
preferably alkyl and polyalkyleneoxy moieties, even more preferably
at least one R.sub.2 and R.sub.3 are polyalkyleneoxy moieties, most
preferably polyoxyethylene moieties, provided that at least one of
R.sub.2 and R.sub.3 comprises a carboxylic acid group, preferably
one with a pKa value below about 4, or even below about 3 or even
below about 2; [0081] D is an aromatic or heteroaromatic group,
preferably a heteroaromatic group, even more preferably a thiophene
group. The ordinarily skilled artisan understands that even
substantially pure starting materials used in industrial
preparations may contain minor or trace components that could be
carried forward along with the intended starting materials to form
other minor or trace components not necessarily captured in the
list above, which is intended to be illustrative and not
exhaustive. For example, when utilizing 3-methyl aniline as a
starting material, there could be minor components present such as
aniline or 2-methyl aniline. Each of these could participate in the
coupling reaction with the D-NH.sub.2 group and form a unique
mixture of materials present at very low levels. A similar
possibility exists for the aromatic or heteroaromatic amine
employed. For example, using
5-amino-3-methyl-2,4-thiophenedicarbonitrile as a starting
material, low levels of other aminothiophenes may be present that
can be carried forward in a similar manner resulting in additional
minor components. Such low level contaminants in a starting
material may include, for example, aminothiophenes D'-NH.sub.2 of
the following structure:
##STR00024##
[0081] wherein R.sub.4 and R.sub.6 are independently selected from
--CN, --C(O)NH.sub.2, and --CO.sub.2H, and R.sub.5 is selected from
H and C.sub.1-C.sub.2 alkyl, provided that when both R.sub.4 and
R.sub.6 are --CN, R.sub.5 is other than methyl. As will be
appreciated by one skilled in the art, such low level D'-NH.sub.2
may be carried forward along with the intended starting D-NH.sub.2
to form other minor or trace components such as those illustrated
in the list above, provided the minor aminothiophene radical D' is
substituted for D in the structures shown above. Said another way,
each aminothiophene present at the beginning of the synthetic
process has the ability to be carried forward to a mixture of
products, including D'-NH.sub.2 present as minor components in the
starting D-NH.sub.2.
[0082] As will be appreciated by those skilled in the art the above
noted unreacted starting materials and additional components to
said bluing agent will typically be present at levels that are
unlikely to significantly impact said bluing agent's performance,
as perceived by the average consumer. As will further be
appreciated, when present at levels that may impact said bluing
agent's performance, or the overall performance of a detergent
formulation containing said mixture, as perceived by the average
consumer, such additional components may be removed or retained as
desired.
[0083] Non-limiting examples of suitable fabric shading dyes
are:
##STR00025## ##STR00026##
[0084] Dye-Clay Conjugates
[0085] Suitable dye clay conjugates include dye clay conjugates
selected from the group comprising at least one cationic/basic dye
and a smectite clay; a preferred clay may be selected from the
group consisting of Montmorillonite clay, Hectorite clay, Saponite
clay and mixtures thereof. In another aspect, suitable dye clay
conjugates include dye clay conjugates selected from the group
consisting of a clay and one cationic/basic dye selected from the
group consisting of C.I. Basic Yellow 1 through 108, C.I. Basic
Orange 1 through 69, C.I. Basic Red 1 through 118, C.I. Basic
Violet 1 through 51, C.I. Basic Blue 1 through 164, C.I. Basic
Green 1 through 14, C.I. Basic Brown 1 through 23, CI Basic Black 1
through 11 In still another aspect, suitable dye clay conjugates
include dye clay conjugates selected from the group consisting of:
Montmorillonite Basic Blue B7 C.I. 42595 conjugate, Montmorillonite
Basic Blue B9 C.I. 52015 conjugate, Montmorillonite Basic Violet V3
C.I. 42555 conjugate, Montmorillonite Basic Green G1 C.I. 42040
conjugate, Montmorillonite Basic Red R1 C.I. 45160 conjugate,
Montmorillonite C.I. Basic Black 2 conjugate, Hectorite Basic Blue
B7 C.I. 42595 conjugate, Hectorite Basic Blue B9 C.I. 52015
conjugate, Hectorite Basic Violet V3 C.I. 42555 conjugate,
Hectorite Basic Green G1 C.I. 42040 conjugate, Hectorite Basic Red
R1 C.I. 45160 conjugate, Hectorite C.I. Basic Black 2 conjugate,
Saponite Basic Blue B7 C.I. 42595 conjugate, Saponite Basic Blue B9
C.I. 52015 conjugate, Saponite Basic Violet V3 C.I. 42555
conjugate, Saponite Basic Green G1 C.I. 42040 conjugate, Saponite
Basic Red R1 C.I. 45160 conjugate, Saponite C.I. Basic Black 2
conjugate and mixtures thereof.
Pigments
[0086] Suitable pigments include pigments selected from the group
consisting of flavanthrone, indanthrone, chlorinated indanthrone
containing from 1 to 4 chlorine atoms, pyranthrone,
dichloropyranthrone, monobromodichloropyranthrone,
dibromodichloropyranthrone, tetrabromopyranthrone,
perylene-3,4,9,10-tetracarboxylic acid diimide, wherein the imide
groups may be unsubstituted or substituted by C1-C3-alkyl or a
phenyl or heterocyclic radical, and wherein the phenyl and
heterocyclic radicals may additionally carry substituents,
anthrapyrimidinecarboxylic acid amides, violanthrone,
isoviolanthrone, dioxazine pigments, copper phthalocyanine which
may contain up to 2 chlorine atoms per molecule, polychloro-copper
phthalocyanine or polybromochloro-copper phthalocyanine containing
up to 14 bromine atoms per molecule and mixtures thereof. Other
suitable pigments are described in WO2008/090091. In another
aspect, suitable pigments include pigments selected from the group
consisting of Ultramarine Blue (C.I. Pigment Blue 29), Ultramarine
Violet (C.I. Pigment Violet 15), Monastral Blue and mixtures
thereof. Particularly preferred are Pigment Blues 15 to 20,
especially Pigment Blue 15 and/or 16. Other suitable pigments
include those selected from the group consisting of Ultramarine
Blue (C.I. Pigment Blue 29), Ultramarine Violet (C.I. Pigment
Violet 15), Monastral Blue and mixtures thereof.
[0087] The amount of additional fabric shading dye present in the
cleaning composition of the invention is typically from 0.0001 to
0.05 wt % based on the total cleaning composition, preferably from
0.0001 to 0.005 wt %. Based on the wash liquor, the concentration
of additional fabric shading dye typically is from 1 ppb to 5 ppm,
preferably from 10 ppb to 500 ppb. Of course this will depend on
the equivalent weight of the additional fabric shading agent. These
values are generally acceptable when the equivalent weight (EW) of
the additional fabric shading agent, the molecular weight (MW)
divided by the number of dye chromophores in the shading agent, is
between 200 and 2000. Where the equivalent weight of the shading
agent is >2000, these ranges should be multiplied by the
equivalent weight of the additional shading agent divided by 2000.
Thus if a shading agent has a MW of 1,000 with a single dye
chromophore, its EW is the same as its MW. If the MW is 5,000 and
the shading agent has two chromophores, its EW would be 2,500 and
the ranges indicated above should be multiplied by (2,500/2,000),
so that for example the amount of such an additional fabric shading
dye present in the cleaning composition of the invention is
typically from 0.00125 to 0.0625 wt % based on the total cleaning
composition. Such corrections to levels may be required depending
on the number of chromophores attached to a polymer of high MW, for
example.
[0088] The additional fabric shading dye and/or pigment may be
incorporated into the detergent composition as part of a reaction
mixture which is the result of the organic synthesis for the dye,
pigment or brightener molecule, with optional purification step(s).
Such reaction mixtures generally comprise the fabric shading
molecule itself and in addition may comprise un-reacted starting
materials and/or by-products of the organic synthesis route.
[0089] Encapsulates.
[0090] The composition may comprise an encapsulate. In one aspect,
an encapsulate comprising a core, a shell having an inner and outer
surface, said shell encapsulating said core. The core may comprise
any laundry care adjunct, though typically the core may comprise
material selected from the group consisting of perfumes;
brighteners; dyes; insect repellants; silicones; waxes; flavors;
vitamins; fabric softening agents; skin care agents in one aspect,
paraffins; enzymes; anti-bacterial agents; bleaches; sensates; and
mixtures thereof; and said shell may comprise a material selected
from the group consisting of polyethylenes; polyamides;
polyvinylalcohols, optionally containing other co-monomers;
polystyrenes; polyisoprenes; polycarbonates; polyesters;
polyacrylates; aminoplasts, in one aspect said aminoplast may
comprise a polyureas, polyurethane, and/or polyureaurethane, in one
aspect said polyurea may comprise polyoxymethyleneurea and/or
melamine formaldehyde; polyolefins; polysaccharides, in one aspect
said polysaccharide may comprise alginate and/or chitosan; gelatin;
shellac; epoxy resins; vinyl polymers; water insoluble inorganics;
silicone; and mixtures thereof. Preferred encapsulates comprise
perfume. Preferred encapsulates comprise a shell which may comprise
melamine formaldehyde and/or cross linked melamine formaldehyde.
Preferred encapsulates comprise a core material and a shell, said
shell at least partially surrounding said core material, is
disclosed. At least 75%, 85% or even 90% of said encapsulates may
have a fracture strength of from 0.2 MPa to 10 MPa, and a benefit
agent leakage of from 0% to 20%, or even less than 10% or 5% based
on total initial encapsulated benefit agent. Preferred are those in
which at least 75%, 85% or even 90% of said encapsulates may have
(i) a particle size of from 1 microns to 80 microns, 5 microns to
60 microns, from 10 microns to 50 microns, or even from 15 microns
to 40 microns, and/or (ii) at least 75%, 85% or even 90% of said
encapsulates may have a particle wall thickness of from 30 nm to
250 nm, from 80 nm to 180 nm, or even from 100 nm to 160 nm.
Formaldehyde scavengers may be employed with the encapsulates, for
example, in a capsule slurry and/or added to a composition before,
during or after the encapsulates are added to such composition.
Suitable capsules that can be made by following the teaching of
USPA 2008/0305982 A1; and/or USPA 2009/0247449 A1. Alternatively,
suitable capsules can be purchased from Appleton Papers Inc. of
Appleton, Wis. USA.
[0091] In a preferred aspect the composition may comprise a
deposition aid, preferably in addition to encapsulates. Preferred
deposition aids are selected from the group consisting of cationic
and nonionic polymers. Suitable polymers include cationic starches,
cationic hydroxyethylcellulose, polyvinylformaldehyde, locust bean
gum, mannans, xyloglucans, tamarind gum, polyethyleneterephthalate
and polymers containing dimethylaminoethyl methacrylate, optionally
with one or more monomers selected from the group comprising
acrylic acid and acrylamide.
[0092] Perfume.
[0093] Preferred compositions of the invention comprise perfume.
Typically the composition comprises a perfume that comprises one or
more perfume raw materials, selected from the group as described in
WO08/87497. However, any perfume useful in a laundry care
composition may be used. A preferred method of incorporating
perfume into the compositions of the invention is via an
encapsulated perfume particle comprising either a water-soluble
hydroxylic compound or melamine-formaldehyde or modified polyvinyl
alcohol. In one aspect the encapsulate comprises (a) an at least
partially water-soluble solid matrix comprising one or more
water-soluble hydroxylic compounds, preferably starch; and (b) a
perfume oil encapsulated by the solid matrix. In a further aspect
the perfume may be pre-complexed with a polyamine, preferably a
polyethylenimine so as to form a Schiff base.
[0094] Polymers.
[0095] The composition may comprise one or more polymers. Examples
are optionally modified carboxymethylcellulose,
poly(vinyl-pyrrolidone), poly (ethylene glycol), poly(vinyl
alcohol), poly(vinylpyridine-N-oxide), poly(vinylimidazole),
polycarboxylates such as polyacrylates, maleic/acrylic acid
copolymers and lauryl methacrylate/acrylic acid co-polymers.
[0096] The composition may comprise one or more amphiphilic
cleaning polymers such as the compound having the following general
structure:
bis((C.sub.2H.sub.5O)(C.sub.2H.sub.4O)n)(CH.sub.3)--N.sup.+--C.sub.xH.sub-
.2x--N.sup.+--(CH.sub.3)-bis((C.sub.2H.sub.5O)(C.sub.2H.sub.4O)n),
wherein n=from 20 to 30, and x=from 3 to 8, or sulphated or
sulphonated variants thereof. In one aspect, this polymer is
sulphated or sulphonated to provide a zwitterionic soil suspension
polymer.
[0097] The composition preferably comprises amphiphilic alkoxylated
grease cleaning polymers which have balanced hydrophilic and
hydrophobic properties such that they remove grease particles from
fabrics and surfaces. Preferred amphiphilic alkoxylated grease
cleaning polymers comprise a core structure and a plurality of
alkoxylate groups attached to that core structure. These may
comprise alkoxylated polyalkylenimines, preferably having an inner
polyethylene oxide block and an outer polypropylene oxide block.
Typically these may be incorporated into the compositions of the
invention in amounts of from 0.005 to 10 wt %, generally from 0.5
to 8 wt %.
