U.S. patent application number 15/648918 was filed with the patent office on 2017-10-26 for capsules and compositions comprising the same.
The applicant listed for this patent is Milliken & Company. Invention is credited to Gregory E. Fernandes, Robert M. MacMeccan.
Application Number | 20170306274 15/648918 |
Document ID | / |
Family ID | 46719407 |
Filed Date | 2017-10-26 |
United States Patent
Application |
20170306274 |
Kind Code |
A1 |
Fernandes; Gregory E. ; et
al. |
October 26, 2017 |
CAPSULES AND COMPOSITIONS COMPRISING THE SAME
Abstract
A seamless capsule comprises at least one core and a shell
layer. The capsule can further comprise an intermediate layer which
surrounds the core(s) and is surrounded by the shell layer. The
shell layer comprises a material selected from the group consisting
of water-soluble polymers, water-dispersible polymer, hydrogels.
The shell layer can further comprise a disintegration aid.
Inventors: |
Fernandes; Gregory E.;
(Lubbock, TX) ; MacMeccan; Robert M.; (Greer,
SC) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Milliken & Company |
Spartanburg |
SC |
US |
|
|
Family ID: |
46719407 |
Appl. No.: |
15/648918 |
Filed: |
July 13, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13035445 |
Feb 25, 2011 |
9725684 |
|
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15648918 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C11D 17/0039
20130101 |
International
Class: |
C11D 17/00 20060101
C11D017/00 |
Claims
1. A capsule comprising: (a) at least one core; and (b) a
continuous shell layer surrounding the core, the shell layer
comprising: (i) a material selected from the group consisting of
hydrogels, dehydrated hydrogels, water-soluble polymers,
water-dispersible polymers, and combinations thereof; and (ii) a
disintegration aid disposed in the shell layer, the disintegration
aid exhibiting an absorption of 5 grams or more of solution per
gram of disintegration aid as measured in an aqueous solution
having an electrical conductivity of about 5 .mu.S/cm or less.
2. The capsule of claim 1, wherein the water-soluble polymer and
water-dispersable polymer are selected from the group consisting of
acrylates, polyhydric alcohol, polysaccharides, polyvinyl acetate,
polyvinyl pyrrolidone, carboxymethyl cellulose, hydroxyethyl
cellulose, acrylamides, acrylates, polyethylene glycols, and
mixtures thereof.
3. The capsule of claim 2, wherein the water-soluble polymer is a
polyvinyl alcohol.
4. The capsule of claim 1, wherein the continuous shell layer
further comprises a gelling agent.
5. The capsule of claim 4, wherein the gelling agent is selected
from the group consisting of polysaccharides, gelatin, sodium
alginate, agar, carrageenans, and mixtures thereof.
6. A composition comprising at least one surfactant and at least
one capsule of claim 1.
7. A cleaning composition comprising at least one cleaning agent
and at least one capsule of claim 1.
8. A laundry care composition comprising: (a) at least one laundry
care ingredient; and (b) at least one capsule, the capsule
comprising: (i) at least one core; and (ii) a continuous shell
layer surrounding the core, the shell layer comprising: (A) a
material selected from the group consisting of hydrogels,
dehydrated hydrogels, water-soluble polymers, water-dispersible
polymers, and combinations thereof; and (B) a disintegration aid
disposed in the shell layer, the disintegration aid exhibiting an
absorption of 5 grams or more of solution per gram of
disintegration aid as measured in an aqueous solution having an
electrical conductivity of about 5 .mu.S/cm or less.
9. The laundry care composition of claim 8, wherein the laundry
care ingredient is selected from the group consisting of
surfactants, builders, chelating agents, dye transfer inhibiting
agents, dispersants, enzymes, enzyme stabilizers, catalytic
materials, bleach activators, polymeric dispersing agents, clay
soil removal/anti-redeposition agents, brighteners, suds
suppressors, dyes, additional perfume and perfume delivery systems,
structure elasticizing agents, fabric softeners, carriers,
hydrotropes, processing aids, pigments, and mixtures thereof.
10. The laundry care composition of claim 8, wherein the laundry
care composition further comprises a liquid medium, the laundry
care ingredient is dissolved or dispersed in the liquid medium, and
the capsule is suspended in the liquid medium.
11. The laundry care composition of claim 8, wherein the
water-soluble polymer and water-dispersable polymer are selected
from the group consisting of acrylates, polyhydric alcohol,
polysaccharides, polyvinyl acetate, polyvinyl pyrrolidone,
carboxymethyl cellulose, hydroxyethyl cellulose, acrylamides,
acrylates, polyethylene glycols, and mixtures thereof.
12. The laundry care composition of claim 11, wherein the
water-soluble polymer is a polyvinyl alcohol.
13. The laundry care composition of claim 8, wherein the continuous
shell layer further comprises a gelling agent.
14. The laundry care composition of claim 13, wherein the gelling
agent is selected from the group consisting of polysaccharides,
gelatin, sodium alginate, agar, carrageenans, and mixtures
thereof.
15. A capsule comprising: (a) at least one core, the core
comprising a lipophobic material; (b) a continuous, intermediate
layer surrounding each core, the intermediate layer comprising a
lipophilic material that is immiscible with or insoluble in aqueous
media; and (c) a continuous shell layer surrounding the
intermediate layer, the shell layer comprising: (i) a material
selected from the group consisting of hydrogels, dehydrated
hydrogels, water-soluble polymers, water-dispersible polymers, and
combinations thereof; and (ii) a disintegration aid disposed in the
shell layer, the disintegration aid exhibiting an absorption of 5
grams or more of solution per gram of disintegration aid as
measured in an aqueous solution having an electrical conductivity
of about 5 .mu.S/cm or less.
16. The capsule of claim 15, wherein the intermediate layer
comprises a lipophilic material selected from the group consisting
of vegetable oils, vegetable fats, animal oils, animal fats,
mineral oil, paraffinic oils, parrafinic waxes, silicone oils, and
mixtures thereof.
17. The capsule of claim 15, wherein the intermediate layer further
comprises a hydrophobic, particulate material dispersed in the
lipophilic material.
18. The capsule of claim 15, wherein the water-soluble, polymer and
water-dispersable, polymer are selected from the group consisting
of acrylates, polyhydric alcohol, polysaccharides, polyvinyl
acetate, polyvinyl pyrrolidone, carboxymethyl cellulose,
hydroxyethyl cellulose, acrylamides, acrylates, polyethylene
glycols, and mixtures thereof.
19. The capsule of claim 18, wherein the water-soluble, polymer is
a polyvinyl alcohol.
20. The capsule of claim 15, wherein the continuous shell layer
further comprises a gelling agent.
21. The capsule of claim 20, wherein the gelling agent is selected
from the group consisting of polysaccharides, gelatin, sodium
alginate, agar, carrageenans, and mixtures thereof.
22. A composition comprising at least one surfactant and at least
one capsule of claim 15.
23. A cleaning composition comprising at least one cleaning agent
and at least one capsule of claim 15.
24. A laundry care composition comprising; (a) at least one laundry
care ingredient; and (b) at least one capsule, the capsule
comprising: (a) at least one core, the core comprising a lipophobic
material; (i) a continuous, intermediate layer surrounding each
core, the intermediate layer comprising a lipophilic material that
is immiscible with or insoluble in aqueous media; and (ii) a
continuous shell layer surrounding the intermediate layer, the
shell layer comprising: (A) a material selected from the group
consisting of hydrogels, dehydrated hydrogels, water-soluble
polymers, water-dispersible polymers, and combinations thereof; and
(B) a disintegration aid disposed in the shell layer, the
disintegration aid exhibiting an absorption of 5 grams or more of
solution per gram of disintegration aid as measured in an aqueous
solution having an electrical conductivity of about 5 .mu.S/cm or
less.
25. The laundry care composition of claim 24, wherein the laundry
care ingredient is selected from the group consisting of
surfactants, builders, chelating agents, dye transfer inhibiting
agents, dispersants, enzymes, enzyme stabilizers, catalytic
materials, bleach activators, polymeric dispersing agents, clay
soil removal/anti-redeposition agents, brighteners, suds
suppressors, dyes, additional perfume and perfume delivery systems,
structure elasticizing agents, fabric softeners, carriers,
hydrotropes, processing aids, pigments, and mixtures thereof.
26. The laundry care composition of claim 24, wherein the laundry
care composition further comprises a liquid medium, the laundry
care ingredient is dissolved or dispersed in the liquid medium, and
the capsule is suspended in the liquid medium.
27. The laundry care composition of claim 24, wherein the
intermediate layer comprises a lipophilic material selected from
the group consisting of vegetable oils, vegetable fats, animal
oils, animal fats, mineral oil, paraffinic oils, parrafinic waxes,
silicone oils, and mixtures thereof.
28. The laundry care composition of claim 24, wherein the
intermediate layer further comprises a hydrophobic, particulate
material dispersed in the lipophilic material.
29. The laundry care composition of claim 24, wherein the
water-soluble, polymer and water-dispersable, polymer are selected
from the group consisting of acrylates, polyhydric alcohol,
polysaccharides, polyvinyl acetate, polyvinyl pyrrolidone,
carboxymethyl cellulose, hydroxyethyl cellulose, acrylamides,
acrylates, polyethylene glycols, and mixtures thereof.
30. The laundry care composition of claim 29, wherein the
water-soluble, polymer is a polyvinyl alcohol.
31. The laundry care composition of claim 24, wherein the
continuous shell layer further comprises a gelling agent.
32. The laundry care composition of claim 31, wherein the gelling
agent is selected from the group consisting of polysaccharides,
gelatin, sodium alginate, agar, carrageenans, and mixtures thereof.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent
application Ser. No. 13/035,445 filed on Feb. 25, 2011, which
application is herein incorporated by reference.
TECHNICAL FIELD OF THE INVENTION
[0002] This application relates to capsules and encapsulated
materials that are suitable for use in a variety of
applications.
BRIEF SUMMARY OF THE INVENTION
[0003] As noted above, the present invention provides capsules
(e.g., microcapsules). The capsules generally comprise one or more
encapsulated materials and a continuous shell layer surrounding the
encapsulated materials. Unlike the capsules that are familiar from
pharmaceutical applications, these capsules are not formed by
mating two preformed halves. Rather, the shell layer of the capsule
is continuous and formed in such a way that it does not have a seam
or joint where two halves meet or are joined. The encapsulated
materials can be one or more cores, or the encapsulated materials
can be a number of discrete cores each surrounded by a continuous
intermediate layer. The capsules provided by the invention are
believed to be particularly well-suited for the protection of
certain components from, for example, deleterious interactions with
other components in a system (e.g., cleaning composition, such as a
laundry detergent). The capsules are also believed to provide a
convenient means by which a bluing agent can be added to a
composition, such as a laundry detergent composition, without
affecting the overall aesthetics of the composition. In other
words, the composition can be provided with virtually any visual
appearance because the composition would contain a relatively small
number of colored capsules (i.e., capsules containing the bluing
agent), whereas the straight addition of the same amount of bluing
agent to the composition would result in a composition exhibiting
the color of the bluing agent.
[0004] In a first embodiment, the invention provides a capsule
comprising:
[0005] (a) about 1 to about 5 discrete cores, each core
independently comprising at least one lipophobic material selected
from the group consisting of dyes, pigments, polymeric colorants,
optical brighteners, fluorescing dyes, bleaching agents, bleach
activators, bleach catalysts, bleach stabilizers, textile hand
modifiers, fabric softeners, fabric stiffeners, soil release
agents, enzymes, oxidizing agents, antimicrobials, antifungal
agents, disinfectants, antioxidants, water softening agents,
detergent builders, antiredeposition agents, foam boosters,
humectants, water soluble polymers, odor removers, dye-transfer
inhibitors, UV absorbers, UV stabilizers, botanic extracts, urea,
sequestrants, abrasives, water, and combinations thereof;
[0006] (b) a continuous, intermediate layer surrounding each core,
the intermediate layer comprising a lipophilic material that is
immiscible with or insoluble in aqueous media; and
[0007] (c) a continuous shell layer surrounding the intermediate
layer, the shell layer comprising a material selected from the
group consisting of hydrogels, dehydrated hydrogels, water-soluble
polymers, water-dispersible polymers, and combinations thereof.
[0008] In a second embodiment, the invention provides a capsule
comprising:
[0009] (a) at least one core; and
[0010] (b) a continuous shell layer surrounding the core, the shell
layer comprising: [0011] (i) a material selected from the group
consisting of hydrogels, dehydrated hydrogels, water-soluble
polymers, water-dispersible polymers, and combinations thereof; and
[0012] (ii) a disintegration aid disposed in the shell layer, the
disintegration aid exhibiting an absorption of 5 grams or more of
solution per gram of disintegration aid as measured in an aqueous
solution having an electrical conductivity of about 5 .mu.S/cm or
less.
[0013] In a third embodiment, the invention provides a capsule
comprising:
[0014] (a) at least one core, the core comprising a lipophobic
material;
[0015] (b) a continuous, intermediate layer surrounding each core,
the intermediate layer comprising a lipophilic material that is
immiscible with or insoluble in aqueous media; and
[0016] (c) a continuous shell layer surrounding the intermediate
layer, the shell layer comprising: [0017] (i) a material selected
from the group consisting of hydrogels, dehydrated hydrogels,
water-soluble polymers, water-dispersible polymers, and
combinations thereof; and [0018] (ii) a disintegration aid disposed
in the shell layer, the disintegration aid exhibiting an absorption
of 5 grams or more of solution per gram of disintegration aid as
measured in an aqueous solution having an electrical conductivity
of about 5 .mu.S/cm or less.
