U.S. patent application number 15/487491 was filed with the patent office on 2017-08-03 for high strength microcapsules.
The applicant listed for this patent is The Procter & Gamble Company. Invention is credited to Biao DUAN, Linsheng FENG, Nianxi YAN.
Application Number | 20170216161 15/487491 |
Document ID | / |
Family ID | 55747387 |
Filed Date | 2017-08-03 |
United States Patent
Application |
20170216161 |
Kind Code |
A1 |
YAN; Nianxi ; et
al. |
August 3, 2017 |
HIGH STRENGTH MICROCAPSULES
Abstract
High strength, high integrity microcapsules containing a
hydrophobic core material wherein said microcapsule walls are
formed of copolymers of select monomers through a multistep
oil-in-water emulsification polymerization process.
Inventors: |
YAN; Nianxi; (Appleton,
WI) ; DUAN; Biao; (Appleton, WI) ; FENG;
Linsheng; (Appleton, WI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Procter & Gamble Company |
Cincinnati |
OH |
US |
|
|
Family ID: |
55747387 |
Appl. No.: |
15/487491 |
Filed: |
April 14, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14884671 |
Oct 15, 2015 |
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15487491 |
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62199340 |
Jul 31, 2015 |
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62117604 |
Feb 18, 2015 |
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62064906 |
Oct 16, 2014 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C11D 3/0015 20130101;
C11D 11/0023 20130101; A61K 9/5026 20130101; A61L 15/60 20130101;
A61K 2800/10 20130101; A61K 2800/412 20130101; C11D 11/0017
20130101; A61L 15/46 20130101; A61Q 15/00 20130101; C11D 17/06
20130101; A61K 8/8129 20130101; C11B 9/00 20130101; A61Q 19/00
20130101; A61Q 19/10 20130101; C11D 3/505 20130101; C11D 17/0039
20130101; A61K 9/5089 20130101; A61K 8/11 20130101; A61K 2800/56
20130101; A61Q 5/02 20130101; C11D 3/001 20130101; C11D 17/0013
20130101 |
International
Class: |
A61K 8/11 20060101
A61K008/11; A61Q 5/02 20060101 A61Q005/02; A61Q 15/00 20060101
A61Q015/00; C11D 11/00 20060101 C11D011/00; C11B 9/00 20060101
C11B009/00; C11D 3/50 20060101 C11D003/50; C11D 3/00 20060101
C11D003/00; C11D 17/06 20060101 C11D017/06; A61Q 19/10 20060101
A61Q019/10; A61L 15/46 20060101 A61L015/46 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 16, 2015 |
US |
PCT/US2015/055905 |
Claims
1. A method of making a consumer product comprising combining a
consumer product ingredient and microcapsules comprising a high
strength wall material and an encapsulated hydrophobic core
material said microcapsules being made by a method comprising (a)
forming a dispersion of an oil phase composition comprising a
hydrophobic core material and one or more polymerizable
ethylenically unsaturated monomers, the core monomer, that are
wholly or partially soluble in the hydrophobic core material in a
water or water-based solution, the continuous phase, said
continuous phase, also referred to as the water phase composition,
comprising water and at least one or more ethylenically unsaturated
polymerizable monomers, the water phase monomer, all or a portion
of which are poor to moderately hydrophilic, (b) subjecting the
dispersion to one or more conditions that initiate or effectuate
the polymerization of the water phase monomer and the core monomer,
(c) maintaining the dispersion under such conditions so as to
continue polymerization of the monomers until such time as the full
capsule walls are formed and, optionally, thereafter (d) isolating
the formed microcapsules from the continuous phase.
2. The method of claim 1 wherein each of the oil phase composition
and the water phase composition contains at least one initiator for
effecting or initiating the polymerization of the monomers of each
phase.
3. The method of claim 1 wherein prior to or concurrent with step
(a), either the oil phase composition, the water phase composition,
or both is subjected to such conditions as will induce
oligomerization/prepolymerization, in whole or in part, of one or
more of the monomers of said composition.
4. The method of claim 3 wherein each phase to be subjected to
oligomerization/prepolymerization contains at least two initiators,
at least one of which is activated by conditions different from the
other, and which initiates said
oligomerization/prepolymerization.
5. The method of claim 3 wherein core monomers are subjected to
said oligomerization/prepolymerization.
6. The method of claim 3 wherein both the core monomers and the
water phase monomers are subjected to said
oligomerization/prepolymerization.
7. The method of claim 1 wherein step (b) comprises a two or more
step polymerization process wherein in a first step at least one of
the core monomer and the water phase monomer or both is subjected
to conditions that initiate or effectuate the oligomerization or
pre-polymerization of, in whole or in part, one or more of said
core monomer, water phase monomer, or both, and in a second or
subsequent step the dispersion is subjected to one or more
conditions that initiates or effectuates the full polymerization of
the polymerizable monomers including the oligomers/prepolymers and
any remaining monomer of the oligomerization/pre-polymerization
step.
8. The method of claim 7 wherein each phase to be subjected to
oligomerization/prepolymerization contains at least two initiators,
at least one of which is activated by conditions different from the
other, and which initiates said
oligomerization/prepolymerization.
9. The method of claim 7 wherein the emulsion is subjected to
conditions that induce or promote the movement of the so formed
oligomers/prepolymers to the oil phase/water phase interface
concurrent with or subsequent to the
oligomerization/prepolymerization step.
10. The method of claim 7 wherein the core monomers are subjected
to conditions that effectuate the oligomerization or
prepolymerization thereof.
11. The method of claim 7 wherein both the core monomers and the
water phase monomers are subjected to conditions that effectuate
the oligomerization or prepolymerization thereof.
12. The method of claim 11 wherein the conditions which effect
oligomerization and/or prepolymerization of the monomers of each
phase is the same and said oligomerization or pre-polymerization
occurs concurrently in each phase.
13. The method of claim 11 wherein the conditions which effect
oligomerization and/or prepolymerization are different and occur in
sequence.
14. The method of claim 7 wherein following completion of the
oligomerization/pre-polymerization step, the dispersion is
subjected to such conditions as will initiate or effectuate the
full polymerization of the monomers, including the already formed
oligomers and prepolymers, and building of the microcapsule wall or
shell at the interface of the oil phase composition and the
continuous phase.
15. The method of claim 14 wherein full polymerization is
concurrently initiated in both the oil phase and the water
phase.
16. The method of claim 14 wherein polymerization of the monomers
and/or oligomers/prepolymers of one phase relative to the other is
staggered.
17. The method of claim 16 wherein the stagger is such that capsule
wall is only partially formed prior to initiation of polymerization
of the monomers and/or oligomers/prepolymers of the other
phase.
18. The method of claim 16 wherein a seed capsule is formed of the
first initiated monomer and/or oligomer/prepolymer which seed
capsule still possesses areas of oil phase/water phase
interface.
19. The method of claim 1 wherein during step (b) the emulsion is
subjected to conditions that induce or promote the movement of the
polymerizing monomers to the oil phase/water phase interface.
20. The method of claim 1 wherein the microcapsules are formed in a
sequential manner with at least one of the core phase monomer and
water phase monomer, preferably both, undergoing a two-step
polymerization whereby oligomerization/prepolymerization of each
monomer material is initiated and maintained for a period of time
in their respective phases and full polymerization of each occurs
subsequently at the oil phase/water phase interface, with the
oligomers/prepolymers continuing to build upon the wall as it
forms: the core phase monomers building on the inner surface of the
shell and the water phase monomers building upon the outer surface
of the shell.
21. The method of claim 1 wherein the core material is selected
from UV absorbers, UV reflectors, pigments, dyes, colorants, scale
inhibitors, corrosion inhibitors, antioxidants, pour point
depressants, waxes, deposition inhibitors, dispersants, flame
retardants, biocides, active dye tracer materials, odor control
agents, natural oils, flavor and perfumes oils, crop protection
agents, and phase change materials.
22. The method of claim 1 wherein the core material is a phase
change material.
23. The method of claim 1 wherein the water phase monomers comprise
1-100 wt % of at least one ethylenically unsaturated monomer
manifesting poor to moderately hydrophilic properties; 0-99 wt % of
at least one polyfunctional ethylenically unsaturated monomer, and
0-60 wt % of other mono-functional monomers and the core monomers
comprise one or more mono-, di- and/or poly-functional
ethylenically unsaturated monomers, provided at least 50 mole % of
the core monomer is a difunctional monomer having a water
solubility of not more than about 1 g/L water as measured in
deionized water at 20.degree. C.
Description
FIELD
[0001] The present disclosure relates to high strength
microcapsules formed by an oil in water microencapsulation process
employing an oil phase composition comprising a hydrophobic core
material, especially a hydrophobic wax or a hydrophobic liquid,
most especially a hydrophobic phase change material, and one or
more ethylenically unsaturated monomers which are wholly or
partially soluble or dispersible in the core material and an
aqueous or water phase composition as the continuous phase
comprising water and one or more ethylenically unsaturated monomers
which are wholly or partially water soluble or water dispersible:
the wall forming monomers of each of the oil phase composition and
the water phase composition having certain hydrophilic/hydrophobic
characteristics. Preferably the shell of the microcapsules is
formed from a plurality of monomers, at least one of which is
generally hydrophobic and is contained in the oil phase composition
and at least one of which is moderately hydrophilic and is
contained in the water phase composition. Most preferably the shell
is formed, in whole or in part, from oligomers/prepolymers of the
specified monomers of each phase composition.
[0002] The present disclosure also relates to a method of making
high strength microcapsules from a plurality of ethylenically
unsaturated monomers of certain hydrophilic/hydrophobic
characteristics which method involves (i) the creation of an
oil-in-water emulsion comprising a core phase composition
comprising a core material and at least one hydrophobic monomer
which is wholly or partially soluble or dispersible in the core
material and an aqueous phase composition comprising water and at
least one poor to moderately hydrophilic monomer which is wholly or
partially water soluble or water dispersible and (ii) the formation
of a shell wall through the polymerization of the monomers of each
of the oil phase and the water phase at the interface of the oil
phase and the water phase. Preferably, the disclosed method
involves the use of at least two initiators, one in the oil phase
and one in the water phase, each of which is activated at different
temperatures and/or by different conditions and is capable of
polymerizing the monomers of their respective phase. More
preferably, the disclosed method involves the use of three or, most
preferably, four initiators, at least two of which are activated by
different temperatures/conditions and/or have different
decomposition rates under the same activation conditions. Most
preferably the method employs four initiators, preferably two in
each phase, thereby enabling one to stage or sequence the shell
formation whereby all or at least a portion of each of the wall
forming monomers of each phase are oligomerized/prepolymerized
prior to effecting actual polymerization and shell wall
formation.
BACKGROUND
[0003] Microcapsules and microencapsulation technology are old and
well known and their commercial applications varied. Microcapsules
have played a significant role in various print technologies where
a paper or other like substrate is coated with microcapsules
containing ink or an ink-forming or inducing ingredient which
microcapsules release the ingredient, generating an image, when
fractured by pressure, as by a printing press or a stylus.
Microcapsules have also played a significant role in various
adhesive and sealant technologies including the encapsulation of
solvents for solvent swellable/tackified preapplied adhesives
whereby fracture of the microcapsules releases the solvent which
softens or tackifies the adhesive to enable bonding and which
re-hardened upon evaporation of the solvent. In other adhesive and
sealant applications, the microcapsules contain one or more
components of a curable or polymerizable adhesive or sealant
composition which, upon release, leads to the cure or
polymerization of the adhesive or sealant. In all of these early
applications, functionality and efficacy, especially for long term
storage and utility, is dependent upon the integrity of the
microcapsule walls where the sought after integrity pertains to
both strength, so as to avoid premature fracture, as well as
impermeability, so as to prevent leakage and/or passage of the
contents of the microcapsule through the microcapsule walls while
also have easily attained break points to allow them to perform
their function when intended by, e.g., simply screwing parts coated
with coatings containing the microcapsules together.
[0004] Evolution of microencapsulation technology has led to many
new commercial applications for encapsulated material, including
applications that require microcapsules that fracture more readily,
with less pressure, but not prematurely. Other applications require
microcapsules that specifically allow for a controlled, slow
release or permeation of the contents from within the microcapsules
without the need to actually fracture the same. For example,
perfume containing microcapsules are oftentimes applied to
advertising inserts in magazines so that the reader can sample the
smell of the perfume. Here strength is needed to avoid premature
fracturing of the microcapsules due to the weight and handling of
the magazine; yet, the microcapsules need ease of fracture so that
the reader can simply scratch the treated area to release the
contents of the microcapsule. At the same time, it is desirable to
allow for some release of the contents, even without fracturing, to
induce the reader to want to scratch the sample to get a more
accurate sense of the smell.
[0005] Microcapsules are also finding increasing utility in
laundering and fabric treatments: an application that requires both
strength and defined release or break points. For example, a number
of products exist wherein microcapsules of various ingredients,
including perfumes, are applied to strips of a fabric material and
added to the dryer wherein the tumbling action and/or heat of the
dryer causes the microcapsules to fracture and/or become more
permeable, releasing the ingredients which, in a volatilized state,
permeate and deposit upon the contents of the dryer. This
methodology applies that "fresh out of the dryer" smell, but is
short lived as the perfume continues to volatilize from the treated
fabric. Other products exist whereby microcapsules containing
perfumes, odor controlling or masking materials, and other
ingredients are applied directly or indirectly to the fabric,
especially apparel, to provide a longer lived freshness to the
same. Here, the integrity of the microcapsules is such that the
microcapsules will not readily break during washing and handling,
but will break during normal use and wearing of the garment which
allows for the continued release of the contents of the
microcapsules.
[0006] Despite the historical need for a break or fracturing of
microcapsules, new potential applications are developing where
capsule strength, specifically high strength, is becoming more and
more critical. In these applications and intended applications, the
microcapsules must be able to withstand conditions of high
pressure, including pressures up to 100 psi, even 200 psi, or more
as well as high temperatures, e.g., in excess of 150.degree. C.,
even 200.degree. C., without fracture and without an increase in
the permeability of the shell wall, at least not until specific
trigger events are attained which allow for such fracture or
increased permeability. Still other applications require
microcapsules that are not intended to break or release their
contents at all. These demands are especially necessary for
microcapsules containing phase change materials. For example,
microcapsules containing phase change materials are being
incorporated into fabrics so as to allow the fabric to draw heat
away from the body. Most often these fabrics are incorporated into
sporting garments and must withstand harsh wear due to physical
exertion by the wearer, repeated washings with strong cleaning
materials, etc., all without fracturing the microcapsules
containing the phase change material. Other uses for microcapsules
containing phase change materials include medical devices,
construction materials, bedding, refrigerated transport, energy
storage, cooling fluids, absorptive chillers such as for circuitry,
solar devices, and applications where temperature moderation is
desired. Where the microcapsule core is phase change material, uses
can include such encapsulated materials in mattresses, pillows,
bedding, textiles, sporting equipment, medical devices, building
products, construction products, HVAC, renewable energy, clothing,
athletic surfaces, electronics, automotive, aviation, shoes, beauty
care, laundry, and solar energy.
[0007] Despite all the advances and improvements, there is still a
need for improved specialty microcapsules that provide a suitable
mix of containment or release/permeability characteristics and
physical properties, especially high strength properties, for
today's demanding applications. This is especially so in the area
of perfumes and other odiferous ingredients, particularly in
relation to fabric, textile and garment treatment, where controlled
release and longevity as well as capsule strength and integrity are
necessary.
[0008] Various methods and shell wall forming compositions have
been proposed in the art in an effort to make microcapsules capable
of withstanding certain harsher conditions, particularly higher
temperatures. For instance, Sinclair (U.S. Pat. No. 4,396,670)
encapsulated hydrophobic liquids using aminoplast resin capsules
prepared from melamine formaldehyde pre-condensate; however, these
become more permeable at elevated temperatures and may release
formaldehyde. Jahns et. al. (U.S. Pat. No. 6,200,681) encapsulated
latent heat storage materials in a shell formed by free radical
polymerization of a monomer mixture comprising 30-100% of one or
more C.sub.1-C.sub.24 alkyl esters of (meth)acrylic acid, 0-80% of
a water insoluble or low solubility bi- or polyfunctional monomer
and 0-40% of other monomers; however, the specific microcapsules
described do not possess sufficient strength and will enable too
much loss of core material at higher temperature. Weston et. al.
(U.S. Pat. No. 6,716,526) prepare microcapsules having a shell
comprising a copolymer formed from a monomer blend of 30-90%
methacrylic acid, 10-70% of an alkyl ester of (meth)acrylic acid
whose homopolymer has a Tg in excess of 60.degree. C., and 0-40%
other ethylenically unsaturated monomer. Although an improvement in
that the permeability is improved even at high temperatures, these
too lack the desired strength characteristics. Building on Weston
et. al., Grey (U.S. Pat. No. 8,784,984) microencapsulates
hydrophobic core materials in a polymer shell comprising the
reaction product of a monomer mixture containing 1-95% of at least
one hydrophobic mono-functional ethylenically unsaturated monomer,
5-99% of at least one polyfunctional ethylenically unsaturated
monomer, and 0-60% of other mono-functional monomers wherein a
hydrophobic polymer is incorporated into the monomer mixture prior
to the polymerization thereof.
[0009] Despite the advances, the need still exists for improved
microcapsules for hydrophobic materials and, perhaps more
importantly, a more convenient and simpler method for their
production. Most especially there is still a need for high
integrity microcapsules that will withstand the forces and
environments associated with their intended use, particularly in
the encapsulation of phase change materials, without rupture or
compromising the integrity of the microcapsule walls.
SUMMARY
[0010] According to the present disclosure, high strength
microcapsules suitable for the encapsulation of hydrophobic core
materials, especially phase change materials, are formed through an
oil-in-water microencapsulation process in which the hydrophobic
material is encapsulated in a polymer shell comprising the reaction
product of one or more ethylenically unsaturated monomers which is
wholly or partially soluble in the core material (the "core
monomers"), and the reaction product of one or more ethylenically
unsaturated monomers which is wholly or partially soluble in the
aqueous or water continuous phase and has certain
hydrophilic/hydrophobic characteristics (the "water phase
monomers"): each of said reaction products also comprising a
copolymer material derived from core monomers and water phase
monomers and/or oligomers and/or prepolymers thereof, to the extent
they are copolymerizable. Specifically, the core monomers are such
that while wholly or partially soluble in the core material in
their monomer state, as they oligomerize/prepolymerize they become
less and less soluble in the core material, less lipophilic, to the
extent they are lipophilic, and/or less hydrophobic whereby they
begin to/tend to migrate within the oil phase composition to the
interface between the oil phase and the water or continuous phase.
The core monomers may be a single monomer or a mixture of monomers:
though as a matter of convenience and cost, a single monomer is
preferred. Additionally, the core monomers may be mono-, di- or
polyfunctional monomers; though it is preferable that the core
monomer is a di-functional monomer or comprises a predominant
amount, i.e., 50 mole % or more, of a difunctional monomer. The
water phase monomers, on the other hand, must include one or more
monomers that manifest, at most, poor to moderate hydrophilic
properties and/or whose oligomers/prepolymers manifest poor or
limited solubility (particularly as compare to the monomer) in the
water phase, whereby the oligomers/prepolymers of the water phase
monomers are less hydrophilic and/or are less soluble in the water
phase composition and, in a similar fashion to the prepolymers of
the core monomers, begin to/tend to migrate within the water or
continuous phase to the interface between the oil phase and the
water or continuous phase. The water phase monomers generally
comprise 1-100 wt %, preferably 30-100 wt %, of at least one
ethylenically unsaturated monomer, most especially a difunctional
monomer, manifesting poor to moderately hydrophilic properties;
0-99 wt %, preferably, 0-70 wt %, of at least one polyfunctional
ethylenically unsaturated monomer, and 0-60 wt %, preferably 0-30
wt %, of other mono-functional monomers. Preferably the at least
one water phase monomer manifesting poor to moderately hydrophilic
properties is a difunctional monomer or comprises a predominant
amount, i.e., 50 mole % or more, of a difunctional monomer.
[0011] According to the present disclosure there is also provided a
method of making high strength microcapsules whose core material is
a hydrophobic material, most preferably a hydrophobic phase change
material, which method involves (i) preparing a oil phase
composition comprising the hydrophobic core material and one or
more ethylenically unsaturated monomers that are wholly or
partially soluble in the core material, preferably one or more
hydrophobic monomers, (ii) creating a dispersion of the oil phase
composition in a water or water-based continuous phase composition
comprising water and one or more ethylenically unsaturated
monomers, all or a portion of which are poorly to moderately
hydrophilic, and (iii) effecting the polymerization of the monomers
of each phase, sequentially or concurrently or both, with or
without first effecting an oligomerization/prepolymerization of one
or both of the core phase monomers and the water phase monomers,
and allowing the polymerization to continue until the microcapsules
are formed. Preferably, the polymerization and, hence, formation of
the capsule or shell wall occurs in a sequential manner with at
least one of the core phase monomers and the water phase monomer,
preferably both, undergoing a two-step polymerization whereby
oligomerization/prepolymerization of some or all of the different
core phase monomers and/or different water phase monomers and/or
all or a portion of each of said core phase monomers and/or said
water phase monomers is initiated and maintained for a period of
time in their respective phases to form their respective
oligomers/prepolymers after which full polymerization of the
oligomers/prepolymers and any remaining monomer occurs at the
interface of the oil and continuous phases during the wall forming
stage of the process. Once a seed capsule is formed and the capsule
wall continues to build, the capsule wall achieves a state where
the oil phase and water phase are isolated from one another by the
capsule wall.
[0012] Thereafter, the oligomers/prepolymers and remaining monomers
of each of the oil phase composition and the water phase
composition continue to build upon the wall as it forms: the core
phase monomers building on the inner surface of the shell and the
water phase monomers building upon the outer surface of the shell.
Though somewhat dependent upon the reaction conditions and
selection of monomers and their relative reactivity, particularly
under the conditions of free radical polymerization, it is believed
that wall formation involves, at least to some extent, the
copolymerization of the core monomers and/or their
oligomers/prepolymers with the water phase monomers and/or their
oligomers/prepolymers, particularly during the early stages of
shell wall formation at which point the
monomers/oligomers/-prepolymers of each phase are readily
accessible to one another at the oil phase/water phase
interface.
[0013] Shell formation is achieved through the use of at least two
initiators, at least one initiator in each of the core phase and
the water phase. Preferably the process employs at least two
initiators and a two-step polymerization process in at least one
phase for effecting oligomerization/prepolymerization of at least a
portion of the monomers of that phase before effecting full
polymerization of the wall forming materials of both phases. Most
preferably, the process employs four initiators, two in each phase,
wherein the initiators in each phase are initiated or activated by
different conditions and/or have a different rate of activation
under the same conditions. In this way, the oligomers/prepolymer of
each shell forming monomer composition may be generated in each
phase and a period of time allowed to lapse before activation of
the second initiator in each phase which then causes the full
polymerization of the oligomers/prepolymers and any remaining
monomer and rapid shell wall formation. It is also to be
appreciated that the initiators in one phase may be initiated or
activated by the same or similar conditions as the initiators in
the other phase whereby oligomerization/prepolymerization and/or
full polymerization in each phase is effected concurrently, or
nearly so, by the same or similar conditions. While it is preferred
that the second initiator in each phase be effected concurrently,
the first initiator, that which effects
oligomerization/prepolymerization, may be effected by different
conditions and/or the same conditions as the second initiator,
preferably different conditions. Additionally,
oligomerization/prepolymerization of the core monomer may be
initiated prior to, concurrent with or subsequent to emulsification
of the oil phase composition in the water phase composition.