[0098] Alkoxylated polycarboxylates such as those prepared from
polyacrylates are useful herein to provide additional grease
removal performance. Such materials are described in WO 91/08281
and PCT 90/01815. Chemically, these materials comprise
polyacrylates having one ethoxy side-chain per every 7-8 acrylate
units. The side-chains are of the formula
--(CH.sub.2CH.sub.2O).sub.m (CH.sub.2).sub.nCH.sub.3 wherein m is
2-3 and n is 6-12. The side-chains are ester-linked to the
polyacrylate "backbone" to provide a "comb" polymer type structure.
The molecular weight can vary, but is typically in the range of
about 2000 to about 50,000. Such alkoxylated polycarboxylates can
comprise from about 0.05% to about 10%, by weight, of the
compositions herein.
[0099] Mixtures of cosurfactants and other adjunct ingredients, are
particularly suited to be used with an amphiphilic graft
co-polymer. Preferred amphiphilic graft co-polymer(s) comprise (i)
polyethyelene glycol backbone; and (ii) and at least one pendant
moiety selected from polyvinyl acetate, polyvinyl alcohol and
mixtures thereof. A preferred amphiphilic graft co-polymer is
Sokalan HP22, supplied from BASF. Suitable polymers include random
graft copolymers, preferably a polyvinyl acetate grafted
polyethylene oxide copolymer having a polyethylene oxide backbone
and multiple polyvinyl acetate side chains. The molecular weight of
the polyethylene oxide backbone is preferably about 6000 and the
weight ratio of the polyethylene oxide to polyvinyl acetate is
about 40 to 60 and no more than 1 grafting point per 50 ethylene
oxide units. Typically these are incorporated into the compositions
of the invention in amounts from 0.005 to 10 wt %, more usually
from 0.05 to 8 wt %. Preferably the composition comprises one or
more carboxylate polymer, such as a maleate/acrylate random
copolymer or polyacrylate homopolymer. In one aspect, the
carboxylate polymer is a polyacrylate homopolymer having a
molecular weight of from 4,000 Da to 9,000 Da, or from 6,000 Da to
9,000 Da. Typically these are incorporated into the compositions of
the invention in amounts from 0.005 to 10 wt %, or from 0.05 to 8
wt %.
[0100] Preferably the composition comprises one or more soil
release polymers. Examples include soil release polymers having a
structure as defined by one of the following Formulae (VI), (VII)
or (VIII):
--[(OCHR.sup.1--CHR.sup.2).sub.a--O--OC--Ar--CO--].sub.d (VI)
--[(OCHR.sup.3--CHR.sup.4).sub.b--O--OC-sAr-CO-].sub.e (VII)
--[(OCHR.sup.5--CHR.sup.6).sub.c--OR.sup.7].sub.f. (VIII)
[0101] wherein:
[0102] a, b and c are from 1 to 200;
[0103] d, e and f are from 1 to 50;
[0104] Ar is a 1,4-substituted phenylene;
[0105] sAr is 1,3-substituted phenylene substituted in position 5
with SO.sub.3Me;
[0106] Me is Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri-,
or tetraalkylammonium wherein the alkyl groups are C.sub.1-C.sub.18
alkyl or C.sub.2-C.sub.10 hydroxyalkyl, or mixtures thereof;
[0107] R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are
independently selected from H or C.sub.1-C.sub.18 n- or iso-alkyl;
and
[0108] R.sup.7 is a linear or branched C.sub.1-C.sub.18 alkyl, or a
linear or branched C.sub.2-C.sub.30 alkenyl, or a cycloalkyl group
with 5 to 9 carbon atoms, or a C.sub.8-C.sub.30 aryl group, or a
C.sub.6-C.sub.30 arylalkyl group.
[0109] Suitable soil release polymers are polyester soil release
polymers such as Repel-o-tex polymers, including Repel-o-tex SF,
SF-2 and SRP6 supplied by Rhodia. Other suitable soil release
polymers include Texcare polymers, including Texcare SRA100,
SRA300, SRN100, SRN170, SRN240, SRN300 and SRN325 supplied by
Clariant. Other suitable soil release polymers are Marloquest
polymers, such as Marloquest SL supplied by Sasol.
[0110] Preferably the composition comprises one or more cellulosic
polymer, including those selected from alkyl cellulose, alkyl
alkoxyalkyl cellulose, carboxyalkyl cellulose, alkyl carboxyalkyl
cellulose. Preferred cellulosic polymers are selected from the
group comprising carboxymethyl cellulose, methyl cellulose, methyl
hydroxyethyl cellulose, methyl carboxymethyl cellulose, and mixures
thereof. In one aspect, the carboxymethyl cellulose has a degree of
carboxymethyl substitution from 0.5 to 0.9 and a molecular weight
from 100,000 Da to 300,000 Da.
[0111] Enzymes.
[0112] Preferably the composition comprises one or more enzymes.
Preferred enzymes 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,
mannanases, pectate lyases, keratinases, reductases, oxidases,
phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,
pentosanases, malanases, .beta.-glucanases, arabinosidases,
hyaluronidase, chondroitinase, laccase, and amylases, or mixtures
thereof. A typical combination is an enzyme cocktail that may
comprise, for example, a protease and lipase in conjunction with
amylase. When present in the composition, the aforementioned
additional enzymes may be present at levels from about 0.00001% to
about 2%, from about 0.0001% to about 1% or even from about 0.001%
to about 0.5% enzyme protein by weight of the composition.
[0113] Proteases.
[0114] Preferably the composition comprises one or more proteases.
Suitable proteases include metalloproteases and serine proteases,
including neutral or alkaline microbial serine proteases, such as
subtilisins (EC 3.4.21.62). Suitable proteases include those of
animal, vegetable or microbial origin. In one aspect, such suitable
protease may be of microbial origin. The suitable proteases include
chemically or genetically modified mutants of the aforementioned
suitable proteases. In one aspect, the suitable protease may be a
serine protease, such as an alkaline microbial protease or/and a
trypsin-type protease. Examples of suitable neutral or alkaline
proteases include:
[0115] (a) subtilisins (EC 3.4.21.62), including those derived from
Bacillus, such as Bacillus lentus, B. alkalophilus, B. subtilis, B.
amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described
in U.S. Pat. No. 6,312,936 B1, U.S. Pat. No. 5,679,630, U.S. Pat.
No. 4,760,025, U.S. Pat. No. 7,262,042 and WO09/021867.
[0116] (b) trypsin-type or chymotrypsin-type proteases, such as
trypsin (e.g., of porcine or bovine origin), including the Fusarium
protease described in WO 89/06270 and the chymotrypsin proteases
derived from Cellumonas described in WO 05/052161 and WO
05/052146.
[0117] (c) metalloproteases, including those derived from Bacillus
amyloliquefaciens described in WO 07/044993A2.
[0118] Preferred proteases include those derived from Bacillus
gibsonii or Bacillus Lentus.
[0119] Suitable commercially available protease enzymes include
those sold under the trade names Alcalase.RTM., Savinase.RTM.,
Primase.RTM., Durazym.RTM., Polarzyme.RTM., Kannase.RTM.,
Liquanase.RTM., Liquanase Ultra.RTM., Savinase Ultra.RTM.,
Ovozyme.RTM., Neutrase.RTM., Everlase.RTM. and Esperase.RTM. by
Novozymes A/S (Denmark), those sold under the tradename
Maxatase.RTM., Maxacal.RTM., Maxapem.RTM., Properase.RTM.,
Purafect.RTM., Purafect Prime.RTM., Purafect Ox.RTM., FN3.RTM.,
FN4.RTM., Excellase.RTM. and Purafect OXP.RTM. by Genencor
International, those sold under the tradename Opticlean.RTM. and
Optimase.RTM. by Solvay Enzymes, those available from
Henkel/Kemira, namely BLAP (sequence shown in FIG. 29 of U.S. Pat.
No. 5,352,604 with the following mutations S99D+S101
R+S103A+V104I+G159S, hereinafter referred to as BLAP), BLAP R (BLAP
with S3T+V4I+V199M+V205I+L217D), BLAP X (BLAP with S3T+V4I+V2051)
and BLAP F49 (BLAP with S3T+V4I+A194P+V199M+V205I+L217D)--all from
Henkel/Kemira; and KAP (Bacillus alkalophilus subtilisin with
mutations A230V+S256G+S259N) from Kao.
[0120] Amylases.
[0121] Preferably the composition may comprise an amylase. Suitable
alpha-amylases include those of bacterial or fungal origin.
Chemically or genetically modified mutants (variants) are included.
A preferred alkaline alpha-amylase is derived from a strain of
Bacillus, such as Bacillus licheniformis, Bacillus
amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis,
or other Bacillus sp., such as Bacillus sp. NCIB 12289, NCIB 12512,
NCIB 12513, DSM 9375 (U.S. Pat. No. 7,153,818) DSM 12368, DSMZ no.
12649, KSM AP1378 (WO 97/00324), KSM K36 or KSM K38 (EP 1,022,334).
Preferred amylases include:
[0122] (a) the variants described in WO 94/02597, WO 94/18314,
WO96/23874 and WO 97/43424, especially the variants with
substitutions in one or more of the following positions versus the
enzyme listed as SEQ ID No. 2 in WO 96/23874: 15, 23, 105, 106,
124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243,
264, 304, 305, 391, 408, and 444.
[0123] (b) the variants described in U.S. Pat. No. 5,856,164 and
WO99/23211, WO 96/23873, WO00/60060 and WO 06/002643, especially
the variants with one or more substitutions in the following
positions versus the AA560 enzyme listed as SEQ ID No. 12 in WO
06/002643:
[0124] 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178,
182, 186, 193, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283,
295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 339,
345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450,
461, 471, 482, 484, preferably that also contain the deletions of
D183* and G184*.
[0125] (c) variants exhibiting at least 90% identity with SEQ ID
No. 4 in WO06/002643, the wild-type enzyme from Bacillus SP722,
especially variants with deletions in the 183 and 184 positions and
variants described in WO 00/60060, which is incorporated herein by
reference.
[0126] (d) variants exhibiting at least 95% identity with the
wild-type enzyme from Bacillus sp.707 (SEQ ID NO:7 in U.S. Pat. No.
6,093,562), especially those comprising one or more of the
following mutations M202, M208, S255, R172, and/or M261. Preferably
said amylase comprises one or more of M202L, M202V, M2025, M202T,
M202I, M202Q, M202W, S255N and/or R172Q. Particularly preferred are
those comprising the M202L or M202T mutations.
[0127] (e) variants described in WO 09/149130, preferably those
exhibiting at least 90% identity with SEQ ID NO: 1 or SEQ ID NO:2
in WO 09/149130, the wild-type enzyme from Geobacillus
Stearophermophilus or a truncated version thereof.
[0128] Suitable commercially available alpha-amylases include
DURAMYL.RTM., LIQUEZYME.RTM., TERMAMYL.RTM., TERMAMYL ULTRA.RTM.,
NATALASE.RTM., SUPRAMYL.RTM., STAINZYME.RTM., STAINZYME PLUS.RTM.,
FUNGAMYL.RTM. and BAN.RTM. (Novozymes A/S, Bagsvaerd, Denmark),
KEMZYM.RTM. AT 9000 Biozym Biotech Trading GmbH Wehlistrasse 27b
A-1200 Wien Austria, RAPIDASE.RTM., PURASTAR.RTM., ENZYSIZE.RTM.,
OPTISIZE HT PLUS.RTM., POWERASE.RTM. and PURASTAR OXAM.RTM.
(Genencor International Inc., Palo Alto, Calif.) and KAM.RTM. (Kao,
14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210,
Japan). In one aspect, suitable amylases include NATALASE.RTM.,
STAINZYME.RTM. and STAINZYME PLUS.RTM. and mixtures thereof.
[0129] Lipases.
[0130] Preferably the invention comprises one or more lipases,
including "first cycle lipases" such as those described in U.S.
Pat. No. 6,939,702 B1 and US PA 2009/0217464. Preferred lipases are
first-wash lipases. In one embodiment of the invention the
composition comprises a first wash lipase. First wash lipases
includes a lipase which is a polypeptide having an amino acid
sequence which: (a) has at least 90% identity with the wild-type
lipase derived from Humicola lanuginosa strain DSM 4109; (b)
compared to said wild-type lipase, comprises a substitution of an
electrically neutral or negatively charged amino acid at the
surface of the three-dimensional structure within 15A of E1 or Q249
with a positively charged amino acid; and (c) comprises a peptide
addition at the C-terminal; and/or (d) comprises a peptide addition
at the N-terminal and/or (e) meets the following limitations: i)
comprises a negative amino acid in position E210 of said wild-type
lipase; ii) comprises a negatively charged amino acid in the region
corresponding to positions 90-101 of said wild-type lipase; and
iii) comprises a neutral or negative amino acid at a position
corresponding to N94 or said wild-type lipase and/or has a negative
or neutral net electric charge in the region corresponding to
positions 90-101 of said wild-type lipase. Preferred arevariants of
the wild-type lipase from Thermomyces lanuginosus comprising one or
more of the T231R and N233R mutations. The wild-type sequence is
the 269 amino acids (amino acids 23-291) of the Swissprot accession
number Swiss-Prot O59952 (derived from Thermomyces lanuginosus
(Humicola lanuginosa)). Preferred lipases would include those sold
under the tradenames Lipex.RTM. and Lipolex.RTM. and
Lipoclean.RTM..