[0019] The invention also provides compositions comprising at least
one of the capsules according to the invention. In a specific
embodiment, the invention provides a composition comprising at
least one surfactant and at least one capsule according to the
invention or a plurality of capsules according to the invention. In
another embodiment, the invention provides a cleaning composition
comprising at least one cleaning agent and at least one capsule
according to the invention or a plurality of capsules according to
the invention. In yet another embodiment, the invention provides a
laundry care composition comprising at least one laundry care
ingredient and at least one capsule according to the invention or a
plurality of capsules according to the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] FIG. 1 is a cross-section view of a capsule according to the
invention.
[0021] FIG. 2 is a cross-section view of another capsule according
to the invention.
[0022] FIG. 3 is a cross-section view of another capsule according
to the invention.
[0023] FIG. 4 is a cross-section view of a triple nozzle
coextrusion apparatus suitable for use in making the capsules
according to the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0024] As utilized herein, the term "core" refers to a discrete
body residing within the interior of a capsule. The core has a
distinct boundary separating it from either the surrounding
intermediate layer or, in other embodiments, the shell layer. The
core can be a solid, a liquid, or both (e.g., a solid dispersed or
suspended within a liquid). Furthermore, the core can be a solution
containing a solid or a semi-solid dissolved within a suitable
solvent (e.g., water, an alcohol, or a mixture thereof).
[0025] As utilized herein, the terms "lipophobic" and "lipophilic"
are generally used in a relative sense intended to convey the
affinity of one component of the capsule (e.g., the core) for
another component (e.g., the continuous intermediate layer). Thus,
unless specifically noted in the specification, the terms are not
intended to indicate that a component exhibits any particular
hydrophilic-lipophilic balance value.
[0026] In a first embodiment, such as that depicted in FIGS. 1 and
2, the invention provides a capsule 100, 200 comprising a
relatively small number of cores 110, a continuous intermediate
layer 120 surrounding each core 110, and a continuous shell layer
130 surrounding the intermediate layer 120. In such an embodiment,
the capsule can comprise any suitable number of cores. In one
particular embodiment, the capsule comprises about 10 cores or
less, or about 5 cores or less. In another embodiment, the capsule
comprises about 1 to about 5 discrete cores.
[0027] In this embodiment, the core comprises a lipophobic
material. As utilized in connection with this embodiment, the term
"lipophobic" is generally used to denote a material that exhibits a
sufficient aversion to the intermediate layer that at least a
portion of the material can form a discrete, separate phase when
the two are combined and this phase separation remains stable for a
substantial period of time (e.g., about 24 hours or more). In a
preferred embodiment, the lipophobic material exhibits an
octanol-water partition coefficient (log Pow) of less than 6 (e.g.,
about 5 or less, about 4 or less, about 3 or less, about 2 or less,
or about 1 or less). The lipophobic material present in the core
can be any suitable lipophobic material. Suitable lipophobic
materials include, but are not necessarily limited to, dyes (e.g.,
acid dyes), pigments, polymeric colorants, optical brighteners,
fluorescing dyes, bleaches, textile hand modifiers, fabric
softeners, soil release agents, enzymes, oxidizing agents,
antimicrobials, antioxidants, water-soluble polymers (e.g.,
polyethylene glycols, polyvinylpyrrolidone, and cellulose ethers),
non-ionic surfactants, anionic surfactants, cationic surfactants,
amphoteric surfactants, detergent builders, alkalis, acids, bases,
complexing agents, ion-exchangers, bleaching agents, bleach
activators, bleach catalysts, bleach stabilizers, enzymes, soil
antiredeposition agents, soil repellant agents, soil release
agents, foam regulators, corrosion inhibitors, fluorescent
whitening agents, fabric softeners, fabric stiffeners, odor
removers, dye-transfer inhibitors, polyacrylate dispersants,
rheology modifiers, buffers, defoamers, hydrotopes, foam
stabilizers, foam boosters, antifungal agents, UV absorbers,
botanic extracts, protein hydrolytes, urea, sequestrants,
humectants, exfoliants, abrasives, disinfectants, peracids,
chelants, UV stabilizers, water, water miscible solvents (e.g.,
alcohols, DMSO, glycerine, glycol ethers, diethanolamine, other
alkanolamines, and amides thereof), and combinations thereof. In
certain possibly preferred embodiments, the lipophobic material can
be a colorant, such as a dye, pigment, polymeric colorant, or a
combination thereof. In certain preferred embodiments, the
lipophobic material is a polymeric colorant.
[0028] As utilized herein, the term "polymeric colorant" refers to
a colorant comprising a chromophore and an oligomeric constituent
bound to the chromophore. The oligomeric constituent can be bound
to the chromophore via any suitable means, such as a covalent bond,
an ionic bond, or suitable electrostatic interaction. The
oligomeric constituent can have any suitable formula weight. As
utilized herein in reference to the oligomeric constituent, the
term "formula weight" refers to the weight (in grams) of the
oligomeric constituent per mole of the polymeric colorant. In other
words, the "formula weight" of the oligomeric constituent refers to
the portion of the polymeric colorant's molecular weight
attributable to the oligomeric constituent (the remainder being
attributable to the chromophore and any other groups attached
thereto). Typically, the oligomeric constituent has a formula
weight of about 40 or more. The oligomeric constituent typically
has a formula weight of about 3,000 or less. In certain possibly
preferred embodiments, the oligomeric constituent has a formula
weight of about 40 to about 3,000.
[0029] Polymeric colorants suitable for use in the invention
include, but are not limited to, those colorants conforming to the
structure of Formula (I) or Formula (II) below:
##STR00001##
[0030] In the structure of Formula (I), R.sub.1 or
R.sub.1-[E].sub.a is an organic chromophore. Each E is a linking
moiety independently selected from the group consisting of
nitrogen, oxygen, sulfur, a sulfonyl group, a sulfonate group, a
sulfonamide group, and a carboxyl group. Each R.sub.2 is
independently selected from the group consisting of hydrogen, alkyl
groups, alkoxy groups, and aryl groups. The variable a is a
positive integer. The variables b and c are independently selected
from the group consisting of integers from 0 to 2. If E is nitrogen
or a sulfonamide group, the sum of b and c is 2. If E is oxygen,
sulfur, a sulfonyl group, a sulfonated group, or a carbonyl, the
variable b is 0 and c is 1. Also, the polymeric colorant conforming
to the structure of Formula (I) contains at least one -Z-X
substituent bound to R.sub.1 through a linking moiety E. In other
words, if the polymeric colorant contains only one liking moiety E
(i.e., a is 1), then at least one -Z-X substituent is bound to the
linking moiety E (i.e., c is at least 1). If the polymeric colorant
contains multiple linking moieties E (i.e., a is 2 or more), then
at least one of the linking moieties has at least one -Z-X
substituent thereto (i.e., at least one of the variables c is 1 or
greater).
[0031] In the structure of Formula (II), R.sub.4 or
R.sub.4(G).sub.h is an organic chromophore. G is selected from the
group consisting of SO.sub.3.sup.- and CO.sub.2.sup.-. Each R.sub.5
is independently selected from the group consisting of hydrogen,
alkyl groups, and aryl groups; and M is selected from the group
consisting of nitrogen atoms and phosphorous atoms. The variable h
is an integer from 1 to 4, the variable k is an integer from 0 to
5, and the variable j is an integer from 1 to 6. The sum of k and j
is equal to 4 when M is a nitrogen atom and 6 when M is a
phosphorous atom.
[0032] In each of the structures of Formula (I) or Formula (II),
each Z is a divalent organic moiety independently selected from the
group consisting of C.sub.1-C.sub.20 alkyl moieties, aryl moieties,
alkoxyl moieties, and oligomeric substituents. The oligomeric
substituents are selected from the group consisting of (A) divalent
oligomeric substituents comprising two or more divalent repeating
units independently selected from repeating units conforming to the
structure of Formula (III)
##STR00002##
wherein R.sub.20 and R.sub.21 are independently selected from the
group consisting of hydrogen, alkyl, hydroxyalkyl, aryl,
alkoxyalkyl, and aryloxyalkyl; (B) divalent substituents conforming
to the structure of Formula (VIII)
##STR00003##
wherein R.sub.25 and R.sub.26 are independently selected from the
group consisting of hydrogen, hydroxyl, and C.sub.1-C.sub.10 alkyl,
f is an integer from 1 to 12, and g is an integer from 1 to 100;
and (C) divalent substituents comprising two or more substituents
selected from (A) and (B). Also, each X is an end group
independently selected from the group consisting of hydrogen, a
hydroxyl group, a sulfhydryl group, thiol groups, amine groups,
alkyl groups, aryl groups, alkyl ester groups, aryl ester groups,
organic sulfonate groups, organic sulfate groups, and amide groups.
In certain embodiments, at least one -Z-X substituent of the
colorant conforming to the structure of Formula (I) or Formula (II)
terminates in a group selected from the group consisting of a
hydroxyl group, a sulfhydryl group, thiol groups, primary amine
groups, secondary amine groups, primary amide groups, and secondary
amide groups. Lastly, in each of the structures of Formula (I) or
Formula (II), at least one -Z-X substituent comprises an oligomeric
substituent as defined above.
[0033] In those embodiments in which the capsule comprises more
than one core, the cores can be the same or different. In other
words, each core can contain the same component(s), each core can
contain different components, or some of the cores can contain the
same components and other cores contain different components.
[0034] The core(s) can comprise any suitable percentage of the
capsule's total volume. In certain embodiments, such as when the
shell layer is hydrated (e.g., the shell contains a hydrogel), the
core(s) can comprise about 5% to about 95% of the capsule's total
volume. In certain other embodiments, such as when the shell layer
is dehydrated, the core(s) can comprise about 5% to about 99% of
the capsule's total volume. In certain possibly preferred
embodiments, the core(s) can comprise about 30% to about 80% of the
capsule's total volume.
[0035] As noted above, the capsules of the first embodiment
comprise a continuous, intermediate layer surrounding each core.
The intermediate layer can be any suitable material, but generally
the intermediate layer comprises a lipophilic material that is
immiscible with or insoluble in aqueous media. As with the term
"lipophobic," the term "lipophilic" is used in connection with this
embodiment to describe the relative affinity of the core material
for the intermediate layer. Thus, the term "lipophilic" is used to
describe a material that exhibits a sufficient aversion to the core
material that at least a portion of the core material can form a
discrete, separate phase when the two are combined and this phase
separation remains stable for a substantial period of time (e.g.,
about 24 hours or more). In a preferred embodiment, the lipophilic
material exhibits an octanol-water partition coefficient of 6 or
greater (e.g., about 7 or more, about 8 or more, about 9 or more,
or about 10 or more). In certain other embodiments, the lipophilic
material exhibits a water solubility of less than about one gram
per 100 grams of water at 20.degree. C. and 1 atm pressure.
[0036] The intermediate layer can comprise any suitable material
exhibiting the properties described above. The intermediate layer
can be a solid, a liquid, or both (e.g., a solid dispersed or
suspended within a liquid). Furthermore, the intermediate layer can
be a solution containing a solid dissolved within a suitable
solvent. Lipophilic materials suitable for use as the intermediate
layer include, but are not limited to, vegetable oils (e.g., corn
oil), vegetable fats, animal oils, animal fats, mineral oil,
paraffinic oils, parrafinic waxes, silicone oils, and mixtures
thereof. In certain possibly preferred embodiments, the
intermediate layer comprises a vegetable oil (e.g., corn oil) or a
silicone oil.
[0037] The intermediate layer can comprise any suitable percentage
of the capsule's total volume. In certain embodiments, the
intermediate layer can comprise about 2% to about 90% of the
capsule's total volume. In certain preferred embodiments, the
intermediate layer can comprise about 4% to about 50% of the
capsule's total volume or about 6% to about 30% of the capsule's
total volume.
[0038] While the lipophobic material of the core and the lipophilic
material of the intermediate layer can be selected to yield
capsules in which the core(s) will remain stable for an extended
period of time, it may be desirable to increase the stability of
the core(s) by incorporating additional components into the
intermediate layer. For example, the stability of the cores can be
increased by dispersing or suspending a hydrophobic, particulate
material in the intermediate layer. In such an embodiment, the
hydrophobic, particulate material can be any suitable particulate
material that can be stably dispersed or suspended in the
intermediate layer. Suitable hydrophobic, particulate materials
include, but are not limited to, hydrophobic silica (e.g.,
hydrophobic fumed silica, hydrophobic precipitated silica, and
mixtures thereof), hydrophobic clays, hydrophobic sands,
hydrophobic minerals, hydrophobic carbonaceous particles, and
combinations thereof. While not wishing to be bound to any
particular theory, it is believed that such hydrophobic,
particulate materials act as barriers that help to contain the
cores and block the cores from contacting the shell layer, which
can result in the rupture of the shell layer and capsule.
[0039] If a hydrophobic particulate material is used, the
hydrophobic particles can be present in the intermediate layer in
any suitable amount. Generally, the hydrophobic particles are added
to the intermediate layer in an amount sufficient to appreciably
increase the stability of the core(s) and the capsule. In those
embodiments in which the intermediate layer contains a hydrophobic
particulate material, the hydrophobic particulate material can be
present in the intermediate layer in an amount of about 45% or less
(e.g., about 25% or less, about 20% or less, about 15% or less,
about 10% or less, or about 5% or less), based on the total weight
of the intermediate layer. In those embodiments in which the
intermediate layer contains a hydrophobic particulate material, the
hydrophobic material can be present in the intermediate layer in an
amount of about 0.1 wt. % or more (e.g., about 0.2 wt. % or more,
about 0.3 wt. % or more, about 0.4 wt. % or more, about 0.5 wt. %
or more, about 0.6 wt. % or more, about 0.7 wt. % or more, about
0.8 wt. % or more, about 0.9 wt. % or more, or about 1 wt. % or
more).