Similarly, oligomerization/-prepolymerization of the water phase
monomer may occur prior to, concurrent with or subsequent to the
emulsification of the oil phase composition in the continuous phase
where the water phase composition or both the oil phase composition
and the water phase composition comprise a first initiator and a
second initiator.
DESCRIPTION OF THE FIGURES
[0014] FIG. 1 presents a plot of the correlation between the amount
of free wax extractable from a given microcapsule and the water
solubility of the water phase monomer(s) used in making that
microcapsule from Example 2 herein.
DETAILED DESCRIPTION
[0015] For the purpose of this disclosure it is to be appreciated
that all patents, patent publications and other publications
mentioned herein are hereby incorporated herein in their entirety
by reference. Additionally, for the purpose of this disclosure and
the appended claims the term "core monomer" refers to that wall
forming monomer or monomer mixture that is wholly or partially
soluble or dispersible in the oil phase composition and is
incorporated into the oil phase composition prior to the
emulsification or dispersion thereof in the continuous or water
phase. The term "water phase monomer" refers to that wall forming
monomer or monomer mixture that is wholly or partially soluble or
dispersible in the water phase composition and is contained in the
water or continuous phase. The phrase "poor to moderately
hydrophilic" means that the monomer or other referenced component,
as allowed, is insufficiently hydrophilic such that it will not
form a gel as it oligomerizes/prepolymerizes in the water phase
and, preferably, is sufficiently hydrophobic, but not so
hydrophobic, such that oligomers/prepolymers thereof will tend to
migrate to the water/oil phase interface rather than form discrete
particles or beads of the polymerized polymer in the water phase.
Generally, a poor to moderately hydrophilic monomer is one that has
a solubility of less than about 50 grams per liter (g/L), or even
less than 30 g/L, or preferably from 0.01 g/L to about 50 g/L, or
even from 0.01 g/L to 25 g/L, or even from 0.2 g/L to 30 g/L, or
even from 0.05 to 25 g/L as measured in deionized water at
20.degree. C. In following, it is to be understood that reference
to a monomer, or another material, being soluble or disperable in a
given material or composition means that the named monomer is
wholly or partially soluble or dispersible therein on its own or
such solubility or dispersability may be as a result of the
addition of suitable emulsifies and/or solubilizers and/or as a
result of elevating the temperature of the mixture and/or adjusting
the pH to enhance solubility and/or dispersability. Further, as
used herein and in the claims, the term "difunctional;" when used
in relation to the requisite water phase monomers and core monomers
refers to the presence of two ethylenically unsaturated
polymerizable groups in the given monomer. Finally, as used in the
specification and claims, the term "(meth)acrylate" refers to the
acrylate as well as the methacrylate: when just the acrylate is
intended to be exemplified, it will be so presented, e.g.,
isobornyl acrylate, and when just the methacrylate is intended to
be exemplified, it will be so presented, e.g., isobornyl
methacrylate. Hence, isobornyl (meth)acrylate refers to both
isobornyl acrylate and isobornyl methacrylate. Similarly, a
di(meth)acrylate may have two acrylate groups, two methacrylate
groups or one acrylate group and one methacrylate group.
[0016] Although described below in greater specificity, the
critical elements of the present teaching pertain to the selection
of wall forming monomers and the sequencing and/or stepwise
formation of the shell wall itself. Generally speaking, suitable
poor to moderately hydrophilic water phase monomers are
characterized as having one or more acrylate or methacrylate groups
or other hydrophilic groups such as amino, urethane, alcohol and/or
ether groups and a hydrophobic or non-hydrophilic hydrocarbon or
hetero-hydrocarbon portion wherein the hydrocarbon portion is
generally large enough such that, as the monomer polymerizes, the
so formed oligomer/prepolymer becomes less soluble in the water
phase and/or tends to manifest less hydrophilicity and/or tend to
increase in hydrophobicity or lipophilicity than the monomer
whereby their oligomers and prepolymers tend to migrate to the
interface of the oil phase and the water phase, typically as a
result of a lessening of attractiveness or increased repellency to
the water phase and/or an increased attractiveness or drawing of
the oligomer/prepolymer to the oil phase. The hydrocarbon or
heterohydrocarbon portion of the water phase monomers may be a
saturated or unsaturated hydrocarbon moiety such as an alkyl,
alkenyl, alkylene or alkenylene group or a heteroalkyl,
heteroalkenyl, heteroalkylene or heteroalkenylene group:
hydrocarbon referring to moieties consisting essentially of carbon
and hydrogen atoms and hetero referring to the presence of atoms
other than, though in addition to, hydrogen and carbon (hetero
atoms), most typically oxygen, nitrogen, sulfur and/or a halogen.
Where such hetero atoms are present, they typically comprise less
than 60 wt %, preferably, less than 40 wt %, more preferably less
than 20 wt %, most preferably less than 10 wt % of the given
hydrocarbon moiety of which they form a part and may be present in
the main chain or as substituents thereto, e.g., an ether group or
an hydroxy group, respectively. It is also to be appreciated that
any of these hydrocarbon and/or heterohydrocarbon moieties may
comprise or include cyclic structures and/or branched structures
provided that the monomer manifest the requisite poor to moderately
hydrophilic character as described herein, and provided that the
resulting oligomer/prepolymer of the monomer is not insufficiently
hydrophobic as described herein above. Preferred hydrocarbon and
heterohydrocarbon portions of the monomer generally have from 1 to
8 carbon atoms and most preferably have from 1 to 3 carbon atoms,
especially desired are those monomers having one or more methyl,
ethyl, and propyl groups.
[0017] Preferably, the hydrophobic portion of the monomer can be a
saturated hydrocarbon moiety such as:
##STR00001##
or even an unsaturated hydrocarbon moiety such as
##STR00002##
where n is an integer of 1 or greater, preferably 1 to 20. Of
course the foregoing structures could also be modified with various
hetero atoms, as will be appreciated by those skilled in the art.
Furthermore, it is to be appreciated that combinations of the
forgoing monomers, combinations of analogous heterohydrocarbon
monomers as well as combinations of hydrocarbon and
heterohydrocarbon monomers can also be advantageously used.
[0018] Suitable core monomers will comprise the same general
make-up as the water phase monomers, indeed, there will be some
(though certainly not all nor many) monomers that may be used in
either phase; however, the core monomers are such that as they
oligomerize and prepolymerize they become less soluble in the core
material and/or they become less hydrophobic, more hydrophilic
and/or less lipophilic or, in any event, their affinity for water
increases and/or their affinity for the oil phase decreases,
whereby they tend to migrate towards the interface of the oil phase
composition and the water phase rather than form a gel or discrete
particles of the polymerized monomer in the core phase composition.
Thus, in considering the structures and limitations of the water
phase monomers above, for purposes of identifying further suitable
core monomers, the characteristics required of the core monomers
may simply be substituted for the recitation of the characteristics
of the water phase monomers in the foregoing discussion.
Furthermore, while certain monomers may be used in either the water
phase or the core phase, and while the same monomer may be present
in both phases, it is especially preferred, if not critical, that
where the same monomer is in both phases, at least one of the water
phase and the core phase have a second monomer or a multi-step
process is employed, i.e., oligomerization followed by
polymerization. Most preferably, each of the water phase and the
core phase has different monomers. However, if a common monomer is
present in both phases, then, as noted above, at least one other
monomer is present in at least one of the phases and, most
preferably, the common monomer represents less than 50 mole % of
the monomer of at least one of those phases.
[0019] According to a first embodiment of the present teaching
there are provided high strength microcapsules having an
encapsulated hydrophobic core material, especially a phase change
material, which are formed through an oil-in-water
microencapsulation process in which the hydrophobic core material
is encapsulated in a polymer shell comprising the reaction product
of one or more ethylenically unsaturated monomers which is wholly
or partially soluble in the oil phase composition, and the reaction
product of one or more ethylenically unsaturated monomers which is
wholly or partially soluble in the water phase composition and has
certain hydrophilic/hydrophobic characteristics, said reaction
products also comprising copolymers of the core monomers and water
phase monomers and/or their oligomers and/or prepolymers, to the
extent said monomers, oligomers and/or prepolymers are
copolymerizable. As noted hereinabove and below, the core monomers
are such that while wholly or partially soluble in the oil phase
composition in their monomer state, as they
oligomerize/prepolymerize they become less and less soluble in the
oil phase composition, less lipophilic (to the extent they are
lipophilic), and/or less hydrophobic whereby they begin to/tend to
migrate within the oil phase composition to the interface between
the oil phase and the water or continuous phase. The water phase
monomers, on the other hand, must include one or more monomers that
manifest, at most, poor to moderate hydrophilic properties and/or
whose oligomers/-prepolymers manifest poor or limited solubility
(particularly as compared to the monomer) in the water phase,
whereby the oligomers/prepolymers of the water phase monomers are
less hydrophilic and/or are less soluble in the water phase and, in
a similar fashion to the prepolymers of the core monomers, begin
to/tend to migrate within the water or continuous phase to the
interface between the oil phase and the water or continuous
phase.
[0020] Although copolymerization is contemplated, at least in
certain embodiments, it is to be appreciated that selection of the
core monomers and water phase monomers and/or a staggered
polymerization or strict sequential polymerization of each may not
allow for or prevent or mitigate copolymerization as between the
monomers and/or oligomers/prepolymers of each phase. In the case
where initiation of polymerization of the monomers and/or
oligomers/prepolymers of one phase is staggered or delayed relative
to initiation of polymerization of the monomers and/or
oligomers/prepolymers of the other phase, but prior to the first
material achieving isolation of the water phase from the core
phase, and the monomers of each phase a not or not substantially
copolymerizable and/or conditions do not favor copolymerization,
the shell wall at the interface will generally comprise an
interpenetrating network of the polymer of one phase with the
polymer of the other phase. The degree or extent of the formation
of an interpenetrating network and/or the thickness of the
cross-sectional region of the shell wall comprising the
interpenetrating network will depend, in part, upon the extent of
the stagger or delay. Where the polymerization of the wall forming
material of the second phase is shortly after initiation of
polymerization of the wall forming material of the first phase, the
degree of interpenetrating network is high and the region of
interpenetration network is thick as compared to the same system
where initiation of polymerization of the second wall forming
material is considerably later. Furthermore, it is to be
appreciated that the degree and extent of interpenetrating network
formation will also depend, in part, upon the ability of the
monomers to pass and/or protrude through the interface of the oil
phase and water phase. In contrast where initiation of the second
wall forming material is after formation of a seed capsule and/or
following isolation of the two phases by the capsule wall arising
from the first wall forming material the capsule wall will be more
in the form of a two layered microcapsule wall or shell, the core
monomer forming the inner layer of the shell and the water phase
monomer forming the outer layer of the shell. In this instance,
where monomers of each phase are copolymerizable with each other,
the monomers/oligomers/prepolymers of the second wall forming
material may copolymerize with functional groups of the first wall
forming material on the surface of the shell wall available to the
monomers/oligomers/prepolymers of the second wall forming.
Otherwise, in these instances, the interface between the two shell
layers will comprise polymer chains of the first wall forming
material embedded in, with or without interpenetration, the initial
polymer layer(s) of the second wall forming material as the latter
polymerizes upon the shell of the first wall forming material. It
is also contemplated that the shell may comprise, in whole or in
part, discrete domains of one polymer in the other.
[0021] Most preferably, the core monomers and the water phase
monomers and/or their respective oligomers/prepolymers will be
capable of and undergo at least some degree of copolymerization.
The extent of copolymerization and the resultant copolymers that
are formed and become integrated into and/or form the shell wall
will depend upon a number of factors including their relative
reactivity, the amounts and relative amounts by which each is
present in their respective phase and the extent to which they are
present at the interface and/or are caused to migrate to the
interface of the water and oil phase, the selection and activation
of the initiators, the delay or stagger, if any, in initiation of
the polymerization of the wall forming materials of the two phases,
etc. Here, the mid-region of the microcapsule wall will comprise
interwoven and/or an interpenetrating network of copolymer chains
of the core and water phase monomers as well as polymer chains
formed wholly of monomers of each phase. However, once the initial
wall or shell is formed and the monomer of one phase is no longer
accessible to the monomer of the other phase and/or cross-transfer
of the monomer of one phase to the other is no longer possible, the
respective build-up of the shell or microcapsule wall on the inside
of the microcapsule is wholly due to and derived from the core
phase monomer while that on the outside of the shell is wholly due
to and derived from the water phase monomer. Hence, the chemical
structure or make-up of the shell or microcapsule wall if one were
to look at the cross-section of the same, will markedly vary from
the inner surface to the exterior surface with the original
interface point having the most diversity of monomer make-up and
each surface having the least amount of diversity, if any, relative
to the monomer make-up: the exterior surface being wholly or
substantially so made up of water phase monomer and the interior
surface being wholly or substantially made up of core phase
monomer. In this regard, diversity refers to the amount of monomer
from both phases, irrespective of the number of different monomers
in each phase. Hence, the composition of the shell wall becomes
more wholly made up of core phase monomer as one moves form the
interface point to the inner core and more wholly made up on water
phase monomer as one moves from the interface point to the outer
shell surface. Of course, it is to be understood that the
microcapsule or shell wall may also have embedded therein discrete
domains of emulsifier and other aids used in making the
microcapsules that become entrapped and, hence, embedded, in the
polymer as it polymerizes.
[0022] The hydrophobic core of the microcapsules of the present
teaching are derived from an oil phase composition comprising a
hydrophobic core material, at least one core monomer and at least
one initiator for initiating and/or effecting polymerization of the
core monomer.
[0023] Hydrophobic Core Material
[0024] The hydrophobic core material may be any of a number of
different materials depending upon the intended utility of the
microcapsules. Typical core materials include UV absorbers, UV
reflectors, pigments, dyes, colorants, scale inhibitors, corrosion
inhibitors, antioxidants, pour point depressants, waxes, deposition
inhibitors, dispersants, flame retardants, biocides, active dye
tracer materials, odor control agents, natural oils, flavor and
perfumes oils, crop protection agents, phase change materials and
the like. Specific examples of suitable hydrophobic core materials
include: [0025] aliphatic hydrocarbon compounds such as saturated
or unsaturated C.sub.10-C.sub.40 hydrocarbons which are branched or
preferably linear, e.g. n-tetradecane, n-pentadecane, n-hexadecane,
n-heptadecane, n-octadecane, n-nonadecane, n-eicosane,
n-heneicosane, n-docosane, n-tricosane, n-tetracosane,
n-pentaco-sane, n-hexacosane, n-heptacosane, n-octacosane, and also
cyclic hydrocarbons, e.g. cyclohexane, cyclooctane, cyclodecane;
[0026] aromatic hydrocarbon compounds such as benzene, napthalene,
biphenyl, o- or n-terphenyl, C.sub.1-C.sub.4 alkyl-substituted
aromatic hydrocarbons such as dodecylbenzene, tetradecylbenzene,
hexadecylbenzene, hexylnaphthalene or decylnaphthalene; [0027]
saturated or unsaturated C.sub.6-C.sub.30 fatty acids such as
lauric acid, stearic acid, oleic acid or behenic acid, preferably
eutectic mixtures of decanoic acid with, for example, myristic,
palmitic or lauric acid; [0028] fatty alcohols such as lauryl,
stearyl, oleyl, myristyl, cetyl alcohol, mixtures such as coconut
fatty alcohol and also oxo alcohols which are obtained by
hydroformylation of alpha-olefins and further reactions; [0029]
C.sub.6-C.sub.30 fatty amines such as decylamine, dodecylamine,
tetradecylamine or hexadecylamine; [0030] esters such as
C.sub.1-C.sub.10 alkyl esters of fatty acids, e.g. propyl
palmitate, methyl stearate or methyl palmitate, and preferably
their eutectic mixtures, or methyl cinnamate; [0031] natural and
synthetic waxes such as montan waxes, montan ester waxes, carnauba
wax, polyethylene wax, oxidized waxes, polyvinyl ether wax,
ethylene-vinyl acetate wax or hard waxes obtained from the
Fischer-Tropsch process; [0032] halogenated hydrocarbons such as
chloroparaffins, bromooctadecane, bromopentadecane,
bromononadecane, bromoeicosane, and bromodocosane.
[0033] Most especially the microcapsule according to the present
teachings have a phase change material as the core material.
Suitable phase change materials are typically known hydrocarbons
that melt at a temperature of between -30.degree. C. and
150.degree. C. Generally the substance is a wax or an oil and
preferably has a melting point at between 20.degree. C. and
80.degree. C., often around 40.degree. C. Desirably the phase
change substance may be a C.sub.8-C.sub.40 alkane or cycloalkane.
Suitable phase change materials include all isomers of the alkanes
or cycloalkanes. In addition it may also be desirably to use
mixtures of these alkanes and/or cycloalkanes. The phase change
material may be for instance any of the compounds selected from
n-octadecane, n-tetradecane, n-pentadecane, n-heptadecane,
n-octadecane, n-nonadecane, n-docosane, n-tricosane, n-pentacosane,
n-hexacosane, cyclohexane, cyclooctane, cyclodecane and also
isomers and/or mixtures thereof. Other phase change materials
include aromatic hydrocarbons such as benzene, naphthalene, etc.;
fatty acids such as lauric acid, stearic acid, etc.; alcohols such
as lauryl alcohol, stearyl alcohol; and ester compounds such alkyl
myristate, alkyl palmitate, alkyl stearate, etc., including,
specifically, methyl stearate, methyl cinnamate, etc.
[0034] Another preferred core material consists essentially of a
hydrophobic liquid, preferably an oil, or a hydrophobic wax which
is a non-polymeric material, and most preferably a phase change
material. Although the preferred hydrophobic oils and waxes are
essentially non-polymeric, it is contemplated that these materials
may contain smaller amounts, generally less than 10%, preferably
less than 5% (e.g., 0.5 to 2%), by total weight of core of
polymeric additives. Particularly desirable polymeric additives are
those that modify the properties of the phase change material. For
example, it is known that the temperature at which a phase change
material melts on absorbing heat can be significantly different
from the temperature at which it solidifies when losing heat.
Alternatively, or in addition thereto, especially where the
hydrophobic liquid or wax is a phase change material used for
thermal storage, the core phase composition may further comprise
select nucleating agents, which may also be a polymeric additive,
that are found to prevent supercooling of hydrophobic liquids or
waxes into which they are incorporated. Especially desirable
polymeric additives and nucleating agents are those substances or
compounds that will bring the melting and solidifying temperatures
of the phase change material closer together. The use of such
polymeric additives and/or nucleating agents is particularly
desirable for encapsulated phase change materials to be used in
various domestic applications or for garments.
[0035] Suitable nucleating agents are well known and include metal
powders and claim powders. Especially preferred nucleating are
those disclosed in Isiguro (U.S. Pat. No. 5,456,852) which is
incorporated herein by reference. Generally speaking these
nucleating agents have a melting point that is typically 20.degree.
C. to 110.degree. C., preferably 30.degree. C. to 100.degree. C.,
higher than that of the phase change material into which it is
incorporated. Suitable exemplary nucleating agents include
aliphatic hydrocarbon compounds, aromatic compounds, esters
(including fats and oils), fatty acids, alcohols and amides,
including, specifically, but not limited thereto, cetyl alcohol,
stearyl alcohol, eicosanol, myristic acid, palmitic acid, behenic
acid, stearic acid amide, ethylenebisoleic acid amide,
methylolbehenic acid amide and N-phenyl-N'-stearylurea, as well as
combinations of two or more thereof. When the phase change compound
is a nonpolar compound such as an aliphatic hydrocarbon or an
aromatic hydrocarbon, preferable examples of the nucleating agent
are fatty acids, alcohols and amides which have a higher polarity
than does the nonpolar compound. Generally speaking the nucleating
agent is used in an amount of from 0.5 to 40 weight %, preferably 1
to 35 weight %, relative to the amount or weight of the phase
change material.
[0036] Alternatively, the phase change material may be a substance
other than a hydrocarbon. For example, the phase change material
could be an inorganic substance that absorbs and desorbs latent
heat during a liquefying and solidifying phase transition and/or
during dissolving/crystallization transition. Such inorganic
compounds include for instance sodium sulphate decahydrate or
calcium chloride hexahydrate as well as other inorganic compounds
containing a large amount of water of crystallization, for example,
sodium hydrogenphosphate dodecahydrate, sodium thiosulfate
pentahydrate, and nickel nitrate hexahydrate. Thus the inorganic
phase change material may be any inorganic substance that can
absorb or desorb thermal energy during a transition at a particular
temperature.
[0037] In following, the inorganic phase change material may be in
the form of finely dispersed crystals which are dispersed
throughout the core matrix which comprises a hydrophobic liquid or
wax. In one form, the inorganic phase change material is dispersed
throughout a solid hydrophobic substance such as a wax. In another
form, crystals of the inorganic phase change material may be
dispersed in a hydrophobic liquid or wax which remains
substantially liquid, preferably a hydrocarbon liquid or wax.
During a phase change these crystals become liquid droplets
dispersed throughout the liquid. In order to prevent coalescence of
these dispersed liquid droplets, it is advantageous to include a
suitable surfactant, such as a water-in-oil emulsifier into the
hydrophobic liquid. In yet another iteration of this embodiment
where the core material comprises an inorganic phase change
material dispersed throughout a matrix of a hydrophobic liquid or
wax, the hydrophobic liquid or wax is itself a phase change
material. In this preferred embodiment the hydrocarbon and
inorganic materials may both absorb or desorb heat. Still, the
hydrocarbon may not be a phase change material and may just serve
as a carrier and/or process aid.
[0038] Although the discussion above with respect to the use of
nucleating agents with phase change materials is presented with
respect to certain hydrocarbon oils and waxes, it is to be
appreciated that such nucleating agents, at the stated levels, are
also suitably used with any phase change materials, including the
aforementioned inorganic materials, to address supercooling and the
like.
[0039] Core Monomer
[0040] The second component of the oil phase composition is the
core monomer. As disclosed above, the core monomer comprises one or
more ethylenically unsaturated monomers, preferably free-radically
polymerizable ethylenically unsaturated monomers, that are wholly
or partially soluble or dispersible in the oil phase composition,
especially the core material, and whose oligomers/prepolymers
become less soluble and/or less lipophilic and/or less hydrophobic
(preferably more hydrophilic) as they oligomerize/prepolymerize
whereby the oligomers and/or prepolymers tend to migrate through
the oil phase composition to the interface of the oil phase
composition and the water or continuous phase. Preferably, the core
monomers are hydrophobic monomers, by which is meant a monomer with
a water solubility of not more than about 25 g/L, preferably not
more than 10 g/L, more preferably not more than 5 g/L as measured
in deionized water at 20.degree. C. In certain embodiments the
hydrophobic monomers will have water solubility of no more than 1
g/L water, preferably not more than 0.1 g/L as measured in
deionized water at 20.degree. C.