[0131] Endoglucanases. Other preferred enzymes include
microbial-derived endoglucanases exhibiting endo-beta-1,4-glucanase
activity (E.C. 3.2.1.4), including a bacterial polypeptide
endogenous to a member of the genus Bacillus which has a sequence
of at least 90%, 94%, 97% and even 99% identity to the amino acid
sequence SEQ ID NO:2 in U.S. Pat. No. 7,141,403B2) and mixtures
thereof. Suitable endoglucanases are sold under the tradenames
Celluclean.RTM. and Whitezyme.RTM. (Novozymes A/S, Bagsvaerd,
Denmark).
[0132] Pectate Lyases.
[0133] Other preferred enzymes include pectate lyases sold under
the tradenames Pectawash.RTM., Pectaway.RTM., Xpect.RTM. and
mannanases sold under the tradenames Mannaway.RTM. (all from
Novozymes A/S, Bagsvaerd, Denmark), and Purabrite.RTM. (Genencor
International Inc., Palo Alto, Calif.).
[0134] Bleaching Agents.
[0135] It may be preferred for the composition to comprise one or
more bleaching agents. Suitable bleaching agents other than
bleaching catalysts include photobleaches, bleach activators,
hydrogen peroxide, sources of hydrogen peroxide, pre-formed
peracids and mixtures thereof. In general, when a bleaching agent
is used, the compositions of the present invention may comprise
from about 0.1% to about 50% or even from about 0.1% to about 25%
bleaching agent or mixtures of bleaching agents by weight of the
subject composition. Examples of suitable bleaching agents
include:
(1) photobleaches for example sulfonated zinc phthalocyanine
sulfonated aluminium phthalocyanines, xanthene dyes and mixtures
thereof; (2) pre-formed peracids: Suitable preformed peracids
include, but are not limited to compounds selected from the group
consisting of pre-formed peroxyacids or salts thereof typically a
percarboxylic acids and salts, percarbonic acids and salts,
perimidic acids and salts, peroxymonosulfuric acids and salts, for
example, Oxone.RTM., and mixtures thereof. Suitable examples
include peroxycarboxylic acids or salts thereof, or peroxysulphonic
acids or salts thereof. Typical peroxycarboxylic acid salts
suitable for use herein have a chemical structure corresponding to
the following chemical formula:
##STR00027##
wherein: R.sup.14 is selected from alkyl, aralkyl, cycloalkyl, aryl
or heterocyclic groups; the R.sup.14 group can be linear or
branched, substituted or unsubstituted; having, when the peracid is
hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12 carbon
atoms and, when the peracid is hydrophilic, less than 6 carbon
atoms or even less than 4 carbon atoms and Y is any suitable
counter-ion that achieves electric charge neutrality, preferably Y
is selected from hydrogen, sodium or potassium. Preferably,
R.sup.14 is a linear or branched, substituted or unsubstituted
C.sub.6-9 alkyl. Preferably, the peroxyacid or salt thereof is
selected from peroxyhexanoic acid, peroxyheptanoic acid,
peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid, any
salt thereof, or any combination thereof. Particularly preferred
peroxyacids are phthalimido-peroxy-alkanoic acids, in particular
.epsilon.-phthalimido peroxy hexanoic acid (PAP). Preferably, the
peroxyacid or salt thereof has a melting point in the range of from
30.degree. C. to 60.degree. C.
[0136] The pre-formed peroxyacid or salt thereof can also be a
peroxysulphonic acid or salt thereof, typically having a chemical
structure corresponding to the following chemical formula:
##STR00028##
[0137] wherein: R.sup.15 is selected from alkyl, aralkyl,
cycloalkyl, aryl or heterocyclic groups; the R.sup.15 group can be
linear or branched, substituted or unsubstituted; and Z is any
suitable counter-ion that achieves electric charge neutrality,
preferably Z is selected from hydrogen, sodium or potassium.
Preferably R.sup.15 is a linear or branched, substituted or
unsubstituted C.sub.4-14, preferably C.sub.6-14 alkyl. Preferably
such bleach components may be present in the compositions of the
invention in an amount from 0.01 to 50%, most preferably from 0.1%
to 20%.
(3) sources of hydrogen peroxide, for example, inorganic perhydrate
salts, including alkali metal salts such as sodium salts of
perborate (usually mono- or tetra-hydrate), percarbonate,
persulphate, perphosphate, persilicate salts and mixtures thereof.
In one aspect of the invention the inorganic perhydrate salts are
selected from the group consisting of sodium salts of perborate,
percarbonate and mixtures thereof. When employed, inorganic
perhydrate salts are typically present in amounts of from 0.05 to
40 wt %, or 1 to 30 wt % of the overall fabric and home care
product and are typically incorporated into such fabric and home
care products as a crystalline solid that may be coated. Suitable
coatings include, inorganic salts such as alkali metal silicate,
carbonate or borate salts or mixtures thereof, or organic materials
such as water-soluble or dispersible polymers, waxes, oils or fatty
soaps; and (4) bleach activators having R--(C.dbd.O)-L wherein R is
an alkyl group, optionally branched, having, when the bleach
activator is hydrophobic, from 6 to 14 carbon atoms, or from 8 to
12 carbon atoms and, when the bleach activator is hydrophilic, less
than 6 carbon atoms or even less than 4 carbon atoms; and L is
leaving group. Examples of suitable leaving groups are benzoic acid
and derivatives thereof--especially benzene sulphonate. Suitable
bleach activators include dodecanoyl oxybenzene sulphonate,
decanoyl oxybenzene sulphonate, decanoyl oxybenzoic acid or salts
thereof, 3,5,5-trimethyl hexanoyloxybenzene sulphonate, tetraacetyl
ethylene diamine (TAED) and nonanoyloxybenzene sulphonate (NOBS).
Suitable bleach activators are also disclosed in WO 98/17767. While
any suitable bleach activator may be employed, in one aspect of the
invention the subject composition may comprise NOBS, TAED or
mixtures thereof. (5) Bleach Catalysts. The compositions of the
present invention may also include one or more bleach catalysts
capable of accepting an oxygen atom from a peroxyacid and/or salt
thereof, and transferring the oxygen atom to an oxidizeable
substrate. Suitable bleach catalysts include, but are not limited
to: iminium cations and polyions; iminium zwitterions; modified
amines; modified amine oxides; N-sulphonyl imines; N-phosphonyl
imines; N-acyl imines; thiadiazole dioxides; perfluoroimines;
cyclic sugar ketones and alpha amino-ketones and mixtures thereof.
Suitable alpha amino ketones are for example as described in WO
2012/000846 A1, WO 2008/015443 A1, and WO 2008/014965 A1. Suitable
mixtures are as described in USPA 2007/0173430 A1.
[0138] Without wishing to be bound by theory, the inventors believe
that controlling the electophilicity and hydrophobicity in this
above described manner enables the bleach ingredient to be
delivered substantially only to areas of the fabric that are more
hydrophobic, and that contain electron rich soils, including
visible chromophores, that are susceptible to bleaching by highly
electrophilic oxidants.
[0139] In one aspect, the bleach catalyst has a structure
corresponding to general formula below:
##STR00029##
[0140] wherein R.sup.13 is selected from the group consisting of
2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl,
2-hexyldecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl,
iso-nonyl, iso-decyl, iso-tridecyl and iso-pentadecyl;
(6) The composition may preferably comprise catalytic metal
complexes. One preferred 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. Pat. No.
4,430,243.
[0141] 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. Pat. No. 5,576,282. Cobalt bleach
catalysts useful herein are known, and are described, for example,
in U.S. Pat. No. 5,597,936; U.S. Pat. No. 5,595,967. Such cobalt
catalysts are readily prepared by known procedures, such as taught
for example in U.S. Pat. No. 5,597,936, and U.S. Pat. No.
5,595,967.
[0142] Compositions herein may also suitably include a transition
metal complex of ligands such as bispidones (WO 05/042532 A1)
and/or macropolycyclic rigid ligands--abbreviated as "MRLs". As a
practical matter, and not by way of limitation, the compositions
and processes herein can be adjusted to provide on the order of at
least one part per hundred million of the active MRL species in the
aqueous washing medium, and will typically 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.
[0143] Suitable transition-metals in the instant transition-metal
bleach catalyst include, for example, manganese, iron and chromium.
Suitable MRLs include
5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane.
Suitable transition metal MRLs are readily prepared by known
procedures, such as taught for example in WO 00/32601, and U.S.
Pat. No. 6,225,464.
[0144] When present, the source of hydrogen peroxide/peracid and/or
bleach activator is generally present in the composition in an
amount of from about 0.1 to about 60 wt %, from about 0.5 to about
40 wt % or even from about 0.6 to about 10 wt % based on the fabric
and home care product. One or more hydrophobic peracids or
precursors thereof may be used in combination with one or more
hydrophilic peracid or precursor thereof.
[0145] Typically hydrogen peroxide source and bleach activator will
be incorporated together. The amounts of hydrogen peroxide source
and peracid or bleach activator may be selected such that the molar
ratio of available oxygen (from the peroxide source) to peracid is
from 1:1 to 35:1, or even 2:1 to 10:1.
[0146] Surfactant.
[0147] Preferably the composition comprises a surfactant or
surfactant system. The surfactant can be selected from nonionic,
anionic, cationic, amphoteric, ampholytic, amphiphilic,
zwitterionic, semi-polar nonionic surfactants and mixtures thereof.
Preferred compositions comprise a mixture of surfactants/surfactant
system. Preferred surfactant systems comprise one or more anionic
surfactants, most preferably in combination with a co-surfactant,
most preferably a nonionic and/or amphoteric and/or zwitterionic
surfactant. Preferred surfactant systems comprise both anionic and
nonionic surfactant, preferably in weight ratios from 90:1 to 1:90.
In some instances a weight ratio of anionic to nonionic surfactant
of at least 1:1 is preferred. However a ratio below 10:1 may be
preferred. When present, the total surfactant level is preferably
from 0.1% to 60%, from 1% to 50% or even from 5% to 40% by weight
of the subject composition.
[0148] Preferably the composition comprises an anionic detersive
surfactant, preferably sulphate and/or sulphonate surfactants.
Preferred examples include alkyl benzene sulphonates, alkyl
sulphates and alkyl alkoxylated sulphates. Preferred sulphonates
are C.sub.10-13 alkyl benzene sulphonate. Suitable alkyl benzene
sulphonate (LAS) may be obtained, by sulphonating commercially
available linear alkyl benzene (LAB); suitable LAB includes low
2-phenyl LAB, such as those supplied by Sasol under the tradename
Isochem.RTM. or those supplied by Petresa under the tradename
Petrelab.RTM., other suitable LAB include high 2-phenyl LAB, such
as those supplied by Sasol under the tradename Hyblene.RTM.. A
suitable anionic detersive surfactant is alkyl benzene sulphonate
that is obtained by DETAL catalyzed process, although other
synthesis routes, such as HF, may also be suitable. In one aspect a
magnesium salt of LAS is used.
[0149] Preferred sulphate detersive surfactants include alkyl
sulphate, typically C.sub.8-18 alkyl sulphate, or predominantly
C.sub.12 alkyl sulphate. A further preferred alkyl sulphate is
alkyl alkoxylated sulphate, preferably a C.sub.8-18 alkyl
alkoxylated sulphate. Preferably the alkoxylating group is an
ethoxylating group. Typically the alkyl alkoxylated sulphate has an
average degree of alkoxylation of from 0.5 to 30 or 20, or from 0.5
to 10. Particularly preferred are C.sub.8-18 alkyl ethoxylated
sulphate having an average degree of ethoxylation of from 0.5 to
10, from 0.5 to 7, from 0.5 to 5 or even from 0.5 to 3.
[0150] The alkyl sulphate, alkyl alkoxylated sulphate and alkyl
benzene sulphonates may be linear or branched, substituted or
un-substituted. When the surfactant is branched, preferably the
surfactant will comprise a mid-chain branched sulphate or
sulphonate surfactant. Preferably the branching groups comprise
C.sub.1-4 alkyl groups, typically methyl and/or ethyl groups.
[0151] Preferably the composition comprises a nonionic detersive
surfactant. Suitable non-ionic surfactants are selected from the
group consisting of: C.sub.8-C.sub.18 alkyl ethoxylates, such as,
NEODOL.RTM. non-ionic surfactants from Shell; C.sub.6-C.sub.12
alkyl phenol alkoxylates wherein the alkoxylate units may be
ethyleneoxy units, propyleneoxy units or a mixture thereof;
C.sub.12-C.sub.18 alcohol and C.sub.6-C.sub.12 alkyl phenol
condensates with ethylene oxide/propylene oxide block polymers such
as Pluronic.RTM. from BASF; C.sub.14-C.sub.22 mid-chain branched
alcohols; C.sub.14-C.sub.22 mid-chain branched alkyl alkoxylates,
typically having an average degree of alkoxylation of from 1 to 30;
alkylpolysaccharides, in one aspect, alkylpolyglycosides;
polyhydroxy fatty acid amides; ether capped poly(oxyalkylated)
alcohol surfactants; and mixtures thereof.