[0040] In addition to the lipophilic material and the hydrophobic
particulate material described above, the intermediate layer can
comprise additional components. Due to the lipophilic nature of the
materials contained in the intermediate layer, the suitable
additional components typically are those that can be dissolved or
dispersed in the lipophilic material described above. Suitable
examples include, but are not limited to, hydrophobic/lipophilic
colorants (e.g., pigments, dyes, polymeric colorants),
hydrophobic/lipophilic perfumes, hydrophobic/lipophilic fragrances,
hydrophobic/lipophilic antifoaming agents, hydrophobic/lipophilic
suds depressants, opacifiers, hydrophobic/lipophilic fluorescent
whitening agents, hydrophobic/lipophilic fabric softeners,
hydrophobic/lipophilic antistatic agents, other oils (e.g.,
eucalyptus oils or pine oils), and combinations thereof.
[0041] In this first embodiment, the capsule comprises a shell
layer surrounding the intermediate layer. The shell layer can be
made from any suitable material that forms a shell of sufficient
durability to encapsulate the core and intermediate layer and is
stable for an extended period of time when in contact with the
intermediate layer. Thus, in this embodiment, the shell layer
typically is not comprised of a material that exhibits an
appreciable solubility in the lipophilic material present in the
intermediate layer. Accordingly, the shell layer typically
comprises a material that is water-soluble, water-dispersible, or
contains a significant amount of water (e.g., a hydrogel). Suitable
materials for the shell layer include, but are not limited to,
hydrogels, dehydrated hydrogels, water-soluble polymers,
water-dispersible polymers, and combinations thereof. The hydrogels
can be formed using any suitable gelling agent. Suitable gelling
agents include, but are not necessarily limited to,
polysaccharides, gelatin, alginates, agarose, carrageenans (e.g.,
.kappa.-carrageenan), pectin, gellan, collagen, and mixtures
thereof. In certain possibly preferred embodiments, the gelling
agent is agar. In certain embodiments, the water-soluble polymer
and water-dispersable polymer can be selected from the group
consisting of acrylates, polyhydric alcohols, polysaccharides and
modified versions thereof, polyvinyl acetate, polyvinyl
pyrrolidone, methyl cellulose, carboxymethyl cellulose,
hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxybutyl
cellulose, hydroxylpropyl methylcellulose, acrylamides, acrylates,
chitosan, polyethylene glycols, locust bean gum, xanthan gum, guar
gum, pectin, carrageenans, alginates, agarose, gelatin, and
mixtures thereof. In certain possibly preferred embodiments, the
shell layer comprises a water-soluble polymer, and the
water-soluble polymer is a polyvinyl alcohol. As noted above, when
the shell material is a water-soluble or water-dispersable polymer,
the shell can also contain a gelling agent, such as any of the
gelling agents listed above.
[0042] In certain embodiments, such as when the shell layer
comprises a hydrogel or dehydrated hydrogel, the shell layer can
further comprise a crosslinking agent. The function of the
crosslinking agent is to cause the gelling agent to gel, thereby
yielding a hydrogel that is capable of forming the shell layer of
the capsule. Suitable cross-linking agents include, but are not
limited to, boric acid, caustic, formaldehyde, glutaraldehyde,
acetaldehyde, polyaldehydes, zirconium salts (e.g., zirconium
chloride, zirconium tetrachloride, zirconyl chloride), salts
containing di or trivalent counter ions (e.g., calcium salts),
diisocyanates, triols, epichlorohydrin, dextranaldehydes,
dialdehydes, tripolyphosphates, carbodiimides, polyepoxides,
isocyanates and combinations thereof.
[0043] The capsules of the invention are generally designed to be
used in a composition (e.g., cleaning composition or laundry
detergent composition) that is added to or diluted with an
appreciable amount of water during use. With such addition or
dilution, the water can dissolve or otherwise disintegrate the
shell layer thereby releasing the contents of the capsule (e.g.,
core(s) and, if present, intermediate layer). While the material
used in the shell layer can be selected so that it is readily
soluble in water, it has been found that the disintegration of the
shell layer can, under certain conditions, proceed relatively
slowly leading to a delayed release of the contents of the capsule.
Furthermore, in the case of a capsule having a hydrogel shell, the
shell layer will not dissolve or disintegrate to release the
capsule contents because, once the hydrogel shell has formed, it is
stable in aqueous environments. Accordingly, in certain
embodiments, it may be desirable to incorporate into the shell
layer a material that promotes the disintegration of the shell
layer. Such a material will be referred to herein as a
"disintegration aid." The disintegration aid can be any suitable
material that promotes a more rapid disintegration of the shell
layer. The disintegration aid can function to promote or accelerate
the disintegration of the shell layer by any suitable mechanism.
For example, the disintegration aid can be a material that
dissolves under certain conditions, which would leave voids or weak
spots in the shell layer that allow the capsule to rupture more
easily. The disintegration aid can also be a material that expands
or swells under certain conditions, which would exert forces on the
shell layer as it expands and cause the shell layer to rupture.
[0044] In certain embodiments, the disintegration aid exhibits an
absorption of 5 grams or more of solution per gram of
disintegration aid as measured in an aqueous solution having an
electrical conductivity of about 5 .mu.S/cm or less. In certain
other embodiments, the disintegration aid exhibits an absorption of
about 10 grams or more, about 20 grams or more, about 30 grams or
more, about 40 grams or more, about 50 grams or more, about 60
grams or more, about 70 grams or more, or about 75 grams or more of
solution per gram of disintegration aid as measured in an aqueous
solution having an electrical conductivity of about 5 .mu.S/cm or
less. Suitable disintegration aids include, but are not limited to,
superabsorbent polymers, swellable clays, xerogels, and
combinations thereof. In those embodiments in which the
disintegration aid is a superabsorbent polymer, the superabsorbent
polymer can be added to the shell layer composition as particles of
the final, crosslinked polymer or the superabsorbent polymer can be
in situ formed in the shell by adding an polymer precursor that is
then crosslinked during shell formation.
[0045] If the disintegration aid is used, the disintegration aid
can be present in the shell layer in any suitable amount.
Generally, the disintegration aid is added to the shell layer in an
amount sufficient to appreciably accelerate the disintegration of
the shell layer and release of the contents of the capsule. For
example, the disintegration aid can be present in the shell layer
in an amount of about 0.1 wt. % or more, about 0.2 wt. % or more,
about 0.3 wt. % or more, 0.4 wt. % or more, or about 0.5 wt. % or
more based on the total weight of the shell layer. Further, the
disintegration aid can be present in the shell layer in an amount
of about 85 wt. % or less, about 80 wt. % or less, about 75 wt. %
or less, about 70 wt. % or less, about 65 wt. % or less, about 60
wt. % or less, about 55 wt. % or less, about 50 wt. % or less,
about 45 wt. % or less, about 40 wt. % or less, about 35 wt. % or
less, or about 30 wt. % or less based on the total weight of the
shell layer. In certain embodiments, the disintegration aid is
present in the shell layer in an amount of about 0.1 wt. % to about
80 wt. % based on the total weight of the shell layer. In certain
other embodiments, such as when the disintegration aid is a
superabsorbent polymer incorporated into the shell layer in
particulate form, the disintegration aid can be present in the
shell layer in an amount of about 0.5 wt. % to about 10 wt. % based
on the total weight of the shell layer.
[0046] In addition to the polymers and the disintegration aid
described above, the shell layer can comprise additional
components. For example, in certain embodiments it may be desirable
for the capsule's shell layer to be opaque or at least relatively
translucent. In order to produce such capsules, a suitable
opacifier can be incorporated into the shell layer by, for example,
adding the opacifier to the shell layer composition.
[0047] In a second embodiment, such as that depicted in FIG. 3, the
invention provides a capsule 300 comprising at least one core 110
and a continuous shell layer 130 surrounding the core(s) 110. In
such an embodiment, the core can be any suitable material,
including those described above for the core or the intermediate
layer of the first capsule embodiment of the invention. Preferably,
in such an embodiment of the invention, the core is a solid,
semi-solid, or a lipophilic material such as those described above
for the intermediate layer of the first capsule embodiment of the
invention. The shell layer comprises a material for forming the
shell and a disintegration aid disposed in the shell layer. The
material for forming the shell and the disintegration aid used in
such shell layer can be any suitable materials, including those
described above for the first capsule embodiment of the
invention.
[0048] In a third embodiment, the invention provides a capsule
comprising at least one core, a continuous, intermediate layer
surrounding the core, and a continuous shell layer surrounding the
intermediate layer. In such an embodiment, the core can be any
suitable material, but generally the core comprises a lipophobic
material such as those described above for the first capsule
embodiment of the invention. The intermediate layer can be any
suitable material, but generally the intermediate layer comprises a
lipophobic material, such as those described above for the first
capsule embodiment of the invention. The shell layer comprises a
material for forming the shell and a disintegration aid disposed in
the shell layer. The material for forming the shell and the
disintegration aid used in such shell layer can be any suitable
materials, including those described above for the first capsule
embodiment of the invention.
[0049] The capsules of the invention can have any suitable
dimensions. For example, the capsules of the invention typically
have a diameter of about 10 mm or less, about 9 mm or less, about 8
mm or less, about 7 mm or less, about 6 mm or less, or about 5 mm
or less. In certain possibly preferred embodiments, the capsules of
the invention can have a diameter of about 0.05 mm to about 10 mm
(e.g., about 0.05 mm to about 9 mm, about 0.05 mm to about 8 mm,
about 0.05 mm to about 7 mm, about 0.05 mm to about 6 mm, about
0.05 mm to about 5 mm, about 0.06 mm to about 5 mm, about 0.07 mm
to about 5 mm, about 0.08 mm to about 5 mm, about 0.09 mm to about
5 mm, or about 0.1 mm to about 5 mm).
[0050] The capsules of the invention can be made by any method
known in the art to be suitable for producing microencapsulated
materials. For example, the capsules can be made by centrifugal
coextrusion encapsulation processes, jet cutting encapsulation
processes, vibrating nozzle encapsulation process, and multiple
nozzle coextrusion encapsulation processes. In certain possibly
preferred embodiments, the capsules of the invention are made by a
triple nozzle coextrusion encapsulation process. A suitable triple
nozzle coextrusion process and apparatus are described, for
example, in U.S. Pat. No. 5,330,835 (Kikuchi et al.), the
disclosure of which is hereby incorporated by reference.
[0051] As noted above, FIG. 4 depicts a triple nozzle coextrusion
apparatus suitable for use in producing capsules according to the
invention. The apparatus 400 comprises a first nozzle 410, a second
nozzle 420, and a third nozzle 430. The first nozzle 410, second
nozzle 420, and third nozzle 430 are each positioned in an
concentric arrangement. The first nozzle 410 has a smaller diameter
than the second nozzle 420 and is positioned within the second
nozzle 420. The second nozzle 420 has a smaller diameter than the
third nozzle 420 and is positioned within the third nozzle 430. The
first nozzle 410 has an interior passage (not marked) that is
adapted to convey the material for the core(s) to the nozzle tip
440. The second nozzle 420 has an interior passage (not marked)
that is adapted to convey the material for the intermediate layer
to the nozzle tip 440. The third nozzle 430 has an interior passage
(not marked) that is adapted to convey the material for the shell
layer to the nozzle tip 440.
[0052] In operation, the components for forming the core(s) 415,
the intermediate layer 425, and the shell layer 435 are each fed to
the first nozzle 410, second nozzle 420, and third nozzle 430,
respectively, in a liquid state so that the components can be
extruded through each nozzle to form the capsule. If the
component(s) for forming either the core(s), the intermediate
layer, or the shell layer are solid at room temperature, the
component(s) can heated to a temperature sufficient to melt the
component(s) and yield a flowable liquid that can be extruded
through the nozzle. Alternatively, these component(s) can be
dissolved in a suitable solvent or suspended in a suitable
medium.
[0053] As the components for forming the core(s) 415, the
intermediate layer 425, and the shell layer 435 each exit the
nozzle tip 440, the component(s) for the shell layer 435 envelops
the component(s) for the intermediate layer 425, and the
component(s) for the intermediate layer 425 envelops the
component(s) for the core(s) 415. The result is a capsule
intermediate 450 that then passes through a cooling solution 460,
which cools the intermediate and allows the shell layer to solidify
to the desired degree. The end result is a capsule 100 having at
least one core 110 surrounded by a continuous, intermediate layer
120 and a shell layer 130 surrounding the intermediate layer 120.
The cooling solution 460 can be circulated so that it flows past
the nozzle tip 440 in the same direction as the emerging capsule
intermediate 450.
[0054] In the above-described process, the flow rates of the
components for the core(s) 415, the intermediate layer 425, and the
shell layer 435 can each be individually controlled to adjust the
size of the capsules and the percentage of capsule mass or volume
contributed by the core, intermediate layer, and shell layer. For
example, the flow rates can be adjusted so as to produce capsules
containing multiple cores. Furthermore, the flow rate of the
cooling solution can be varied to control the thickness of the
shell layer. In general and with all other variables being the
same, higher flow rates of the cooling solution will produce
capsules having thinner shell layers.
[0055] As noted above, the capsules of the invention are believed
to be particularly well-suited for use in applications in which the
capsules, or a composition containing the capsules, are added to or
diluted with water. With such addition to or dilution with water,
the shell layer of the capsules disintegrates and/or dissolves,
which releases the contents of the capsule (e.g., core(s) and, if
present, intermediate layer). Thus, the capsules of the invention
are believed to be well-suited for use in a variety of compositions
that are typically used in conjunction with water, such as cleaning
compositions (e.g., household cleaning compositions, dish soaps,
dishwashing detergent compositions, and laundry detergent
compositions), personal care compositions (e.g., liquid hand soaps,
liquid body washes, and shampoos), pet care compositions (e.g.,
liquid pet washes and liquid pet shampoos), and automotive care
compositions (e.g., automotive cleaners and automotive
degreasers).