[0041] The preferred core monomers are those difunctional monomers
having the requisite characteristics defined above alone or in
combination with other core monomers provided that at least 50 mole
% of the core monomers are difunctional. Monomers which do not meet
the requirements of the core monomers may also be present and may
copolymerize with the requisite core monomer so long as the overall
properties of the oligomers/prepolymers is retained. Generally
speaking, such other monomers, if present, will be present at less
than 50 mole %, preferably less than 25 mole % of the monomer in
the core phase. Suitable difunctional core monomers include, but
are not limited to, ethylene glycol di(meth)acrylate; 1,3-butylene
glycol di(meth)acrylate; 1,4-butylene glycol di(meth)acrylate;
propylene glycol di(meth)acrylate; divinyl adipate; divinyl
benzene; vinyl methacrylate; allyl (meth)acrylate; diallyl maleate;
diallyl phthalate; diallyl fumarate; triallyl cyanurate;
(meth)acryl polyesters of polyhydroxylated compounds; divinyl
esters of polycarboxylic acids; diallyl esters of polycarboxylic
acids; diallyl terephthalate; N,N'-methylene diacrylamide;
hexamethylene bis maleimide; diallyl succinate; divinyl ether; the
divinyl ethers of ethylene glycol or diethylene glycol; n-methylol
acrylamide; n-isobutoxymethyl acrylamide; hexanediol diacrylate;
neopentyl glycol diacrylate; divinyl benzene; triethylene glycol
di(meth)acrylate; the butylene glycol di(meth)acrylates;
tetraethylene glycol di(meth)acrylate; polyethylene glycol
di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene
glycol di(meth)acrylate; 1,6 hexanediol di(meth)acrylate; neopentyl
glycol diacrylate; tripropylene glycol diacrylate; ethoxylated
bisphenol A di(meth)acrylate; dipropylene glycol diacrylate;
alkoxylated hexanediol diacrylate; alkoxylated cyclohexane
dimethanol diacrylate; propoxylated neopentyl glycol diacrylate;
allyl methacrylate; bisphenol A di(meth)acrylate; and the like.
[0042] While the difunctional core monomers are preferred, mono-
and poly-functional monomers are suitable as well, as well as
combinations thereof and combinations of such monomers with
difunctional monomers. Exemplary mono-functional monomers include,
but are not limited to, vinyl 2-ethylhexanoate, vinyl laurate,
vinyl stearate, vinyl alkyl or aryl ethers with (C.sub.9-C.sub.30)
alkyl groups such as stearyl vinyl ether; (C.sub.6-C.sub.30) alkyl
esters of (meth-) acrylic acid, such as hexyl (meth)acrylate,
heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl acrylate,
isononyl acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate,
dodecyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl
(meth)acrylate, lauryl (meth)acrylate, oleyl (meth)acrylate,
palmityl (meth)acrylate, and stearyl (meth)acrylate; unsaturated
vinyl esters of (meth)acrylic acid such as those derived from fatty
acids and fatty alcohols; monomers derived from cholesterol;
olefinic monomers such as 1-butene, 2-butene, 1-pentene, 1-hexene,
1-octene, isobutylene and isoprene; and the like. Exemplary
polyfunctional monomers include, but are not limited to aliphatic
or aromatic urethane acrylates, such as hexa-functional aromatic
urethane (meth)acrylates; ethoxylated aliphatic difunctional
urethane (meth)acrylates; aliphatic or aromatic urethane
(meth)acrylates, such as tetra-functional aromatic (meth)acrylates;
epoxy acrylates; epoxymethacrylates; glyceryl tri(meth)acrylate,
trimethylolpropane tri(meth)acrylate; pentaerythritol
tetra(meth)-acrylate; ethoxylated trimethylolpropane
tri(meth)acrylate; propoxylated trimethylolpropane
tri(meth)acrylate; propoxylated glyceryl tri(meth)acrylate;
ditrimethylolpropane tetra(meth)acrylate; dipentaerythritol
pentaacrylate; ethoxylated pentaerythritol tetraacrylate; and the
like.
[0043] The amount of core monomer present in the oil phase
composition may vary, but is generally within the range of from
about 5-25 wt %, preferably from about 10-20 wt %, based on the
total weight of the oil phase composition. Lower concentrations may
be used but too low an amount of the core monomer results in a
lessening in the physical properties attained. Higher amounts could
also be used but are not needed and, in any event, the more wall
material, the less the core material. Hence, it is desirable, as
will be noted below, to optimize the amount of the core material
while minimizing the amount of shell wall material.
[0044] Core Initiator
[0045] The last critical component of the oil phase composition is
the one or more core initiators that are suitable for effecting
oligomerization/prepolymerization and/or polymerization of the core
monomer. Preferably, the core initiator comprises two free radical
initiators each of which is initiated or activated by different
conditions or, if by the same conditions, by different intensities
of that condition. For example, if the core initiators are both
activated by heat, then each will have a primary activation
temperature that is different from the other, preferably, the
activation temperatures will differ by at least 5.degree. C., more
preferably by at least 10.degree. C., most preferably by at least
15.degree. C. Here the concept of primary activation temperature or
primary activation condition refers to that condition under which a
given initiator achieves a 10 hour half-life. Selection of the
initiator will depend upon the mode of activation and the monomer
to be polymerized. In this regard, although it may be possible to
use an actinic radiation activated initiator, at least in the
oligomerization/prepolymerization stage, it is most desirable that
the core initiator is a heat activated initiator. Similarly, the
quantity of the activator to be incorporated into the oil phase
composition will depend, in part, upon the amount of core monomer
present and/or the decomposition rate at the anticipated reaction
conditions. All of these factors are well known and generally set
forth in the suppliers' guidelines and product specifications and,
in any event can be determined by simple, direct
experimentation.
[0046] Water/Continuous Phase
[0047] The second composition critical for the formation of the
microcapsules of the present teaching is the water or aqueous phase
composition which serves as the continuous phase of the reaction
mix in which the microcapsules are formed and which contributes the
second component of the shell wall to the microcapsules. The water
or aqueous phase composition comprises water, a wall forming
composition comprising one or more polymerizable ethylenically
unsaturated monomers, preferably free radically polymerizable
ethylenically unsaturated monomers, and at least one initiator,
especially a free radical initiator, for the
oligomerization/prepolymerization and/or polymerization of the
ethylenically unsaturated monomer.
[0048] Water Phase Monomer
[0049] The key component of the water phase composition is the
water phase monomer which comprises one or more polymerizable
ethylenically unsaturated monomers, preferably free-radically
polymerizable ethylenically unsaturated monomers, that manifest, at
most, poor to moderate hydrophilic properties. The water phase
monomer generally comprises 1-100 wt %, preferably 30-100 wt %, of
at least one ethylenically unsaturated monomer manifesting poor to
moderately hydrophilic properties; 0-99 wt %, preferably, 0-70 wt
%, of at least one polyfunctional ethylenically unsaturated
monomer, and 0-60 wt %, preferably 0-30 wt %, of other
mono-functional monomers. Preferably the "at least one monomer
manifesting poor to moderately hydrophilic properties" is a
difunctional monomer or comprises a predominant amount, i.e., 50
mole % or more, of a difunctional monomer.
[0050] As noted above, where a second water phase composition is
employed the second water phase composition preferably comprises
one or more water soluble or dispersible (meth)acrylate monomers
and/or oligomers/prepolymers; otherwise they will typically be in
the single water phase composition. Those skilled in the art will
readily recognize and appreciate that certain of the core monomers
will have some water solubility or water dispersability,
particularly in the presence of a suitable emulsifier and or
solubilizer and/or at elevated temperature and/or adjusted pH, and
may be used as or as a portion of the water phase monomer; however,
it is preferred that the water phase monomer be different from the
core phase monomer. Monomers that may be used as both a core
monomer and a water phase monomer generally are amphiphilic, having
constituents or groups that make them both hydrophilic and
hydrophobic: the degree of hydrophilicity and/or hydrophobicity (or
even lipophilicity) will be determinative of the extent of their
use in one phase or the other.
[0051] The water phase monomers generally comprise 1-100 wt %,
preferably 30-100 wt %, of at least one ethylenically unsaturated
monomer manifesting poor to moderately hydrophilic properties; 0-99
wt %, preferably, 0-70 wt %, of at least one polyfunctional
ethylenically unsaturated monomer, and 0-60 wt %, preferably 0-30
wt %, of other mono-functional monomers. Preferably the at least
one monomer manifesting poor to moderately hydrophilic properties
is a difunctional monomer or comprises a predominant amount, i.e.,
50 mole % or more, of a difunctional monomer. As noted, other
monomers may be present, particularly those that may copolymerize
with the requisite water phase monomers, provided that if such
other monomers do not themselves manifest or possess the requisite
characteristics of the water phase monomers, then their selection
and/or the amount of their presence is such that the
oligomer/prepolymer arising from the
oligomerization/prepolymerization retains the properties required
of said oligomers/prepolymers, i.e., reduced solubility and/or
hydrophilicity.
[0052] Exemplary ethylenically unsaturated monomer manifesting poor
to moderately hydrophilic properties include, but are not limited
to, amine modified polyether (meth)acrylate oligomers,
hexafunctional aromatic urethane (meth)acrylate oligomers,
hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, methyl
methacrylate, butanediol di(meth)acrylate, hexanediol
di(meth)acrylate, ethoxylated bisphenol-A diacrylate, ethoxylated
bisphenol-A dimethacrylate, isobornyl (meth)acrylate,
pentaerythritol tri(meth)acrylate, pentaerythritol
tetra(meth)acrylate, penta(meth)acrylate ester, diethylene glycol
di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene
glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate,
neopentyl glycol di(meth)acrylate, trimethylolpropane
tri(meth)acrylate, methoxy polyethylene glycol mono(meth)acrylate,
ethoxylated trimethylolpropane tri(meth)acrylate, and ethoxylated
pentaerythritol tetra(meth)acrylate, difunctional aliphatic epoxy
(meth)acrylates, polyethylene glycol di(meth)acrylate,
polypropylene glycol di(meth)acrylate, alkoxylated mono- or
multi-functional (meth)acrylate ester, polyester (meth)acrylate
oligomers, amine modified polyether (meth)acrylate oligomers and
the like. Especially preferred water soluble or water dispersible
(meth)acrylates are those having few hydrophilic groups, i.e., few
amino, urethane, alcohol and/or ether groups.
[0053] Other monomers, e.g., mono-functional monomer and
polyfunctional monomers that will co-polymerize with the
aforementioned poor to moderately hydrophilic monomers are well
known and widely used in free-radical encapsulation processes.
Further exemplification is not deemed necessary.
[0054] The amount of water phase monomer employed in the water
phase composition is dependent, at least in part, on the amount of
core phase monomer present in the core phase composition. Generally
speaking, the ratio by weight of the water phase monomer to the oil
or core phase monomer is preferably in the range of from about 1:3
to about 1:50 or more, preferably from about 1:6 to 1:50.
Generally, such weight ratios will relate to the presence of less
than 20 wt %, preferably less than 10 wt % of the water phase
monomer based on the water phase composition. Although no lower
level is given, it is to be appreciated that sufficient monomer
must be present to form a satisfactory wall and to enable a
somewhat rapid cell wall formation. In this regard, if the
concentration of the water phase monomer is too low, the
encapsulation process is drawn out since it takes too long for
sufficient monomer or oligomer/prepolymer to reach the interface of
the oil phase composition and the water phase. Hence it is likely
that the concentration of the water phase monomer is at least 0.5
wt %, more likely at least 1% or more. Nevertheless, it is also to
be noted that lower, though acceptable, concentrations of water
phase monomer are desired as higher concentrations, especially
those near or in excess of 20 wt %, tend to form gels or, at least,
have a greater risk of forming a gel.
[0055] Another factor that is controlling the amount of water phase
monomer incorporated in the water phase composition is the amount
of core phase composition present in the emulsion and the desired
thickness of the shell walls. In this regard, the weight ratio of
oil phase composition to water phase monomer is from 50:50 to 98:2,
respectively. An especially preferred microcapsule will have from
70 to 90% core and 30-10% shell, more preferably from 75 to 85%
core, with an especially preferred microcapsule comprising about
82% core and about 18% shell.
[0056] Water Phase Initiator
[0057] The last critical component of the water phase composition
is the one or more water phase initiators that are suitable for
effecting oligomerization/prepolymerization and/or polymerization
of the water phase monomer. Preferably, like the core initiator,
the water phase initiator comprises two free radical initiators
each of which is initiated or activated by different conditions or,
if by the same conditions, by different intensities of that
condition. Again, for example, if the core initiators are both
activate by heat, then each will have a primary activation
temperature that is different from the other, preferably, the
activation temperatures will differ by at least 5.degree. C., more
preferably at least 10.degree. C., most preferably by at least
15.degree. C.; wherein the primary activation temperature or
primary activation condition refers to that condition under which a
given initiator achieves a 10 hour half-life. Selection of the
water phase initiator will depend upon the mode of activation and
the monomer to be polymerized. In this regard, while the water
phase initiator may be actinic radiation, (e.g., UV light),
activated, like the core initiators, the water phase initiators are
preferably heat activated. Similarly, the quantity of the water
phase activator to be incorporated into the water phase composition
will depend, in part, upon the amount of water phase monomer
present and/or the decomposition rate of the water phase activator
under the given reaction conditions. All of these factors are well
known and generally set forth in the suppliers' guidelines and
product specifications and, in any event can be determined by
simple, direct experimentation.
[0058] Generally, the water phase initiators are different from the
core phase initiators since the later are not generally soluble in
water and vice versa. Nonetheless, in selecting the initiators it
is oftentimes desirable, though not necessary, that the initial
initiator for each of the core monomer and the water phase monomer
have the same or similar primary activation conditions. This is
particularly so where four initiators are employed so that the
oligomers/prepolymers of each monomer composition is formed at the
same or generally the same point in the encapsulation process
whereby both oligomers/prepolymers congregate at the interface of
the oil phase composition and the water phase. Similarly, though
not necessary, it is desirable that the second initiator contained
in each phase has the same or similar primary activation conditions
or are activated concurrently to optimize shell wall formation.
[0059] Processing Aids
[0060] Emulsifier
[0061] Optionally, though preferably, the water phase composition
or, in the case of microcapsules prepared from two or more water
phase compositions, one or both of said water phase compositions
will contain an emulsifier to aid in the creation of the dispersion
or emulsification of the oil phase composition in the continuous
water phase. Similarly, where dual water phase wall forming
materials are employed an emulsifier is employed to disperse the
oil phase composition in that water phase. Less critical, but
again, preferably, an emulsifier, preferably a non-ionic
emulsifier, is added to one or both water phase compositions to aid
in the dispersion and/or solubility of the poor to moderately
hydrophilic water phase monomer in that water phase
composition.
[0062] Emulsifiers of all types are suitable for use in the
practice of the present process though it is to be appreciated, and
those skilled in the art will readily recognize that different
systems, e.g., different core monomer and/or core materials, will
be better suited with one or more classes of emulsifiers than
others. Specifically, while the present teachings are applicable to
anionic, cationic, non-ionic and amphoteric emulsifiers generally,
preferred emulsifiers are the cationic and non-ionic emulsifiers,
particularly those having polyalkylether units, especially
polyethylene oxide units, with degrees of polymerization of the
alkylene ether unit of greater than about 6. Preferred emulsifiers
are those which significantly reduce the interfacial tension
between the continuous water phase and dispersed oil phase
composition, and thereby reduce the tendency for droplet
coalescence. In this regard, generally the emulsifiers for use in
the first water phase for aiding in the oil in water emulsion or
dispersion will have HLB values of from 11 to 17. While emulsifiers
of the same HLB value may also be used in the second water phase,
those emulsifiers that are used to enhance the solubility and/or
dispersability of the water phase monomer in the second water phase
will generally have HLB values of 16 to 20. Of course,
emulsifiers/surfactants of lower and higher HLB values that achieve
the same objective as noted are also included.
[0063] Exemplary emulsifiers include, but are not limited to
polyvinyl alcohols, especially those that are partially hydrolyzed;
cellulose derivatives such as ethyl hydroxyethyl cellulose,
2-hydroxyethyl cellulose, hydroxybutyl methycellulose,
hydroxypropyl methylcellulose, etc.; gums such as acacia gum and
xantham gum; poly(meth)acrylic acids and derivatives; and
poly(styrene-co-maleic acid) and derivatives and the like. Most
preferably, the emulsifier/emulsion stabilizer is a polyvinyl
alcohol, particularly a polyvinyl alcohol that has been derived
from polyvinyl acetate, wherein between 85 and 95%, preferably 88
to 90% of the vinyl acetate groups have been hydrolyzed to vinyl
alcohol units.
[0064] Additional exemplary anionic surfactants and classes of
anionic surfactants suitable for use in the practice of the present
invention include: sulfonates; sulfates; sulfosuccinates;
sarcosinates; alcohol sulfates; alcohol ether sulfates; alkylaryl
ether sulfates; alkylaryl sulfonates such as alkylbenzene
sulfonates and alkylnaphthalene sulfonates and salts thereof; alkyl
sulfonates; mono- or di-phosphate esters of polyalkoxylated alkyl
alcohols or alkylphenols; mono- or di-sulfosuccinate esters of
C.sub.12 to C.sub.15 alkanols or polyalkoxylated C.sub.12 to
C.sub.15 alkanols; ether carboxylates, especially alcohol ether
carboxylates; phenolic ether carboxylates; polybasic acid esters of
ethoxylated polyoxyalkylene glycols consisting of oxybutylene or
the residue of tetrahydrofuran; sulfoalkylamides and salts thereof
such as N-methyl-N-oleoyltaurate Na salt; polyoxyalkylene
alkylphenol carboxylates; polyoxyalkylene alcohol carboxylates
alkyl polyglycoside/alkenyl succinic anhydride condensation
products; alkyl ester sulfates; naphthalene sulfonates; naphthalene
formaldehyde condensates; alkyl sulfonamides; sulfonated aliphatic
polyesters; sulfate esters of styrylphenyl alkoxylates; and
sulfonate esters of styrylphenyl alkoxylates and their
corresponding sodium, potassium, calcium, magnesium, zinc,
ammonium, alkylammonium, diethanolammonium, or triethanolammonium
salts; salts of ligninsulfonic acid such as the sodium, potassium,
magnesium, calcium or ammonium salt; polyarylphenol polyalkoxyether
sulfates and polyarylphenol polyalkoxyether phosphates; and
sulfated alkyl phenol ethoxylates and phosphated alkyl phenol
ethoxylates; sodium lauryl sulfate; sodium laureth sulfate;
ammonium lauryl sulfate; ammonium laureth sulfate; sodium methyl
cocoyl taurate; sodium lauroyl sarcosinate; sodium cocoyl
sarcosinate; potassium coco hydrolyzed collagen; TEA
(triethanolamine) lauryl sulfate; TEA (Triethanolamine) laureth
sulfate; lauryl or cocoyl sarcosine; disodium oleamide
sulfosuccinate; disodium laureth sulfosuccinate; disodium dioctyl
sulfosuccinate; N-methyl-N-oleoyltaurate Na salt; tristyrylphenol
sulphate; ethoxylated lignin sulfonate; ethoxylated nonylphenol
phosphate ester; calcium alkylbenzene sulfonate; ethoxylated
tridecylalcohol phosphate ester; dialkyl sulfosuccinates; perfluoro
(C.sub.6-C.sub.18)alkyl phosphonic acids;
perfluoro(C.sub.6-C.sub.18)alkyl-phosphinic acids;
perfluoro(C.sub.3-C.sub.20)alkyl esters of carboxylic acids;
alkenyl succinic acid diglucamides; alkenyl succinic acid
alkoxylates; sodium dialkyl sulfosuccinates; and alkenyl succinic
acid alkylpolyglykosides. Further exemplification of suitable
anionic emulsifiers include, but are not limited to, water-soluble
salts of alkyl sulfates, alkyl ether sulfates, alkyl isothionates,
alkyl carboxylates, alkyl sulfosuccinates, alkyl succinamates,
alkyl sulfate salts such as sodium dodecyl sulfate, alkyl
sarcosinates, alkyl derivatives of protein hydrolyzates, acyl
aspartates, alkyl or alkyl ether or alkylaryl ether phosphate
esters, sodium dodecyl sulphate, phospholipids or lecithin, or
soaps, sodium, potassium or ammonium stearate, oleate or palmitate,
alkylarylsulfonic acid salts such as sodium
dodecylbenzenesulfonate, sodium dialkylsulfosuccinates, dioctyl
sulfosuccinate, sodium dilaurylsulfosuccinate, poly(styrene
sulfonate) sodium salt, alkylene-maleic anhydride copolymers such
as isobutylene-maleic anhydride copolymer, or ethylene maleic
anhydride copolymer gum arabic, sodium alginate,
carboxymethylcellulose, cellulose sulfate and pectin, poly(styrene
sulfonate), pectic acid, tragacanth gum, almond gum and agar;
semi-synthetic polymers such as carboxymethyl cellulose, sulfated
cellulose, sulfated methylcellulose, carboxymethyl starch,
phosphated starch, lignin sulfonic acid; maleic anhydride
copolymers (including hydrolyzates thereof), polyacrylic acid,
polymethacrylic acid, acrylic acid alkyl acrylate copolymers such
as acrylic acid butyl acrylate copolymer or crotonic acid
homopolymers and copolymers, vinylbenzenesulfonic acid or
2-acrylamido-2-methylpropanesulfonic acid homopolymers and
copolymers, and partial amide or partial ester of such polymers and
copolymers, carboxymodified polyvinyl alcohol, sulfonic
acid-modified polyvinyl alcohol and phosphoric acid-modified
polyvinyl alcohol, phosphated or sulfated tristyrylphenol
ethoxylates.
[0065] Exemplary amphoteric and cationic emulsifiers include
alkylpolyglycosides; betaines; sulfobetaines; glycinates; alkanol
amides of C.sub.8 to C.sub.18 fatty acids and C.sub.8 to C.sub.18
fatty amine polyalkoxylates; C.sub.10 to C.sub.18
alkyldimethylbenzylammonium chlorides; coconut
alkyldimethylaminoacetic acids; phosphate esters of C.sub.8 to
C.sub.18 fatty amine polyalkoxylates; alkylpolyglycosides (APG)
obtainable from an acid-catalyzed Fischer reaction of starch or
glucose syrups with fatty alcohols, in particular C.sub.8 to
C.sub.18 alcohols, especially the C.sub.8 to C.sub.10 and C.sub.12
to C.sub.14 alkylpolyglycosides having a degree of polymerization
of 1.3 to 1.6., in particular 1.4 or 1.5. Additional cationic
emulsifiers include quaternary ammonium compounds with a long-chain
aliphatic radical, e.g. distearyldiammonium chloride, and fatty
amines Among the cationic emulsifiers which may be mentioned are
alkyldimethylbenzylammonium halides, alkyldimethylethyl ammonium
halides, etc. specific cationic emulsifiers include
palmitamidopropyl trimonium chloride, distearyl dimonium chloride,
cetyltrimethylammonium chloride, and polyethyleneimine Additional
amphoteric emulsifiers include alkylaminoalkane carboxylic acids
betaines, sulphobetaines, imidazoline derivatives,
lauroamphoglycinate, sodium cocoaminopropionate, and the
zwitterionic emulsifier cocoamidopropyl betaine.