[0152] Suitable non-ionic detersive surfactants include alkyl
polyglucoside and/or an alkyl alkoxylated alcohol.
[0153] In one aspect, non-ionic detersive surfactants include alkyl
alkoxylated alcohols, in one aspect C.sub.8-18 alkyl alkoxylated
alcohol, for example a C.sub.8-18 alkyl ethoxylated alcohol, the
alkyl alkoxylated alcohol may have an average degree of
alkoxylation of from 1 to 80, preferably from 1 to 50, most
preferably from 1 to 30, from 1 to 20, or from 1 to 10. In one
aspect, the alkyl alkoxylated alcohol may be a C.sub.8-18 alkyl
ethoxylated alcohol having an average degree of ethoxylation of
from 1 to 10, from 1 to 7, more from 1 to 5 or from 3 to 7, or even
below 3 or 2. The alkyl alkoxylated alcohol can be linear or
branched, and substituted or un-substituted.
[0154] Suitable nonionic surfactants include those with the
tradename Lutensol.RTM. from BASF.
[0155] Suitable cationic detersive surfactants include alkyl
pyridinium compounds, alkyl quaternary ammonium compounds, alkyl
quaternary phosphonium compounds, alkyl ternary sulphonium
compounds, and mixtures thereof.
[0156] Suitable cationic detersive surfactants are quaternary
ammonium compounds having the general formula:
(R)(R.sub.1)(R.sub.2)(R.sub.3)N.sup.+X.sup.-
[0157] wherein, R is a linear or branched, substituted or
unsubstituted C.sub.6-18 alkyl or alkenyl moiety, R.sub.1 and
R.sub.2 are independently selected from methyl or ethyl moieties,
R.sub.3 is a hydroxyl, hydroxymethyl or a hydroxyethyl moiety, X is
an anion which provides charge neutrality, suitable anions include:
halides, for example chloride; sulphate; and sulphonate. Suitable
cationic detersive surfactants are mono-C.sub.6-18 alkyl
mono-hydroxyethyl di-methyl quaternary ammonium chlorides. Highly
suitable cationic detersive surfactants are mono-C.sub.8-10 alkyl
mono-hydroxyethyl di-methyl quaternary ammonium chloride,
mono-C.sub.10-12 alkyl mono-hydroxyethyl di-methyl quaternary
ammonium chloride and mono-C.sub.10 alkyl mono-hydroxyethyl
di-methyl quaternary ammonium chloride.
[0158] Suitable amphoteric/zwitterionic surfactants include amine
oxides and betaines.
[0159] Amine-neutralized anionic surfactants-Anionic surfactants of
the present invention and adjunct anionic cosurfactants, may exist
in an acid form, and said acid form may be neutralized to form a
surfactant salt which is desirable for use in the present detergent
compositions. Typical agents for neutralization include the metal
counterion base such as hydroxides, eg, NaOH or KOH. Further
preferred agents for neutralizing anionic surfactants of the
present invention and adjunct anionic surfactants or cosurfactants
in their acid forms include ammonia, amines, or alkanolamines.
Alkanolamines are preferred. Suitable non-limiting examples
including monoethanolamine, diethanolamine, triethanolamine, and
other linear or branched alkanolamines known in the art; for
example, highly preferred alkanolamines include 2-amino-1-propanol,
1-aminopropanol, monoisopropanolamine, or 1-amino-3-propanol. Amine
neutralization may be done to a full or partial extent, e.g. part
of the anionic surfactant mix may be neutralized with sodium or
potassium and part of the anionic surfactant mix may be neutralized
with amines or alkanolamines.
[0160] Builders.
[0161] Preferably the composition comprises one or more builders or
a builder system. When a builder is used, the composition of the
invention will typically comprise at least 1%, from 2% to 60%
builder. It may be preferred that the composition comprises low
levels of phosphate salt and/or zeolite, for example from 1 to 10
or 5 wt %. The composition may even be substantially free of strong
builder; substantially free of strong builder means "no
deliberately added" zeolite and/or phosphate. Typical zeolite
builders include zeolite A, zeolite P and zeolite MAP. A typical
phosphate builder is sodium tri-polyphosphate.
[0162] Chelating Agent.
[0163] Preferably the composition comprises chelating agents and/or
crystal growth inhibitor. Suitable molecules include copper, iron
and/or manganese chelating agents and mixtures thereof. Suitable
molecules include aminocarboxylates, aminophosphonates, succinates,
salts thereof, and mixtures thereof. Non-limiting examples of
suitable chelants for use herein include
ethylenediaminetetracetates,
N-(hydroxyethyl)ethylenediaminetriacetates, nitrilotriacetates,
ethylenediamine tetraproprionates,
triethylenetetraaminehexacetates, diethylenetriamine-pentaacetates,
ethanoldiglycines, ethylenediaminetetrakis (methylenephosphonates),
diethylenetriamine penta(methylene phosphonic acid) (DTPMP),
ethylenediamine disuccinate (EDDS),
hydroxyethanedimethylenephosphonic acid (HEDP),
methylglycinediacetic acid (MGDA), diethylenetriaminepentaacetic
acid (DTPA), salts thereof, and mixtures thereof. Other nonlimiting
examples of chelants of use in the present invention are found in
U.S. Pat. Nos. 7,445,644, 7,585,376 and 2009/0176684A1. Other
suitable chelating agents for use herein are the commercial DEQUEST
series, and chelants from Monsanto, DuPont, and Nalco, Inc.
[0164] Dye Transfer Inhibitor (DTI).
[0165] The composition may comprise one or more dye transfer
inhibiting agents. In one embodiment of the invention the inventors
have surprisingly found that compositions comprising polymeric dye
transfer inhibiting agents in addition to the specified dye give
improved performance. This is surprising because these polymers
prevent dye deposition. Suitable dye transfer inhibitors 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. Suitable examples include PVP-K15, PVP-K30,
ChromaBond S-400, ChromaBond S-403E and Chromabond S-100 from
Ashland Aqualon, and Sokalan HP165, Sokalan HP50, Sokalan HP53,
Sokalan HP59, Sokalan.RTM. HP 56K, Sokalan.RTM. HP 66 from BASF.
Other suitable DTIs are as described in WO2012/004134. When present
in a subject composition, the dye transfer inhibiting agents may be
present at levels from about 0.0001% to about 10%, from about 0.01%
to about 5% or even from about 0.1% to about 3% by weight of the
composition.
[0166] Fluorescent Brightener.
[0167] Preferably the composition comprises one or more fluorescent
brightener. Commercial optical brighteners which may be useful in
the present invention can be classified into subgroups, which
include, but are not limited to, derivatives of stilbene,
pyrazoline, coumarin, carboxylic acid, methinecyanines,
dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring
heterocycles, and other miscellaneous agents. Particularly
preferred brighteners are selected from: sodium 2
(4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]triazole, disodium
4,4'-bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino
1,3,5-triazin-2-yl)]amino}stilbene-2-2-disulfonate, disodium
4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino}stilbene-2-2'
disulfonate, and disodium 4,4'-bis (2-sulfostyryl) biphenyl. Other
examples of such brighteners are disclosed in "The Production and
Application of Fluorescent Brightening Agents", M. Zahradnik,
Published by John Wiley & Sons, New York (1982). Specific
nonlimiting examples of optical brighteners which are useful in the
present compositions are those identified in U.S. Pat. No.
4,790,856 and U.S. Pat. No. 3,646,015.
[0168] A preferred brightener has the structure below:
##STR00030##
[0169] Suitable fluorescent brightener levels include lower levels
of from about 0.01, from about 0.05, from about 0.1 or even from
about 0.2 wt % to upper levels of 0.5 or even 0.75 wt %.
[0170] In one aspect the brightener may be loaded onto a clay to
form a particle.
[0171] Preferred brighteners are totally or predominantly
(typically at least 50 wt %, at least 75 wt %, at least 90 wt %, at
least 99 wt %), in alpha-crystalline form. A highly preferred
brightener comprises C.I. fluorescent brightener 260, preferably
having the following structure:
##STR00031##
[0172] This can be particularly useful as it dissolves well in cold
water, for example below 30 or 25 or even 20.degree. C.
[0173] Preferably brighteners are incorporated in the composition
in micronized particulate form, most preferably having a weight
average primary particle size of from 3 to 30 micrometers, from 3
micrometers to 20 micrometers, or from 3 to 10 micrometers.
[0174] The composition may comprise C.I. fluorescent brightener 260
in beta-crystalline form, and the weight ratio of: (i) C.I.
fluorescent brightener 260 in alpha-crystalline form, to (ii) C.I.
fluorescent brightener 260 in beta-crystalline form may be at least
0.1, or at least 0.6.
[0175] BE680847 relates to a process for making C.I fluorescent
brightener 260 in alpha-crystalline form.
[0176] Silicate Salts.
[0177] The composition may preferably also contain silicate salts,
such as sodium or potassium silicate. The composition may comprise
from 0 wt % to less than 10 wt % silicate salt, to 9 wt %, or to 8
wt %, or to 7 wt %, or to 6 wt %, or to 5 wt %, or to 4 wt %, or to
3 wt %, or even to 2 wt %, and preferably from above 0 wt %, or
from 0.5 wt %, or even from 1 wt % silicate salt. A suitable
silicate salt is sodium silicate.
[0178] Dispersants.
[0179] The composition may preferably also contain dispersants.
Suitable water-soluble organic materials include the homo- or
co-polymeric acids or their salts, in which the polycarboxylic acid
comprises at least two carboxyl radicals separated from each other
by not more than two carbon atoms.
[0180] Enzyme Stabilisers.
[0181] The composition may preferably comprise enzyme stabilizers.
Any conventional enzyme stabilizer may be used, for example by the
presence of water-soluble sources of calcium and/or magnesium ions
in the finished fabric and home care products that provide such
ions to the enzymes. In case of aqueous compositions comprising
protease, a reversible protease inhibitor, such as a boron compound
including borate, or preferably 4-formyl phenylboronic acid,
phenylboronic acid and derivatives thereof, or compounds such as
calcium formate, sodium formate and 1,2-propane diol can be added
to further improve stability.
[0182] Solvent System.
[0183] The solvent system in the present compositions can be a
solvent system containing water alone or mixtures of organic
solvents either without or preferably with water. Preferred organic
solvents include 1,2-propanediol, ethanol, glycerol, dipropylene
glycol, methyl propane diol and mixtures thereof. Other lower
alcohols, C1-C4 alkanolamines such as monoethanolamine and
triethanolamine, can also be used. Solvent systems can be absent,
for example from anhydrous solid embodiments of the invention, but
more typically are present at levels in the range of from about
0.1% to about 98%, preferably at least about 1% to about 50%, more
usually from about 5% to about 25%.
[0184] In some embodiments of the invention, the composition is in
the form of a structured liquid. Such structured liquids can either
be internally structured, whereby the structure is formed by
primary ingredients (e.g. surfactant material) and/or externally
structured by providing a three dimensional matrix structure using
secondary ingredients (e.g. polymers, clay and/or silicate
material), for use e.g. as thickeners. The composition may comprise
a structurant, preferably from 0.01 wt % to 5 wt %, from 0.1 wt %
to 2.0 wt % structurant. Examples of suitable structurants are
given in US2006/0205631A1, US2005/0203213A1, U.S. Pat. No.
7,294,611, U.S. Pat. No. 6,855,680. The structurant is typically
selected from the group consisting of diglycerides and
triglycerides, ethylene glycol distearate, microcrystalline
cellulose, cellulose-based materials, microfiber cellulose,
hydrophobically modified alkali-swellable emulsions such as Polygel
W30 (3VSigma), biopolymers, xanthan gum, gellan gum, hydrogenated
castor oil, derivatives of hydrogenated castor oil such as
non-ethoxylated derivatieves thereof and mixtures thereof, in
particular, those selected from the group of hydrogenated castor
oil, derivatives of hydrogenated castor oil, microfibullar
cellulose, hydroxyfunctional crystalline materials, long chain
fatty alcohols, 12-hydroxystearic acids, clays and mixtures
thereof. A preferred structurant is described in. U.S. Pat. No.
6,855,680 which defines suitable hydroxyfunctional crystalline
materials in detail. Preferred is hydrogenated castor oil.
Non-limiting examples of useful structurants include. Such
structurants have a thread-like structuring system having a range
of aspect ratios. Other suitable structurants and the processes for
making them are described in WO2010/034736.
[0185] The composition of the present invention may comprise a high
melting point fatty compound. The high melting point fatty compound
useful herein has a melting point of 25.degree. C. or higher, and
is selected from the group consisting of fatty alcohols, fatty
acids, fatty alcohol derivatives, fatty acid derivatives, and
mixtures thereof. Such compounds of low melting point are not
intended to be included in this section. Non-limiting examples of
the high melting point compounds are found in International
Cosmetic Ingredient Dictionary, Fifth Edition, 1993, and CTFA
Cosmetic Ingredient Handbook, Second Edition, 1992. When present,
the high melting point fatty compound is preferably included in the
composition at a level of from 0.1% to 40%, preferably from 1% to
30%, more preferably from 1.5% to 16% by weight of the composition,
from 1.5% to 8% in view of providing improved conditioning benefits
such as slippery feel during the application to wet hair, softness
and moisturized feel on dry hair.