[0056] While the liquid compositions mentioned above typically
contain water, it is believed that the capsules of the invention
can remain stable in these compositions for extended periods of
time. For example, it has been found that capsules of the invention
having a hydrogel shell can remain stable in water for extended
periods of time. Therefore, it is believed that such capsules will,
under standard or normal conditions, also remain stable in the
aqueous compositions mentioned above. This extended stability of
the capsule provides a means to protect the capsule's contents from
the harsh conditions present in many of the above-mentioned
compositions. Furthermore, the capsules generally will not rupture
and release their contents until the capsules (or a composition
containing the capsules) are exposed to a substantial change in
conditions, such as high temperatures or aggressive mechanical
forces (e.g., aggressive agitation).
[0057] The above-mentioned compositions also typically contain
relatively large amounts of ionic surfactants (e.g., anionic
surfactants), and the presence of these ionic compounds produces a
composition exhibiting a relatively high ionic strength. When such
compositions are added to or diluted with water, the ionic strength
of the resulting mixture (i.e., the composition plus water) will be
appreciably lower than that of the composition itself. This change
in ionic strength between the composition and the diluted
composition can also provide a means by which the capsule's rupture
can be triggered. For example, the capsule can be designed so that
the shell layer (e.g., a hydrogel-based shell layer) contains a
disintegration aid whose swelling is inhibited in high ionic
strength environments. One example of such a disintegration aid
would be a superabsorbent polymer. When a composition containing
such capsules is added to or diluted with water, the ionic strength
of the resulting mixture (i.e., the composition plus water) will be
appreciably lower than that of the composition itself. In this
lower ionic strength environment, the superabsorbent polymer
readily swells, causing the shell layer to disintegrate and
releases the contents of the capsule. Indeed, this very behavior is
observed when such capsules of the invention are added to, for
example, a liquid laundry detergent composition. The capsules are
stable in the composition for an extended period of time, with none
or only a very small number of the capsules rupturing in the
detergent composition. However, when the laundry detergent
composition is added to water under normal washing conditions, the
capsules rupture and release their contents (e.g., the core(s) and,
if present, the intermediate layer). This behavior is believed to
make the capsules of the invention particularly well-suited for the
delivery of components that would typically be degraded or
otherwise unstable if added directly to the composition.
[0058] Thus, the invention also provides compositions comprising
the capsules of the invention. In one embodiment, the invention
provides a composition comprising at least one surfactant and at
least one capsule according to the invention or a plurality of
capsules according to the invention. The surfactant used in such
embodiment can be any suitable surfactant, such as those typically
used in cleaning compositions (e.g., liquid laundry detergents,
fabric softeners, dish washing detergents), personal care
compositions (e.g., liquid hand soaps, liquid body washes, and
shampoos), pet care compositions, and automotive care compositions.
In this embodiment, the composition can be provided in any suitable
form (e.g., solid or liquid), with liquid compositions being
preferred. In such a liquid composition, the surfactant and
capsule(s) of the invention can be incorporated into any suitable
liquid medium or carrier, with aqueous media or carriers being
preferred.
[0059] In another embodiment, the invention provides a cleaning
composition comprising at least one cleaning agent and at least one
capsule according to the invention or a plurality of capsules
according to the invention. In this embodiment, the cleaning agent
can be any suitable agent or compound typically used in cleaning
compositions (e.g., household cleaning compositions). Suitable
cleaning agents include, but are not limited to, surfactants (e.g.,
detersive surfactants), disinfectants, degreasers, bleaches, and
combinations thereof.
[0060] In view of their properties and performance, the capsules of
the invention are believed to be particularly well-suited for use
in laundry care compositions. Thus, in yet another embodiment, the
invention provides a laundry care composition comprising at least
one laundry care ingredient and at least one capsule according to
the invention or a plurality of capsules according to the
invention. The following paragraphs describe in detail such laundry
care compositions and components suitable for use in the same.
[0061] As used herein, the term "laundry care composition"
includes, unless otherwise indicated, granular, powder, liquid,
gel, paste, bar form and/or flake type washing agents and/or fabric
treatment compositions. As used herein, the term "fabric treatment
composition" includes, unless otherwise indicated, fabric softening
compositions, fabric enhancing compositions, fabric freshening
compositions and combinations thereof. Such compositions can be,
but need not be, rinse added compositions.
[0062] The capsules described in the present specification can be
incorporated into a laundry care composition including, but not
limited to, laundry detergents and fabric care compositions. Such
compositions comprise a plurality of said capsules and a laundry
care ingredient. The laundry care compositions including laundry
detergents can be in solid or liquid form, including a gel form.
The laundry detergent composition comprises a surfactant in an
amount sufficient to provide desired cleaning properties.
[0063] The capsules can be present in the laundry detergent
composition in an amount from about 0.0001% to about 10% by weight
of the composition, more preferably from about 0.001% to about 5%
by weight of the composition, and even more preferably from about
0.01% to about 1% by weight of the composition.
[0064] The laundry detergent composition comprises a surfactant in
an amount sufficient to provide desired cleaning properties. In one
embodiment, the laundry detergent composition comprises, by weight,
from about 5% to about 90% of the surfactant, and more specifically
from about 5% to about 70% of the surfactant, and even more
specifically from about 5% to about 40%. The surfactant can
comprise anionic, nonionic, cationic, zwitterionic and/or
amphoteric surfactants. In a more specific embodiment, the
detergent composition comprises anionic surfactant, nonionic
surfactant, or mixtures thereof.
[0065] Suitable anionic surfactants useful herein can comprise any
of the conventional anionic surfactant types typically used in
liquid detergent products. These include the alkyl benzene sulfonic
acids and their salts as well as alkoxylated or non-alkoxylated
alkyl sulfate materials.
[0066] Exemplary anionic surfactants are the alkali metal salts of
C.sub.10-C.sub.16 alkyl benzene sulfonic acids, preferably
C.sub.11-C.sub.14 alkyl benzene sulfonic acids. Preferably the
alkyl group is linear and such linear alkyl benzene sulfonates are
known as "LAS". Alkyl benzene sulfonates, and particularly LAS, are
well known in the art. Such surfactants and their preparation are
described for example in U.S. Pat. Nos. 2,220,099 and 2,477,383.
Especially preferred are the sodium and potassium linear straight
chain alkylbenzene sulfonates in which the average number of carbon
atoms in the alkyl group is from about 11 to 14. Sodium
C.sub.11-C.sub.14, e.g., C.sub.12, LAS is a specific example of
such surfactants.
[0067] Another exemplary type of anionic surfactant comprises
ethoxylated alkyl sulfate surfactants. Such materials, also known
as alkyl ether sulfates or alkyl polyethoxylate sulfates, are those
which correspond to the formula:
R'--O--(C.sub.2H.sub.4O).sub.n--SO.sub.3M wherein R' is a
C.sub.8-C.sub.20 alkyl group, n is from about 1 to 20, and M is a
salt-forming cation. In a specific embodiment, R' is
C.sub.10-C.sub.18 alkyl, n is from about 1 to 15, and M is sodium,
potassium, ammonium, alkylammonium, or alkanolammonium. In more
specific embodiments, R' is a C.sub.12-C.sub.16 alkyl, n is from
about 1 to 6, and M is sodium.
[0068] The alkyl ether sulfates will generally be used in the form
of mixtures comprising varying R' chain lengths and varying degrees
of ethoxylation. Frequently such mixtures will inevitably also
contain some non-ethoxylated alkyl sulfate materials, i.e.,
surfactants of the above ethoxylated alkyl sulfate formula wherein
n=0. Non-ethoxylated alkyl sulfates can also be added separately to
the compositions of this invention and used as or in any anionic
surfactant component which may be present. Specific examples of
non-alkoxylated, e.g., non-ethoxylated, alkyl ether sulfate
surfactants are those produced by the sulfation of higher
C.sub.8-C.sub.20 fatty alcohols. Conventional primary alkyl sulfate
surfactants have the general formula: ROSO.sub.3.sup.-M.sup.+
wherein R is typically a linear C.sub.8-C.sub.20 hydrocarbyl group,
which can be straight chain or branched chain, and M is a
water-solubilizing cation. In specific embodiments, R is a
C.sub.10-C.sub.15 alkyl, and M is alkali metal, more specifically R
is C.sub.12-C.sub.14 and M is sodium.
[0069] Specific, non-limiting examples of anionic surfactants
useful herein include: a) C.sub.11-C.sub.18 alkyl benzene
sulfonates (LAS); b) C.sub.10-C.sub.20 primary, branched-chain and
random alkyl sulfates (AS); c) C.sub.10-C.sub.18 secondary (2,3)
alkyl sulfates having formulae (I) and (II): wherein M in formulae
(I) and (II) is hydrogen or a cation which provides charge
neutrality, and all M units, whether associated with a surfactant
or adjunct ingredient, can either be a hydrogen atom or a cation
depending upon the form isolated by the artisan or the relative pH
of the system wherein the compound is used, with non-limiting
examples of preferred cations including sodium, potassium,
ammonium, and mixtures thereof, and x is an integer of at least
about 7, preferably at least about 9, and y is an integer of at
least 8, preferably at least about 9; d) C.sub.10-C.sub.18 alkyl
alkoxy sulfates (AE.sub.xS) wherein preferably x is from 1-30; e)
C.sub.10-C.sub.18 alkyl alkoxy carboxylates preferably comprising
1-5 ethoxy units; f) mid-chain branched alkyl sulfates as discussed
in U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,060,443; g)
mid-chain branched alkyl alkoxy sulfates as discussed in U.S. Pat.
No. 6,008,181 and U.S. Pat. No. 6,020,303; h) modified alkylbenzene
sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242, WO
99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO
00/23549, and WO 00/23548; i) methyl ester sulfonate (MES); and j)
alpha-olefin sulfonate (AOS).
[0070] Suitable nonionic surfactants useful herein can comprise any
of the conventional nonionic surfactant types typically used in
liquid detergent products. These include alkoxylated fatty alcohols
and amine oxide surfactants. Preferred for use in the liquid
detergent products herein are those nonionic surfactants which are
normally liquid.
[0071] Suitable nonionic surfactants for use herein include the
alcohol alkoxylate nonionic surfactants. Alcohol alkoxylates are
materials which correspond to the general formula:
R.sup.1(C.sub.mH.sub.2mO).sub.nOH wherein R.sup.1 is a
C.sub.8-C.sub.16 alkyl group, m is from 2 to 4, and n ranges from
about 2 to 12. Preferably R.sup.1 is an alkyl group, which can be
primary or secondary, that comprises from about 9 to 15 carbon
atoms, more preferably from about 10 to 14 carbon atoms. In one
embodiment, the alkoxylated fatty alcohols will also be ethoxylated
materials that contain from about 2 to 12 ethylene oxide moieties
per molecule, more preferably from about 3 to 10 ethylene oxide
moieties per molecule.
[0072] The alkoxylated fatty alcohol materials useful in the liquid
detergent compositions herein will frequently have a
hydrophilic-lipophilic balance (HLB) which ranges from about 3 to
17. More preferably, the HLB of this material will range from about
6 to 15, most preferably from about 8 to 15. Alkoxylated fatty
alcohol nonionic surfactants have been marketed under the
tradenames Neodol and Dobanol by the Shell Chemical Company.
[0073] Another suitable type of nonionic surfactant useful herein
comprises the amine oxide surfactants. Amine oxides are materials
which are often referred to in the art as "semi-polar" nonionics.
Amine oxides have the formula:
R(EO).sub.x(PO).sub.y(BO).sub.zN(O)(CH.sub.2R').sub.2.qH.sub.2O. In
this formula, R is a relatively long-chain hydrocarbyl moiety which
can be saturated or unsaturated, linear or branched, and can
contain from 8 to 20, preferably from 10 to 16 carbon atoms, and is
more preferably C.sub.12-C.sub.16 primary alkyl. R' is a
short-chain moiety, preferably selected from hydrogen, methyl and
--CH.sub.2OH. When x+y+z is different from 0, EO is ethyleneoxy, PO
is propyleneneoxy and BO is butyleneoxy. Amine oxide surfactants
are illustrated by C.sub.12-C.sub.14 alkyldimethyl amine oxide.
[0074] Non-limiting examples of nonionic surfactants include: a)
C.sub.12-C.sub.18 alkyl ethoxylates, such as, NEODOL.RTM. nonionic
surfactants from Shell; b) C.sub.6-C.sub.12 alkyl phenol
alkoxylates wherein the alkoxylate units are a mixture of
ethyleneoxy and propyleneoxy units; c) 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; d) C.sub.14-C.sub.22 mid-chain branched alcohols, BA, as
discussed in U.S. Pat. No. 6,150,322; e) C.sub.14-C.sub.22
mid-chain branched alkyl alkoxylates, BAE.sub.x, wherein x is from
1-30, as discussed in U.S. Pat. No. 6,153,577, U.S. Pat. No.
6,020,303 and U.S. Pat. No. 6,093,856; f) Alkylpolysaccharides as
discussed in U.S. Pat. No. 4,565,647 to Llenado, issued Jan. 26,
1986; specifically alkylpolyglycosides as discussed in U.S. Pat.
No. 4,483,780 and U.S. Pat. No. 4,483,779; g) Polyhydroxy fatty
acid amides as discussed in U.S. Pat. No. 5,332,528, WO 92/06162,
WO 93/19146, WO 93/19038, and WO 94/09099; and h) ether capped
poly(oxyalkylated) alcohol surfactants as discussed in U.S. Pat.
No. 6,482,994 and WO 01/42408.
[0075] In the laundry detergent compositions herein, the detersive
surfactant component can comprise combinations of anionic and
nonionic surfactant materials. When this is the case, the weight
ratio of anionic to nonionic will typically range from 10:90 to
90:10, more typically from 30:70 to 70:30.