[0066] Suitable non-ionic emulsifiers are characterized as having
at least one non-ionic hydrophilic functional group. Preferred
non-ionic hydrophilic functional groups are alcohols and amides and
combinations thereof. Examples of non-ionic emulsifiers include:
mono and diglycerides; polyarylphenol polyethoxy ethers;
polyalkylphenol polyethoxy ethers; polyglycol ether derivatives of
saturated fatty acids; polyglycol ether derivatives of unsaturated
fatty acids; polyglycol ether derivatives of aliphatic alcohols;
polyglycol ether derivatives of cycloaliphatic alcohols; fatty acid
esters of polyoxyethylene sorbitan; alkoxylated vegetable oils;
alkoxylated acetylenic diols; polyalkoxylated alkylphenols; fatty
acid alkoxylates; sorbitan alkoxylates; sorbitol esters; C.sub.8 to
C.sub.22 alkyl or alkenyl polyglycosides; polyalkoxy styrylaryl
ethers; amine oxides especially alkylamine oxides; block copolymer
ethers; polyalkoxylated fatty glyceride; polyalkylene glycol
ethers; linear aliphatic or aromatic polyesters; organo silicones;
polyaryl phenols; sorbitol ester alkoxylates; and mono- and
diesters of ethylene glycol and mixtures thereof; ethoxylated
tristyrylphenol; ethoxylated fatty alcohol; ethoxylated lauryl
alcohol; ethoxylated castor oil; and ethoxylated nonylphenol;
alkoxylated alcohols, amines or acids; amides of fatty acids such
as stearamide, lauramide diethanolamide, and lauramide
monoethanolamide; long chain fatty alcohols such as cetyl alcohol
and stearyl alcohol; glycerol esters such as glyceryl laurate;
polyoxyalkylene glycols and alkyl and aryl ethers of
polyoxyalkylene glycols such as polyoxyethylene glycol nonylphenyl
ether and polypropylene glycol stearyl ether. Polyethylene glycol
oligomers and alkyl or aryl ethers or esters of oligomeric
polyethylene glycol are preferred. Also preferred as non-ionic
emulsifiers are polyvinyl alcohol, polyvinyl acetate, copolymers of
polyvinyl alcohol and polyvinylacetate, carboxylated or partially
hydrolyzed polyvinyl alcohol, methyl cellulose, various latex
materials, stearates, lecithins, and various surfactants. It is
known that polyvinyl alcohol is typically prepared by the partial
or complete hydrolysis of polyvinyl acetate. Accordingly, by
reference to polyvinyl alcohol we intend to include both completely
and partially hydrolyzed polyvinyl acetate. With respect to the
latter, it is preferred that the polyvinyl acetate be at least 50
mole % hydrolyzed, more preferably, at least 75 mole %
hydrolyzed.
[0067] Where the emulsifier is a polymeric emulsifier, especially
one having or derived from an acrylic ester, e.g., a polyacrylate,
the molecular weight is generally at least 10,000, preferably at
least 20,000, most preferably 30,000 or more. Additionally, the
amount of emulsifier is typically from about 0.1 to about 40% by
weight, more preferably from about 0.2 to about 15 percent, most
preferably from about 0.5 to about 10 percent by weight based on
the total weight of the formulation. It is to be appreciated that
certain acrylic polymers and copolymers may perform both as an
emulsifier as well as a polymerizable and/or non-polymerizable
component in forming the microcapsule wall. With respect to the
latter, the polymeric emulsifier, particularly those in the nature
of higher molecular weight polymers, are trapped and/or
incorporated into the polymer wall as it is formed. This is
especially likely where the nature of the water phase changes and
the solubilized polymer comes out of solution.
[0068] Other stabilizing substances that may be used, alone or in
combination with the aforementioned materials, include ionic
monomers. Typical cationic monomers include dialkyl amino alkyl
acrylate or methacrylate including quaternary ammonium or acid
addition salts and dialkyl amino alkyl acrylamide or methacrylamide
including quaternary ammonium or acid addition salts. Typical
anionic monomers include ethylenically unsaturated carboxylic or
sulphonic monomers such as acrylic acid, methacrylic acid, itaconic
acid, allyl sulphonic acid, vinyl sulphonic acid especially alkali
metal or ammonium salts. Particularly preferred anionic monomers
are ethylenically unsaturated sulphonic acids and salts thereof,
especially 2-acrylamido-2-methyl propane sulphonic acid, and salts
thereof.
[0069] The water phase compositions and the core phase compositions
may further contain other ingredients conventional in the art
including, e.g., chain transfer agents and/or agents which help
control the molecular weight/degree of polymerization of the wall
forming monomer, thereby aiding in the movement of the
oligomer/prepolymer through the respective oil phase and water
phase compositions. In this regard, optionally, though preferably,
the water phase, particularly the second water phase composition,
further includes at least one chain transfer agent and/or agent
which aids in movement of the oligomer/prepolymer. Suitable chain
transfer agents include, but are not limited to, lower alkyl
alcohols having from 1 to 5 carbon atoms, mercaptoethanol,
mercaptopropanol, thioglycolic acid, isooctylmercaptoproprionate,
tert-nonylmercaptan, pentaerythritol
tetrakis(3-mercaptoproprionate), dodecylmercaptan, formic acid,
halogenated hydrocarbons, such as bromoethane,
bromotrichloromethane, or carbon tetrachloride, and the sulfate,
bisulfate, hydrosulfate, phosphate, monohydrogen phosphate,
dihydrogen phosphate, toluene sulfonate, and benzoate salts of
sodium and potassium, especially sodium hypophosphite and sodium
bisulfate. If present, the chain transfer agents are preferably
used in amounts ranging from 0.01 to 5%, preferably from 0.5 to 3%,
by weight with respect to the monomers and/or oligomers
employed.
[0070] The microcapsules according to the present teaching are made
in a multi-step process as described below. For convenience, the
process is presented in the preferred mode which involves two water
phase components and a single core phase composition. Nonetheless,
those skilled in the art will readily appreciate that the water
phase composition may be prepared as a single composition to which
the core phase composition is added or a three or more component
composition where various ingredients are preferably isolated from
one another until desired so as to avoid undue or undesired
activation of the water phase activators and/or
oligomerization/prepolymerization/polymerization of the water phase
monomers.
[0071] In a first step a first water phase composition (WP1)
comprising water and, preferably, an emulsifier and/or surfactant,
is prepared by combining the two ingredients in a reaction vessel.
Emulsifiers and/or stabilizers are desired in that they aid in the
emulsification of the core phase composition as well as in
stabilizing the same so as to avoid coalescence of the droplets.
The volume of the first water phase component (WP1) is such as to
simplify the formation of the emulsion of the core phase
composition. If too little WP1 is employed, then it is difficult to
attain a stable emulsion of the desired droplet size of the core
phase composition as the droplets will tend to coalesce. On the
other hand, if too much WP1 is used or if a single water phase
composition were used, then again it is difficult to form the
desired droplet size as one is having to needlessly emulsify in a
much larger volume. In this regard, it maybe difficult, if not
impossible, to generate sufficient shear in the mixture to produce
droplets of the desired size.
[0072] Additionally, the second water phase composition (WP2) is
prepared comprising water, the water phase monomer, and the water
phase initiator(s). Again, though not required, it is desirable to
include an emulsifier and/or surfactant in WP2. Here it is
preferred to first incorporate the water phase monomer into a
solution of the water and the emulsifier/surfactant, if present. It
is also desirable to elevate the temperature to aid in the
solubilization and/or dispersion of the monomer in the water phase.
Thereafter, the water phase initiator is added to the mixture;
however, if the temperature of the mixture had been elevated to aid
in getting the water phase monomer into solution/suspension, then
the mixture should be cooled or allowed to cool to a temperature
that is safely below the lowest activation temperature of the one
or more water phase initiators.
[0073] As noted previously, either of the WP1 or WP2 or both may
contain other ingredients of the water phase composition; however,
if there is any concern that these other ingredients will adversely
affect the water phase monomer or another component of WP1 or
adversely affect the water phase initiator, e.g., cause premature
activation, or other ingredients in WP2, then those ingredients
will be incorporated into the other water phase component or in yet
a third water phase component (WP3). Generally, it is not necessary
to employ a WP3; though it is mentioned as a possibility if
needed.
[0074] The oil phase composition is formed by combining the core
phase monomer and the core material. Most preferably this is
conducted under moderate increased temperature so as to facilitate
the solubilization or suspension of the monomer and other
ingredients that may be present, including nucleating agents, in
the core material: this is particularly so if the core material is
a solid or wax or a high viscosity material. One may also add other
ingredients such as surfactants and the like to aid in the
solubilization/suspension of the core phase monomer in the core
material. Once a stable solution or suspension of the core monomer
in the core material is prepared, the core phase initiator is then
added to the combination and the composition mixed to ensure good
dispersion of the core phase initiator. Once again, if the
temperature of the mixture had been elevated to aid in getting the
core phase monomer into solution/suspension, then the mixture
should be cooled or allowed to cool to a temperature that is safely
below the lowest key activation temperature of the one or more core
phase initiators. It is to be appreciated that certain initiators
may have more of a bell curve type initiation response and, in
those instances, it may not be possible or necessary to decrease
the temperature below the lower end of that bell curve; rather, it
is to be understood that a low level of activation and, hence,
oligomerization/-prepolymerization of the core monomer in the oil
phase composition is possible and allowable prior to emulsification
without adversely affecting performance of the microcapsules of the
present teaching. Indeed, it may be desirable to wholly or at least
partially oligomerize/prepolymerize the core monomer before the
emulsification step. Here, the conditions for effecting the
initiator for said oligomerization/prepolymerization are preferably
removed or reversed prior to emulsification to prevent a premature
activation of the monomer in water phase. For example, if the
temperature of the oil phase composition is elevated to initiate
oligomerization/prepolymerization, it is best to cool the resultant
oil phase composition before adding it to the water phase
composition.
[0075] Once a stable oil phase composition is attained, it is added
to and mixed with the WP1 composition in the reactor vessel. The
mixture is milled until the desired droplet size of oil phase
composition is attained. Thereafter the second water phase
composition (WP2) is added to the reactor. The mixture is then
mixed and the temperature raised to the primary activation
temperature of the first water phase and core phase initiators. In
this regard, it is desirable to select first initiators whose
primary activation temperature is the same or fairly close to one
another, generally within 5.degree. C. of each other, more
preferably within 2.degree. C. of each other. On the other hand, it
is to be appreciated that the activation temperatures of the two
first initiators may be more widely separated and that difference
may be advantageously exploited when, due to selection of monomers
and/or core material, it is desirable to initiate oligomerization
or prepolymerization of one of the water phase monomer or core
phase monomer before the other. For instance, if the viscosity of
the oil phase composition is such that migration of the
oligomer/prepolymer of the core phase monomer is slow, one may wish
to initiate oligomerization/prepolymerization of the core phase
monomer prior to initiation oligomerization/prepolymerization of
the water phase monomer. Conversely, if the droplets of core
material are very small and the volume of the water phase high with
a relatively low concentration of water phase monomer, it may be
desirable to initiate oligomerization/prepolymerization of the
water phase monomer prior to initiating
oligomerization/prepolymerization of the core phase monomer. Not
wishing to be bound by theory, the objective here is to ensure
adequate levels of oligomer/prepolymer of both the core phase
monomer and the water phase monomer at the interface of the oil
phase composition and the water phase composition prior to
initiating full polymerization and/or wall formation, or at least
substantial wall formation.
[0076] Regardless, once oligomerization/prepolymerization of the
core phase monomer and the water phase monomer is initiated, it is
allowed to continue to allow for all or substantially all of the
monomers to oligomerize/prepolymerize, generally from 3 to 5 hours.
Once completed, the temperature of the reaction vessel is raised
again to the activation temperature of the second core phase and
water phase initiators. Again, it is desirable to select second
initiators whose primary activation temperature is the same or
fairly close to one another, generally within 5.degree. C. of each
other, more preferably within 2.degree. C. of each other. Again,
activation temperatures may be more widely differentiated, but such
is not necessary (unless due to requirements of the monomers
themselves) since it is desirable to have the shell wall build from
the core phase and from the water phase concurrently. The higher
temperatures of the second core phase and water phase initiators
drive the cross-linking of the monomer/oligomer/prepolymer to form
a strong polymer composition. Here, the higher temperature is
maintained until the capsules are fully formed, generally from
about 5 to 8 hours.
[0077] Although not critical to the basic embodiment of the present
teaching, the rate of temperature increase in the activation of the
initiators can also influence the ultimate performance and
characteristics of the resultant microcapsules. In this regard it
is preferred that temperature increases be performed over an
extended period of time, preferably over a period of 25 to 40
minutes, more preferably about 30 minutes. The rate of increase
during that period may vary from about 20.degree. C. per hour to
about 40.degree. C. per hour. Of course these are general ranges
and the same may be somewhat lower or somewhat higher depending
upon the selected materials and the activation temperatures of the
initiators.
[0078] Unless otherwise indicated, all ratios, percents, and
proportions herein are on the basis of weight, and all measurements
are in the metric system. Having described the present process in
general and specific terms, attention is now directed to the
following specific examples which demonstrate the marked benefit of
the present process and of the microcapsules resulting
therefrom.
EXAMPLES
[0079] A plurality of microencapsulation processes were performed
as set forth below. The key ingredients employed are listed in
Table 1. In order to test the properties of the formed
microcapsules, they were subjected to a plurality of tests as
follows.
TABLE-US-00001 TABLE 1 Solubility in water (g/L @ Monomers
Chemistry 25.degree. C.) SR206 Ethylene glycol dimethacrylate 2.4
SR247 Neopentyl glycol diacrylate 0.94 SR602 Ethoxylated (10)
bisphenol A diacrylate SR601 Ethoxylated (4) bisphenol A diacrylate
0.45 SR256 2-(2-ethoxyethoxy) ethyl acrylate 25.33 SR399
Polyethylene glycol 200 diacrylate 40.68 SR399 DIPENTAERYTHRITOL
PENTAACRYLATE SR349 Ethoxylated (3) bisphenol A diacrylate SR9035
15-mole, ethoxylated, trimethylolpropane Water triacrylate soluble
SR9038 ethoxylated (30) bisphenol A diacrylate Water soluble SR344
Polyethylene glycol 400 diacrylate Water soluble SR610 polyethylene
glycol (600) diacrylate Water soluble SR295 PENTAERYTHRITOL
TETRAACRYLATE 4.23 MMA Methyl methacrylate V-50
2,2'-azobis(2-amidinopropane) hydrochloride - 10 hour 1/2 life at
56.degree. C. Vazo-67 2,2'-azobis(2-methylbutyronitrile) - 10 hour
1/2 life at 67.degree. C. VA-086 2,2'-Azobis[2-methyl-N-(2-
hydroxyethyl)propionamide] - 10 hour 1/2 life at 86.degree. C.
Vazo-88 1,1'-Azobis(cyclohexanecarbonitrile) - 10 hour 1/2 life at
88.degree. C. Na.sub.2SO.sub.4 Sodium sulfate KPS Potassium
persulfate BPO Benzyl peroxide Polywax .TM. Alkanes M90 Wax PVA523
Polyvinyl alcohol, partially hydrolyzed Monomers SR206, SR247,
SR295, SR256, SR259, SR344, SR349, SR399, SR601, SR602, SR610,
SR9035 and SR9038 were supplied by Sartomer Americas (502 Thomas
Jones Way, Exton, PA 19341, USA). MMA, KPS and BPO were purchased
from Sigma-Aldrich (3050 Spruce Street, Saint Louis, Missouri
63103, USA). V-50 and VA-086 were supplied by Wako Chemicals USA,
Inc. (1600 Bellwood Road, Richmond, VA 23237, USA). Vazo-67 and
Vazo-88 were supplied by E.I. du Pont de Nemours and Company,
Wilmington, DE 19880. PVA523 was purchased from Sekisui Specialty
Chemicals America, LLC (1501 LBJ Freeway, Suite 530, Dallas, TX
75234, USA), and sodium sulfate was supplied by Hydrite Chemical
Co. (Oshkosh, WI 54902, USA). Polywax .TM. M90 Wax was supplied by
Baker Hughes, Inc., 12645 W. Airport Blvd., Suger Land, TX
77478
[0080] Free Wax
[0081] Samples of the microcapsule powders were obtained by drying
the slurry in a Buchi Mini Spray Dryer B-290. The amount of free
wax in the powders was determined by GC analysis using hexane wash.
Approximately 0.2 grams of the dried capsules were combined with 10
ml of hexane in a 20 ml scintillation vial and capped tightly and
placed on a vortex mixer for 5 seconds before being pipetted into
an autosampler vial and analyze by Agilent 7890N GC with Chem
Station Software. Column: Phenomenex's ZB-1HT Inferno column @ 10M,
0.32 mm, 0.25 .mu.m, 100%-dimethylpolysiloxane phase or equivalent.
Temp: 50.degree. C. for 1 minute then heat to 270.degree. C. @
10.degree. C./min Injector: 270.degree. C. with Split Ration of
10:1. Detector: 320.degree. C., 2 .mu.l injection. The % free wax
was calculated by dividing the mg of free wax measured by the
sample weight (mg) and multiplying by 100. Free wax is an indicator
of the permeability and/or strength of the capsule: a permeable
and/or weak wall will show higher levels of free wax.
[0082] TGA Analysis
[0083] TGA analysis was performed at a temperature ramp up rate of
10.degree. C./min in the TGA Q500 thermal gravimetric analyzer from
TA Instruments. The temperature at 10% and 20% weight loss was
recorded.
[0084] DSC (Differential Scanning Calorimetry) Analysis
[0085] Thermal properties of the encapsulated phase change
materials are analyzed with DSC Q2000 from TA Instruments with a
temperature ramp up rate of 1.degree. C./min. The melting point,
latent heat, supercooling %, and AT (temperature difference between
melting peak and cooling peak) are recorded.
[0086] Monomer Solubility in Water
[0087] Solubility of the monomers in water is determined by
combining 5 g of monomer and 5 g of deionized water in a sealed 20
ml vial for 30 min, after which the sample is allowed to sit at
room temperature for 24 hours to establish equilibrium and phase
separation of monomer from water. The water phase was then removed
and analyzed to determine the monomer concentration GC/MS (7890B GC
with a 5977A MSD Mass Spectrophotometer), both from Agilent. Inlet
temperature at 270 C. Ramp starting at 100.degree. C. to
320.degree. C. at 10 degrees per min. The mass spec was scanning
from a molecular weight of 30-500. The GC column was a Agilent
DB-5MS 30M.times.0.250 mm
Example 1
[0088] A microcapsule according to the present teaching was
prepared using a two-part water phase and a single core phase. The
composition/make up of each phase was as presented in Table 2.
TABLE-US-00002 TABLE 2 Ingredients Amount (g) Water Phase 1
Deionized Water 186 PVA523 (5%) 124 Capsule Core (IP) Octadecane
166.00 Polywax .TM. M90 wax 1.66 SR206 29.30 Vazo-67 0.293 Vazo-88
0.200 Water Phase 2 Dl Water 50 PVA523(5%) 33.3 SR247 5.00 V-50
0.50 VA-086 0.20 Total = 596.45
[0089] As a first step in the preparation of the Example 1
microcapsules, a 5% PVA 523 stock solution was prepared by
dissolving polyvinyl alcohol in deionized water at 85.degree. C.
for 30 minutes. Thereafter the first water phase component (WP1)
was prepared by combining water with the stock PVA solution in a
main reactor, mixing the same and elevating and holding the
temperature at 55.degree. C. Next, the second water phase component
(WP2) was prepared by combining and mixing the stock PVA solution
with water in a mixing tank at ambient temperature. Thereafter, the
SR247 was added and mixed vigorously to form a suspension thereof
in the stock PVA/water solution, following which the water phase
initiators were added. The core phase composition was prepared by
first dissolving Polywax.TM. M90 wax in octadecane at 70.degree. C.
for 10 minutes with mixing following which the SR206 monomer was
added. The mixture was cooled to 55.degree. C. and the oil soluble
initiators added and the temperature maintained at 55.degree. C.
for 30 minutes.
[0090] In preparation for the encapsulation process, the main
reactor was purged with pure nitrogen following which the core
phase composition was added and the combined mixture milled until
the desired droplet size was attained. Thereafter, the second water
phase component (WP2) was added to the main reactor and the
temperature of the mixture elevated to 75.degree. C. over a 30
minute period and held at that temperature for an additional 4
hours. Thereafter, the temperature was further elevated to
85.degree. C. over a 30 minute period and held at that temperature
for an additional 6 hours. Following this processing, the reactor
mix was allowed to cool to ambient temperature resulting in a
slurry of the desired microcapsules.
Example 2
[0091] A series of microcapsules both according to the present
teachings and comparative examples, showing the closest art, were
prepared according to the same general methodology as presented in
Example 1. The formulation of the water phase components and core
phase composition were as presented in Table 3. Table 3 also
presents the results attained therewith with respect to free wax
and TGA as well as general observations made of the mixture and
resultant product. Samples A-D are comparative examples and
demonstrate a microcapsule whose shell wall is a copolymer, but
wherein the copolymer is formed solely from multiple monomers in
the core phase. This contrasts with the microcapsules made
according to the present teachings wherein monomers contributed by
both the core phase and the water phase are required. These
comparative microcapsules did not manifest the strength and
integrity sought and attained by those of the present teaching.
Comparative examples E and F demonstrate microcapsules formed of
the requisite core monomer, but again, without a water phase
monomer. Again, the formed microcapsules do not attain the
necessary physical properties. Comparative examples EE thru HH
demonstrate the production of microcapsules according to the
general process of the presently claimed method except that readily
soluble water phase monomers are used rather than the requisite
poor to moderately hydrophilic monomers. As indicated, all of these
samples resulted in gelation of the water phase. The remaining
examples all manifest various iterations of the method and
resultant microcapsules according to the present teaching. As seen,
variations in water phase monomer, initiator, one-step v. two-step
formation, etc. all affected the resultant properties of the so
formed microcapsules; however, all of the so formed microcapsules
manifested consistent properties of strength and integrity.
Finally, a comparison of comparative example E with example Z
demonstrates the importance of the monomer coming from both phases
as here the microcapsule wall is formed from the same monomer
except that in example Z the monomer is contributed from both
phases which allows building of the shell wall from both within as
well as on its outer surface. Based on these results, it is also to
be noted that microcapsule integrity, especially integrity as
evidenced by free wax, manifested a direct correlation to the
solubility of the water phase monomer as shown in FIG. 1.