[0186] Cationic Polymer.
[0187] The compositions of the present invention may contain a
cationic polymer. Concentrations of the cationic polymer in the
composition typically range from 0.05% to 3%, in another embodiment
from 0.075% to 2.0%, and in yet another embodiment from 0.1% to
1.0%. Suitable cationic polymers will have cationic charge
densities of at least 0.5 meq/gm, in another embodiment at least
0.9 meq/gm, in another embodiment at least 1.2 meq/gm, in yet
another embodiment at least 1.5 meq/gm, but in one embodiment also
less than 7 meq/gm, and in another embodiment less than 5 meq/gm,
at the pH of intended use of the composition, which pH will
generally range from pH 3 to pH 9, in one embodiment between pH 4
and pH 8. Herein, "cationic charge density" of a polymer refers to
the ratio of the number of positive charges on the polymer to the
molecular weight of the polymer. The average molecular weight of
such suitable cationic polymers will generally be between 10,000
and 10 million, in one embodiment between 50,000 and 5 million, and
in another embodiment between 100,000 and 3 million.
[0188] Suitable cationic polymers for use in the compositions of
the present invention contain cationic nitrogen-containing moieties
such as quaternary ammonium or cationic protonated amino moieties.
Any anionic counterions can be used in association with the
cationic polymers so long as the polymers remain soluble in water,
in the composition, or in a coacervate phase of the composition,
and so long as the counterions are physically and chemically
compatible with the essential components of the composition or do
not otherwise unduly impair product performance, stability or
aesthetics. Nonlimiting examples of such counterions include
halides (e.g., chloride, fluoride, bromide, iodide), sulfate and
methylsulfate.
[0189] Nonlimiting examples of such polymers are described in the
CTFA Cosmetic Ingredient Dictionary, 3rd edition, edited by Estrin,
Crosley, and Haynes, (The Cosmetic, Toiletry, and Fragrance
Association, Inc., Washington, D.C. (1982)).
[0190] Other suitable cationic polymers for use in the composition
include polysaccharide polymers, cationic guar gum derivatives,
quaternary nitrogen-containing cellulose ethers, synthetic
polymers, copolymers of etherified cellulose, guar and starch. When
used, the cationic polymers herein are either soluble in the
composition or are soluble in a complex coacervate phase in the
composition formed by the cationic polymer and the anionic,
amphoteric and/or zwitterionic surfactant component described
hereinbefore. Complex coacervates of the cationic polymer can also
be formed with other charged materials in the composition.
[0191] Suitable cationic polymers are described in U.S. Pat. Nos.
3,962,418; 3,958,581; and U.S. Publication No. 2007/0207109A1.
[0192] Nonionic Polymer.
[0193] The composition of the present invention may include a
nonionic polymer as a conditioning agent. Polyalkylene glycols
having a molecular weight of more than 1000 are useful herein.
Useful are those having the following general formula:
##STR00032##
[0194] wherein R95 is selected from the group consisting of H,
methyl, and mixtures thereof. Conditioning agents, and in
particular silicones, may be included in the composition. The
conditioning agents useful in the compositions of the present
invention typically comprise a water insoluble, water dispersible,
non-volatile, liquid that forms emulsified, liquid particles.
Suitable conditioning agents for use in the composition are those
conditioning agents characterized generally as silicones (e.g.,
silicone oils, cationic silicones, silicone gums, high refractive
silicones, and silicone resins), organic conditioning oils (e.g.,
hydrocarbon oils, polyolefins, and fatty esters) or combinations
thereof, or those conditioning agents which otherwise form liquid,
dispersed particles in the aqueous surfactant matrix herein. Such
conditioning agents should be physically and chemically compatible
with the essential components of the composition, and should not
otherwise unduly impair product stability, aesthetics or
performance.
[0195] The concentration of the conditioning agent in the
composition should be sufficient to provide the desired
conditioning benefits. Such concentration can vary with the
conditioning agent, the conditioning performance desired, the
average size of the conditioning agent particles, the type and
concentration of other components, and other like factors.
[0196] The concentration of the silicone conditioning agent
typically ranges from about 0.01% to about 10%. Non-limiting
examples of suitable silicone conditioning agents, and optional
suspending agents for the silicone, are described in U.S. Reissue
Pat. No. 34,584, U.S. Pat. Nos. 5,104,646; 5,106,609; 4,152,416;
2,826,551; 3,964,500; 4,364,837; 6,607,717; 6,482,969; 5,807,956;
5,981,681; 6,207,782; 7,465,439; 7,041,767; 7,217,777; US Patent
Application Nos. 2007/0286837A1; 2005/0048549A1; 2007/0041929A1;
British Pat. No. 849,433; German Patent No. DE 10036533, which are
all incorporated herein by reference; Chemistry and Technology of
Silicones, New York: Academic Press (1968); General Electric
Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76;
Silicon Compounds, Petrarch Systems, Inc. (1984); and in
Encyclopedia of Polymer Science and Engineering, vol. 15, 2d ed.,
pp 204-308, John Wiley & Sons, Inc. (1989).
[0197] Organic Conditioning Oil.
[0198] The compositions of the present invention may also comprise
from about 0.05% to about 3% of at least one organic conditioning
oil as the conditioning agent, either alone or in combination with
other conditioning agents, such as the silicones (described
herein). Suitable conditioning oils include hydrocarbon oils,
polyolefins, and fatty esters. Also suitable for use in the
compositions herein are the conditioning agents described by the
Procter & Gamble Company in U.S. Pat. Nos. 5,674,478, and
5,750,122. Also suitable for use herein are those conditioning
agents described in U.S. Pat. Nos. 4,529,586, 4,507,280, 4,663,158,
4,197,865, 4,217, 914, 4,381,919, and 4,422, 853.
[0199] Hygiene Agent.
[0200] The compositions of the present invention may also comprise
components to deliver hygiene and/or malodour benefits such as one
or more of zinc ricinoleate, thymol, quaternary ammonium salts such
as Bardac.RTM., polyethylenimines (such as Lupasol.RTM. from BASF)
and zinc complexes thereof, silver and silver compounds, especially
those designed to slowly release Ag+ or nano-silver
dispersions.
[0201] Probiotics.
[0202] The composition may comprise probiotics, such as those
described in WO2009/043709.
[0203] Suds Boosters.
[0204] The composition may preferably comprise suds boosters if
high sudsing is desired. Suitable examples are the C10-C16
alkanolamides or C10-C14 alkyl sulphates, which are preferably
incorporated at 1%-10% levels. The C10-C14 monoethanol and
diethanol amides illustrate a typical class of such suds boosters.
Use of such suds boosters with high sudsing adjunct surfactants
such as the amine oxides, betaines and sultaines noted above is
also advantageous. If desired, water-soluble magnesium and/or
calcium salts such as MgCl2, MgSO4, CaCl2, CaSO4 and the like, can
be added at levels of, typically, 0.1%-2%, to provide additional
suds and to enhance grease removal performance.
[0205] Suds Supressor.
[0206] Compounds for reducing or suppressing the formation of suds
may be incorporated into the compositions of the present invention.
Suds suppression can be of particular importance in the so-called
"high concentration cleaning process" as described in U.S. Pat.
Nos. 4,489,455 and 4,489,574, and in front-loading-style washing
machines. A wide variety of materials may be used as suds
suppressors, and suds suppressors are well known to those skilled
in the art. See, for example, Kirk Othmer Encyclopedia of Chemical
Technology, Third Edition, Volume 7, pages 430-447 (John Wiley
& Sons, Inc., 1979). Examples of suds supressors include
monocarboxylic fatty acid and soluble salts therein, high molecular
weight hydrocarbons such as paraffin, fatty acid esters (e.g.,
fatty acid triglycerides), fatty acid esters of monovalent
alcohols, aliphatic C18-C40 ketones (e.g., stearone), N-alkylated
amino triazines, waxy hydrocarbons preferably having a melting
point below about 100.degree. C., silicone suds suppressors, and
secondary alcohols. Suds supressors are described in U.S. Pat. Nos.
2,954,347; 4,265,779; 4,265,779; 3,455,839; 3,933,672; 4,652,392;
4,978,471; 4,983,316; 5,288,431; 4,639,489; 4,749,740; and
4,798,679; 4,075,118; European Patent Application No. 89307851.9;
EP 150,872; and DOS 2,124,526.
[0207] For any detergent compositions to be used in automatic
laundry washing machines, suds should not form to the extent that
they overflow the washing machine. Suds suppressors, when utilized,
are preferably present in a "suds suppressing amount. By "suds
suppressing amount" is meant that the formulator of the composition
can select an amount of this suds controlling agent that will
sufficiently control the suds to result in a low-sudsing laundry
detergent for use in automatic laundry washing machines. The
compositions herein will generally comprise from 0% to 10% of suds
suppressor. When utilized as suds suppressors, monocarboxylic fatty
acids, and salts therein, will be present typically in amounts up
to 5%, by weight, of the detergent composition. Preferably, from
0.5% to 3% of fatty monocarboxylate suds suppressor is utilized.
Silicone suds suppressors are typically utilized in amounts up to
2.0%, by weight, of the detergent composition, although higher
amounts may be used. Monostearyl phosphate suds suppressors are
generally utilized in amounts ranging from 0.1% to 2%, by weight,
of the composition. Hydrocarbon suds suppressors are typically
utilized in amounts ranging from 0.01% to 5.0%, although higher
levels can be used. The alcohol suds suppressors are typically used
at 0.2%-3% by weight of the finished compositions.
[0208] Pearlescent Agents.
[0209] Pearlescent agents as described in WO2011/163457 may be
incorporated into the compositions of the invention.
[0210] Perfume.
[0211] Preferably the composition comprises a perfume, preferably
in the range from 0.001 to 3 wt %, most preferably from 0.1 to 1 wt
%. Many suitable examples of perfumes are provided in the CTFA
(Cosmetic, Toiletry and Fragrance Association) 1992 International
Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals
Buyers Directory 80.sup.th Annual Edition, published by Schnell
Publishing Co. It is usual for a plurality of perfume components to
be present in the compositions of the invention, for example four,
five, six, seven or more. In perfume mixtures preferably 15 to 25
wt % are top notes. Top notes are defined by Poucher (Journal of
the Society of Cosmetic Chemists 6(2):80 [1995]). Preferred top
notes include rose oxide, citrus oils, linalyl acetate, lavender,
linalool, dihydromyrcenol and cis-3-hexanol.
[0212] Packaging.
[0213] Any conventional packaging may be used and the packaging may
be fully or partially transparent so that he consumer can see the
colour of the product which may be provided or contributed to by
the colour of the dyes essential to the invention. UV absorbing
compounds may be included in some or all of the packaging.
[0214] Process of Making Compositions
[0215] The compositions of the invention may be in any useful form,
as described above. They may be made by any process chosen by the
formulator, non-limiting examples of which are described in the
examples and in U.S. Pat. No. 4,990,280; U.S. 20030087791A1; U.S.
20030087790A1; U.S. 20050003983A1; U.S. 20040048764A1; U.S. Pat.
No. 4,762,636; U.S. Pat. No. 6,291,412; U.S. 20050227891A1; EP
1070115A2; U.S. Pat. No. 5,879,584; U.S. Pat. No. 5,691,297; U.S.
Pat. No. 5,574,005; U.S. Pat. No. 5,569,645; U.S. Pat. No.
5,565,422; U.S. Pat. No. 5,516,448; U.S. Pat. No. 5,489,392; U.S.
5,486.
[0216] When in the form of a liquid, the laundry care compositions
of the invention may be aqueous (typically above 2 wt % or even
above 5 or 10 wt % total water, up to 90 or up to 80 wt % or 70 wt
% total water) or non-aqueous (typically below 2 wt % total water
content). Typically the compositions of the invention will be in
the form of an aqueous solution or uniform dispersion or suspension
of surfactant, shading dye, 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.
When in the form of a liquid, the laundry care compositions of the
invention preferably have viscosity from 1 to 1500 centipoises
(1-1500 mPa*s), more preferably from 100 to 1000 centipoises
(100-1000 mPa*s), and most preferably from 200 to 500 centipoises
(200-500 mPa*s) at 20 s-1 and 21.degree. C. Viscosity can be
determined by conventional methods. Viscosity may be measured using
an AR 550 rheometer from TA instruments using a plate steel spindle
at 40 mm diameter and a gap size of 500 .mu.m. The high shear
viscosity at 20 s-1 and low shear viscosity at 0.05-1 can be
obtained from a logarithmic shear rate sweep from 0.1-1 to 25-1 in
3 minutes time at 21 C. The preferred rheology described therein
may be achieved using internal existing structuring with detergent
ingredients or by employing an external rheology modifier. More
preferably the laundry care compositions, such as detergent liquid
compositions have a high shear rate viscosity of from about 100
centipoise to 1500 centipoise, more preferably from 100 to 1000
cps. Unit Dose laundry care compositions, such as detergent liquid
compositions have high shear rate viscosity of from 400 to 1000
cps. Laundry care compositions such as laundry softening
compositions typically have high shear rate viscosity of from 10 to
1000, more preferably from 10 to 800 cps, most preferably from 10
to 500 cps. Hand dishwashing compositions have high shear rate
viscosity of from 300 to 4000 cps, more preferably 300 to 1000
cps.