[0076] Cationic surfactants are well known in the art and
non-limiting examples of these include quaternary ammonium
surfactants, which can have up to 26 carbon atoms. Additional
examples include a) alkoxylate quaternary ammonium (AQA)
surfactants as discussed in U.S. Pat. No. 6,136,769; b) dimethyl
hydroxyethyl quaternary ammonium as discussed in U.S. Pat. No.
6,004,922; c) polyamine cationic surfactants as discussed in WO
98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006;
d) cationic ester surfactants as discussed in U.S. Pat. Nos.
4,228,042, 4,239,660 4,260,529 and U.S. Pat. No. 6,022,844; and e)
amino surfactants as discussed in U.S. Pat. No. 6,221,825 and WO
00/47708, specifically amido propyldimethyl amine (APA).
[0077] Non-limiting examples of zwitterionic surfactants include
derivatives of secondary and tertiary amines, derivatives of
heterocyclic secondary and tertiary amines, or derivatives of
quaternary ammonium, quaternary phosphonium or tertiary sulfonium
compounds. See U.S. Pat. No. 3,929,678 to Laughlin et al., issued
Dec. 30, 1975 at column 19, line 38 through column 22, line 48, for
examples of zwitterionic surfactants; betaine, including alkyl
dimethyl betaine and cocodimethyl amidopropyl betaine, C.sub.8 to
C.sub.18 (preferably C.sub.12 to C.sub.18) amine oxides and sulfo
and hydroxy betaines, such as N-alkyl-N,N-dimethylammino-1-propane
sulfonate where the alkyl group can be C.sub.8 to C.sub.18,
preferably C.sub.10 to C.sub.14.
[0078] Non-limiting examples of ampholytic surfactants include
aliphatic derivatives of secondary or tertiary amines, or aliphatic
derivatives of heterocyclic secondary and tertiary amines in which
the aliphatic radical can be straight- or branched-chain. One of
the aliphatic substituents comprises at least about 8 carbon atoms,
typically from about 8 to about 18 carbon atoms, and at least one
comprises an anionic water-solubilizing group, e.g. carboxy,
sulfonate, sulfate. See U.S. Pat. No. 3,929,678 to Laughlin et al.,
issued Dec. 30, 1975 at column 19, lines 18-35, for examples of
ampholytic surfactants.
[0079] As noted, the compositions can be in the form of a solid,
either in tablet or particulate form, including, but not limited
to, particles, flakes, or the like, or the compositions can be in
the form of a liquid. The liquid detergent compositions comprise an
aqueous, non-surface active liquid carrier. Generally, the amount
of the aqueous, non-surface active liquid carrier employed in the
compositions herein will be effective to solubilize, suspend or
disperse the composition components. For example, the compositions
can comprise, by weight, from about 5% to about 90%, more
specifically from about 10% to about 70%, and even more
specifically from about 20% to about 70% of the aqueous,
non-surface active liquid carrier.
[0080] The most cost effective type of aqueous, non-surface active
liquid carrier is, of course, water itself. Accordingly, the
aqueous, non-surface active liquid carrier component will generally
be mostly, if not completely, comprised of water. While other types
of water-miscible liquids, such alkanols, diols, other polyols,
ethers, amines, and the like, have been conventionally been added
to liquid detergent compositions as co-solvents or stabilizers, for
purposes of the present invention, the utilization of such
water-miscible liquids should be minimized to hold down composition
cost. Accordingly, the aqueous liquid carrier component of the
liquid detergent products herein will generally comprise water
present in concentrations ranging from about 5% to about 90%, more
preferably from about 20% to about 70%, by weight of the
composition.
[0081] Detergent compositions can also contain bleaching agents.
Suitable bleaching agents include, for example, hydrogen peroxide
sources, such as those described in detail in the herein
incorporated Kirk Othmer's Encyclopedia of Chemical Technology, 4th
Ed (1992, John Wiley & Sons), Vol. 4, pp. 271-300 "Bleaching
Agents (Survey)." These hydrogen peroxide sources include the
various forms of sodium perborate and sodium percarbonate,
including various coated and modified forms of these compounds.
[0082] The preferred source of hydrogen peroxide used herein can be
any convenient source, including hydrogen peroxide itself. For
example, perborate, e.g., sodium perborate (any hydrate but
preferably the mono- or tetra-hydrate), sodium carbonate
peroxyhydrate or equivalent percarbonate salts, sodium
pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide
can be used herein. Also useful are sources of available oxygen
such as persulfate bleach (e.g., OXONE, manufactured by DuPont).
Sodium perborate monohydrate and sodium percarbonate are
particularly preferred. Mixtures of any convenient hydrogen
peroxide sources can also be used.
[0083] A suitable percarbonate bleach comprises dry particles
having an average particle size in the range from about 500
micrometers to about 1,000 micrometers, not more than about 10% by
weight of said particles being smaller than about 200 micrometers
and not more than about 10% by weight of said particles being
larger than about 1,250 micrometers. Optionally, the percarbonate
can be coated with a silicate, borate or water-soluble surfactants.
Percarbonate is available from various commercial sources such as
FMC, Solvay and Tokai Denka.
[0084] Compositions of the present invention can also comprise as
the bleaching agent a chlorine-type bleaching material. Such agents
are well known in the art, and include for example sodium
dichloroisocyanurate ("NaDCC"). However, chlorine-type bleaches are
less preferred for compositions which comprise enzymes.
[0085] (a) Bleach Activators--
[0086] Preferably, the peroxygen bleach component in the
composition is formulated with an activator (peracid precursor).
The activator is present at levels of from about 0.01%, preferably
from about 0.5%, more preferably from about 1% to about 15%,
preferably to about 10%, more preferably to about 8%, by weight of
the composition. A bleach activator as used herein is any compound
which, when used in conjunction with a hydrogen peroxide, source
leads to the in situ production of the peracid corresponding to the
bleach activator. Various non-limiting examples of activators are
disclosed in U.S. Pat. Nos. 5,576,282; 4,915,854 and 4,412,934. See
also U.S. Pat. No. 4,634,551 for other typical bleaches and
activators useful herein.
[0087] Preferred activators are selected from the group consisting
of tetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL),
4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam,
benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate
(NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate
(C.sub.10-OBS), benzoylvalerolactam (BZVL),
octanoyloxybenzenesulphonate (C.sub.8-OBS), perhydrolyzable esters
and mixtures thereof, most preferably benzoylcaprolactam and
benzoylvalerolactam. Particularly preferred bleach activators in
the pH range from about 8 to about 11 are those selected having an
OBS or VL leaving group.
[0088] Preferred hydrophobic bleach activators include, but are not
limited to, nonanoyloxybenzenesulphonate (NOBS); 4-[N-(nonanoyl)
amino hexanoyloxy]-benzene sulfonate sodium salt (NACA-OBS), an
example of which is described in U.S. Pat. No. 5,523,434;
dodecanoyloxybenzenesulphonate (LOBS or C.sub.12-OBS);
10-undecenoyloxybenzenesulfonate (UDOBS or C.sub.11-OBS with
unsaturation in the 10 position); and decanoyloxybenzoic acid
(DOBA).
[0089] Preferred bleach activators are those described in U.S. Pat.
No. 5,998,350 to Burns et al.; U.S. Pat. No. 5,698,504 to Christie
et al.; U.S. Pat. No. 5,695,679 to Christie et al.; U.S. Pat. No.
5,686,401 to Willey et al.; U.S. Pat. No. 5,686,014 to Hartshorn et
al.; U.S. Pat. No. 5,405,412 to Willey et al.; U.S. Pat. No.
5,405,413 to Willey et al.; U.S. Pat. No. 5,130,045 to Mitchel et
al.; and U.S. Pat. No. 4,412,934 to Chung et al., all of which are
incorporated herein by reference.
[0090] The mole ratio of peroxygen source (as AvO) to bleach
activator in the present invention generally ranges from at least
1:1, preferably from about 20:1, more preferably from about 10:1 to
about 1:1, preferably to about 3:1.
[0091] Quaternary substituted bleach activators can also be
included. The present laundry compositions preferably comprise a
quaternary substituted bleach activator (QSBA) or a quaternary
substituted peracid (QSP, preferably a quaternary substituted
percarboxylic acid or a quaternary substituted peroxyimidic acid);
more preferably, the former. Preferred QSBA structures are further
described in U.S. Pat. No. 5,686,015 to Willey et al.; U.S. Pat.
No. 5,654,421 to Taylor et al.; U.S. Pat. No. 5,460,747 to
Gosselink et al.; U.S. Pat. No. 5,584,888 to Miracle et al.; U.S.
Pat. No. 5,578,136 to Taylor et al.; all of which are incorporated
herein by reference.
[0092] Highly preferred bleach activators useful herein are
amide-substituted as described in U.S. Pat. Nos. 5,698,504;
5,695,679; and 5,686,014, each of which are cited herein above.
Preferred examples of such bleach activators include:
(6-octanamidocaproyl) oxybenzenesulfonate,
(6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)
oxybenzenesulfonate and mixtures thereof.
[0093] Other useful activators are disclosed in U.S. Pat. Nos.
5,698,504; 5,695,679; and 5,686,014, each of which is cited herein
above, and in U.S. Pat. No. 4,966,723 to Hodge et al. These
activators include benzoxazin-type activators, such as a
C.sub.6H.sub.4 ring to which is fused in the 1,2-positions a moiety
--C(O)OC(R.sup.1).dbd.N--.
[0094] Nitriles, such as acetonitriles and/or ammonium nitriles and
other quaternary nitrogen containing nitriles, are another class of
activators that are useful herein. Non-limiting examples of such
nitrile bleach activators are described in U.S. Pat. Nos.
6,133,216; 3,986,972; 6,063,750; 6,017,464; 5,958,289; 5,877,315;
5,741,437; 5,739,327; 5,004,558; and in EP Nos. 790 244, 775 127, 1
017 773, 1 017 776; and in WO 99/14302, WO 99/14296, WO96/40661,
all of which are incorporated herein by reference.
[0095] Depending on the activator and precise application, good
bleaching results can be obtained from bleaching systems having an
in-use pH of from about 6 to about 13, and preferably from about
9.0 to about 10.5. Typically, for example, activators with
electron-withdrawing moieties are used for near-neutral or
sub-neutral pH ranges. Alkalis and buffering agents can be used to
secure such pH.
[0096] Acyl lactam activators, as described in U.S. Pat. Nos.
5,698,504; 5,695,679 and 5,686,014, each of which is cited herein
above, are very useful herein, especially the acyl caprolactams
(see for example WO 94-28102 A) and acyl valerolactams (see U.S.
Pat. No. 5,503,639 to Willey et al. incorporated herein by
reference).
[0097] (b) Organic Peroxides, Especially Diacyl Peroxides--
[0098] These are extensively illustrated in Kirk Othmer,
Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons,
1982 at pages 27-90 and especially at pages 63-72, all incorporated
herein by reference. If a diacyl peroxide is used, it will
preferably be one which exerts minimal adverse impact on fabric
care, including color care.
[0099] (c) Metal-Containing Bleach Catalysts--
[0100] The compositions and methods of the present invention can
also optionally include metal-containing bleach catalysts,
preferably manganese and cobalt-containing bleach catalysts.
[0101] One type of metal-containing bleach catalyst is a catalyst
system comprising a transition metal cation of defined bleach
catalytic activity (such as copper, iron, titanium, ruthenium
tungsten, molybdenum, or manganese cations), an auxiliary metal
cation having little or no bleach catalytic activity (such as zinc
or aluminum cations), and a sequestrate having defined stability
constants for the catalytic and auxiliary metal cations,
particularly ethylenediaminetetraacetic acid, ethylenediaminetetra
(methylenephosphonic acid) and water-soluble salts thereof. Such
catalysts are disclosed in U.S. Pat. No. 4,430,243 to Bragg.
[0102] Manganese Metal Complexes--
[0103] 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. Nos. 5,576,282; 5,246,621;
5,244,594; 5,194,416; and 5,114,606; and European Pat. App. Pub.
Nos. 549,271 A1; 549,272 A1; 544,440 A2; and 544,490 A1. Preferred
examples of these catalysts include
Mn(IV).sub.2(u-O).sub.3(1,4,7-trimethyl-1,4,7-triazacyclononane).sub.2(PF-
.sub.6).sub.2,
Mn(III).sub.2(u-O).sub.1(u-OAc).sub.2(1,4,7-trimethyl-1,4,7-triazacyclono-
nane).sub.2(ClO.sub.4).sub.2,
Mn(IV).sub.4(u-O).sub.6(1,4,7-triazacyclononane).sub.4(ClO.sub.4).sub.4,
Mn(III)Mn(IV).sub.4(u-O).sub.1(u-OAc).sub.2-(1,4,7-trimethyl-1,4,7-triaza-
cyclononane).sub.2(ClO.sub.4).sub.3,
Mn(IV)(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH.sub.3).sub.3(PF.sub.-
6), and mixtures thereof. Other metal-based bleach catalysts
include those disclosed in U.S. Pat. Nos. 4,430,243 and 5,114,611.
The use of manganese with various complex ligands to enhance
bleaching is also reported in the following: U.S. Pat. Nos.
4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147;
5,153,161; and 5,227,084.
[0104] Cobalt Metal Complexes--
[0105] Cobalt bleach catalysts useful herein are known, and are
described, for example, in U.S. Pat. Nos. 5,597,936; 5,595,967; and
5,703,030; and M. L. Tobe, "Base Hydrolysis of Transition-Metal
Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. The
most preferred cobalt catalyst useful herein are cobalt pentaamine
acetate salts having the formula [Co(NH.sub.3).sub.5OAc] Ty,
wherein "OAc" represents an acetate moiety and "Ty" is an anion,
and especially cobalt pentaamine acetate chloride,
[Co(NH.sub.3).sub.5OAc]Cl.sub.2; as well as
[Co(NH.sub.3).sub.5OAc](OAc).sub.2;
[Co(NH.sub.3).sub.5OAc](PF.sub.6).sub.2;
[Co(NH.sub.3).sub.5OAc](SO.sub.4);
[Co(NH.sub.3).sub.5OAc](BF.sub.4).sub.2; and
[Co(NH.sub.3).sub.5OAc](NO.sub.3).sub.2 (herein "PAC").