TABLE-US-00003 TABLE 3 Core Oil-phase Water-phase % Free TGA at
Sample Monomer Water Phase initiators initiators Wax, 10%/20% ID
~30 g Monomer Vazo-67 g Vazo-88 g V-50 g VA-086 g Other
Na.sub.2SO.sub.4 Powders w. loss), C. Observation A 95% SR206/ n/a
0.3 0 0.0 0 -- 0 5.46 182/230 5% SR256 Sample B 95% SR206/ n/a 0.3
0 0.3 0 -- 0 1.56 207/222 thickened up 5% SR256 C 95% SR206/ n/a
0.3 0 0 0 0.3 g 0 2.97 199/222 5% SR256 KPS D 95% SR206/ n/a 0.3 0
0 0 0.3 g 0 5.48 5% SR256 BPO E SR206 n/a 0.3 0 0.1 0 -- 0 1.76
203/221 thickened up F SR206 n/a 0.3 0.2 0.1 0.2 -- 0 2.05 202/220
no thickening G SR206 SR259, 5 g 0.3 0.2 0.1 0.2 -- 4 g 3.27
197/223 thickened up H SR206 SR259, 5 g 0.3 0.2 0.0 0.2 -- 4 g 7.65
193/220 no thickening I SR206 SR247, 5 g 0.3 0.2 0.0 0.2 -- 4 g
4.31 178/200 no thickening, no agglomeration J SR206 SR247, 5 g 0.3
0.2 0.1 0.2 -- 4 g 0.99 187/234 no thickening, no agglomeration. K
SR206 SR247, 5 g 0.3 0.2 0 0.2 0.3 g 4 g 3.77 205/239 no
thickening, no BPO agglomeration. L SR206 SR247, 5 g 0.3 0.2 0.1
0.2 -- 0 0.38 214/233 no thickening, no agglomeration M SR206
SR247, 10 g 0.3 0.2 0.1 0.2 -- 0 0.50 214/235 no thickening, no
agglomeration N SR206 SR247, 5 g 0.3 0.2 0.1 0.2 -- 0 0.53 213/233
no thickening, no agglomeration O SR206 SR247, 5 g 0.3 0.2 0.0 0.2
-- 0 3.43 203/239 no thickening, no agglomeration P SR206 SR247, 5
g 0.3 0.2 0 0.2 0.3 g 0 2.62 208/240 no thickening, no BPO
agglomeration Q SR206 SR247, 5 g 0.3 0.2 0.1 0.2 -- 0 2.47 197/221
one step process R SR206 SR247, 5 g 0.3 0 0.1 0.2 -- 0 1.03 207/230
S SR206 SR247, 5 g 0.3 0.2 0.1 0 -- 0 0.89 207/230 T SR206 SR247, 5
g 0.3 0.2 0.1 0.2 1.23 211/231 40% Solids a few aggregations
<500u, dried ok U SR206 SR247, 5 g 0.3 0.2 0.1 0.2 1.05 208/230
40% Solids, one step, a few aggregations <400u, dried ok V 33%
SR206/ SR247, 5 g 0.3 0.2 0.1 0.2 1.89 190/206 67% MMA W 67% SR206/
SR247, 5 g 0.3 0.2 0.1 0.2 0.68 188/211 33% MMA X 90% SR206/ SR247,
5 g 0.3 0.2 0.1 0.2 0.41 196/217 10% MMA Y SR206 SR247, 20 g 0.3
0.2 0.1 0.2 1.34 thickened up, agglomeration. Z SR206 SR206, 5 g
0.3 0.2 0.1 0.2 0.54 217/223 AA SR206 SR256, 5 g 0.3 0.2 0.1 0.2
1.39 209/222 BB SR206 SR259, 5 g 0.3 0.2 0.1 0.2 6.92 183/214 CC
SR206 SR399, 5 g 0.3 0.2 0.1 0.2 1.23 220/227 DD SR206 SR349, 5 g
0.3 0.2 0.1 0.2 1.90 198/220 EE SR206 SR9035, 5 g 0.3 0.2 0.0 0.2
Water-soluble monomers in water phase. Batch gelled. FF SR206
SR9038, 5 g 0.3 0.2 0.0 0.2 Water-soluble monomers in water phase.
Batch gelled. GG SR206 SR344, 5 g 0.3 0.2 0.0 0.2 Water-soluble
monomers in water phase. Batch gelled. HH SR206 SR610, 5 g 0.3 0
0.0 0 Water-soluble monomers in water phase. Batch gelled.
Example 3
[0092] Microcapsules containing phase change materials according to
the present invention are prepared using a process with a two-part
water phase and a single core phase.
[0093] As a first step in the preparation of the Example 3
microcapsules, a 5% PVA 523 stock solution is prepared by
dissolving polyvinyl alcohol in deionized water at 85.degree. C.
for 30 minutes. Thereafter the first water phase component (WP1) is
prepared by combining 186 g deionized water with 124 g stock PVA
solution in a main reactor, mixing the same and elevating and
holding the temperature at 55.degree. C. Next, the second water
phase component (WP2) is prepared by combining and mixing 33.3 g
stock PVA solution with 50 g deionized water in a 250 ml beaker at
ambient temperature. Thereafter, 7 g SR247 is added and mixed
vigorously to form a suspension thereof in the stock PVA/water
solution, following which the water phase initiators V-50 and
VA-086 are added.
[0094] The core phase composition is prepared in a reactor by first
dissolving 1.66 g Polywax.TM. M90 Wax in 166 g octadecane at
70.degree. C. for 10 minutes with mixing following which 29.3 g
SR206 monomer is added. The mixture is cooled to 55.degree. C. and
the oil soluble initiators, 0.5 g V-50 and 0.2 g VA-086, are added.
Temperature of the reactor is maintained at 55.degree. C. for
another 30 minutes.
[0095] In preparation for the encapsulation process, the main
reactor is purged with pure nitrogen following which the core phase
composition is added and the combined mixture milled until the
desired droplet size is attained. Thereafter, the second water
phase component (WP2) is added to the main reactor and the
temperature of the mixture elevated to 75.degree. C. over a 30
minute period and held at that temperature for an additional 4
hours. Thereafter, the temperature is further elevated to
85.degree. C. over a 30 minute period and held at that temperature
for an additional 6 hours. Following this processing, the reactor
mix is allowed to cool to ambient temperature resulting in slurry
of the desired microcapsules.
[0096] The resulting microcapsules were isolated and subjected to a
number of physical tests to assess their physical properties and
attributes. The results thereof are presented in Table 4.
[0097] Commercial Applications
[0098] The microcapsules formed according to the present teachings
have a number of commercial applications. For convenience, before
addressing specific application, the following definitions are
presented as they pertain to the discussion on commercial
applications.
TABLE-US-00004 TABLE 4 Microcapsule Size, micron 4.83 Free Wax, %
0.45 TGA at 10% weight loss, .degree. C. 215 TGA at 20% weight
loss, .degree. C. 240 Latent Heat, J/g 188 Supercooling, % 25
Melting Point, .degree. C. 36.5 .quadrature.T, .degree. C. 1.6
[0099] As used herein "consumer product" means baby care, beauty
care, fabric & home care, family care, feminine care, health
care, snack and/or beverage products or devices intended to be used
or consumed in the form in which it is sold, and not intended for
subsequent commercial manufacture or modification. Such products
include but are not limited to fine fragrances (e.g. perfumes,
colognes eau de toilettes, after-shave lotions, pre-shave, face
waters, tonics, and other fragrance-containing compositions for
application directly to the skin), diapers, bibs, wipes; products
for and/or methods relating to treating hair (human, dog, and/or
cat), including, bleaching, coloring, dyeing, conditioning,
shampooing, styling; deodorants and antiperspirants; personal
cleansing; cosmetics; skin care including application of creams,
lotions, and other topically applied products for consumer use; and
shaving products, products for and/or methods relating to treating
fabrics, hard surfaces and any other surfaces in the area of fabric
and home care, including: air care, car care, dishwashing, fabric
conditioning (including softening), laundry detergency, laundry and
rinse additive and/or care, hard surface cleaning and/or treatment,
and other cleaning for consumer or institutional use; products
and/or methods relating to bath tissue, facial tissue, paper
handkerchiefs, and/or paper towels; tampons, feminine napkins;
products and/or methods relating to oral care including
toothpastes, tooth gels, tooth rinses, denture adhesives, tooth
whitening; over-the-counter health care including cough and cold
remedies, pain relievers, RX pharmaceuticals, pet health and
nutrition, and water purification; processed food products intended
primarily for consumption between customary meals or as a meal
accompaniment (non-limiting examples include potato chips, tortilla
chips, popcorn, pretzels, corn chips, cereal bars, vegetable chips
or crisps, snack mixes, party mixes, multigrain chips, snack
crackers, cheese snacks, pork rinds, corn snacks, pellet snacks,
extruded snacks and bagel chips); and coffee.
[0100] As used herein "cleaning and/or treatment compositions"
means products comprising fluid laundry detergents, fabric
enhancers, laundry and/or rinse additives, fluid dishwashing
detergents, fluid hard surface cleaning and/or treatment
compositions, fluid toilet bowl cleaners that may or may not be
contained in a unit dose delivery product all for consumer,
agricultural, industrial or institutional use.
[0101] The term "absorbent article" is used herein in a very broad
sense including any article able to receive and/or absorb and/or
contain and/or retain fluids and/or exudates, especially bodily
fluids/bodily exudates. Exemplary absorbent articles in the context
of the present invention are disposable absorbent articles. The
term "disposable" is used herein to describe articles, which are
not intended to be laundered or otherwise restored or reused as an
article (i.e. they are intended to be discarded after a single use
and preferably to be recycled, composted or otherwise disposed of
in an environmentally compatible manner). Typical disposable
absorbent articles according to the present invention are diapers,
surgical and wound dressings, breast and perspiration pads,
incontinence pads and pants, bed pads as well as absorbent articles
for feminine hygiene like sanitary napkins, panty liners, tampons,
interlabial devices or the like. Absorbent articles suitable for
use in the present invention include any type of structures, from a
single absorbent layer to more complex multi-layer structures.
Certain absorbent articles include a fluid pervious topsheet, a
backsheet, which may be fluid impervious and/or may be water vapor
and/or gas pervious, and an absorbent element comprised there
between, often also referred to as "absorbent core" or simply
"core".
[0102] The term "Sanitary tissue product" or "tissue product" as
used herein means a wiping implement for post-urinary and/or
post-bowel movement cleaning (toilet tissue products), for
otorhinolaryngological discharges (facial tissue products) and/or
multi-functional absorbent and cleaning uses (absorbent towels such
as paper towel products and/or wipe products). The sanitary tissue
products of the present invention may comprise one or more fibrous
structures and/or finished fibrous structures, traditionally, but
not necessarily, comprising cellulose fibers.
[0103] The term "tissue-towel paper product" refers to products
comprising paper tissue or paper towel technology in general,
including, but not limited to, conventional felt-pressed or
conventional wet-pressed tissue paper, pattern densified tissue
paper, starch substrates, and high bulk, uncompacted tissue paper.
Non-limiting examples of tissue-towel paper products include
towels, facial tissue, bath tissue, table napkins, and the
like.
[0104] "Personal care composition" refers to compositions intended
for topical application to skin or hair and can be, for example, in
the form of a liquid, semi-liquid cream, lotion, gel, or solid.
Examples of personal care compositions can include, but are not
limited to, bar soaps, shampoos, conditioning shampoos, body
washes, moisturizing body washes, shower gels, skin cleansers,
cleansing milks, in-shower body moisturizers, pet shampoos, shaving
preparations, etc.
[0105] "Bar soap" refers to compositions intended for topical
application to a surface such as skin or hair to remove, for
example, dirt, oil, and the like. The bar soaps can be rinse-off
formulations, in which the product is applied topically to the skin
or hair and then subsequently rinsed within minutes from the skin
or hair with water. The product could also be wiped off using a
substrate. Bar soaps can be in the form of a solid (e.g.,
non-flowing) bar soap intended for topical application to skin. The
bar soap can also be in the form of a soft solid which is compliant
to the body. The bar soap additionally can be wrapped in a
substrate which remains on the bar during use.
[0106] "Rinse-off" means the intended product usage includes
application to skin and/or hair followed by rinsing and/or wiping
the product from the skin and/or hair within a few seconds to
minutes of the application step.
[0107] "Ambient" refers to surrounding conditions at about one
atmosphere of pressure, 50% relative humidity and about 25.degree.
C.
[0108] "Anhydrous" refers to compositions and/or components which
are substantially free of added or free water.
[0109] "Antiperspirant composition" refers to antiperspirant
compositions, deodorant compositions, and the like. For example,
antiperspirant creams, gels, soft solid sticks, body sprays, and
aerosols.
[0110] "Soft solid" refers to a composition with a static yield
stress of about 200 Pa to about 1,300 Pa. The term "solid" includes
granular, powder, bar and tablet product forms.
[0111] The term "fluid" includes liquid, gel, paste and gas product
forms.
[0112] The term "situs" includes paper products, fabrics, garments,
hard surfaces, hair and skin.
[0113] The term "substantially free of" refers to about 2% or less,
about 1% or less, or about 0.1% or less of a stated ingredient.
"Free of" refers to no detectable amount of the stated ingredient
or thing.
[0114] As used herein, the terms "a" and "an" mean "at least
one".
[0115] As used herein, the terms "include", "includes" and
"including" are meant to be non-limiting.
[0116] Unless specifically stated otherwise, the test methods
disclosed in the Test Methods Section of the present application
should be used to determine the respective values of the parameters
of Applicants' inventions.
[0117] Unless otherwise noted, in discussing the commercial
applications below, all component or composition levels are in
reference to the active portion of that component or composition,
and are exclusive of impurities, for example, residual solvents or
by-products, which may be present in commercially available sources
of such components or compositions.
[0118] Similarly, all percentages and ratios are calculated by
weight unless otherwise indicated and are calculated based on the
total composition unless otherwise indicated.
[0119] It should be understood that every maximum numerical
limitation given throughout this specification includes every lower
numerical limitation, as if such lower numerical limitations were
expressly written herein. Every minimum numerical limitation given
throughout this specification will include every higher numerical
limitation, as if such higher numerical limitations were expressly
written herein. Every numerical range given throughout this
specification will include every narrower numerical range that
falls within such broader numerical range, as if such narrower
numerical ranges were all expressly written herein.
[0120] Consumer Products
[0121] A method of making a consumer product comprising combining a
consumer product ingredient and microcapsules made by a method
comprising (a) forming a dispersion of a hydrophobic oil phase
composition comprising a hydrophobic material and one or more
polymerizable ethylenically unsaturated monomers, the core monomer,
that are wholly or partially soluble in the hydrophobic material in
a water or water-based solution, the continuous phase, said
continuous phase comprising water and at least one or more
ethylenically unsaturated polymerizable monomers, the water phase
monomer, all or a portion of which are poorly to moderately
hydrophilic, (b) subjecting the dispersion to one or more
conditions that initiate or effectuate the polymerization of the
water phase and core monomers, (c) maintaining the dispersion under
such conditions as effectuate polymerization of the monomers until
such time as the full capsule walls are formed and, optionally,
thereafter (d) isolating the formed microcapsules from the
continuous phase, is disclosed.
[0122] In one aspect of said method, prior to or concurrent with
step (a), the oil phase composition is subjected to such conditions
as will induce oligomerization/pre-polymerization of the monomer in
the oil phase composition.
[0123] In one aspect of said method, the emulsion is subjected to
conditions that induce or promote the movement of the polymerizable
monomers and/or an oligomer/prepolymer of said core monomers and/or
water phase monomers within the core material and within the
continuous phase, respectively, to the interface of the oil phase
composition and the aqueous phase concurrent with the
polymerization thereof.
[0124] In one aspect of said method, said conditions of said
movement is effected by the oligomerization or pre-polymerization
of the monomer.
[0125] In one aspect of said method, step (b) comprises a two or
more step polymerization processes wherein in a first step at least
one of the core monomer and the water phase monomer or both in the
oil phase composition or water phase composition, respectively, is
subjected to conditions that initiate or effectuate the
oligomerization or pre-polymerization of the said monomer and in a
second or subsequent step the dispersion is subjected to one or
more conditions that initiates or effectuates the full
polymerization of the polymerizable monomers including the
oligomers/prepolymers and any remaining monomer of the
oligomerization/pre-polymerization step.
[0126] In one aspect of said method, the monomers of both the oil
phase composition and the water phase composition are subjected to
conditions that effectuate the oligomerization or prepolymerization
of the monomers in each of said phases.
[0127] In one aspect of said method, the conditions which effect
oligomerization and/or prepolymerization of the monomers of each
phase is the same and said oligomerization or pre-polymerization
occurs concurrently in each phase.
[0128] In one aspect of said method, the conditions which effect
oligomerization and/or pre-polymerization are different and occur
in sequence.
[0129] In one aspect of said method, following completion of the
oligomerization/pre-polymerization step, the dispersion is
subjected to such conditions as will initiate or effectuate the
full polymerization of the monomers, including the already formed
oligomers and prepolymers, and building of the microcapsule wall or
shell at the interface of the oil phase composition and the
continuous phase.
[0130] In one aspect of said method, the microcapsules are formed
in a sequential manner with at least one of the core phase and
water phase monomer, preferably both, undergoing a two-step
polymerization whereby oligomerization/pre-polymerization of each
monomer material is initiated and maintained for a period of time
in their respective phases and full polymerization of each occurs
subsequently at the interface of the oil phase composition and
continuous phase, with the oligomers/pre-polymers continuing to
build upon the wall as it forms: the core phase monomers building
on the inner surface of the shell and the water phase monomers
building upon the outer surface of the shell.
[0131] In one aspect of said method, each of the oil phase
composition and the water phase composition contains at least one
initiator for effecting or initiating the polymerization of the
monomers of each phase.
[0132] In one aspect of said method, at least two initiators are
present in the oil phase composition or the water phase composition
or both if the monomer of said oil phase composition, said water
phase composition or both, respectively, is to be subjected to
oligomerization/pre-polymerization.
[0133] In one aspect of said method, the two step shell formation
is achieved through the use of four initiators, two in each phase,
each initiator in each phase being initiated or activated by
different conditions and/or having a different rate of activation
under the same conditions, whereby the first of each pair of
initiators is initiated or activated to effect formation of the
oligomers/pre-polymer of each shell forming monomer and a period of
time allowed to lapse before activation of the second initiator in
each phase which then causes the full polymerization of the
oligomers/pre-polymers and rapid shell wall formation.
[0134] In one aspect of said method, the first of each pair of
initiators in each phase is activated by the same or similar
conditions and each of second of each pair of initiators in each
phase is activated by the same or similar conditions.
[0135] In one aspect of said method, the monomers of each of the
oil phase composition and the water phase composition are capable
of copolymerization.
[0136] In one aspect of said method, a sufficient amount of said
microcapsules is combined with said at least one consumer product
ingredient to provide, based on total consumer product weight, said
consumer product with from 0.001% about to about 25%, preferably
from about 0.01% to about 10%, more preferably from about 0.05% to
about 5%, most preferably from about 0.1% to about 0.5% of said
microcapsules.
[0137] A consumer product produced by any preceding method is
disclosed
[0138] Benefit Agents that can Serve as Core Material for
Microcapsules
[0139] Useful core materials include perfume raw materials,
sensates, silicone oils, waxes, hydrocarbons, higher fatty acids,
essential oils, lipids, skin coolants, vitamins, sunscreens,
antioxidants, glycerine, catalysts, bleach particles, silicon
dioxide particles, malodor reducing agents, odor-controlling
materials, chelating agents, antistatic agents, softening agents,
insect and moth repelling agents, colorants, antioxidants,
chelants, bodying agents, drape and form control agents, smoothness
agents, wrinkle control agents, sanitization agents, disinfecting
agents, germ control agents, mold control agents, mildew control
agents, antiviral agents, drying agents, stain resistance agents,
soil release agents, fabric refreshing agents and freshness
extending agents, chlorine bleach odor control agents, dye
fixatives, dye transfer inhibitors, color maintenance agents,
optical brighteners, color restoration/rejuvenation agents,
anti-fading agents, whiteness enhancers, anti-abrasion agents, wear
resistance agents, fabric integrity agents, anti-wear agents,
anti-pilling agents, defoamers and anti-foaming agents, UV
protection agents for fabrics and skin, sun fade inhibitors,
anti-allergenic agents, enzymes, water proofing agents, fabric
comfort agents, shrinkage resistance agents, stretch resistance
agents, stretch recovery agents, skin care agents, glycerin, and
natural actives such as aloe vera, vitamin E, shea butter, cocoa
butter, and the like, brighteners, antibacterial actives,
antiperspirant actives, cationic polymers, dyes and mixtures
thereof. In one aspect, said perfume raw material is selected from
the group consisting of alcohols, ketones, aldehydes, esters,
ethers, nitriles alkenes. In one aspect the core material comprises
a perfume. In one aspect, said perfume comprises perfume raw
materials selected from the group consisting of alcohols, ketones,
aldehydes, esters, ethers, nitriles alkenes and mixtures thereof.
In one aspect, said perfume may comprise a perfume raw material
selected from the group consisting of perfume raw materials having
a boiling point (B.P.) lower than about 250.degree. C. and a C log
P lower than about 3, perfume raw materials having a B.P. of
greater than about 250.degree. C. and a C log P of greater than
about 3, perfume raw materials having a B.P. of greater than about
250.degree. C. and a C log P lower than about 3, perfume raw
materials having a B.P. lower than about 250.degree. C. and a C log
P greater than about 3 and mixtures thereof. Perfume raw materials
having a boiling point B.P. lower than about 250.degree. C. and a C
log P lower than about 3 are known as Quadrant I perfume raw
materials, perfume raw materials having a B.P. of greater than
about 250.degree. C. and a C log P of greater than about 3 are
known as Quadrant IV perfume raw materials, perfume raw materials
having a B.P. of greater than about 250.degree. C. and a C log P
lower than about 3 are known as Quadrant II perfume raw materials,
perfume raw materials having a B.P. lower than about 250.degree. C.
and a C log P greater than about 3 are known as a Quadrant III
perfume raw materials. In one aspect, said perfume comprises a
perfume raw material having B.P. of lower than about 250.degree. C.
In one aspect, said perfume comprises a perfume raw material
selected from the group consisting of Quadrant I, II, III perfume
raw materials and mixtures thereof. In one aspect, said perfume
comprises a Quadrant III perfume raw material. Suitable Quadrant I,
II, III and IV perfume raw materials are disclosed in U.S. Pat. No.
6,869,923 B1.
[0140] In one aspect, said perfume comprises a Quadrant IV perfume
raw material. While not being bound by theory, it is believed that
such Quadrant IV perfume raw materials can improve perfume odor
"balance". Said perfume may comprise, based on total perfume
weight, less than about 30%, less than about 20%, or even less than
about 15% of said Quadrant IV perfume raw material.
[0141] Additional Consumer Product Specifics
[0142] Additional consumer product specifics are found below. Such
disclosure is also intended to cover the process of making the
disclosed consumer products wherein said process comprises combing
the materials as disclosed to form the described consumer
product.
[0143] Cleaning and/or Treatment Compositions and Methods of
Use
[0144] Preferably, said consumer product is a cleaning and/or
treatment composition having a viscosity of from about 10 mPas to
about 50,000 mPas, preferably from about 50 mPas to about 2000
mPas, most preferably from about 75 mPas to about 400 mPas, a pH
from about 3 to about 10, preferably from about 4 to about 8, most
preferably from about 5 to about 8, said composition comprising,
based on total cleaning and/or treatment composition weight with
from 0.001% about to about 25%, preferably from about 0.01% to
about 10%, more preferably from about 0.05% to about 5%, most
preferably from about 0.1% to about 0.5% of the microcapsules
disclosed here in.
[0145] As the viscosity range of the cleaning and/or treatment
composition is tightened, it is easier to suspend certain materials
such as polymers and waxes.
[0146] Preferably said cleaning and/or treatment composition
comprises: [0147] (a) a surfactant selected from the group
consisting of nonionic surfactants, anionic surfactants, cationic
surfactants, ampholytic surfactants, zwitterionic surfactants,
semi-polar nonionic surfactants and mixtures thereof; [0148] (b) a
solvent wherein the solvent is preferably selected from the group
consisting of hydrogenated castor oil, glycols, alcohols, and
mixtures thereof; [0149] (c) a fabric softener active wherein the
fabric softener active is preferably selected from the group
consisting of a quaternary ammonium compound, an amine and mixtures
thereof, preferably said quaternary ammonium compound is selected
from the group consisting of bis-(2-hydroxypropyl)-dimethylammonium
methylsulphate fatty acid ester,
1,2-di(acyloxy)-3-trimethylammoniopropane chloride., N,
N-bis(stearoyl-oxy-ethyl) N,N-dimethyl ammonium chloride,
N,N-bis(tallowoyl-oxy-ethyl) N,N-dimethyl ammonium chloride,
N,N-bis(stearoyl-oxy-ethyl) N-(2 hydroxyethyl) N-methyl ammonium
methylsulfate, 1, 2 di-(stearoyl-oxy) 3 trimethyl ammoniumpropane
chloride, dicanoladimethylammonium chloride,
di(hard)tallowdimethylammonium chloride, dicanoladimethylammonium
methylsulfate,
1-methyl-1-stearoylamidoethyl-2-stearoylimidazolinium
methylsulfate, 1-tallowylamidoethyl-2-tallowylimidazoline,
dipalmethyl hydroxyethylammoinum methosulfate and mixtures thereof,
and [0150] (d) mixtures of (a) through (c).