[0217] The liquid compositions, preferably 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 process for preparing such
compositions, a liquid matrix is formed containing at least a major
proportion, or even 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.
[0218] In one aspect of forming the liquid compositions, the dye is
first combined with one or more liquid components to form a dye
premix, and this dye premix is added to a composition formulation
containing a substantial portion, for example more than 50% by
weight, more specifically, more than 70% by weight, and yet more
specifically, more than 90% by weight, of the balance of components
of the laundry detergent composition. For example, in the
methodology described above, both the dye premix and the enzyme
component are added at a final stage of component additions. In
another aspect, the dye is encapsulated prior to addition to the
detergent composition, the encapsulated dye 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.
[0219] Pouches.
[0220] In a preferred embodiment of the invention, the composition
is provided in the form of a unitized dose, either tablet form or
preferably in the form of a liquid/solid (optionally
granules)/gel/paste held within a water-soluble film in what is
known as a pouch or pod. The composition can be encapsulated in a
single or multi-compartment pouch. Multi-compartment pouches are
described in more detail in EP-A-2133410. When the composition is
present in a multi-compartment pouch, the composition of the
invention may be in one or two or more compartments, thus the dye
may be present in one or more compartments, optionally all
compartments. Non-shading dyes or pigments or other aesthetics may
also be used in one or more compartments. In one embodiment the
composition is present in a single compartment of a
multi-compartment pouch.
[0221] Suitable film for forming the pouches is soluble or
dispersible in water, and preferably has a
water-solubility/dispersibility of at least 50%, preferably at
least 75% or even at least 95%, as measured by the method set out
here after using a glass-filter with a maximum pore size of 20
microns:
[0222] 50 grams.+-.0.1 gram of pouch material is added in a
pre-weighed 400 ml beaker and 245 ml.+-.1 ml of distilled water is
added. This is stirred vigorously on a magnetic stirrer set at 600
rpm, for 30 minutes. Then, the mixture is filtered through a folded
qualitative sintered-glass filter with a pore size as defined above
(max. 20 micron). The water is dried off from the collected
filtrate by any conventional method, and the weight of the
remaining material is determined (which is the dissolved or
dispersed fraction). Then, the percentage solubility or
dispersability can be calculated. Preferred film materials are
polymeric materials. The film material can be obtained, for
example, by casting, blow-moulding, extrusion or blown extrusion of
the polymeric material, as known in the art. Preferred polymers,
copolymers or derivatives thereof suitable for use as pouch
material are selected from polyvinyl alcohols, polyvinyl
pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid,
cellulose, cellulose ethers, cellulose esters, cellulose amides,
polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids
or peptides, polyamides, polyacrylamide, copolymers of
maleic/acrylic acids, polysaccharides including starch and
gelatine, natural gums such as xanthum and carragum. More preferred
polymers are selected from polyacrylates and water-soluble acrylate
copolymers, methylcellulose, carboxymethylcellulose sodium,
dextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl
methylcellulose, maltodextrin, polymethacrylates, and most
preferably selected from polyvinyl alcohols, polyvinyl alcohol
copolymers and hydroxypropyl methyl cellulose (HPMC), and
combinations thereof. Preferably, the level of polymer in the pouch
material, for example a PVA polymer, is at least 60%. The polymer
can have any weight average molecular weight, preferably from about
1000 to 1,000,000, more preferably from about 10,000 to 300,000 yet
more preferably from about 20,000 to 150,000. Mixtures of polymers
can also be used as the pouch material. This can be beneficial to
control the mechanical and/or dissolution properties of the
compartments or pouch, depending on the application thereof and the
required needs. Suitable mixtures include for example mixtures
wherein one polymer has a higher water-solubility than another
polymer, and/or one polymer has a higher mechanical strength than
another polymer. Also suitable are mixtures of polymers having
different weight average molecular weights, for example a mixture
of PVA or a copolymer thereof of a weight average molecular weight
of about 10,000-40,000, preferably around 20,000, and of PVA or
copolymer thereof, with a weight average molecular weight of about
100,000 to 300,000, preferably around 150,000. Also suitable herein
are polymer blend compositions, for example comprising
hydrolytically degradable and water-soluble polymer blends such as
polylactide and polyvinyl alcohol, obtained by mixing polylactide
and polyvinyl alcohol, typically comprising about 1-35% by weight
polylactide and about 65% to 99% by weight polyvinyl alcohol.
Preferred for use herein are polymers which are from about 60% to
about 98% hydrolysed, preferably about 80% to about 90% hydrolysed,
to improve the dissolution characteristics of the material.
[0223] Naturally, different film material and/or films of different
thickness may be employed in making the compartments of the present
invention. A benefit in selecting different films is that the
resulting compartments may exhibit different solubility or release
characteristics.
[0224] Most preferred film materials are PVA films known under the
MonoSol trade reference M8630, M8900, H8779 (as described in the
Applicants co-pending applications ref 44528 and 11599) and those
described in U.S. Pat. No. 6,166,117 and U.S. Pat. No. 6,787,512
and PVA films of corresponding solubility and deformability
characteristics.
[0225] The film material herein can also comprise one or more
additive ingredients. For example, it can be beneficial to add
plasticisers, for example glycerol, ethylene glycol,
diethyleneglycol, propylene glycol, sorbitol and mixtures thereof.
Other additives include functional detergent additives to be
delivered to the wash water, for example organic polymeric
dispersants, etc.
[0226] Process for Making the Water-Soluble Pouch
The compositions of the invention in pouch form may be made using
any suitable equipment and method. However the multi-compartment
pouches are preferably made using the horizontal form filling
process. The film is preferably wetting, more preferably heated to
increase the malleability thereof. Even more preferably, the method
also involves the use of a vacuum to draw the film into a suitable
mould. The vacuum drawing the film into the mould can be applied
for 0.2 to 5 seconds, preferably 0.3 to 3 or even more preferably
0.5 to 1.5 seconds, once the film is on the horizontal portion of
the surface. This vacuum may preferably be such that it provides an
under-pressure of between -100 mbar to -1000 mbar, or even from
-200 mbar to -600 mbar.
[0227] The moulds, in which the pouches are made, can have any
shape, length, width and depth, depending on the required
dimensions of the pouches. The moulds can also vary in size and
shape from one to another, if desirable. For example, it may be
preferred that the volume of the final pouches is between 5 and 300
ml, or even 10 and 150 ml or even 20 and 100 ml and that the mould
sizes are adjusted accordingly.
[0228] Heat can be applied to the film, in the process commonly
known as thermoforming, by any means. For example the film may be
heated directly by passing it under a heating element or through
hot air, prior to feeding it onto the surface or once on the
surface. Alternatively it may be heated indirectly, for example by
heating the surface or applying a hot item onto the film. Most
preferably the film is heated using an infra red light. The film is
preferably heated to a temperature of 50 to 120.degree. C., or even
60 to 90.degree. C. Alternatively, the film can be wetted by any
mean, for example directly by spraying a wetting agent (including
water, solutions of the film material or plasticizers for the film
material) onto the film, prior to feeding it onto the surface or
once on the surface, or indirectly by wetting the surface or by
applying a wet item onto the film.
[0229] In the case of pouches comprising powders it is advantageous
to pin prick the film for a number of reasons: (a) to reduce the
possibility of film defects during the pouch formation, for example
film defects giving rise to rupture of the film can be generated if
the stretching of the film is too fast; (b) to permit the release
of any gases derived from the product enclosed in the pouch, as for
example oxygen formation in the case of powders containing bleach;
and/or (c) to allow the continuous release of perfume. Moreover,
when heat and/or wetting is used, pin pricking can be used before,
during or after the use of the vacuum, preferably during or before
application of the vacuum. Preferred is thus that each mould
comprises one or more holes which are connected to a system which
can provide a vacuum through these holes, onto the film above the
holes, as described herein in more detail.
[0230] Once a film has been heated/wetted, it is drawn into an
appropriate mould, preferably using a vacuum. The filling of the
moulded film can be done by any known method for filling (moving)
items. The most preferred method will depend on the product form
and speed of filling required. Preferably the moulded film is
filled by in-line filling techniques. The filled, open pouches are
then closed, using a second film, by any suitable method.
Preferably, this is also done while in horizontal position and in
continuous, constant motion. Preferably the closing is done by
continuously feeding a second material or film, preferably
water-soluble film, over and onto the web of open pouches and then
preferably sealing the first film and second film together,
typically in the area between the moulds and thus between the
pouches.
[0231] Preferred methods of sealing include heat sealing, solvent
welding, and solvent or wet sealing. It is preferred that only the
area which is to form the seal, is treated with heat or solvent.
The heat or solvent can be applied by any method, preferably on the
closing material, preferably only on the areas which are to form
the seal. If solvent or wet sealing or welding is used, it may be
preferred that heat is also applied. Preferred wet or solvent
sealing/welding methods include applying selectively solvent onto
the area between the moulds, or on the closing material, by for
example, spraying or printing this onto these areas, and then
applying pressure onto these areas, to form the seal. Sealing rolls
and belts as described above (optionally also providing heat) can
be used, for example.
[0232] The formed pouches can then be cut by a cutting device.
Cutting can be done using any known method. It may be preferred
that the cutting is also done in continuous manner, and preferably
with constant speed and preferably while in horizontal position.
The cutting device can, for example, be a sharp item or a hot item,
whereby in the latter case, the hot item `burns` through the
film/sealing area.
[0233] The different compartments of a multi-compartment pouch may
be made together in a side-by-side style and consecutive pouches
are not cut. Alternatively, the compartments can be made
separately. According to this process and preferred arrangement,
the pouches are made according to the process comprising the steps
of: [0234] a) forming an first compartment (as described above);
[0235] b) forming a recess within some or all of the closed
compartment formed in step (a), to generate a second moulded
compartment superposed above the first compartment; [0236] c)
filling and closing the second compartments by means of a third
film; [0237] d) sealing said first, second and third films; and
[0238] e) cutting the films to produce a multi-compartment
pouch.
[0239] Said recess formed in step b is preferably achieved by
applying a vacuum to the compartment prepared in step a).
[0240] Alternatively the second, and optionally third,
compartment(s) can be made in a separate step and then combined
with the first compartment as described in our co-pending
application EP 08101442.5 which is incorporated herein by
reference. A particularly preferred process comprises the steps of:
[0241] a) forming a first compartment, optionally using heat and/or
vacuum, using a first film on a first forming machine; [0242] b)
filling said first compartment with a first composition; [0243] c)
on a second forming machine, deforming a second film, optionally
using heat and vacuum, to make a second and optionally third
moulded compartment; [0244] d) filling the second and optionally
third compartments; [0245] e) sealing the second and optionally
third compartment using a third film; [0246] f) placing the sealed
second and optionally third compartments onto the first
compartment; [0247] g) sealing the first, second and optionally
third compartments; and [0248] h) cutting the films to produce a
multi-compartment pouch
[0249] The first and second forming machines are selected based on
their suitability to perform the above process. The first forming
machine is preferably a horizontal forming machine. The second
forming machine is preferably a rotary drum forming machine,
preferably located above the first forming machine.
[0250] It will be understood moreover that by the use of
appropriate feed stations, it is possible to manufacture
multi-compartment pouches incorporating a number of different or
distinctive compositions and/or different or distinctive liquid,
gel or paste compositions.
[0251] Solid Form.
[0252] As noted previously, the laundry care compositions may be in
a solid form. Suitable solid forms include tablets and particulate
forms, for example, granular particles, flakes or sheets. Various
techniques for forming detergent compositions in such solid forms
are well known in the art and may be used herein. In one aspect,
for example when the composition is in the form of a granular
particle, the dye is provided in particulate form, optionally
including additional but not all components of the laundry
detergent composition. The dye particulate is combined with one or
more additional particulates containing a balance of components of
the laundry detergent composition. Further, the dye, optionally
including additional but not all components of the laundry
detergent composition, may be provided in an encapsulated form, and
the shading dye encapsulate is combined with particulates
containing a substantial balance of components of the laundry
detergent composition. Suitable pre-mix particles for incorporation
of dyes/benefit agents into laundry care compositions of the
invention are described for example in WO2010/084039,
WO2007/039042, WO2010/022775, WO2009/132870, WO2009/087033,
WO2007/006357, WO2007/039042, WO2007/096052, WO2011/020991,
WO2006/053598, WO2003/018740 and WO2003/018738.
[0253] Method of Use. The compositions of this invention, prepared
as hereinbefore described, can be used to form aqueous
washing/treatment solutions for use in the laundering/treatment of
fabrics. Generally, an effective amount of such compositions is
added to water, for example in a conventional fabric automatic
washing machine, to form such aqueous laundering solutions. The
aqueous washing solution so formed is then contacted, typically
under agitation, with the fabrics to be laundered/treated
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, or from about 1,000 to
3,000 ppm of the detergent compositions herein will be provided in
aqueous washing solution.