[0106] These cobalt catalysts are readily prepared by known
procedures, such as taught for example in U.S. Pat. Nos. 6,302,921;
6,287,580; 6,140,294; 5,597,936; 5,595,967; and 5,703,030; in the
Tobe article and the references cited therein; and in U.S. Pat. No.
4,810,410; J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and
Characterization of Inorganic Compounds, W. L. Jolly
(Prentice-Hall; 1970), pp. 461-3; Inorg. Chem., 18, 1497-1502
(1979); Inorg. Chem., 21, 2881-2885 (1982); Inorg. Chem., 18,
2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of
Physical Chemistry, 56, 22-25 (1952).
[0107] Transition Metal Complexes of Macropolycyclic Rigid
Ligands--
[0108] Compositions herein can also suitably include as bleach
catalyst a transition metal complex of a macropolycyclic rigid
ligand. The amount used is a catalytically effective amount,
suitably about 1 ppb or more, for example up to about 99.9%, more
typically about 0.001 ppm or more, preferably from about 0.05 ppm
to about 500 ppm (wherein "ppb" denotes parts per billion by weight
and "ppm" denotes parts per million by weight).
[0109] Transition-metal bleach catalysts of Macrocyclic Rigid
Ligands which are suitable for use in the invention compositions
can in general include known compounds where they conform with the
definition herein, as well as, more preferably, any of a large
number of novel compounds expressly designed for the present
laundry or laundry uses, and are non-limitingly illustrated by any
of the following: [0110]
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II) [0111]
Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II) [0112]
Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(I-
I) Hexafluorophosphate [0113]
Diaquo-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II-
) Hexafluorophosphate [0114]
Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(III) Hexafluorophosphate [0115]
Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(I-
I) Tetrafluoroborate [0116] Dichloro-5,12-dimethyl-1,5,8,12
tetraazabicyclo[6.6.2]hexadecane Manganese(III) Hexafluorophosphate
[0117]
Dichloro-5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(III) Hexafluorophosphate [0118]
Dichloro-5,12-di-n-butyl-1,5,8,12-tetraaza bicyclo[6.6.2]hexadecane
Manganese(II) [0119]
Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II) [0120]
Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane
Manganese(II) [0121]
Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane
Manganese(II) [0122]
Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane
Manganese(II).
[0123] As a practical matter, and not by way of limitation, the
compositions and methods herein can be adjusted to provide on the
order of at least one part per hundred million of the active bleach
catalyst species in the composition comprising a lipophilic fluid
and a bleach system, and will preferably provide from about 0.01
ppm to about 25 ppm, more preferably from about 0.05 ppm to about
10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, of
the bleach catalyst species in the composition comprising a
lipophilic fluid and a bleach system.
[0124] (d) Bleach Boosting Compounds--
[0125] The compositions herein can comprise one or more bleach
boosting compounds. Bleach boosting compounds provide increased
bleaching effectiveness in lower temperature applications. The
bleach boosters act in conjunction with conventional peroxygen
bleaching sources to provide increased bleaching effectiveness.
This is normally accomplished through in situ formation of an
active oxygen transfer agent such as a dioxirane, an oxaziridine,
or an oxaziridinium. Alternatively, preformed dioxiranes,
oxaziridines and oxaziridiniums can be used.
[0126] Among suitable bleach boosting compounds for use in
accordance with the present invention are cationic imines,
zwitterionic imines, anionic imines and/or polyionic imines having
a net charge of from about +3 to about -3, and mixtures thereof.
These imine bleach boosting compounds of the present invention
include those of the general structure:
##STR00004##
where R.sup.1-R.sup.4 can be a hydrogen or an unsubstituted or
substituted radical selected from the group consisting of phenyl,
aryl, heterocyclic ring, alkyl and cycloalkyl radicals.
[0127] Among preferred bleach boosting compounds are zwitterionic
bleach boosters, which are described in U.S. Pat. Nos. 5,576,282
and 5,718,614. Other bleach boosting compounds include cationic
bleach boosters described in U.S. Pat. Nos. 5,360,569; 5,442,066;
5,478,357; 5,370,826; 5,482,515; 5,550,256; and WO 95/13351, WO
95/13352, and WO 95/13353.
[0128] Peroxygen sources are well-known in the art and the
peroxygen source employed in the present invention can comprise any
of these well known sources, including peroxygen compounds as well
as compounds, which under consumer use conditions, provide an
effective amount of peroxygen in situ. The peroxygen source can
include a hydrogen peroxide source, the in situ formation of a
peracid anion through the reaction of a hydrogen peroxide source
and a bleach activator, preformed peracid compounds or mixtures of
suitable peroxygen sources. Of course, one of ordinary skill in the
art will recognize that other sources of peroxygen can be employed
without departing from the scope of the invention. The bleach
boosting compounds, when present, are preferably employed in
conjunction with a peroxygen source in the bleaching systems of the
present invention.
[0129] (e) Preformed Peracids--
[0130] Also suitable as bleaching agents are preformed peracids.
The preformed peracid compound as used herein is any convenient
compound which is stable and which under consumer use conditions
provides an effective amount of peracid or peracid anion. The
preformed peracid compound can be selected from the group
consisting of percarboxylic acids and salts, percarbonic acids and
salts, perimidic acids and salts, peroxymonosulfuric acids and
salts, and mixtures thereof. Examples of these compounds are
described in U.S. Pat. No. 5,576,282 to Miracle et al.
[0131] One class of suitable organic peroxycarboxylic acids have
the general formula:
##STR00005##
wherein R is an alkylene or substituted alkylene group containing
from 1 to about 22 carbon atoms or a phenylene or substituted
phenylene group, and Y is hydrogen, halogen, alkyl, aryl, --C(O)OH
or --C(O)OOH.
[0132] Organic peroxyacids suitable for use in the present
invention can contain either one or two peroxy groups and can be
either aliphatic or aromatic. When the organic peroxycarboxylic
acid is aliphatic, the unsubstituted peracid has the general
formula:
##STR00006##
wherein Y can be, for example, H, CH.sub.3, CH.sub.2Cl, C(O)OH, or
C(O)OOH; and n is an integer from 0 to 20. When the organic
peroxycarboxylic acid is aromatic, the unsubstituted peracid has
the general formula:
##STR00007##
wherein Y can be, for example, hydrogen, alkyl, alkylhalogen,
halogen, C(O)OH or C(O)OOH.
[0133] Typical monoperoxy acids useful herein include alkyl and
aryl peroxyacids such as: [0134] (i) peroxybenzoic acid and
ring-substituted peroxybenzoic acid, e.g. peroxy-a-naphthoic acid,
monoperoxyphthalic acid (magnesium salt hexahydrate), and
o-carboxybenzamidoperoxyhexanoic acid (sodium salt); [0135] (ii)
aliphatic, substituted aliphatic and arylalkyl monoperoxy acids,
e.g. peroxylauric acid, peroxystearic acid,
N-nonanoylaminoperoxycaproic acid (NAPCA),
N,N-(3-octylsuccinoyl)aminoperoxycaproic acid (SAPA) and
N,N-phthaloylaminoperoxycaproic acid (PAP); [0136] (iii)
amidoperoxyacids, e.g. monononylamide of either peroxysuccinic acid
(NAPSA) or of peroxyadipic acid (NAPAA).
[0137] Typical diperoxyacids useful herein include alkyl
diperoxyacids and aryldiperoxyacids, such as: [0138] (i)
1,12-diperoxydodecanedioic acid; [0139] (ii) 1,9-diperoxyazelaic
acid; [0140] (iii) diperoxybrassylic acid; diperoxysebacic acid and
diperoxyisophthalic acid; [0141] (iv)
2-decyldiperoxybutane-1,4-dioic acid; [0142] (v)
4,4'-sulfonylbisperoxybenzoic acid.
[0143] Such bleaching agents are disclosed in U.S. Pat. No.
4,483,781 to Hartman and U.S. Pat. No. 4,634,551 to Burns et al.;
European Patent Application 0,133,354 to Banks et al.; and U.S.
Pat. No. 4,412,934 to Chung et al. Sources also include
6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Pat. No.
4,634,551 to Burns et al. Persulfate compounds such as for example
OXONE, manufactured commercially by E.I. DuPont de Nemours of
Wilmington, Del. can also be employed as a suitable source of
peroxymonosulfuric acid. PAP is disclosed in, for example, U.S.
Pat. Nos. 5,487,818; 5,310,934; 5,246,620; 5,279,757 and
5,132,431.
[0144] (f) Photobleaches--
[0145] Suitable photobleaches for use in the treating compositions
of the present invention include, but are not limited to, the
photobleaches described in U.S. Pat. Nos. 4,217,105 and
5,916,481.
[0146] (g) Enzyme Bleaching--
[0147] Enzymatic systems can be used as bleaching agents. The
hydrogen peroxide can also be present by adding an enzymatic system
(i.e. an enzyme and a substrate therefore) which is capable of
generating hydrogen peroxide at the beginning or during the washing
and/or rinsing process. Such enzymatic systems are disclosed in EP
Patent Application 91202655.6 filed Oct. 9, 1991.
[0148] The present invention compositions and methods can utilize
alternative bleach systems such as ozone, chlorine dioxide and the
like. Bleaching with ozone can be accomplished by introducing
ozone-containing gas having ozone content from about 20 to about
300 g/m.sup.3 into the solution that is to contact the fabrics. The
gas:liquid ratio in the solution should be maintained from about
1:2.5 to about 1:6. U.S. Pat. No. 5,346,588 describes a process for
the utilization of ozone as an alternative to conventional bleach
systems and is herein incorporated by reference.
[0149] The detergent compositions of the present invention can also
include any number of additional optional ingredients. These
include conventional laundry detergent composition components such
as non-tinting dyes, detersive builders, enzymes, enzyme
stabilizers (such as propylene glycol, boric acid and/or borax),
suds suppressors, soil suspending agents, soil release agents,
other fabric care benefit agents, pH adjusting agents, chelating
agents, smectite clays, solvents, hydrotropes and phase
stabilizers, structuring agents, dye transfer inhibiting agents,
opacifying agents, optical brighteners, perfumes and coloring
agents. The various optional detergent composition ingredients, if
present in the compositions herein, should be utilized at
concentrations conventionally employed to bring about their desired
contribution to the composition or the laundering operation.
Frequently, the total amount of such optional detergent composition
ingredients can range from about 0.01% to about 50%, more
preferably from about 0.1% to about 30%, by weight of the
composition.
[0150] The liquid detergent compositions are in the form of an
aqueous solution or uniform dispersion or suspension of surfactant,
optical brightener, and certain optional other ingredients, some of
which may normally be in solid form, that have been combined with
the normally liquid components of the composition, such as the
liquid alcohol ethoxylate nonionic, the aqueous liquid carrier, and
any other normally liquid optional ingredients. Such a solution,
dispersion or suspension will be acceptably phase stable and will
typically have a viscosity which ranges from about 100 to 600 cps,
more preferably from about 150 to 400 cps. For purposes of this
invention, viscosity is measured with a Brookfield LVDV-II+
viscometer apparatus using a #21 spindle.
[0151] The liquid detergent compositions herein can be prepared by
combining the components thereof in any convenient order and by
mixing, e.g., agitating, the resulting component combination to
form a phase stable liquid detergent composition. In a preferred
process for preparing such compositions, a liquid matrix is formed
containing at least a major proportion, and preferably
substantially all, of the liquid components, e.g., nonionic
surfactant, the non-surface active liquid carriers and other
optional liquid components, with the liquid components being
thoroughly admixed by imparting shear agitation to this liquid
combination. For example, rapid stirring with a mechanical stirrer
may usefully be employed. While shear agitation is maintained,
substantially all of any anionic surfactants and the solid form
ingredients can be added. Agitation of the mixture is continued,
and if necessary, can be increased at this point to form a solution
or a uniform dispersion of insoluble solid phase particulates
within the liquid phase. After some or all of the solid-form
materials have been added to this agitated mixture, particles of
any enzyme material to be included, e.g., enzyme prills, are
incorporated. As a variation of the composition preparation
procedure hereinbefore described, one or more of the solid
components can 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.
[0152] In an alternate embodiment for forming the liquid detergent
compositions, the optical brightener is first combined with one or
more liquid components to form a optical brightener premix, and
this optical brightener 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 optical brightener premix
and the enzyme component are added at a final stage of component
additions. In a further embodiment, the optical brightener is
encapsulated prior to addition to the detergent composition, the
encapsulated optical brightener 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.
[0153] As noted previously, the detergent compositions can be in a
solid form. Suitable solid forms include tablets and particulate
forms, for example, granular particles or flakes. Various
techniques for forming detergent compositions in such solid forms
are well known in the art and can be used herein. In one
embodiment, for example when the composition is in the form of a
granular particle, the optical brightener is provided in
particulate form, optionally including additional but not all
components of the laundry detergent composition. The optical
brightener particulate is combined with one or more additional
particulates containing a balance of components of the laundry
detergent composition. Further, the optical brightener, optionally
including additional but not all components of the laundry
detergent composition, can be provided in an encapsulated form, and
the optical brightener encapsulate is combined with particulates
containing a substantial balance of components of the laundry
detergent composition.
[0154] The compositions of this invention, prepared as hereinbefore
described, can be used to form aqueous washing solutions for use in
the laundering of fabrics. Generally, an effective amount of such
compositions is added to water, preferably in a conventional fabric
laundering automatic washing machine, to form such aqueous
laundering solutions. The aqueous washing solution so formed is
then contacted, preferably under agitation, with the fabrics to be
laundered therewith. An effective amount of the liquid detergent
compositions herein added to water to form aqueous laundering
solutions can comprise amounts sufficient to form from about 500 to
7,000 ppm of composition in aqueous washing solution. More
preferably, from about 1,000 to 3,000 ppm of the detergent
compositions herein will be provided in aqueous washing
solution.