[0151] Preferably said cleaning and/or treatment composition,
comprises an adjunct ingredient selected from the group consisting
of builders, chelating agents, dye transfer inhibiting agents,
dispersants, enzymes, and enzyme stabilizers, catalytic materials,
bleach activators, hydrogen peroxide, sources of hydrogen peroxide,
preformed peracids, polymeric dispersing agents, clay soil
removal/anti-redeposition agents, brighteners, suds suppressors,
dyes, hueing dyes, perfumes, perfume delivery systems, structure
elasticizing agents, carriers, structurants, hydrotropes,
processing aids, solvents in addition to said solubilizing agent, a
fabric softener active selected from the group consisting of a
silicone polymer, a polysaccharide, a clay, a fatty ester, a
dispersible polyolefin, a polymer latex and mixtures thereof,
pigments, and mixtures thereof, preferably said composition
comprises an organic acid, preferably citric acid and/or lactic
acid, hydrogenated castor oil, ethoxylated polyethleneimines,
preferably PEI 600 EO 20 and/or PEI 600, an enzyme, preferably a
cold water amylase, cold water protease and/or xylogluconase.
[0152] In one aspect of Applicants' cleaning and/or treatment
composition, said cleaning and/or treatment composition comprises a
fabric softener active selected from the group consisting of a
quaternary ammonium compound, a silicone polymer, a polysaccharide,
a clay, an amine, a fatty ester, a dispersible polyolefin, a
polymer latex and mixtures thereof, preferably [0153] (a) said
quaternary ammonium compound comprises an alkyl quaternary ammonium
compound, preferably said alkyl quaternary ammonium compound is
selected from the group consisting of a monoalkyl quaternary
ammonium compound, a dialkyl quaternary ammonium compound, a
trialkyl quaternary ammonium compound and mixtures thereof; [0154]
(b) said silicone polymer is selected from the group consisting of
cyclic silicones, polydimethylsiloxanes, aminosilicones, cationic
silicones, silicone polyethers, silicone resins, silicone
urethanes, and mixtures thereof; [0155] (c) said polysaccharide
comprises a cationic starch; [0156] (d) said clay comprises a
smectite clay; [0157] (e) said dispersible polyolefin is selected
from the group consisting of polyethylene, polypropylene and
mixtures thereof; and [0158] (f) said fatty ester is selected from
the group consisting of a polyglycerol ester, a sucrose ester, a
glycerol ester and mixtures thereof.
[0159] In one aspect of Applicants' cleaning and/or treatment
composition, said cleaning and/or treatment composition comprises a
fabric softener active comprising a material selected from the
group consisting of monoesterquats, diesterquats, triesterquats,
and mixtures thereof, preferably, said monoesterquats and
diesterquats are selected from the group consisting of
bis-(2-hydroxypropyl)-dimethylammonium methylsulfate fatty acid
ester and isomers of bis-(2-hydroxypropyl)-dimethylammonium
methylsulfate fatty acid ester and/or mixtures thereof,
1,2-di(acyloxy)-3-trimethylammoniopropane chloride,
N,N-bis(stearoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride,
N,N-bis(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride,
N,N-bis(stearoyl-oxy-ethyl)-N-(2-hydroxyethyl)-N-methyl ammonium
methylsulfate,
N,N-bis-(stearoyl-2-hydroxypropyl)-N,N-dimethylammonium
methylsulfate,
N,N-bis-(tallowoyl-2-hydroxypropyl)-N,N-dimethylammonium
methylsulfate,
N,N-bis-(palmitoyl-2-hydroxypropyl)-N,N-dimethylammonium
methylsulfate,
N,N-bis-(stearoyl-2-hydroxypropyl)-N,N-dimethylammonium chloride,
1,2-di-(stearoyl-oxy)-3-trimethyl ammoniumpropane chloride,
dicanoladimethyl-ammonium chloride, di(hard)tallowdimethylammonium
chloride, dicanoladimethyl ammonium methylsulfate,
1-methyl-1-stearoylamidoethyl-2-stearoylimidazolinium
methylsulfate, 1-tallowylamidoethyl-2-tallowylimidazoline,
dipalmylmethyl hydroxyethylammoinum methylsulfate and mixtures
thereof.
[0160] In one aspect of Applicants' cleaning and/or treatment
composition, said composition comprises a quaternary ammonium
compound and a silicone polymer, preferably said composition
comprises from 0.001% to 10%, from 0.1% to 8%, more preferably from
0.5% to 5%, of said silicone polymer.
[0161] In one aspect of Applicants' cleaning and/or treatment
composition, said fabric softening active has an Iodine Value of
between 0-140, preferably 5-100, more preferably 10-80, even more
preferably, 15-70, most preferably 18-25 or when said fabric
softening active comprises a partially hydrogenated fatty acid
quaternary ammonium compound said fabric softening active most
preferably has a Iodine Value of 25-60.
[0162] In one aspect of Applicants' cleaning and/or treatment
composition, said cleaning and/or treatment composition is a
soluble unit-dose product said soluble unit dose product comprising
one or more cleaning and/or treatment compositions contained within
one or more chambers said chambers being formed from one or more
films, preferably said one or more films comprise PVA film.
[0163] The compositions of the present invention may be used in any
conventional manner. In short, they may be used in the same manner
as products that are designed and produced by conventional methods
and processes. For example, compositions of the present invention
can be used to treat a situs inter alia a surface or fabric.
Typically at least a portion of the situs is contacted with an
aspect of Applicants' composition, in neat form or diluted in a
wash liquor, and then the situs is optionally washed and/or rinsed.
For purposes of the present invention, washing includes but is not
limited to, scrubbing, and mechanical agitation. The fabric may
comprise any fabric capable of being laundered in normal consumer
use conditions. When the wash solvent is water, the water
temperature typically ranges from about 5.degree. C. to about
90.degree. C. and, when the situs comprises a fabric, the water to
fabric mass ratio is typically from about 1:1 to about 100:1.
[0164] The cleaning and/or treatment compositions of the present
invention may be used as liquid fabric enhancers wherein they are
applied to a fabric and the fabric is then dried via line drying
and/or drying the an automatic dryer.
[0165] In one aspect, a method of controlling malodors comprising:
contacting a situs comprising a malodor and/or a situs that will
become malodorous with a cleaning and/or treatment composition
selected from the group consisting of Applicants' cleaning and/or
treatment compositions and mixtures thereof, is disclosed.
[0166] In one aspect of Applicants' method, said situs comprises a
fabric and said contacting step comprises contacting said fabric
with a sufficient amount of Applicants' cleaning and/or treatment
compositions to provide said fabric with at least 0.0025 mg of
benefit agent, such as perfume, per kg of fabric, preferably from
about 0.0025 mg of benefit agent/kg of fabric to about 50 mg of
malodor reduction material/kg of fabric, more preferably from about
0.25 mg of benefit agent/kg of fabric to about 25 mg of benefit
agent/kg of fabric, most preferably from about 0.5 of benefit
agent/kg of fabric to about 10 mg of benefit agent/kg of fabric of
said sum of malodor reduction materials.
[0167] Solid Consumer Products and Methods of Use
[0168] Preferably said consumer product is a powder, granule,
flake, bar or bead, said consumer product comprising, based on
total product weight: [0169] (a) with from 0.001% about to about
25%, preferably from about 0.01% to about 10%, more preferably from
about 0.05% to about 5%, most preferably from about 0.1% to about
0.5% of the microcapsules disclosed here in; [0170] (b) a carrier
that is a solid at 25.degree. C., preferably said solid carrier is
selected from the group consisting of clays, sugars, salts,
silicates, zeolites, citric acid, maleic acid, succinic acid,
benzoic acid, urea and polyethylene oxide and mixtures thereof;
preferably said carriers is present at a level of: [0171] (i) from
about 20% to about 95%, more preferably about 30% to about 90%,
even more preferably about 45% to about 90%, and most preferably
about 60% to about 88%; or [0172] (ii) from about 1% to about 60%,
more preferably about 2% to about 50%, even more preferably about
3% to about 45% and most preferably, about 4% to about 40%; and
[0173] (c) optionally, 0.5% to about 50% of an enzyme stable
polymer, preferably said enzyme stable polymer is selected from the
group consisting of polyacrylate polymers, polyamine polymer,
acrylate/maleate copolymer, a polysaccharide, and mixtures thereof,
preferably said polysaccharide is selected from the group
consisting of carboxy methyl cellulose, cationic hydroxy ethyl
cellulose and mixtures thereof.
[0174] In one aspect of said product, said product comprises a
perfume.
[0175] In one aspect of said product, said product comprising an
additional material that is an adjunct ingredient selected from the
group consisting of surfactants, builders, chelating agents, dye
transfer inhibiting agents, dispersants, enzymes, and enzyme
stabilizers, catalytic materials, bleach activators, a fabric
softener active, hydrogen peroxide, sources of hydrogen peroxide,
preformed peracids, polymeric dispersing agents, clay soil
removal/anti-redeposition agents, brighteners, suds suppressors,
dyes, hueing dyes, perfumes, perfume delivery systems, structure
elasticizing agents, carriers, structurants, hydrotropes,
processing aids, solvents, pigments and mixtures thereof.
[0176] The compositions of the present invention may be used in any
conventional manner. In short, they may be used in the same manner
as products that are designed and produced by conventional methods
and processes. For example, compositions of the present invention
can be used to treat a situs inter alia a surface or fabric.
Typically at least a portion of the situs is contacted with an
aspect of Applicants' composition, in neat form or diluted in a
wash liquor, and then the situs is optionally washed and/or rinsed.
For purposes of the present invention, washing includes but is not
limited to, scrubbing, and mechanical agitation. The fabric may
comprise any fabric capable of being laundered in normal consumer
use conditions. When the wash solvent is water, the water
temperature typically ranges from about 5.degree. C. to about
90.degree. C. and, when the situs comprises a fabric, the water to
fabric mass ratio is typically from about 1:1 to about 100:1.
[0177] The compositions of the present invention may be used as
fabric enhancers wherein they are applied to a fabric and the
fabric is then dried via line drying and/or drying the an automatic
dryer.
[0178] A method of freshening comprising: contacting a situs
comprising with a product selected from the group consisting of the
products described herein and mixtures thereof, is disclosed.
[0179] Freshening Compositions, Methods of Use and Delivery
Systems
[0180] Preferably, said consumer product is a freshening
composition having a viscosity of from about 1 mPas to about 50,000
mPas, preferably from about 1 mPas to about 2000 mPas, most
preferably from about 1 mPas to about 400 mPas, a pH from about 3
to about 10, preferably from about 4 to about 8, most preferably
from about 5 to about 8, said freshening composition comprising,
based on total freshening composition weight: [0181] (a) with from
0.001% about to about 25%, preferably from about 0.01% to about
10%, more preferably from about 0.05% to about 5%, most preferably
from about 0.1% to about 0.5% of the microcapsules disclosed here
in; and [0182] (b) from about 0.01% to about 3%, preferably from
about 0.4% to about 1%, more preferably from about 0.1% to about
0.5%, most preferably from about 0.1% to about 0.3% of solublizing
agent, preferably said solublizing agent is selected from the group
consisting of a surfactant, a solvent and mixtures thereof, [0183]
(i) preferably said surfactant comprises a non-ionic surfactant;
[0184] (ii) preferably said solvent comprises an alcohol, a polyol
and mixtures thereof; [0185] (c) optionally, an adjunct
ingredient.
[0186] As the viscosity is lowered you obtain improved
spray-ability and improved penetration into fabric.
[0187] In one aspect of said freshening composition, said
composition comprises an adjunct ingredient selected from the group
consisting of isoalkanes comprising at least 12 carbon atoms, a
compound comprising a quatenary amine moiety, lubricants,
additional solvents, glycols, alcohols, silicones, preservatives,
anti-microbial agents, pH modifiers, a carrier, insect repellants,
metallic salts, cyclodextrins, functional polymers, anti-foaming
agents, antioxidants, oxidizing agents, chelants and mixtures
thereof; preferably lubricants wherein the lubricants preferably
comprise hydrocarbons, more preferably hydrocarbons that comprise
two or more branches or compounds comprising a quatenary amine
moiety comprising at least 10 carbon atoms.
[0188] A device comprising Applicants' freshening compositions,
said device being preferably selected from the group consisting of
trigger sprayers, manual aerosol sprayers, automatic aerosol
sprayers, wick containing devices, fan devices, and thermal
drop-on-demand devices, is disclosed.
[0189] A method of freshening comprising: contacting a situs with a
composition selected from the group consisting of the freshening
compositions disclosed herein and mixtures thereof is
disclosed.
[0190] In one aspect of said method, said contacting step comprises
contacting said situs with a sufficient amount of the compositions
disclosed herein to provide said situs with, from about 0.1
milligrams (mg) to about 10,000 mg, preferably from about 1 mg to
about 5,000 mg most preferably from about 5 mg to about 1000 mg of
a benefit agent, preferably a perfume, per square meter of
projected surface area of said situs.
[0191] The composition of the present invention may be used with a
hard surface cleaner, as is commonly used to clean countertops,
tables and floors. A suitable floor cleaning liquid is sold by the
instant assignee in a replaceable reservoir under the name WetJet.
The cleaning solution may particularly be made according to the
teachings of commonly assigned U.S. Pat. No. 6,814,088. The
reservoir may be used with and dispensed from a floor cleaning
implement, in conjunction with a disposable floor sheet. A suitable
spray implement is also sold under the name WetJet. A suitable
reservoir and fitment therefore may be made according to the
teachings of commonly assigned U.S. Pat. Nos. 6,386,392 and/or
7,172,099. If desired the floor cleaning implement may dispense
steam, according to the teachings of jointly assigned US
2013/0319463. Alternatively a refillable reservoir may be
utilized.
[0192] If desired the composition of the present invention may be
used with a pre-moistened sheet. If the cleaning sheet is
pre-moistened, it is preferably pre-moistened with a liquid which
provides for cleaning of the target surface, such as a floor, but
yet does not require a post-cleaning rinsing operation. The
cleaning sheet may be loaded with at least 1, 1.5 or 2 grams of
cleaning solution per gram of dry substrate, but typically not more
than 5 grams per gram. The cleaning solution may comprise a
surfactant, such as APG surfactant which minimizes streaking since
there is typically not a rinsing operation, according to the
teachings of U.S. Pat. No. 6,716,805.
[0193] The composition of the present invention may be used for
raised hard surfaces, as is sold under the names Mr. Clean and Mr.
Proper. The composition may be dispensed from a trigger sprayer or
aerosol sprayer, as are well known in the art. An aerosol sprayer
dispenses the composition using propellant pressure, while a
trigger sprayer dispenses the composition by pumping the
composition under manual actuation. A suitable aerosol dispenser
may have a dip tube or bag on valve, according to US 2015/0108163
and/or US 2011/0303766. A suitable trigger sprayer is found in U.S.
Pat. No. 8,322,631.
[0194] The present freshening composition may be used in a device
for the delivery of a volatile material to the atmosphere or on
inanimate surfaces (e.g. fabric surfaces as a fabric refresher).
Such device may be configured in a variety of ways. For example,
the device may be configured for use as an energized air freshener
(i.e. powered by electricity; or chemical reactions, such as
catalyst fuel systems; or solar powered; or the like). Exemplary
energized air freshening devices include a powered delivery
assistance means which may include a heating element, fan assembly,
or the like. More particularly, the device may be an electrical
wall-plug air freshener as described in U.S. Pat. No. 7,223,361; a
battery (including rechargeable battery) powered air freshener
having a heating and/or fan element. In energized devices, the
volatile material delivery engine may be placed next to the powered
delivery assistance means to diffuse the volatile perfume material.
The volatile perfume material may be formulated to optimally
diffuse with the delivery assistance means.
[0195] Alternatively, the device may be configured for use as a
non-energized air freshener. An exemplary non-energized air
freshener includes a reservoir and, optionally, capillary or
wicking means or an emanating surface, to help volatile materials
passively diffuse into the air (i.e. without an energized means). A
more specific example includes a delivery engine having a liquid
reservoir for containing a volatile material and a microporous
membrane enclosing the liquid reservoir as disclosed in U.S. Pat.
No. 8,709,337 and U.S. Pat. No. 8,931,711.
[0196] The device may also be configured for use as an aerosol
sprayer or a non-aerosol air sprayer including traditional trigger
sprayers as well as trigger sprayer having a pre-compression and/or
buffer system for fluid therein. In this embodiment, the delivery
engine can deliver volatile materials upon user demand or
programmed to automatically deliver volatile materials to the
atmosphere.
[0197] The apparatus may also be configured for use with an air
purifying system to deliver both purified air and volatile
materials to the atmosphere. Non-limiting examples include air
purifying systems using ionization and/or filtration technology for
use in small spaces (e.g. bedrooms, bathrooms, automobiles, etc.),
and whole house central air conditioning/heating systems (e.g.
HVAC).
[0198] Article and Method of Use
[0199] Preferably said consumer product is an article comprising
[0200] (a) a substrate, preferably a flexible substrate, more
preferably a flexible substrate that is a sheet; preferably said
substrate comprises a fabric softening active, preferably said
fabric softening active coats all or a portion of said substrate;
and [0201] (b) based on total article weight with from 0.001% about
to about 25%, preferably from about 0.01% to about 10%, more
preferably from about 0.05% to about 5%, most preferably from about
0.1% to about 0.5% of the microcapsules disclosed here in.
[0202] Preferably said article has a weight ratio of fabric
softener active to dry substrate ranging from about 10:1 to about
0.5:1, preferably from about 5:1 to about 1:1, preferably said
fabric softener active is selected from the group consisting of a
quaternary ammonium compound, a silicone polymer, a polysaccharide,
a clay, an amine, a fatty ester, a dispersible polyolefin, a
polymer latex and mixtures thereof.
[0203] In one aspect, said article has a weight ratio of fabric
softener active to dry substrate ranging from about 10:1 to about
0.5:1, preferably from about 5:1 to about 1:1, preferably said
fabric softener active is selected from the group consisting of
[0204] (a) a cationic fabric softener active, preferably a
quaternary-ammonium fabric softener active, more preferably a
di(long alkyl chain)dimethylammonium (C.sub.1-C.sub.4 alkyl)
sulfate or chloride, preferably the methyl sulfate; an ester
quaternary ammonium compound, an ester amine precursor of an ester
quaternary ammonium compound, and mixtures thereof, preferably a
diester quaternary ammonium salt; [0205] (b) a carboxylic acid salt
of a tertiary amine and/or ester amine; [0206] (c) a nonionic
fabric softener material, preferably fatty acid partial esters of
polyhydric alcohols, or anhydrides thereof, wherein the alcohol or
anhydride contains from about 2 to about 18 and preferably from
about 2 to about 8 carbon atoms, and each fatty acid moiety
contains from about 8 to about 30 and preferably from about 12 to
about 20 carbon atoms; [0207] (d) alkanolamides; [0208] (e) fatty
acids; and [0209] (f) mixtures of the foregoing.
[0210] Preferably, said article comprises, based on total article
weight, from 1% to 99% by weight, preferably from about 1% to about
80%, more preferably from about 20% to about 70%, most preferably
from about 25% to about 60% of a fabric softening active.
[0211] Preferably said article comprises a quaternary ammonium
compound selected from the group consisting of
bis-(2-hydroxypropyl)-dimethylammonium methylsulphate fatty acid
ester, 1,2-di(acyloxy)-3-trimethylammoniopropane chloride., N,
N-bis(stearoyl-oxy-ethyl) N,N-dimethyl ammonium chloride,
N,N-bis(tallowoyl-oxy-ethyl) N,N-dimethyl ammonium chloride,
N,N-bis(stearoyl-oxy-ethyl) N-(2 hydroxyethyl) N-methyl ammonium
methylsulfate, 1,2 di (stearoyl-oxy) 3 trimethyl ammoniumpropane
chloride, dicanoladimethylammonium chloride,
di(hard)tallowdimethylammonium chloride, dicanoladimethylammonium
methylsulfate, 1-methyl-1-stearoyl
amidoethyl-2-stearoylimidazolinium methylsulfate,
1-tallowylamidoethyl-2-tallowylimidazoline, dipalmethyl
hydroxyethylammoinum methosulfate and mixtures thereof.
[0212] In one aspect of said article, said article comprises a
fabric softening active having an Iodine Value of between 0-140,
preferably 5-100, more preferably 10-80, even more preferably,
15-70, most preferably 18-25.
[0213] In one aspect of said article, said article comprises an
adjunct ingredient selected from the group consisting of
surfactants, builders, chelating agents, dye transfer inhibiting
agents, dispersants, enzymes, and enzyme stabilizers, catalytic
materials, bleach activators, hydrogen peroxide, sources of
hydrogen peroxide, preformed peracids, polymeric dispersing agents,
clay soil removal/anti-redeposition agents, brighteners, suds
suppressors, dyes, hueing dyes, perfumes, perfume delivery systems,
structure elasticizing agents, carriers, structurants, hydrotropes,
processing aids, solvents, pigments anti-oxidants, colorants,
preservatives, optical brighteners, opacifiers, stabilizers such as
guar gum and polyethylene glycol, anti-shrinkage agents,
anti-wrinkle agents, soil release agents, fabric crisping agents,
reductive agents, spotting agents, germicides, fungicides,
anti-corrosion agents, antifoam agents, Color Care Agents including
Chlorine Scavangers, Dye Transfer Inhibitors, Dye Fixatives
Chelants and Anti-Abrasion Agents Perfume, PMC's, Cyclodextrin
Perfume Complexes, Free Cyclodextrin, Pro-Perfumes; Antioxidants
and mixtures thereof.
[0214] A method of controlling softening and/or freshening
comprising: contacting a situs comprising one or more of the
articles Applicants' disclose herein, is disclosed.
[0215] In one aspect of said method, said situs comprises a fabric
and said contacting step comprises contacting said fabric with a
sufficient amount of Applicants' article containing to provide said
fabric with a level of perfume of at least 0.0025 mg of perfume/kg
of fabric, preferably from about 0.00025 mg of perfume/kg of fabric
to about 25 mg of perfume/kg of fabric, more preferably from about
0.025 mg of perfume/kg of fabric to about 20 mg of perfume/kg of
fabric, most preferably from about 0.25 of perfume/kg of fabric to
about 10 mg of malodor reduction material/kg of fabric of said sum
of malodor reduction materials.
[0216] One aspect of the present invention relates to fabric
conditioning compositions which are delivered to fabric via
dryer-added substrate that effectively releases the composition in
an automatic laundry (clothes) dryer. Such dispensing means can be
designed for single usage or for multiple uses. The dispensing
means can also be a "carrier material" that releases the fabric
conditioning composition and then is dispersed and/or exhausted
from the dryer. When the dispensing means is a flexible substrate,
e.g., in sheet configuration, the fabric conditioning composition
is releasably affixed on the substrate to provide a weight ratio of
conditioning composition to dry substrate ranging from about 10:1
to about 0.5:1, preferably from about 5:1 to about 1:1. To insure
release, preferred flexible sheets withstand the dryer environment
without decomposing or changing shape, e.g. combusting, creating
off odors, or shrinking with heat or moisture. Substrates
especially useful herein are rayon and/or polyester non-woven
fabrics.