[0254] Typically, the wash liquor is formed by contacting the
laundry care composition with wash water in such an amount so that
the concentration of the laundry care composition in the wash
liquor is from above 0 g/l to 5 g/l, or from 1 g/l, and to 4.5 g/l,
or to 4.0 g/l, or to 3.5 g/l, or to 3.0 g/l, or to 2.5 g/l, or even
to 2.0 g/l, or even to 1.5 g/l. The method of laundering fabric or
textile may be carried out in a top-loading or front-loading
automatic washing machine, or can be used in a hand-wash laundry
application. In these applications, the wash liquor formed and
concentration of laundry detergent composition in the wash liquor
is that of the main wash cycle. Any input of water during any
optional rinsing step(s) is not included when determining the
volume of the wash liquor.
[0255] The wash liquor may comprise 40 litres or less of water, or
30 litres or less, or 20 litres or less, or 10 litres or less, or 8
litres or less, or even 6 litres or less of water. The wash liquor
may comprise from above 0 to 15 litres, or from 2 litres, and to 12
litres, or even to 8 litres of water. Typically from 0.01 kg to 2
kg of fabric per litre of wash liquor is dosed into said wash
liquor. Typically from 0.01 kg, or from 0.05 kg, or from 0.07 kg,
or from 0.10 kg, or from 0.15 kg, or from 0.20 kg, or from 0.25 kg
fabric per litre of wash liquor is dosed into said wash liquor.
Optionally, 50 g or less, or 45 g or less, or 40 g or less, or 35 g
or less, or 30 g or less, or 25 g or less, or 20 g or less, or even
15 g or less, or even 10 g or less of the composition is contacted
to water to form the wash liquor. Such compositions are typically
employed at concentrations of from about 500 ppm to about 15,000
ppm in solution. When the wash solvent is water, the water
temperature typically ranges from about 5.degree. C. to about
90.degree. C. and, when the situs comprises a fabric, the water to
fabric ratio is typically from about 1:1 to about 30:1. Typically
the wash liquor comprising the laundry care composition of the
invention has a pH of from 3 to 11.5.
[0256] In one aspect, such method comprises the steps of optionally
washing and/or rinsing said surface or fabric, contacting said
surface or fabric with any composition disclosed in this
specification then optionally washing and/or rinsing said surface
or fabric is disclosed, with an optional drying step.
[0257] Drying of such surfaces or fabrics may be accomplished by
any one of the common means employed either in domestic or
industrial settings. The fabric may comprise any fabric capable of
being laundered in normal consumer or institutional use conditions,
and the invention is particularly suitable for synthetic textiles
such as polyester and nylon and especially for treatment of mixed
fabrics and/or fibres comprising synthetic and cellulosic fabrics
and/or fibres. As examples of synthetic fabrics are polyester,
nylon, these may be present in mixtures with cellulosic fibres, for
example, polycotton fabrics. The solution typically has a pH of
from 7 to 11, more usually 8 to 10.5. The compositions are
typically employed at concentrations from 500 ppm to 5,000 ppm in
solution. The water temperatures typically range from about
5.degree. C. to about 90.degree. C. The water to fabric ratio is
typically from about 1:1 to about 30:1.
EXAMPLES
[0258] In the following examples, the dye of formula 1 can be any
dye of formula 1 or mixtures thereof, in particular any of dyes 1
to 13 shown in the Dye Synthesis Examples above, or mixtures
thereof.
Examples 1-6
[0259] Granular laundry detergent compositions for hand washing or
washing machines, typically top-loading washing machines.
TABLE-US-00001 1 2 3 4 5 6 (wt %) (wt %) (wt %) (wt %) (wt %) (wt
%) Linear alkylbenzenesulfonate 20 22 20 15 19.5 20 C.sub.12-14
Dimethylhydroxyethyl 0.7 0.2 1 0.6 0.0 0 ammonium chloride AE3S 0.9
1 0.9 0.0 0.4 0.9 AE7 0.0 0.0 0.0 1 0.1 3 Sodium tripolyphosphate 5
0.0 4 9 2 0.0 Zeolite A 0.0 1 0.0 1 4 1 1.6R Silicate
(SiO.sub.2:Na.sub.2O at 7 5 2 3 3 5 ratio 1.6:1) Sodium carbonate
25 20 25 17 18 19 Polyacrylate MW 4500 1 0.6 1 1 1.5 1 Random graft
copolymer.sup.1 0.1 0.2 0.0 0.0 0.05 0.0 Carboxymethyl cellulose 1
0.3 1 1 1 1 Stainzyme .RTM. (20 mg active/g) 0.1 0.2 0.1 0.2 0.1
0.1 Protease (Savinase .RTM., 32.89 mg 0.1 0.1 0.1 0.1 0.1
active/g) Amylase - Natalase .RTM. (8.65 mg 0.1 0.0 0.1 0.0 0.1 0.1
active/g) Lipase - Lipex .RTM. (18 mg 0.03 0.07 0.3 0.1 0.07 0.4
active/g) Dye of formula 1 0.01 0.001 0.003 0.0005 0.002 0.0009
Fluorescent Brightener 1 0.06 0.0 0.06 0.18 0.06 0.06 Fluorescent
Brightener 2 0.1 0.06 0.1 0.0 0.1 0.1 DTPA 0.6 0.8 0.6 0.25 0.6 0.6
MgSO.sub.4 1 1 1 0.5 1 1 Sodium Percarbonate 0.0 5.2 0.1 0.0 0.0
0.0 Sodium Perborate 4.4 0.0 3.85 2.09 0.78 3.63 Monohydrate NOBS
1.9 0.0 1.66 0.0 0.33 0.75 TAED 0.58 1.2 0.51 0.0 0.015 0.28
Sulphonated zinc 0.0030 0.0 0.0012 0.0030 0.0021 0.0 phthalocyanine
S-ACMC 0.1 0.0 0.0 0.0 0.06 0.0 Direct Violet Dye (DV9 or 0.0 0.0
0.0003 0.0001 0.0001 0.0 DV99 or DV66) Sulfate/Moisture Balance
Examples 7-13
[0260] Granular laundry detergent compositions typically for
front-loading automatic washing machines.
TABLE-US-00002 7 8 9 10 11 12 13 (wt %) (wt %) (wt %) (wt %) (wt %)
(wt %) (wt %) Linear alkylbenzenesulfonate 8 7.1 7 6.5 7.5 7.5 2.0
AE3S 0 4.8 1.0 5.2 4 4 2.5 C12-14 Alkylsulfate 1 0 1 0 0 0 0.5 AE7
2.2 0 2.2 0 0 0 6.5 C.sub.10-12 Dimethyl 0.75 0.94 0.98 0.98 0 0 0
hydroxyethylammonium chloride Crystalline layered silicate
(.delta.- 4.1 0 4.8 0 0 0 0 Na.sub.2Si.sub.2O.sub.5) Zeolite A 5 0
5 0 2 2 0.5 Citric Acid 3 5 3 4 2.5 3 2.5 Sodium Carbonate 15 20 14
20 23 23 23 Silicate 2R (SiO.sub.2:Na.sub.2O at ratio 0.08 0 0.11 0
0 0 0 2:1) Soil release agent 0.75 0.72 0.71 0.72 0 0 0 Acrylic
Acid/Maleic Acid 1.1 3.7 1.0 3.7 2.6 3.8 3.8 Copolymer
Carboxymethylcellulose 0.15 1.4 0.2 1.4 1 0.5 0.5 Protease -
Purafect .RTM. (84 mg active/g 0.2 0.2 0.3 0.15 0.12 0.13 0.13
Amylase - Stainzyme Plus .RTM. (20 mg 0.2 0.15 0.2 0.3 0.15 0.15
0.15 active/g) Lipase - Lipex .RTM. (18.00 mg active/g) 0.05 0.15
0.1 0 0 0 0 Amylase - Natalase .RTM. (8.65 mg 0.1 0.2 0 0 0.15 0.15
0.15 active/g) Cellulase - Celluclean .TM. (15.6 mg 0 0 0 0 0.1 0.1
0.1 active/g) Dye of formula 1 0.01 0.006 0.008 0.007 0.02 0.005
0.005 TAED 3.6 4.0 3.6 4.0 2.2 1.4 1.4 Percarbonate 13 13.2 13 13.2
16 14 1.4 Na salt of Ethylenediamine-N,N'- 0.2 0.2 0.2 0.2 0.2 0.2
0.2 disuccinic acid, (S,S) isomer (EDDS) Hydroxyethane di
phosphonate 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (HEDP) MgSO.sub.4 0.42 0.42
0.42 0.42 0.4 0.4 0.4 Perfume 0.5 0.6 0.5 0.6 0.6 0.6 0.6 Suds
suppressor agglomerate 0.05 0.1 0.05 0.1 0.06 0.05 0.05 Soap 0.45
0.45 0.45 0.45 0 0 0 Sulphonated zinc phthalocyanine 0.0007 0.0012
0.0007 0 0 0 0 (active) S-ACMC 0.01 0.01 0 0.01 0 0 0 Direct Violet
9 (active) 0 0 0.0001 0.0001 0 0 0 Sulfate/Water &
Miscellaneous Balance indicates data missing or illegible when
filed
[0261] Any of the above compositions is used to launder fabrics at
a concentration of 7000 to 10000 ppm in water, 20-90.degree. C.,
and a 5:1 water:cloth ratio. The typical pH is about 10. The
fabrics are then dried. In one aspect, the fabrics are actively
dried using a dryer. In one aspect, the fabrics are actively dried
using an iron. In another aspect, the fabrics are merely allowed to
dry on a line wherein they are exposed to air and optionally
sunlight.
Examples 14-20
Heavy Duty Liquid Laundry Detergent Compositions
TABLE-US-00003 [0262] 14 15 16 17 18 19 20 (wt %) (wt %) (wt %) (wt
%) (wt %) (wt %) (wt %) AES C.sub.12-15 alkyl ethoxy (1.8) sulfate
11 10 4 6.32 0 0 0 AE3S 0 0 0 0 2.4 0 0 Linear alkyl benzene 1.4 4
8 3.3 5 8 19 sulfonate/sulfonic acid HSAS 3 5.1 3 0 0 0 0 Sodium
formate 1.6 0.09 1.2 0.04 1.6 1.2 0.2 Sodium hydroxide 2.3 3.8 1.7
1.9 1.7 2.5 2.3 Monoethanolamine 1.4 1.49 1.0 0.7 0 0 To pH 8.2
Diethylene glycol 5.5 0.0 4.1 0.0 0 0 0 AE9 0.4 0.6 0.3 0.3 0 0 0
AE8 0 0 0 0 0 0 20.0 AE7 0 0 0 0 2.4 6 0 Chelant (HEDP) 0.15 0.15
0.11 0.07 0.5 0.11 0.8 Citric Acid 2.5 3.96 1.88 1.98 0.9 2.5 0.6
C.sub.12-14 dimethyl Amine Oxide 0.3 0.73 0.23 0.37 0 0 0
C.sub.12-18 Fatty Acid 0.8 1.9 0.6 0.99 1.2 0 15.0
4-formyl-phenylboronic acid 0 0 0 0 0.05 0.02 0.01 Borax 1.43 1.5
1.1 0.75 0 1.07 0 Ethanol 1.54 1.77 1.15 0.89 0 3 7 A compound
having the following 0.1 0 0 0 0 0 2.0 general structure:
bis((C.sub.2H.sub.5O)(C.sub.2H.sub.4O)n)(CH.sub.3)--N.sup.+--
C.sub.xH.sub.2x--N.sup.+--(CH.sub.3)-
bis((C.sub.2H.sub.5O)(C.sub.2H.sub.4O)n), wherein n = from 20 to
30, and x = from 3 to 8, or sulphated or sulphonated variants
thereof Ethoxylated (EO.sub.15) tetraethylene 0.3 0.33 0.23 0.17
0.0 0.0 0 pentamine Ethoxylated Polyethylenimine .sup.2 0 0 0 0 0 0
0.8 Ethoxylated hexamethylene diamine 0.8 0.81 0.6 0.4 1 1
1,2-Propanediol 0.0 6.6 0.0 3.3 0.5 2 8.0 Fluorescent Brightener
0.2 0.1 0.05 0.3 0.15 0.3 0.2 Hydrogenated castor oil derivative
0.1 0 0 0 0 0 0.1 structurant Perfume 1.6 1.1 1.0 0.8 0.9 1.5 1.6
Core Shell Melamine-formaldehyde 0.10 0.05 0.01 0.02 0.1 0.05 0.1
encapsulate of perfume Protease (40.6 mg active/g) 0.8 0.6 0.7 0.9
0.7 0.6 1.5 Mannanase: Mannaway .RTM. (25 mg 0.07 0.05 0.045 0.06
0.04 0.045 0.1 active/g) Amylase: Stainzyme .RTM. (15 mg 0.3 0 0.3
0.1 0 0.4 0.1 active/g) Amylase: Natalase .RTM. (29 mg 0 0.2 0.1
0.15 0.07 0 0.1 active/g) Xyloglucanase (Whitezyme .RTM., 20 mg 0.2
0.1 0 0 0.05 0.05 0.2 active/g) Lipex .RTM. (18 mg active/g) 0.4
0.2 0.3 0.1 0.2 0 0 Dye of formula 1 0.006 0.002 0.001 0.01 0.005
0.003 0.004 *Water, dyes & minors Balance *Based on total
cleaning and/or treatment composition weight, a total of no more
than 12% water
Examples 21 to 25
Unit Dose Compositions
[0263] This Example provides various formulations for unit dose
laundry detergents. Such unit dose formulations can comprise one or
multiple compartments.