Fabric Care Compositions/Rinse Added Fabric Softening
Compositions
[0155] In another specific embodiment, the optical brighteners of
the present invention can be included in a fabric care composition.
The fabric care composition can be comprised of at least one
optical brightener and a rinse added fabric softening composition
("RAFS;" also known as rinse added fabric conditioning
compositions). Examples of typical rinse added softening
compositions can be found in U.S. Provisional Patent Application
Ser. No. 60/687,582 filed on Oct. 8, 2004. The rinse added fabric
softening composition can comprise from about 1% to about 90% by
weight of the FSA, more preferably from about 5% to about 50% by
weight of the FSA. The optical brightener can be present in the
rinse added fabric softening composition in an amount from about
0.5 ppb to about 50 ppm, more preferably from about 0.5 ppm to
about 30 ppm.
[0156] In one embodiment of the invention, the fabric softening
active (hereinafter "FSA") is a quaternary ammonium compound
suitable for softening fabric in a rinse step. In one embodiment,
the FSA is formed from a reaction product of a fatty acid and an
aminoalcohol obtaining mixtures of mono-, di-, and, in one
embodiment, triester compounds. In another embodiment, the FSA
comprises one or more softener quaternary ammonium compounds such
as, but not limited to, a monoalkyquaternary ammonium compound, a
diamido quaternary compound and a diester quaternary ammonium
compound, or a combination thereof.
[0157] In one aspect of the invention, the FSA comprises a diester
quaternary ammonium (hereinafter "DQA") compound composition. In
certain embodiments of the present invention, the DQA compounds
compositions also encompasses a description of diamido FSAs and
FSAs with mixed amido and ester linkages as well as the
aforementioned diester linkages, all herein referred to as DQA.
[0158] A first type of DQA ("DQA (1)") suitable as a FSA in the
present CFSC includes a compound comprising the formula:
{R.sub.4-m--N.sup.+--[(CH.sub.2).sub.n--Y--R.sup.1].sub.m}X.sup.-
wherein each R substituent is either hydrogen, a short chain
C.sub.1-C.sub.6, preferably C.sub.1-C.sub.3 alkyl or hydroxyalkyl
group, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl,
and the like, poly (C.sub.2-C.sub.3 alkoxy), preferably polyethoxy,
group, benzyl, or mixtures thereof; each m is 2 or 3; each n is
from 1 to about 4, preferably 2; each Y is --O--(O)C--,
--C(O)--O--, --NR--C(O)--, or --C(O)--NR-- and it is acceptable for
each Y to be the same or different; the sum of carbons in each
R.sup.1, plus one when Y is --O--(O)C-- or --NR--C(O)--, is
C.sub.12-C.sub.22, preferably C.sub.14-C.sub.20, with each R.sup.1
being a hydrocarbyl, or substituted hydrocarbyl group; it is
acceptable for R.sup.1 to be unsaturated or saturated and branched
or linear and preferably it is linear; it is acceptable for each
R.sup.1 to be the same or different and preferably these are the
same; and X.sup.- can be any softener-compatible anion, preferably,
chloride, bromide, methylsulfate, ethylsulfate, sulfate, phosphate,
and nitrate, more preferably chloride or methyl sulfate. Preferred
DQA compounds are typically made by reacting alkanolamines such as
MDEA (methyldiethanolamine) and TEA (triethanolamine) with fatty
acids. Some materials that typically result from such reactions
include N,N-di(acyl-oxyethyl)-N,N-dimethylammonium chloride or
N,N-di(acyl-oxyethyl)-N,N-methylhydroxyethylammonium methylsulfate
wherein the acyl group is derived from animal fats, unsaturated,
and polyunsaturated, fatty acids, e.g., tallow, hardended tallow,
oleic acid, and/or partially hydrogenated fatty acids, derived from
vegetable oils and/or partially hydrogenated vegetable oils, such
as, canola oil, safflower oil, peanut oil, sunflower oil, corn oil,
soybean oil, tall oil, rice bran oil, palm oil, etc.
[0159] Non-limiting examples of suitable fatty acids are listed in
U.S. Pat. No. 5,759,990 at column 4, lines 45-66. In one
embodiment, the FSA comprises other actives in addition to DQA (1)
or DQA. In yet another embodiment, the FSA comprises only DQA (1)
or DQA and is free or essentially free of any other quaternary
ammonium compounds or other actives. In yet another embodiment, the
FSA comprises the precursor amine that is used to produce the
DQA.
[0160] In another aspect of the invention, the FSA comprises a
compound, identified as DTTMAC comprising the formula:
[R.sub.4-m--N.sup.(+)--R.sup.1.sub.m]A.sup.-
wherein each m is 2 or 3, each R.sup.1 is a C.sub.6-C.sub.22,
preferably C.sub.14-C.sub.20, but no more than one being less than
about C.sub.12 and then the other is at least about 16,
hydrocarbyl, or substituted hydrocarbyl substituent, preferably
C.sub.10-C.sub.20 alkyl or alkenyl (unsaturated alkyl, including
polyunsaturated alkyl, also referred to sometimes as "alkylene"),
most preferably C.sub.12-C.sub.18 alkyl or alkenyl, and branch or
unbranched. In one embodiment, the Iodine Value (IV) of the FSA is
from about 1 to 70; each R is H or a short chain C.sub.1-C.sub.6,
preferably C.sub.1-C.sub.3 alkyl or hydroxyalkyl group, e.g.,
methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like,
benzyl, or (R.sup.2O).sub.2-4H where each R.sup.2 is a
C.sub.1-C.sub.6 alkylene group; and A.sup.- is a softener
compatible anion, preferably, chloride, bromide, methylsulfate,
ethylsulfate, sulfate, phosphate, or nitrate; more preferably
chloride or methyl sulfate.
[0161] Examples of these FSAs include dialkydimethylammonium salts
and dialkylenedimethylammonium salts such as
ditallowdimethylammonium and ditallowdimethylammonium
methylsulfate. Examples of commercially available
dialkylenedimethylammonium salts usable in the present invention
are di-hydrogenated tallow dimethyl ammonium chloride and
ditallowdimethyl ammonium chloride available from Degussa under the
trade names Adogen.RTM. 442 and Adogen.RTM. 470 respectively. In
one embodiment, the FSA comprises other actives in addition to
DTTMAC. In yet another embodiment, the FSA comprises only compounds
of the DTTMAC and is free or essentially free of any other
quaternary ammonium compounds or other actives.
[0162] In one embodiment, the FSA comprises an FSA described in
U.S. Pat. Pub. No. 2004/0204337 A1, published Oct. 14, 2004 to
Corona et al., from paragraphs 30-79. In another embodiment, the
FSA is one described in U.S. Pat. Pub. No. 2004/0229769 A1,
published Nov. 18, 2005, to Smith et al., on paragraphs 26-31; or
U.S. Pat. No. 6,494,920, at column 1, line 51 et seq. detailing an
"esterquat" or a quaternized fatty acid triethanolamine ester
salt.
[0163] In one embodiment, the FSA is chosen from at least one of
the following: ditallowoyloxyethyl dimethyl ammonium chloride,
dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride,
ditallow dimethyl ammonium chloride, ditallowoyloxyethyl dimethyl
ammonium methyl sulfate, dihydrogenated-tallowoyloxyethyl dimethyl
ammonium chloride, dihydrogenated-tallowoyloxyethyl dimethyl
ammonium chloride, or combinations thereof.
[0164] In one embodiment, the FSA can also include amide containing
compound compositions. Examples of diamide comprising compounds
include, but are not limited to,
methyl-bis(tallowamidoethyl)-2-hydroxyethylammonium methyl sulfate
(available from Degussa under the trade names Varisoft 110 and
Varisoft 222). An example of an amide-ester containing compound is
N-[3-(stearoylamino)propyl]-N-[2-(stearoyloxy)ethoxy)ethyl)]-N-methylamin-
e.
[0165] Another specific embodiment of the invention provides for a
rinse added fabric softening composition further comprising a
cationic starch. Cationic starches are disclosed in US 2004/0204337
A1. In one embodiment, the rinse added fabric softening composition
comprises from about 0.1% to about 7% of cationic starch by weight
of the fabric softening composition. In one embodiment, the
cationic starch is HCP401 from National Starch.
Suitable Laundry Care Ingredients
[0166] While not essential for the purposes of the present
invention, the non-limiting list of laundry care ingredients
illustrated hereinafter are suitable for use in the laundry care
compositions and can be desirably incorporated in certain
embodiments of the invention, for example to assist or enhance
performance, for treatment of the substrate to be cleaned, or to
modify the aesthetics of the composition as is the case with
perfumes, colorants, dyes or the like. It is understood that such
ingredients are in addition to the components that were previously
listed for any particular embodiment. The total amount of such
adjuncts can range from about 0.1% to about 50%, or even from about
1% to about 30%, by weight of the laundry care composition.
[0167] The precise nature of these additional components, and
levels of incorporation thereof, will depend on the physical form
of the composition and the nature of the operation for which it is
to be used. Suitable laundry care ingredients include, but are not
limited to, polymers, for example cationic polymers, surfactants,
builders, chelating agents, dye transfer inhibiting agents,
dispersants, enzymes, and enzyme stabilizers, catalytic materials,
bleach activators, polymeric dispersing agents, clay soil
removal/anti-redeposition agents, brighteners, suds suppressors,
dyes, additional perfume and perfume delivery systems, structure
elasticizing agents, fabric softeners, carriers, hydrotropes,
processing aids and/or pigments. In addition to the disclosure
below, suitable examples of such other adjuncts and levels of use
are found in U.S. Pat. Nos. 5,576,282, 6,306,812 B1 and 6,326,348
B1 that are incorporated by reference.
[0168] As stated, the laundry care ingredients are not essential to
Applicants' laundry care compositions. Thus, certain embodiments of
Applicants' compositions do not contain one or more of the
following adjuncts materials: bleach activators, surfactants,
builders, chelating agents, dye transfer inhibiting agents,
dispersants, enzymes, and enzyme stabilizers, catalytic metal
complexes, polymeric dispersing agents, clay and soil
removal/anti-redeposition agents, brighteners, suds suppressors,
dyes, additional perfumes and perfume delivery systems, structure
elasticizing agents, fabric softeners, carriers, hydrotropes,
processing aids and/or pigments. However, when one or more adjuncts
are present, such one or more adjuncts can be present as detailed
below:
[0169] Surfactants--
[0170] The compositions according to the present invention can
comprise a surfactant or surfactant system wherein the surfactant
can be selected from nonionic and/or anionic and/or cationic
surfactants and/or ampholytic and/or zwitterionic and/or semi-polar
nonionic surfactants. The surfactant is typically present at a
level of from about 0.1%, from about 1%, or even from about 5% by
weight of the cleaning compositions to about 99.9%, to about 80%,
to about 35%, or even to about 30% by weight of the cleaning
compositions.
[0171] Builders--
[0172] The compositions of the present invention can comprise one
or more detergent builders or builder systems. When present, the
compositions will typically comprise at least about 1% builder, or
from about 5% or 10% to about 80%, 50%, or even 30% by weight, of
said builder. Builders include, but are not limited to, the alkali
metal, ammonium and alkanolammonium salts of polyphosphates, alkali
metal silicates, alkaline earth and alkali metal carbonates,
aluminosilicate builders polycarboxylate compounds. ether
hydroxypolycarboxylates, copolymers of maleic anhydride with
ethylene or vinyl methyl ether,
1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and
carboxymethyl-oxysuccinic acid, the various alkali metal, ammonium
and substituted ammonium salts of polyacetic acids such as
ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well
as polycarboxylates such as mellitic acid, succinic acid,
oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic
acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
[0173] Chelating Agents--
[0174] The compositions herein can also optionally contain one or
more copper, iron and/or manganese chelating agents. If utilized,
chelating agents will generally comprise from about 0.1% by weight
of the compositions herein to about 15%, or even from about 3.0% to
about 15% by weight of the compositions herein.
[0175] Dye Transfer Inhibiting Agents--
[0176] The compositions of the present invention can also include
one or more dye transfer inhibiting agents. Suitable polymeric dye
transfer inhibiting agents include, but are not limited to,
polyvinylpyrrolidone polymers, polyamine N-oxide polymers,
copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.
When present in the compositions herein, the dye transfer
inhibiting agents are present at levels from about 0.0001%, from
about 0.01%, from about 0.05% by weight of the cleaning
compositions to about 10%, about 2%, or even about 1% by weight of
the cleaning compositions.
[0177] Dispersants--
[0178] The compositions of the present invention can also contain
dispersants. Suitable water-soluble organic materials are the homo-
or co-polymeric acids or their salts, in which the polycarboxylic
acid can comprise at least two carboxyl radicals separated from
each other by not more than two carbon atoms.
[0179] Enzymes--
[0180] The compositions can comprise one or more detergent enzymes
which provide cleaning performance and/or fabric care benefits.
Examples of suitable enzymes include, but are not limited to,
hemicellulases, peroxidases, proteases, cellulases, xylanases,
lipases, phospholipases, esterases, cutinases, pectinases,
keratanases, reductases, oxidases, phenoloxidases, lipoxygenases,
ligninases, pullulanases, tannases, pentosanases, malanases,
.beta.-glucanases, arabinosidases, hyaluronidase, chondroitinase,
laccase, and amylases, or mixtures thereof. A typical combination
is a cocktail of conventional applicable enzymes like protease,
lipase, cutinase and/or cellulase in conjunction with amylase.