[0217] Non-limiting examples of the substrates useful herein are
cellulosic rayon and/or polyester non-woven fabrics having basis
weights of from about 0.4 oz./yd.sup.2 to about 1 oz./yd.sup.2,
preferably from about 0.5 oz./yd.sup.2 to about 0.8 oz./yd.sup.2,
more preferably from about 0.5 oz./yd.sup.2 to about 0.6
oz./yd.sup.2. These substrates are typically prepared using, e.g.,
rayon and/or polyester fibers having deniers of from about 1 to
about 8, preferably from about 3 to about 6, and more preferably
about 4 to 6 or mixtures of different deniers. Typically, the fiber
is a continuous filament or a 3/16 inch to 2 inch fiber segment
that is laid down, in a pattern that results in a multiplicity of
layers and intersections between overlayed portions of the filament
or fiber, on a belt, preferably foraminous, and then the fiber
intersections are glued and/or fused into fiber-to-fiber bonds by a
combination of an adhesive binder, and/or heat and/or pressure. As
non-limiting examples, the substrate may be spun-bonded,
melt-bonded, or point bonded or combinations of bonding processes
may be chosen. The substrate breaking strength and elasticity in
the machine and cross direction is sufficient to enable the
substrate to be conveyed through a coating process. The porosity of
the substrate article is sufficient to enable air flow through the
substrate to promote conditioning active release and prevent dryer
vent blinding. The substrate may also have a plurality of
rectilinear slits extended along one dimension of the
substrate.
[0218] The dispensing means will normally carry an effective amount
of fabric conditioning composition. Such effective amount typically
provides sufficient softness, antistatic effect and/or perfume
deposition for at least one treatment of a minimum load in an
automatic laundry dryer. Amounts of the fabric conditioning
composition irrespective of load size for a single article can vary
from about 0.1 g to about 100 g, preferably from about 0.1 g to
about 20 g, most preferably from about 0.1 g to about 10 g. Amounts
of fabric treatment composition for multiple uses, e.g., up to
about 30, can be used.
[0219] Absorbent Article, Polybag or Paper Carton and Methods of
Use
[0220] Preferably said consumer product is an article selected from
an absorbent article, polybag or paper carton, said article
comprising, based on total article weight, with from 0.001% about
to about 25%, preferably from about 0.01% to about 10%, more
preferably from about 0.05% to about 5%, most preferably from about
0.1% to about 0.5% of the microcapsules of the present
invention.
[0221] Preferably said article is an absorbent article, preferably
said absorbent article is a sanitary paper product, said sanitary
paper product comprising one or more layers of conventional
felt-pressed tissue paper, conventional wet-pressed tissue paper,
pattern densified tissue paper, starch substrates, high bulk,
un-compacted tissue paper and mixtures thereof.
[0222] Preferably said absorbent article comprises an absorbent
core, and optionally a backsheet, topsheet, acquisition layer or
outer wrapper, wherein said microcapsules are disposed on the
absorbent core or between one or more of the optional layers.
[0223] In one aspect of said article, said absorbent article is
contained in a polybag or paper carton.
[0224] In one aspect of said article, said microcapsules are
disposed on said polybag or paper carton, and/or on said absorbent
article.
[0225] Preferably said article is an absorbent article comprises a
lotion.
[0226] Preferably, said absorbent article comprises one or more
adjunct ingredients selected from the group consisting of
surfactants, inks, dyes, mineral oils, petrolatum, polysiloxanes,
cyclodextrins, clays, silicates, aluminates, vitamins, isoflavones,
flavones, metal oxides, short chain organic acids
(C.sub.1-C.sub.8), triglycerides (C.sub.8-C.sub.22), and
antioxidants.
[0227] In one aspect, a method of providing a benefit agent,
preferably perfume, comprising: incorporating said microcapsules in
or on an article, preferably an absorbent article, polybag and/or
paper carton, is disclosed.
[0228] A non-limiting list of suppliers of suitable absorbent
articles, polybags, and cartons that can be used in the manufacture
of Applicants' articles is as follows: Procter & Gamble of
Cincinnati, Ohio, USA; International Paper Products of Memphis,
Tenn. USA; and Kimberly Clark, of Irving, Tex., USA. Suitable
equipment and processes for making absorbent articles can be
obtained from Fameccanica Group of Pescara, Italy. Suitable
equipment and processes for adding the malodor reduction materials
to said articles can be obtained from Nordson of Duluth Ga.,
USA.
[0229] Personal Care Compositions and Methods of Use
[0230] Preferably said consumer product is a personal care
composition comprising, based on total composition weight, [0231]
(a) with from 0.001% about to about 10%, preferably from about 0.1%
to about 5%, more preferably from about 0.5% to about 4%, most
preferably from about 1% to about 3% of the microcapsules disclosed
here in; [0232] (b) from about 0.1% to about 99%, preferably from
about 1% to about 80%, more preferably from about 5% to about 70%,
most preferably from about 10% to about 50% of a solvent,
preferably said solvent is selected from, water, glycerin, and
mixtures thereof; and [0233] (c) from about 0% to about 50%,
preferably from about 0% to about 40%, more preferably from about
0.1% to about 30%, most preferably from about 0.1% to about 15% of
a material selected from the group consisting of a structurant, a
humectant, a surfactant, an antimicrobial, and mixtures
thereof.
[0234] Preferably, said personal care composition comprises one or
more neat perfume raw materials--the total of said neat perfume raw
materials being the sum of such neat perfume raw materials based on
weight of each neat perfume raw materials.
[0235] Preferably, said sum total of neat perfume raw materials has
an average Log P, based on weight percent of each perfume raw
material in said sum total of neat perfume raw materials, of from
about 2.5 to about 8, preferably from about 3 to about 8, more
preferably from about 3.5 to about 7, most preferably, each of said
neat perfume raw materials in said sum total of neat perfume raw
materials. This range of Log P will allow the perfume to deposit on
the skin and not wash away in the water phase during use
[0236] Preferably said personal care composition, comprises less
than 10%, preferably less than 5%, more preferably less than 1% of
said one or more perfume raw materials, based on total combined
weight of said one or more perfume raw materials comprise an ionone
moiety.
[0237] Preferably said personal care composition comprises a total
of, based on total personal care composition weight, of from about
3% to 30% of a surfactant, and, optionally, a miscellar phase
and/or lamellar phase.
[0238] Preferably said personal care composition, said composition
comprises a total, based on total personal care composition weight,
of from about 0.1% to about 50% of a material selected from
structurants, humectants, fatty acids, inorganic salts,
antimicrobial agents, antimicrobial agents actives and mixtures
thereof.
[0239] Preferably said personal care composition comprises an
adjunct ingredient selected from the group consisting of clay
mineral powders, pearl pigments, organic powders, emulsifiers,
distributing agents, pharmaceutical active, topical active,
preservatives, surfactants and mixtures thereof.
[0240] A method of freshening comprising: contacting a situs with a
personal care composition selected from the group consisting of the
personal care compositions disclosed herein is disclosed.
[0241] In one aspect of said method, said situs comprises the body
or head of hair and said contacting step comprises contacting said
body or hair containing a malodor with a sufficient amount of
Applicants' personal care composition to provide said body or hair
with a level of encapsulated benefit agent, preferably perfume, of
at least 0.0001 mg of encapsulated benefit agent per body or head
of hair, preferably from about 0.0001 mg of encapsulated benefit
agent per body or head of hair to about 1 mg of encapsulated
benefit agent per body or head of hair, more preferably from about
0.001 mg of encapsulated benefit agent per body or head of hair
about 0.5 mg of encapsulated benefit agent per body or head of
hair, most preferably from about 0.01 of encapsulated benefit agent
per body or head of hair to about 0.2 mg of encapsulated benefit
agent per body or head of hair.
[0242] Antiperspirant and/or Deodorant Compositions and Methods of
Use
[0243] Preferably said consumer product is an antiperspirant and/or
deodorant composition comprising, based on total composition
weight, [0244] (a) with from 0.001% about to about 10%, preferably
from about 0.1% to about 5%, more preferably from about 0.5% to
about 4%, most preferably from about 1% to about 3% of the
microcapsules disclosed here in; [0245] (b) from about 0.1% to
about 99%, preferably from about 1% to about 80%, more preferably
from about 5% to about 55%, most preferably from about 10% to about
50% of a solvent, preferably said solvent is selected from
cyclopentasiloxane, ethanol, water, propylene glycol, dipropylene
glycol, and mixtures thereof; [0246] (c) from about 0% to about
30%, preferably from about 0% to about 20%, more preferably from
about 0.1% to about 4%, most preferably from about 0.1% to about 4%
of a material selected from the group consisting of a structurant,
a residue masker, an antimicrobial, and mixtures thereof
[0247] is disclosed. The aforementioned solvent levels help
disperse perfume into the APDO base to give even coverage when
used
[0248] Preferably said antiperspirant and/or deodorant composition,
comprises one or more perfume raw materials.
[0249] Preferably each of said one or more perfume raw materials
has a boiling point of from about 160.degree. C. to about
400.degree. C., preferably from about 180.degree. C. to about
400.degree. C.
[0250] Preferably less than 10%, preferably less than 5%, more
preferably less than 1% of said one or more perfume raw materials,
based on total combined weight of said one or more perfume raw
materials comprise an ionone moiety.
[0251] Preferably, said antiperspirant and/or deodorant composition
is an antiperspirant composition that comprises a total of, based
on total antiperspirant composition weight, from about 1% to about
25% of an aluminum salt antiperspirant active.
[0252] Preferably said antiperspirant and/or deodorant composition,
is an anhydrous antiperspirant composition, said anhydrous
antiperspirant composition comprising a total of, based on total
anhydrous antiperspirant composition weight, from about 1% to about
25% of an antiperspirant actives selected from the group consisting
of astringent metallic salts, preferably inorganic and organic
salts of aluminum, zirconium and zinc, as well as mixtures thereof,
more preferably aluminum halides, aluminum chlorohydrate, aluminum
hydroxyhalides, zirconyl oxyhalides, zirconyl hydroxyhalides, and
mixtures thereof.
[0253] Preferably said antiperspirant and/or deodorant composition
comprises an adjunct ingredient selected from the group consisting
of clay mineral powders, pearl pigments, organic powders,
emulsifiers, distributing agents, pharmaceutical active, topical
active, preservatives, surfactants and mixtures thereof.
[0254] A method of controlling malodors comprising: contacting a
situs comprising a malodor and/or a situs that may become
malodorous with an antiperspirant or deodorant composition selected
from the group consisting of the antiperspirant and/or deodorant
composition disclosed herein, is disclosed.
[0255] In one aspect of said method, said situs is an underarm and
said contacting step comprises contacting said underarm with a
sufficient amount of Applicants' antiperspirant and/or deodorant
composition containing said sum of malodor reduction materials to
provide said underarm with a level of malodor reduction materials
of at least 0.0001 mg of malodor reduction material per underarm,
preferably from about 0.0001 mg of malodor reduction material per
underarm to about 10 mg of malodor reduction material per underarm,
more preferably from about 0.001 mg of malodor reduction material
per underarm about 5 mg of malodor reduction material per underarm,
most preferably from about 0.01 of malodor reduction material per
underarm to about 0.2 mg of malodor reduction material per
underarm.
[0256] Antiperspirant Compositions
[0257] Antiperspirant compositions can be formulated in many forms.
For example an antiperspirant composition can be, without
limitation, a roll on product, a body spray, a stick including soft
solid sticks and invisible solids, or an aerosol. Each of the
antiperspirant compositions described below can include perfume
materials as described herein.
[0258] A. Roll-On and Clear Gel
[0259] A roll-on antiperspirant composition can comprise, for
example, water, emollient, solubilizer, deodorant actives,
antioxidants, preservatives, or combinations thereof. A clear gel
antiperspirant composition can comprise, for example, water,
emollient, solubilizer, deodorant actives, antioxidants,
preservatives, ethanol, or combinations thereof. [0260] Water--The
roll-on composition can include water. Water can be present in an
amount of about 1% to about 99.5%, about 25% to about 99.5%, about
50% to about 99.5%, about 75% to about 99.5% about 80% to about
99.5%, from about 15% to about 45%, or any combination of the end
points and points encompassed within the ranges, by weight of the
deodorant composition. [0261] Emollients--Roll-on compositions can
comprise an emollient system including at least one emollient, but
it could also be a combination of emollients. Suitable emollients
are often liquid under ambient conditions. Depending on the type of
product form desired, concentrations of the emollient(s) in the
deodorant compositions can range from about 1% to about 95%, from
about 5% to about 95%, from about 15% to about 75%, from about 1%
to about 10%, from about 15% to about 45%, or from about 1% to
about 30%, by weight of the deodorant composition. [0262]
Emollients suitable for use in the roll-on compositions include,
but are not limited to, propylene glycol, polypropylene glycol
(like dipropylene glycol, tripropylene glycol, etc.), diethylene
glycol, triethylene glycol, PEG-4, PEG-8, 1,2 pentanediol, 1,2
hexanediol, hexylene glycol, glycerin, C2 to C20 monohydric
alcohols, C2 to C40 dihydric or polyhydric alcohols, alkyl ethers
of polyhydric and monohydric alcohols, volatile silicone emollients
such as cyclopentasiloxane, nonvolatile silicone emollients such as
dimethicone, mineral oils, polydecenes, petrolatum, and
combinations thereof. One example of a suitable emollient comprises
PPG-15 stearyl ether. Other examples of suitable emollients include
dipropylene glycol and propylene glycol. [0263] Deodorant
Actives--Suitable deodorant actives can include any topical
material that is known or otherwise effective in preventing or
eliminating malodor associated with perspiration. Suitable
deodorant actives may be selected from the group consisting of
antimicrobial agents (e.g., bacteriocides, fungicides),
malodor-absorbing material, and combinations thereof. For example,
antimicrobial agents may comprise cetyl-trimethylammonium bromide,
cetyl pyridinium chloride, benzethonium chloride, diisobutyl
phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, sodium
N-lauryl sarcosine, sodium N-palmethyl sarcosine, lauroyl
sarcosine, N-myristoyl glycine, potassium N-lauryl sarcosine,
trimethyl ammonium chloride, sodium aluminum chlorohydroxy lactate,
triethyl citrate, tricetylmethyl ammonium chloride,
2,4,4'-trichloro-2'-hydroxy diphenyl ether (triclosan),
3,4,4'-trichlorocarbanilide (triclocarban), diaminoalkyl amides
such as L-lysine hexadecyl amide, heavy metal salts of citrate,
salicylate, and piroctose, especially zinc salts, and acids
thereof, heavy metal salts of pyrithione, especially zinc
pyrithione, zinc phenolsulfate, farnesol, and combinations thereof.
The concentration of the optional deodorant active may range from
about 0.001%, from about 0.01%, of from about 0.1%, by weight of
the composition to about 20%, to about 10%, to about 5%, or to
about 1%, by weight of the composition. [0264] Odor Entrappers--The
composition can include an odor entrapper. Suitable odor entrappers
for use herein include, for example, solubilized, water-soluble,
uncomplexed cyclodextrin. As used herein, the term "cyclodextrin"
includes any of the known cyclodextrins such as unsubstituted
cyclodextrins containing from six to twelve glucose units,
especially, alpha-cyclodextrin, beta-cyclodextrin,
gamma-cyclodextrin and/or their derivatives and/or mixtures
thereof. The alpha-cyclodextrin consists of six glucose units, the
beta-cyclodextrin consists of seven glucose units, and the
gamma-cyclodextrin consists of eight glucose units arranged in a
donut-shaped ring. The specific coupling and conformation of the
glucose units give the cyclodextrins a rigid, conical molecular
structure with a hollow interior of a specific volume. The "lining"
of the internal cavity is formed by hydrogen atoms and glycosidic
bridging oxygen atoms, therefore this surface is fairly
hydrophobic. The unique shape and physical-chemical property of the
cavity enable the cyclodextrin molecules to absorb (form inclusion
complexes with) organic molecules or parts of organic molecules
which can fit into the cavity. Many perfume molecules can fit into
the cavity. [0265] Cyclodextrin molecules are described in U.S.
Pat. No. 5,714,137, and U.S. Pat. No. 5,942,217. Suitable levels of
cyclodextrin are from about 0.1% to about 5%, alternatively from
about 0.2% to about 4%, alternatively from about 0.3% to about 3%,
alternatively from about 0.4% to about 2%, by weight of the
composition. [0266] Buffering Agent--The composition can include a
buffering agent which may be alkaline, acidic or neutral. The
buffer can be used in the composition for maintaining the desired
pH. The composition may have a pH from about 3 to about 10, from
about 4 to about 9, from about 5 to about 8, from about 6 to about
7, or it may have a pH of about 6.5. One unique feature of the
polyvinyl amine malodor control polymers is its ability to maintain
active nitrogen sites at high pH levels which can help enhance the
antibacterial effect which comes, at least in part, from the
nitrogen sites. Suitable buffering agents include, for example,
hydrochloric acid, sodium hydroxide, potassium hydroxide, and
combinations thereof. [0267] The compositions can contain at least
about 0%, alternatively at least about 0.001%, alternatively at
least about 0.01%, by weight of the composition, of a buffering
agent. The composition may also contain no more than about 1%,
alternatively no more than about 0.75%, alternatively no more than
about 0.5%, by weight of the composition, of a buffering agent.
[0268] Solubilizer--The composition can contain a solubilizer. A
suitable solubilizer can be, for example, a surfactant, such as a
no-foaming or low-foaming surfactant. Suitable surfactants are
nonionic surfactants, cationic surfactants, amphoteric surfactants,
zwitterionic surfactants, and mixtures thereof. [0269] Suitable
solubilizers include, for example, hydrogenated castor oil,
polyoxyethylene 2 stearyl ether, polyoxyethylene 20 stearyl ether,
and combinations thereof. One suitable hydrogenated castor oil that
may be used in the present composition is polyoxyethylene
hydrogenated castor oil. [0270] When the solubilizing agent is
present, it is typically present at a level of from about 0.01% to
about 5%, alternatively from about 0.01% to about 3%, alternatively
from about 0.05% to about 1%, alternatively from about 0.01% to
about 0.05%, by weight of the composition. [0271]
Preservatives--The composition can include a preservative. The
preservative is included in an amount sufficient to prevent
spoilage or prevent growth of inadvertently added microorganisms
for a specific period of time, but not sufficient enough to
contribute to the odor neutralizing performance of the composition.
In other words, the preservative is not being used as the
antimicrobial compound to kill microorganisms on the surface onto
which the composition is deposited in order to eliminate odors
produced by microorganisms. Instead, it is being used to prevent
spoilage of the composition in order to increase shelf-life. [0272]
The preservative can be any organic preservative material which
will not cause damage to fabric appearance, e.g., discoloration,
coloration, bleaching. Suitable water-soluble preservatives include
organic sulfur compounds, halogenated compounds, cyclic organic
nitrogen compounds, low molecular weight aldehydes, parabens,
propane diol materials, isothiazolinones, quaternary compounds,
benzoates, low molecular weight alcohols, dehydroacetic acid,
phenyl and phenoxy compounds, or mixtures thereof. [0273]
Non-limiting examples of commercially available water-soluble
preservatives include a mixture of about 77%
5-chloro-2-methyl-4-isothiazolin-3-one and about 23%
2-methyl-4-isothiazolin-3-one, a broad spectrum preservative
available as a 1.5% aqueous solution under the trade name
Kathon.RTM. CG by Rohm and Haas Co.; 5-bromo-5-nitro-1,3-dioxane,
available under the tradename Bronidox L.RTM. from Henkel;
2-bromo-2-nitropropane-1,3-diol, available under the trade name
Bronopol.RTM. from Inolex; 1,1'-hexamethylene
bis(5-(p-chlorophenyl)biguanide), commonly known as chlorhexidine,
and its salts, e.g., with acetic and digluconic acids; a 95:5
mixture of
1,3-bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione and
3-butyl-2-iodopropynyl carbamate, available under the trade name
Glydant Plus.RTM. from Lonza;
N-[1,3-bis(hydroxymethyl)2,5-dioxo-4-imidazolidinyl]-N,N'-bis(hydroxy-met-
hyl) urea, commonly known as diazolidinyl urea, available under the
trade name Germall.RTM. II from Sutton Laboratories, Inc.;
N,N''-methylenebis{N'-[1-(hydroxymethyl)-2,5-dioxo-4-imidazolidinyl]-urea-
}, commonly known as imidazolidinyl urea, available, e.g., under
the trade name Abiol.RTM. from 3V-Sigma, Unicide U-13.RTM. from
Induchem, Germall 115.RTM. from Sutton Laboratories, Inc.;
polymethoxy bicyclic oxazolidine, available under the trade name
Nuosept.RTM. C from Hills America; formaldehyde; glutaraldehyde;
polyaminopropyl biguanide, available under the trade name Cosmocil
CQ.RTM. from ICI Americas, Inc., or under the trade name
Mikrokill.RTM. from Brooks, Inc; dehydroacetic acid; and
benzsiothiazolinone available under the trade name Koralone.TM.
B-119 from Rohm and Hass Corporation. [0274] Suitable levels of
preservative can range from about 0.0001% to about 0.5%,
alternatively from about 0.0002% to about 0.2%, alternatively from
about 0.0003% to about 0.1%, by weight of the composition.
[0275] B. Body Spray
[0276] A body spray can contain, for example, a carrier, perfume, a
deodorant active, odor entrappers, propellant, or combinations
thereof. The body spray compositions can be applied as a liquid.
[0277] Carrier--A carrier suitable for use in a body spray can
include, water, alcohol, or combinations thereof. The carrier may
be present in an amount of about 1% to about 99.5%, about 25% to
about 99.5%, about 50% to about 99.5%, about 75% to about 99.5%
about 80% to about 99.5%, from about 15% to about 45%, or any
combination of the end points and points encompassed within the
ranges, by weight of the composition. A suitable example of an
alcohol can include ethanol. [0278] Propellant--The compositions
described herein can include a propellant. Some examples of
propellants include compressed air, nitrogen, inert gases, carbon
dioxide, and mixtures thereof. Propellants may also include gaseous
hydrocarbons like propane, n-butane, isobutene, cyclopropane, and
mixtures thereof. Halogenated hydrocarbons like 1,1-difluoroethane
may also be used as propellants. Some non-limiting examples of
propellants include 1,1,1,2,2-pentafluoroethane, 1,
1,1,2-tetrafluoroethane, 1,1,1,2,3,3,3-heptafluoropropane,
trans-1,3,3,3-tetrafluoroprop-1-ene, dimethyl ether,
dichlorodifluoromethane (propellant 12), 1,
1-dichloro-1,1,2,2-tetrafluoroethane (propellant 114),
1-chloro-1,1-difluoro-2,2-trifluoroethane (propellant 115),
1-chloro-1,1-difluoroethylene (propellant 142B), 1,1-difluoroethane
(propellant 152A), monochlorodifluoromethane, and mixtures thereof.
Some other propellants suitable for use include, but are not
limited to, A-46 (a mixture of isobutane, butane and propane), A-31
(isobutane), A-17 (n-butane), A-108 (propane), AP70 (a mixture of
propane, isobutane and n-butane), AP40 (a mixture of propane,
isobutene and n-butane), AP30 (a mixture of propane, isobutane and
n-butane), and 152A (1,1 diflouroethane). The propellant may have a
concentration from about 15%, 25%, 30%, 32%, 34%, 35%, 36%, 38%,
40%, or 42% to about 70%, 65%, 60%, 54%, 52%, 50%, 48%, 46%, 44%,
or 42%, or any combination thereof, by weight of the total fill of
materials stored within the container.