[0264] The following unit dose laundry detergent formulations of
the present invention are provided below.
TABLE-US-00004 Ingredients 21 22 23 24 25 Alkylbenzene sulfonic
acid C 11-13, 14.5 14.5 14.5 14.5 14.5 23.5% 2-phenyl isomer
C.sub.12-14 alkyl ethoxy 3 sulfate 7.5 7.5 7.5 7.5 7.5 C.sub.12-14
alkyl 7-ethoxylate 13.0 13.0 13.0 13.0 13.0 Citric Acid 0.6 0.6 0.6
0.6 0.6 Fatty Acid 14.8 14.8 14.8 14.8 14.8 Enzymes (as % raw
material not active) 1.7 1.7 1.7 1.7 1.7 Ethoxylated
Polyethylenimine.sup.1 4.0 4.0 4.0 4.0 4.0 Dye of formula 1 0.005
0.006 0.003 0.001 0.1 Hydroxyethane diphosphonic acid 1.2 1.2 1.2
1.2 1.2 Brightener 0.3 0.3 0.3 0.3 0.3 P-diol 15.8 13.8 13.8 13.8
13.8 Glycerol 6.1 6.1 6.1 6.1 6.1 MEA 8.0 8.0 8.0 8.0 8.0 TIPA --
-- 2.0 -- -- TEA -- 2.0 -- -- -- Cumene sulphonate -- -- -- -- 2.0
cyclohexyl dimethanol -- -- -- 2.0 -- Water 10 10 10 10 10
Structurant 0.14 0.14 0.14 0.14 0.14 Perfume 1.9 1.9 1.9 1.9 1.9
Buffers (monoethanolamine) To pH 8.0 Solvents (1,2 propanediol,
ethanol) To 100%
Example 26
Multiple Compartment Unit Dose Compositions
[0265] Multiple compartment unit dose laundry detergent
formulations of the present invention are provided below. In these
examples the unit dose has three compartments, but similar
compositions can be made with two, four or five compartments. The
film used to encapsulate the compartments is polyvinyl alcohol.
TABLE-US-00005 Base Composition Ingredients % 26 27 28 29 Glycerol
5.3 5.0 5.0 4.2 1,2-propanediol 10.0 15.3 17.5 16.4 Citric Acid 0.5
0.7 0.6 0.5 Monoethanolamine 10.0 8.1 8.4 7.6 Caustic soda -- -- --
-- Hydroxyethane diphosphonic 1.1 2.0 0.6 1.5 acid Polyethylene
glycol 0 0 2.5 3.0 Potassium sulfite 0.2 0.3 0.5 0.7 Nonionic
Marlipal C24EO.sub.7 20.1 14.3 13.0 18.6 HLAS 24.6 18.4 17.0 14.8
Fluorescent Brightener 1+/or 2 0.2 0.2 0.02 0.3 Enzymes: protease,
amylase, 1.5 1.5 1.0 0.4 mannanase, lipase, cellulose and/or
pectate lyase C12-15 Fatty acid 16.4 6.0 11.0 13.0
bis((C.sub.2H.sub.5O)(C.sub.2H.sub.4O)n)(CH.sub.3)-- 2.9 0.1 0 0
N.sup.+--C.sub.xH.sub.2x--N.sup.+--(CH.sub.3)-
bis((C.sub.2H.sub.5O)(C.sub.2H.sub.4O)n), wherein n = from 20 to
30, and x = from 3 to 8, or sulphated or sulphonated variants
thereof Polyethyleneimine ethoxylate 1.1 5.1 2.5 4.2 PEI600 E20
Cationic cellulose polymer 0 0 0.3 0.5 Random graft copolymer 0 1.5
0.3 0.2 MgCl.sub.2 0.2 0.2 0.1 0.3 Structurant 0.2 0.12 0.2 0.2
Perfume (may include perfume 0.1 0.3 0.01 0.05 microcapsules)
Solvents (1,2 propanediol, To 100% To 100% To 100% To 100% ethanol)
and optional aesthetics Composition 30 31 Compartment A B C A B C
Volume of each 40 ml 5 ml 5 ml 40 ml 5 ml 5 ml compartment Active
material in Wt. % Perfume 1.6 1.6 1.6 1.6 1.6 1.6 Dye of formula 1
0 0.006 0 0 0 0.04 TiO2 -- -- -- -- 0.1 -- Sodium Sulfite 0.4 0.4
0.4 0.3 0.3 0.3 Acusol 305, -- 2 -- -- Rohm&Haas Hydrogenated
0.14 0.14 0.14 0.14 0.14 0.14 castor oil Base Composition Add to
Add to Add to Add to Add to Add to 26, 27, 28 or 29 100% 100% 100%
100% 100% 100% Composition 32 33 Compartment A B C A B C Volume of
each 40 ml 5 ml 5 ml 40 ml 5 ml 5 ml compartment Active material in
Wt. % Perfume 1.6 1.6 1.6 1.6 1.6 1.6 Dye of formula 1 0 0 <0.05
<0.01 0 0 TiO2 0.1 -- -- -- 0.1 -- Sodium Sulfite 0.4 0.4 0.4
0.3 0.3 0.3 Acusol 305, 1.2 2 -- -- Rohm&Haas Hydrogenated 0.14
0.14 0.14 0.14 0.14 0.14 castor oil Base Composition Add to Add to
Add to Add to Add to Add to 26, 27, 28, 29 100% 100% 100% 100% 100%
100%
Example 34
Bleach & Laundry Additive Detergent Formulations
TABLE-US-00006 [0266] Ingredients A B C D E F AES.sup.1 11.3 6.0
15.4 16.0 12.0 10.0 LAS.sup.2 25.6 12.0 4.6 -- -- 26.1
MEA-HSAS.sup.3 -- -- -- 3.5 -- -- DTPA: Diethylene 0.51 -- 1.5 --
-- 2.6 triamine pentaacetic acid 4,5-Dihydroxy-1,3- 1.82 -- -- --
-- 1.4 benzenedisulfonic acid disodium salt 1,2-propandiol -- 10 --
-- -- 15 Copolymer of 2.0 dimethylterephthalate, 1,2- propylene
glycol, methyl capped PEG Poly(ethyleneimine) 1.8 ethoxylated,
PEI600 E20 Acrylic acid/maleic 2.9 acid copolymer Acusol 880 2.0
1.8 2.9 (Hydrophobically Modified Non-Ionic Polyol) Protease (55
mg/g active) -- -- -- -- 0.1 0.1 Amylase (30 mg/g active) -- -- --
-- -- 0.02 Perfume -- 0.2 0.03 0.17 -- 0.15 Brightener 0.21 -- --
0.15 -- 0.18 Dye of formula 1 0.01 0.005 0.006 0.002 0.007 0.008
water, other optional to 100% to 100% to 100% to 100% to 100% to
100% agents/components* balance balance balance balance balance
balance *Other optional agents/components include suds suppressors,
structuring agents such as those based on Hydrogenated Castor Oil
(preferably Hydrogenated Castor Oil, Anionic Premix), solvents
and/or Mica pearlescent aesthetic enhancer.
Raw Materials and Notes for Composition Examples
[0267] LAS is linear alkylbenzenesulfonate having an average
aliphatic carbon chain length C.sub.9-C.sub.15 supplied by Stepan,
Northfield, Ill., USA or Huntsman Corp. (HLAS is acid form).
C.sub.12-14 Dimethylhydroxyethyl ammonium chloride, supplied by
Clariant GmbH, Germany AE3S is C.sub.12-15 alkyl ethoxy (3) sulfate
supplied by Stepan, Northfield, Ill., USA AE7 is C.sub.12-15
alcohol ethoxylate, with an average degree of ethoxylation of 7,
supplied by Huntsman, Salt Lake City, Utah, USA
AES is C.sub.10-18 alkyl ethoxy sulfate supplied by Shell
Chemicals. AE9 is C.sub.12-13 alcohol ethoxylate, with an average
degree of ethoxylation of 9, supplied by Huntsman, Salt Lake City,
Utah, USA HSAS or HC1617HSAS is a mid-branched primary alkyl
sulfate with average carbon chain length of about 16-17 Sodium
tripolyphosphate is supplied by Rhodia, Paris, France Zeolite A is
supplied by Industrial Zeolite (UK) Ltd, Grays, Essex, UK 1.6R
Silicate is supplied by Koma, Nestemica, Czech Republic Sodium
Carbonate is supplied by Solvay, Houston, Tex., USA Polyacrylate MW
4500 is supplied by BASF, Ludwigshafen, Germany Carboxymethyl
cellulose is Finnfix.RTM. V supplied by CP Kelco, Arnhem,
Netherlands Suitable chelants are, for example,
diethylenetetraamine pentaacetic acid (DTPA) supplied by Dow
Chemical, Midland, Mich., USA or Hydroxyethane di phosphonate
(HEDP) supplied by Solutia, St Louis, Mo., USA Bagsvaerd, Denmark
Savinase.RTM., Natalase.RTM., Stainzyme.RTM., Lipex.RTM.,
Celluclean.TM., Mannaway.RTM. and Whitezyme.RTM. are all products
of Novozymes, Bagsvaerd, Denmark. Proteases may be supplied by
Genencor International, Palo Alto, Calif., USA (e.g. Purafect
Prime.RTM.) or by Novozymes, Bagsvaerd, Denmark (e.g.
Liquanase.RTM., Coronase.RTM.). Fluorescent Brightener 1 is
Tinopal.RTM. AMS, Fluorescent Brightener 2 is Tinopal.RTM. CBS-X,
Sulphonated zinc phthalocyanine and Direct Violet 9 is
Pergasol.RTM. Violet BN-Z all supplied by Ciba Specialty Chemicals,
Basel, Switzerland Sodium percarbonate supplied by Solvay, Houston,
Tex., USA Sodium perborate is supplied by Degussa, Hanau, Germany
NOBS is sodium nonanoyloxybenzenesulfonate, supplied by Future
Fuels, Batesville, USA TAED is tetraacetylethylenediamine, supplied
under the Peractive.RTM. brand name by Clariant GmbH, Sulzbach,
Germany S-ACMC is carboxymethylcellulose conjugated with C.I.
Reactive Blue 19, sold by Megazyme, Wicklow, Ireland under the
product name AZO-CM-CELLULOSE, product code S-ACMC. Soil release
agent is Repel-o-Tex.RTM. PF, supplied by Rhodia, Paris, France
Acrylic Acid/Maleic Acid Copolymer is molecular weight 70,000 and
acrylate:maleate ratio 70:30, supplied by BASF, Ludwigshafen,
Germany Na salt of Ethylenediamine-N,N'-disuccinic acid, (S,S)
isomer (EDDS) is supplied by Octel, Ellesmere Port, UK
Hydroxyethane di phosphonate (HEDP) is supplied by Dow Chemical,
Midland, Mich., USA Suds suppressor agglomerate is supplied by Dow
Corning, Midland, Mich., USA HSAS is mid-branched alkyl sulfate as
disclosed in U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,060,443
C.sub.12-14 dimethyl Amine Oxide is supplied by Procter &
Gamble Chemicals, Cincinnati, USA Random graft copolymer is a
polyvinyl acetate grafted polyethylene oxide copolymer having a
polyethylene oxide backbone and multiple polyvinyl acetate side
chains. The molecular weight of the polyethylene oxide backbone is
about 6000 and the weight ratio of the polyethylene oxide to
polyvinyl acetate is about 40:60 and no more than 1 grafting point
per 50 ethylene oxide units. Ethoxylated polyethyleneimine is
polyethyleneimine (MW=600) with 20 ethoxylate groups per --NH.
Cationic cellulose polymer is LK400, LR400 and/or JR30M from
Amerchol Corporation, Edgewater N.J. Note: all enzyme levels are
expressed as % enzyme raw material
[0268] The dimensions and values disclosed herein are not to be
understood as being strictly limited to the exact numerical values
recited. Instead, unless otherwise specified, each such dimension
is intended to mean both the recited value and a functionally
equivalent range surrounding that value. For example, a dimension
disclosed as "40 mm" is intended to mean "about 40 mm".
[0269] Every document cited herein, including any cross referenced
or related patent or application, is hereby incorporated herein by
reference in its entirety unless expressly excluded or otherwise
limited. The citation of any document is not an admission that it
is prior art with respect to any invention disclosed or claimed
herein or that it alone, or in any combination with any other
reference or references, teaches, suggests or discloses any such
invention. Further, to the extent that any meaning or definition of
a term in this document conflicts with any meaning or definition of
the same term in a document incorporated by reference, the meaning
or definition assigned to that term in this document shall
govern.
[0270] While particular embodiments of the present invention have
been illustrated and described, it would be obvious to those
skilled in the art that various other changes and modifications can
be made without departing from the spirit and scope of the
invention. It is therefore intended to cover in the appended claims
all such changes and modifications that are within the scope of
this invention.
* * * * *