[0181] Enzyme Stabilizers--
[0182] Enzymes for use in compositions, for example, detergents can
be stabilized by various techniques. The enzymes employed herein
can be stabilized by the presence of water-soluble sources of
calcium and/or magnesium ions in the finished compositions that
provide such ions to the enzymes.
[0183] Catalytic Metal Complexes--
[0184] Applicants' compositions can include catalytic metal
complexes. One type of metal-containing bleach catalyst is a
catalyst system comprising a transition metal cation of defined
bleach catalytic activity, such as copper, iron, titanium,
ruthenium, tungsten, molybdenum, or manganese cations, an auxiliary
metal cation having little or no bleach catalytic activity, such as
zinc or aluminum cations, and a sequestrate having defined
stability constants for the catalytic and auxiliary metal cations,
particularly ethylenediaminetetraacetic acid, ethylenediaminetetra
(methyl-enephosphonic acid) and water-soluble salts thereof. Such
catalysts are disclosed in U.S. Pat. No. 4,430,243.
[0185] 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.
[0186] Cobalt bleach catalysts useful herein are known, and are
described, for example, in U.S. Pat. Nos. 5,597,936 and 5,595,967.
Such cobalt catalysts are readily prepared by known procedures,
such as taught for example in U.S. Pat. Nos. 5,597,936, and
5,595,967.
[0187] Compositions herein can also suitably include a transition
metal complex of a macropolycyclic rigid ligand--abbreviated as
"MRL". As a practical matter, and not by way of limitation, the
compositions and cleaning processes herein can be adjusted to
provide on the order of at least one part per hundred million of
the benefit agent MRL species in the aqueous washing medium, and
can 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.
[0188] Preferred transition-metals in the instant transition-metal
bleach catalyst include manganese, iron and chromium. Preferred
MRL's herein are a special type of ultra-rigid ligand that is
cross-bridged such as
5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexa-decane.
[0189] 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.
[0190] The following examples further illustrate the subject matter
described above but, of course, should not be construed as in any
way limiting the scope thereof.
EXAMPLES
[0191] The following examples demonstrate the production of
capsules according to the invention. The capsules were produced
using a triple nozzle coextrusion apparatus such as that depicted
in FIG. 4. Different fluids were used to form the core(s), the
intermediate layer, and the shell layer of the capsules. Fluid 1,
which contained the components that formed the core(s) of the
capsules, was pumped through the first nozzle 410. Fluid 2, which
contained the components that formed the intermediate layer, was
pumped through the second nozzle 420. Fluid 3, which contained the
components that formed the shell layer, was pumped through the
third nozzle 430. The compositions of the fluids used to produce
the capsules in each example are described in further detail below.
The three fluids were simultaneously pumped through their
respective nozzles so that one or more droplets of Fluid 1
emanating from nozzle 410 was encased in a droplet of Fluid 2
emanating from nozzle 420, which droplet was further encased by a
droplet of Fluid 3 emanating from nozzle 430. Each of the resulting
"composite" droplets, which would later form the capsule, was
allowed to grow until it separated itself from the nozzles due to
its growing weight. The droplets were then collected in a bath of
cold oil (e.g., corn oil or vegetable oil), in which the components
of Fluid 3 solidified to form the shell layer of the capsule. The
resulting capsules were then collected and cleaned.
Example 1
[0192] This example demonstrates the production of capsules
according to the invention having a core containing a polymeric
colorant. Specifically, Fluid 1 was a 50 wt. % solution of
Liquitint.RTM. Violet DD (available from Milliken & Company in
Spartanburg, S.C.) in water. Fluid 2 was a silicone oil (i.e., Dow
Corning.RTM. 200 Fluid 500 cSt) containing approximately 2 wt. %
hydrophobic, fumed silica particles (i.e., CAB-O-SIL.RTM. TS-720
fumed silica). Fluid 3 was a 3 wt. % solution of agar in water.
[0193] Fluids 1 and 2 were delivered to their respective nozzles at
room temperature, and Fluid 3 was heated and delivered to the
nozzle at a temperature of greater than approximately 60.degree. C.
The fluids were passed through the triple nozzle coextrusion
apparatus described above, and the droplets emerging from the
apparatus were collected in cold corn oil maintained at a
temperature of approximately 0-10.degree. C. The components of
Fluid 3 coalesced almost instantly on contact with the cold corn
oil to form capsules according to the invention. The capsules
contained at least one core of the polymeric colorant surrounded by
an intermediate silicone layer encased in a solid hydrogel
(agarose) shell layer. Following collection and cleaning, some of
the resulting capsules were placed in a liquid laundry detergent
(i.e., Tide.RTM. laundry detergent from The Procter & Gamble
Company). The capsules did not burst or leak upon addition to the
liquid laundry detergent and remained stable (i.e., did not burst
or leak) for several months.
Example 2
[0194] This example demonstrates the production of capsules
according to the invention having a core containing a polymeric
colorant. Specifically, Fluid 1 was a 50 wt. % solution of
Liquitint.RTM. Violet DD (available from Milliken & Company in
Spartanburg, S.C.) in water. Fluid 2 was a silicone oil (i.e., Dow
Corning.RTM. 200 Fluid 1,000 cSt) containing approximately 2 wt. %
hydrophobic silica particles (i.e., Aerosil.RTM. 816R silica from
Degussa). Fluid 3 was a 3 wt. % solution of agar in water.
[0195] Fluids 1 and 2 were delivered to their respective nozzles at
room temperature, and Fluid 3 was heated and delivered to the
nozzle at a temperature of greater than approximately 60.degree. C.
The fluids were passed through the triple nozzle coextrusion
apparatus described above, and the droplets emerging from the
apparatus were collected in cold corn oil maintained at a
temperature of approximately 0-10.degree. C. The components of
Fluid 3 coalesced almost instantly on contact with the cold corn
oil to form capsules according to the invention. The capsules
contained at least one core of the polymeric colorant surrounded by
an intermediate silicone layer encased in a solid hydrogel
(agarose) shell layer. Following collection and cleaning, some of
the resulting capsules were placed in a liquid laundry detergent
(i.e., Tide.RTM. laundry detergent from The Procter & Gamble
Company). The capsules did not burst or leak upon addition to the
liquid laundry detergent and remained stable (i.e., did not burst
or leak) for several months.
Example 3
[0196] This example demonstrates the production of capsules
according to the invention having a core containing a polymeric
colorant. Specifically, Fluid 1 was a 50 wt. % solution of
Liquitint.RTM. Violet DD (available from Milliken & Company in
Spartanburg, S.C.) in water. Fluid 2 was a silicone oil (i.e., Dow
Corning.RTM. 200 Fluid 500 cSt) containing approximately 3 wt. %
hydrophobic silica particles (i.e., Aerosil.RTM. 816R silica from
Degussa). Fluid 3 was a 3 wt. % solution of agar in water.
[0197] Fluids 1 and 2 were delivered to their respective nozzles at
room temperature, and Fluid 3 was heated and delivered to the
nozzle at a temperature of greater than approximately 60.degree. C.
The fluids were passed through the triple nozzle coextrusion
apparatus described above, and the droplets emerging from the
apparatus were collected in cold corn oil maintained at a
temperature of approximately 0-10.degree. C. The components of
Fluid 3 coalesced almost instantly on contact with the cold corn
oil to form capsules according to the invention. The capsules
contained at least one core of the polymeric colorant surrounded by
an intermediate silicone layer encased in a solid hydrogel
(agarose) shell layer.
Example 4
[0198] This example demonstrates the production of capsules
according to the invention having a core containing a polymeric
colorant. Specifically, Fluid 1 was a 50 wt. % solution of
Liquitint.RTM. Violet DD (available from Milliken & Company in
Spartanburg, S.C.) in water. Fluid 2 was a silicone oil (i.e., Dow
Corning.RTM. 200 Fluid 500 cSt) containing approximately 4 wt. %
hydrophobic silica particles (i.e., Aerosil.RTM. 816R silica from
Degussa). Fluid 3 was a 3 wt. % solution of agar in water.
[0199] Fluids 1 and 2 were delivered to their respective nozzles at
room temperature, and Fluid 3 was heated and delivered to the
nozzle at a temperature of greater than approximately 60.degree. C.
The fluids were passed through the triple nozzle coextrusion
apparatus described above, and the droplets emerging from the
apparatus were collected in cold corn oil maintained at a
temperature of approximately 0-10.degree. C. The components of
Fluid 3 coalesced almost instantly on contact with the cold corn
oil to form capsules according to the invention. The capsules
contained at least one core of the polymeric colorant surrounded by
an intermediate silicone layer encased in a solid hydrogel
(agarose) shell layer.
Example 5
[0200] This example demonstrates the production of capsules
according to the invention having a core containing a polymeric
colorant. Specifically, Fluid 1 was a 50 wt. % solution of
Liquitint.RTM. Violet DD (available from Milliken & Company in
Spartanburg, S.C.) in water. Fluid 2 was a silicone oil (i.e., Dow
Corning.RTM. 200 Fluid 1,000 cSt) containing approximately 2 wt. %
hydrophobic silica particles (i.e., Aerosil.RTM. 816R silica from
Degussa). Fluid 3 was an aqueous solution containing approximately
2 wt. % agar, approximately 1 wt. % sodium polyacrylate (a
superabsorbent polymer), and approximately 10 wt. % sodium
chloride.
[0201] Fluids 1 and 2 were delivered to their respective nozzles at
room temperature, and Fluid 3 was heated and delivered to the
nozzle at a temperature of greater than approximately 60.degree. C.
The fluids were passed through the triple nozzle coextrusion
apparatus described above, and the droplets emerging from the
apparatus were collected in cold corn oil maintained at a
temperature of approximately 0-10.degree. C. The components of
Fluid 3 coalesced almost instantly on contact with the cold corn
oil to form capsules according to the invention. The capsules
contained at least one core of the polymeric colorant surrounded by
an intermediate silicone layer encased in a solid hydrogel
(agarose) shell layer. Following collection and cleaning, some of
the resulting capsules were placed in a liquid laundry detergent
(i.e., Tide.RTM. laundry detergent from The Procter & Gamble
Company). The capsules did not burst or leak upon addition to the
liquid laundry detergent. However, once the liquid laundry
detergent containing the capsules was diluted with water at a level
similar to that encountered in household laundering conditions, the
capsules burst and released the polymeric colorant into the
water.
Example 6
[0202] This example demonstrates the production of capsules
according to the invention having a core containing a polymeric
colorant. Specifically, Fluid 1 was a 50 wt. % solution of
Liquitint.RTM. Violet DD (available from Milliken & Company in
Spartanburg, S.C.) in water. Fluid 2 was a silicone oil (i.e., Dow
Corning.RTM. 200 Fluid 1,000 cSt) containing approximately 2 wt. %
hydrophobic silica particles (i.e., Aerosil.RTM. 816R silica from
Degussa). Fluid 3 was an aqueous solution containing approximately
3 wt. % agar, approximately 2 wt. % sodium polyacrylate (a
superabsorbent polymer), and approximately 10 wt. % sodium
chloride.
[0203] Fluids 1 and 2 were delivered to their respective nozzles at
room temperature, and Fluid 3 was heated and delivered to the
nozzle at a temperature of greater than approximately 60.degree. C.
The fluids were passed through the triple nozzle coextrusion
apparatus described above, and the droplets emerging from the
apparatus were collected in cold corn oil maintained at a
temperature of approximately 0-10.degree. C. The components of
Fluid 3 coalesced almost instantly on contact with the cold corn
oil to form capsules according to the invention. The capsules
contained at least one core of the polymeric colorant surrounded by
an intermediate silicone layer encased in a solid hydrogel
(agarose) shell layer. Following collection and cleaning, some of
the resulting capsules were placed in a liquid laundry detergent
(i.e., Tide.RTM. laundry detergent from The Procter & Gamble
Company). The capsules did not burst or leak upon addition to the
liquid laundry detergent. However, once the liquid laundry
detergent containing the capsules was diluted with water at a level
similar to that encountered in household laundering conditions, the
capsules burst and released the polymeric colorant into the
water.
[0204] All references, including publications, patent applications,
and patents, cited herein are hereby incorporated by reference to
the same extent as if each reference were individually and
specifically indicated to be incorporated by reference and were set
forth in its entirety herein.
[0205] The use of the terms "a" and "an" and "the" and similar
referents in the context of describing the subject matter of this
application (especially in the context of the following claims) are
to be construed to cover both the singular and the plural, unless
otherwise indicated herein or clearly contradicted by context. The
terms "comprising," "having," "including," and "containing" are to
be construed as open-ended terms (i.e., meaning "including, but not
limited to,") unless otherwise noted. Recitation of ranges of
values herein are merely intended to serve as a shorthand method of
referring individually to each separate value falling within the
range, unless otherwise indicated herein, and each separate value
is incorporated into the specification as if it were individually
recited herein. All methods described herein can be performed in
any suitable order unless otherwise indicated herein or otherwise
clearly contradicted by context. The use of any and all examples,
or exemplary language (e.g., "such as") provided herein, is
intended merely to better illuminate the subject matter of the
application and does not pose a limitation on the scope of the
subject matter unless otherwise claimed. No language in the
specification should be construed as indicating any non-claimed
element as essential to the practice of the subject matter
described herein.
[0206] Preferred embodiments of the subject matter of this
application are described herein, including the best mode known to
the inventors for carrying out the claimed subject matter.
Variations of those preferred embodiments may become apparent to
those of ordinary skill in the art upon reading the foregoing
description. The inventors expect skilled artisans to employ such
variations as appropriate, and the inventors intend for the subject
matter described herein to be practiced otherwise than as
specifically described herein. Accordingly, this disclosure
includes all modifications and equivalents of the subject matter
recited in the claims appended hereto as permitted by applicable
law. Moreover, any combination of the above-described elements in
all possible variations thereof is encompassed by the present
disclosure unless otherwise indicated herein or otherwise clearly
contradicted by context.
* * * * *