[0279] C. Invisible Solid
[0280] Invisible solid antiperspirant compositions as described
herein can contain a primary structurant, an antiperspirant active,
a perfume, and additional chassis ingredient(s). The antiperspirant
composition can further comprise other optional ingredient(s). The
compositions can be in the form of a solid stick. The compositions
can have a product hardness of about 600 gram force or more. The
compositions may be free of dipropylene glycol, added water, castor
wax, or any combination thereof. The antiperspirant composition may
be anhydrous. The antiperspirant composition may be free of added
water. [0281] Hardness--The invisible solid can have a product
hardness of least about 600 gram. force, more specifically from
about 600 gram. force to about 5,000 gram. force, still more
specifically from about 750 gram. force to about 2,000 gram. force,
and yet more specifically from about 800 gram. force to about 1,400
gram. force. [0282] The term "product hardness" or "hardness" as
used herein is a reflection of how much force is required to move a
penetration cone a specified distance and at a controlled rate into
an antiperspirant composition under the test conditions described
herein below. Higher values represent harder product, and lower
values represent softer product. These values are measured at
27.degree. C., 15% relative humidity, using a TA-XT2 Texture
Analyzer, available from Texture Technology Corp., Scarsdale, N.Y.,
U.S.A. The product hardness value as used herein represents the
peak force required to move a standard 45-degree angle penetration
cone through the composition for a distance of 10 mm at a speed of
2 mm/second. The standard cone is available from Texture Technology
Corp., as part number TA-15, and has a total cone length of about
24.7 mm, angled cone length of about 18.3 mm, and a maximum
diameter of the angled surface of the cone of about 15.5 mm. The
cone is a smooth, stainless steel construction and weighs about
17.8 grams. [0283] Primary Structurants--The invisible solid can
comprise a suitable concentration of a primary structurant to help
provide the antiperspirant with the desired viscosity, rheology,
texture and/or product hardness, or to otherwise help suspend any
dispersed solids or liquids within the composition. [0284] The term
"solid structurant" as used herein means any material known or
otherwise effective in providing suspending, gelling, viscosifying,
solidifying, and/or thickening properties to the composition or
which otherwise provide structure to the final product form. These
solid structurants include gelling agents, and polymeric or
non-polymeric or inorganic thickening or viscosifying agents. Such
materials will typically be solids under ambient conditions and
include organic solids, crystalline or other gellants, inorganic
particulates such as clays or silicas, or combinations thereof.
[0285] The concentration and type of solid structurant selected for
use in the antiperspirant compositions will vary depending upon the
desired product hardness, rheology, and/or other related product
characteristics. For most structurants suitable for use herein, the
total structurant concentration ranges from about 5% to about 35%,
more typically from about 10% to about 30%, or from about 7% to
about 20%, by weight of the composition. [0286] Non-limiting
examples of suitable primary structurants include stearyl alcohol
and other fatty alcohols; hydrogenated castor wax (e.g., Castorwax
MP80, Castor Wax, etc.); hydrocarbon waxes include paraffin wax,
beeswax, carnauba, candelilla, spermaceti wax, ozokerite, ceresin,
baysberry, synthetic waxes such as Fischer-Tropsch waxes, and
microcrystalline wax; polyethylenes with molecular weight of 200 to
1000 daltons; solid triglycerides; behenyl alcohol, or combinations
thereof. [0287] Other non-limiting examples of primary structurants
suitable for use herein are described in U.S. Pat. No. 5,976,514
and U.S. Pat. No. 5,891,424, the descriptions of which are
incorporated herein by reference. [0288] Antiperspirant Active--The
antiperspirant stick compositions can comprise a particulate
antiperspirant active suitable for application to human skin. The
concentration of antiperspirant active in the composition should be
sufficient to provide the desired perspiration wetness and odor
control from the antiperspirant stick formulation selected. [0289]
The antiperspirant stick compositions can comprise an
antiperspirant active at concentrations of from about 0.5% to about
60%, and more specifically from about 5% to about 35%, by weight of
the composition. These weight percentages are calculated on an
anhydrous metal salt basis exclusive of water and any complexing
agents such as, for example, glycine, and glycine salts. The
antiperspirant active as formulated in the composition can be in
the form of dispersed particulate solids having an average particle
size or equivalent diameter of less than about 100 microns, more
specifically less than about 20 microns, and even more specifically
less than about 10 microns. [0290] The antiperspirant active for
use in the anhydrous antiperspirant compositions of the present
invention can include any compound, composition or other material
having antiperspirant activity. More specifically, the
antiperspirant actives may include astringent metallic salts,
especially inorganic and organic salts of aluminum, zirconium and
zinc, as well as mixtures thereof. Even more specifically, the
antiperspirant actives may include aluminum-containing and/or
zirconium-containing salts or materials, such as, for example,
aluminum halides, aluminum chlorohydrate, aluminum hydroxyhalides,
zirconyl oxyhalides, zirconyl hydroxyhalides, and mixtures thereof.
[0291] Aluminum salts for use in the anhydrous antiperspirant stick
compositions include those that conform to the formula:
[0291] Al.sub.2(OH).sub.aCl.sub.b.xH.sub.2O, wherein a is from
about 2 to about 5; the sum of a and b is about 6; x is from about
1 to about 6; and a, b, and x may have non-integer values. More
specifically, aluminum chlorohydroxides referred to as "5/6 basic
chlorohydroxide" can be used, wherein a=5, and "2/3 basic
chlorohydroxide", wherein a=4. Processes for preparing aluminum
salts are disclosed in U.S. Pat. No. 3,887,692; U.S. Pat. No.
3,904,741; U.S. Pat. No. 4,359,456; and British Patent
Specification 2,048,229, the disclosures of which are incorporated
herein by reference for the purpose of describing processes for
preparing aluminum salts. Mixtures of aluminum salts are described
in British Patent Specification 1,347,950, which description is
also incorporated herein by reference. [0292] Zirconium salts for
use in the anhydrous antiperspirant stick compositions include
those which conform to the formula:
[0292] ZrO(OH).sub.2-aCl.sub.a.xH.sub.2O, wherein a is from about
1.5 to about 1.87; x is from about 1 to about 7; and a and x may
both have non-integer values. These zirconium salts are described
in Belgian Patent 825,146, Schmitz, issued Aug. 4, 1975, which
description is incorporated herein by reference. Zirconium salts
that additionally contain aluminum and glycine, commonly known as
"ZAG complexes," are believed to be especially beneficial. These
ZAG complexes contain aluminum chlorohydroxide and zirconyl hydroxy
chloride conforming to the above-described formulas. Such ZAG
complexes are described in U.S. Pat. No. 3,792,068; Great Britain
Patent Application 2,144,992; and U.S. Pat. No. 4,120,948,
disclosures of which are incorporated herein by reference for the
limited purpose of describing ZAG complexes. [0293] Also suitable
for use herein are enhanced efficacy aluminum-zirconium
chlorohydrex-amino acid which typically has the empirical
formula:
[0293] Al.sub.nZr(OH).sub.[3n+4-m(n+1)](Cl).sub.[m(n+1)]-AA.sub.q
where n is 2.0 to 10.0, preferably 3.0 to 8.0; m is about 0.48 to
about 1.11 (which corresponds to M:Cl approximately equal to
2.1-0.9), preferably about 0.56 to about 0.83 (which corresponds to
M:Cl approximately equal to 1.8-1.2); q is about 0.8 to about 4.0,
preferably about 1.0 to 2.0; and AA is an amino acid such as
glycine, alanine, valine, serine, leucine, isoleucine,
.beta.-alanine, cysteine, .beta.-amino-n-butyric acid, or
.gamma.-amino-n-butyric acid, preferably glycine. These salts also
generally have some water of hydration associated with them,
typically on the order of 1 to 5 moles per mole of salt (typically,
about 1% to about 16%, more typically about 4% to about 13% by
weight). These salts are generally referred to as
aluminum-zirconium trichlorohydrex or tetrachlorohydrex when the
Al:Zr ratio is between 2 and 6 and as aluminum-zirconium
pentachlorohydrex or octachlorohydrex when the Al:Zr ratio is
between 6 and 10. The term "aluminum-zirconium chlorohydrex" is
intended to embrace all of these forms. The preferred
aluminum-zirconium salt is aluminum-zirconium chlorohydrex-glycine.
Additional examples of suitable high efficacy antiperspirant
actives can include Aluminum Zirconium Pentachlorohydrex Glycine,
Aluminum Zirconium Octachlorohydrex Glycine, or a combination
thereof. These high efficacy actives are more fully described in
U.S. App. Pub. No. 2007/0003499 by Shen et al. filed Jun. 30,
2005.
[0294] Additional Chassis Ingredients [0295] Additional
Structurant--The antiperspirant composition can further comprise an
additional structurant. The additional structurant may be present
in an amount from 1% to about 10%, by weight of the composition.
The additional structurant(s) will likely be present at an amount
less than the primary structurant. Non-limiting examples of
suitable additional structurants include stearyl alcohol and other
fatty alcohols; hydrogenated castor wax (e.g., Castorwax MP80,
Castor Wax, etc.); hydrocarbon waxes include paraffin wax, beeswax,
carnauba, candelilla, spermaceti wax, ozokerite, ceresin,
baysberry, synthetic waxes such as Fisher-Tropsch waxes, and
microcrystalline wax; polyethylenes with molecular weight of 200 to
1000 daltons; and solid triglycerides; behenyl alcohol, or
combinations thereof. Other non-limiting examples of additional
structurants suitable for use herein are described in U.S. Pat. No.
5,976,514 and U.S. Pat. No. 5,891,424. [0296] Solvent--The
antiperspirant composition can comprise a solvent at concentrations
ranging from about 20% to about 80%, and more specifically from
about 30% to about 70%, by weight of the composition. The solvent
can be a volatile silicone which may be cyclic or linear. [0297]
"Volatile silicone" as used herein refers to those silicone
materials that have measurable vapor pressure under ambient
conditions. Non-limiting examples of suitable volatile silicones
are described in Todd et al., "Volatile Silicone Fluids for
Cosmetics", Cosmetics and Toiletries, 91:27-32 (1976), which
descriptions are incorporated herein by reference. The volatile
silicone can be a cyclic silicone having from 3 to 7, and more
specifically from 5 to 6, silicon atoms, and still more
specifically 5, like cyclopentasiloxane. These cyclic silicone
materials will generally have viscosities of less than about 10
centistokes at 25.degree. C. The volatile silicone can also be
linear, suitable volatile linear silicone materials for use in the
antiperspirant compositions include those represented by the
formula:
[0297] ##STR00003## wherein n is from 1 to 7, and more specifically
from 2 to 3. These linear silicone materials will generally have
viscosities of less than about 5 centistokes at 25.degree. C.
Specific examples of volatile silicone solvents suitable for use in
the antiperspirant compositions include, but are not limited to,
Cyclomethicone D-5; GE 7207 and GE 7158 (commercially available
from General Electric Co.); Dow Corning 344; Dow Corning 345; Dow
Corning 200; and DC1184 (commercially available from Dow Corning
Corp.); and SWS-03314 (commercially available from SWS Silicones).
[0298] Non-Volatile Organic Fluids--Non-volatile organic fluids may
be present, for example, in an amount of about 15% or less, by
weight of the composition. Non-limiting examples of nonvolatile
organic fluids include mineral oil, PPG-14 butyl ether, isopropyl
myristate, petrolatum, butyl stearate, cetyl octanoate, butyl
myristate, myristyl myristate, C12-15 alkylbenzoate (e.g.,
Finsolv.TM.), octyldodecanol, isostearyl isostearate, octododecyl
benzoate, isostearyl lactate, isostearyl palmitate, and isobutyl
stearate. [0299] Adjunct Ingredients--The anhydrous antiperspirant
compositions can further comprise any optional material that is
known for use in antiperspirant and deodorant compositions or other
personal care products, or which is otherwise suitable for topical
application to human skin. One example of optional materials are
clay mineral powders such as talc, mica, sericite, silica,
magnesium silicate, synthetic fluorphlogopite, calcium silicate,
aluminum silicate, bentonite and montomorillonite; pearl pigments
such as alumina, barium sulfate, calcium secondary phosphate,
calcium carbonate, titanium oxide, finely divided titanium oxide,
zirconium oxide, zinc oxide, hydroxy apatite, iron oxide, iron
titrate, ultramarine blue, Prussian blue, chromium oxide, chromium
hydroxide, cobalt oxide, cobalt titanate, titanium oxide coated
mica; organic powders such as polyester, polyethylene, polystyrene,
methyl methacrylate resin, cellulose, 12-nylon, 6-nylon,
styrene-acrylic acid copolymers, poly propylene, vinyl chloride
polymer, tetrafluoroethylene polymer, boron nitride, fish scale
guanine, laked tar color dyes, laked natural color dyes; and
combinations thereof. Talc, if used at higher levels can produce a
significant amount of white residue which has been found to be a
consumer negative for product acceptance. Therefore it is best to
limit the composition to less than 10%, less than about 8%, less
than about 6%, or less than about 3%, by weight of the composition.
Nonlimiting examples of other optional materials include
emulsifiers, distributing agents, antimicrobials, pharmaceutical or
other topical active, preservatives, surfactants, and so forth.
Examples of such optional materials are described in U.S. Pat. No.
4,049,792; U.S. Pat. No. 5,019,375; and U.S. Pat. No. 5,429,816;
which descriptions are incorporated herein by reference.
[0300] D. Soft Solid
[0301] Soft solid composition can comprise volatile silicone,
antiperspirant active, gellant, residue masking material, or
combinations thereof. In addition, soft solids generally have a
hardness value after dispensing of about 500 gram force or less.
[0302] Volatile Silicone Solvent--The soft solid can comprises a
volatile silicone solvent at concentrations ranging from about 20%
to about 80%, preferably from about 30% to about 70%, more
preferably from about 45% to about 70%, by weight of the
composition. The volatile silicone of the solvent may be cyclic or
linear. [0303] "Volatile silicone" as used herein refers to those
silicone materials which have measurable vapor pressure under
ambient conditions. Nonlimiting examples of suitable volatile
silicones are described in Todd et al., "Volatile Silicone Fluids
for Cosmetics", Cosmetics and Toiletries, 91:27-32 (1976), which
descriptions are incorporated herein by reference. Preferred
volatile silicone materials are those having from about 3 to about
7, preferably from about 4 to about 5, silicon atoms. Cyclic
volatile silicones are preferred for use in the antiperspirant
compositions herein, and include those represented by the
formula:
[0303] ##STR00004## wherein n is from about 3 to about 7,
preferably from about 4 to about 5, most preferably 5. These cyclic
silicone materials will generally have viscosities of less than
about 10 centistokes at 25.degree. C. Linear volatile silicone
materials suitable for use in the antiperspirant compositions
include those represented by the formula:
##STR00005## wherein n is from about 1 to about 7, preferably from
about 2 to about 3. These linear silicone materials will generally
have viscosities of less than about 5 centistokes at 25.degree. C.
Specific examples of volatile silicone solvents suitable for use in
the antiperspirant compositions include, but are not limited to,
Cyclomethicone D-5 (commercially available from G. E. Silicones),
Dow Corning 344, Dow Corning 345 and Dow Corning 200 (commercially
available from Dow Corning Corp.), GE 7207 and 7158 (commercially
available from General Electric Co.) and SWS-03314 (commercially
available from SWS Silicones Corp.). [0304] Gellant Material--The
soft solid can include a gellant material comprising fatty alcohols
having from about 20 to about 60 carbon atoms, or combinations
thereof, at concentrations ranging from about 0.1% to about 8% by
weight of the composition. The gellant material, when combined with
the volatile silicone solvent described hereinbefore, provides the
composition with a physically stable structure within which the
particulate antiperspirant materials are dispersed, and maintained
as such over an extended period of time. Specifically, the gellant
material can comprise saturated or unsaturated, substituted or
unsubstituted, fatty alcohols or mixtures of fatty alcohols having
from about 20 to about 60 carbons atoms, preferably from about 20
to about 40 carbon atoms. Preferred are combinations of the fatty
alcohols. The fatty alcohol gellants are preferably saturated,
unsubstituted monohydric alcohols or combinations thereof, which
have a melting point of at less than about 110.degree. C., more
preferably from about 60.degree. to about 110.degree. C., even more
preferably between about 100.degree. C. and 110.degree. C. [0305]
It has been found that this fatty alcohol-based gellant material,
when combined with volatile silicone solvents provides a stable
structure for maintaining a dispersion of particulate
antiperspirant material in a topical formulation without the
necessity of using conventional particulate thickening agents. This
gellant material is especially useful in maintaining the physical
stability of particulate dispersions containing higher
concentrations of volatile silicone solvents. [0306] It was also
found that penetration force values for the antiperspirant
compositions can be controlled by adjusting total fatty alcohol
concentrations. In controlling penetration force values in this
manner, there is no longer a need to use organic solvents or
thickening agents to control penetration force values, which
solvents or thickening agents often add cost to the formulation,
introduce additional compatibility issues, and often contribute
undesirable cosmetics such as prolonged stickiness, difficulty in
ease of spreading, increased dry-down times and reduced dry feel
after application. [0307] Specific concentrations of the gellant
materials can be selected according to the desired penetration
force value. For roll-on formulations having a penetration force
value of from about 20 gramforce to about 100 gramforce, gellant
material concentrations preferably range from about 0.1% to about
3%, preferably from about 1.5% to about 3%, by weight of the
antiperspirant composition. For other cream formulations, including
those formulations suitable for use in cream applicator devices,
which have a penetration force value of from about 100 gramforce to
about 500 gramforce, gellant material concentrations preferably
range from about 3% to about 8%, preferably from about 3% to about
6%, by weight of the antiperspirant composition. [0308] Specific
examples of fatty alcohol gellants for use in the antiperspirant
compositions that are commercially available include, but are not
limited to, Unilin.RTM. 425, Unilin.RTM. 350, Unilin.RTM.550 and
Unilin.RTM. 700 (supplied by Petrolite) [0309] Residue Masking
Material--The soft solid compositions can further comprise a
nonvolatile emollient as a residue masking material. Such materials
and their use in antiperspirant products are well known in the
antiperspirant art, and any such material may be incorporated into
the composition of the present invention, provided that such
optional material is compatible with the essential elements of the
composition, or does not unduly impair product performance or
cosmetics. Concentrations of the optional residue masking material
can range from about 0.1% to about 40%, preferably from about 1% to
about 10%, by weight of the antiperspirant composition. These
optional materials can be liquid at ambient temperatures, and can
be nonvolatile. The term "nonvolatile" as used in this context
refers to materials which have a boiling point under atmospheric
pressure of at least about 200.degree. C. Nonlimiting examples of
suitable residue masking materials for use in the antiperspirant
products include butyl stearate, diisopropyl adipate, petrolatum,
nonvolatile silicones, octyldodecanol, phenyl trimethicone,
isopropyl myristate, C12-15 ethanol benzoates and PPG-14 Butyl
Ether. Residue masking materials are described, for example, in
U.S. Pat. No. 4,985,238, which description is incorporated herein
by reference. [0310] Other Materials--The soft solid compositions
can further comprise one, or more, other materials which modify the
physical characteristics of the compositions or serve as additional
"active" components when deposited on the skin. Many such materials
are known in the antiperspirant art and can be used in the
antiperspirant compositions herein, provided that such optional
materials are compatible with the essential materials described
herein, or do not otherwise unduly impair product performance Non
limiting examples of materials can include active components such
as bacteriostats and fungiostats, and "non-active" components such
as colorants, perfumes, cosmetic powders, emulsifiers, chelants,
distributing agents, preservatives, and wash-off aids. Examples of
such optional materials are described in U.S. Pat. No. 4,049,792;
Canadian Patent 1,164,347; U.S. Pat. No. 5,019,375; and U.S. Pat.
No. 5,429,816; which descriptions are incorporated herein by
reference.
[0311] E. Aerosol
[0312] An aerosol composition can comprise a concentrate, a
propellant, or a combination thereof. Alcohol is a predominant
component of the concentrates provided herein. Useful alcohols
include C.sub.1-C.sub.3 alcohols, with the preferred alcohol being
ethanol. In certain examples, the alcohol is employed at a
concentration level of from at least about 40%, 50% or 55% to about
80%, by weight of the concentrate.
[0313] An antiperspirant active is dissolved in the alcohol, at a
level of from about 1% to about 15%, by weight of the concentrate.
Various antiperspirant actives can be employed, including, for
example, aluminum chloride, aluminum chlorohydrate, aluminum
chlorohydrex, aluminum chlorohydrex PG, aluminum chlorohydrex PEG,
aluminum dichlorohydrate, aluminum dichlorohydrex PG, aluminum
dichlorohydrex PEG, aluminum sesquichlorohydrate, aluminum
sesquichlorohydrex PG, aluminum sesquichlorohydrex PEG, aluminum
sulfate, aluminum zirconium octachlorohydrate, aluminum zirconium
octachlorohydrex GLY, aluminum zirconium pentachlorohydrate,
aluminum zirconium pentachlorohydrex GLY, aluminum zirconium
tetrachlorohydrate, aluminum zirconium trichlorohydrate, aluminum
zirconium tetrachlorohydrate GLY, and aluminum zirconium
trichlorohydrate GLY. In one example, aluminum chlorohydrex PG is
the chosen antiperspirant active.
[0314] The antiperspirant concentrates can also include an oil or a
mixture of two or more oils. Useful oils include, for example,
volatile silicone oils and non-volatile organic oils. "Volatile
silicone", as used herein, refers to those silicone materials that
have measurable vapor pressure under ambient conditions.
Non-limiting examples of suitable volatile silicones are described
in Todd et al., "Volatile Silicone Fluids for Cosmetics", Cosmetics
and Toiletries, 91:27-32 (1976). The volatile silicone can be a
cyclic silicone having from at least about 3 silicone atoms or from
at least about 5 silicone atoms but no more than about 7 silicone
atoms or no more than about 6 silicone atoms. For example, volatile
silicones can be used which conform to the formula:
##STR00006##
wherein n is from about 3 or from about 5 but no more than about 7
or no more than about 6. These volatile cyclic silicones generally
have a viscosity of less than about 10 centistokes at 25.degree. C.
Suitable volatile silicones for use herein include, but are not
limited to, Cyclomethicone D5 (commercially available from G. E.
Silicones); Dow Corning 344, and Dow Corning 345 (commercially
available from Dow Corning Corp.); and GE 7207, GE 7158 and
Silicone Fluids SF-1202 and SF-1173 (available from General
Electric Co.). SWS-03314, SWS-03400, F-222, F-223, F-250, F-251
(available from SWS Silicones Corp.); Volatile Silicones 7158,
7207, 7349 (available from Union Carbide); MASIL SF-V (available
from Mazer) and combinations thereof. Suitable volatile silicone
oils can also include linear silicone oils such as, for example,
DC200 (1 cSt), DC200 (0.65 cSt), and DC2-1184, all of which are
available from Dow Corning Corp. In certain examples, the volatile
silicone oil can have a viscosity of less than 10 centistokes at
25.degree. C.
[0315] Non-volatile organic, emollient oils can also be employed. A
representative, non-limiting list of emollient oils includes CETIOL
CC (dicaprylyl carbonate), CETIOL OE (dicaprylyl ether), CETIOL S
(diethylhexylcyclohexane), and CETIOL B (dibutyl adipate), all of
which are available from Cognis, and LEXFEEL 7 (neopentyl glycol
diheptanoate) from Inolex. In certain examples, the organic
emollient oils have a viscosity of less than 50 centistokes at
25.degree. C. The term "organic emollient oil" as used herein means
silicon-free emollient oils that are liquid at 25.degree. C., and
that are safe and light to skin and can be miscible with volatile
silicone oils (as described above) and the antiperspirant
active-alcohol solution in the concentration ranges described
below.
[0316] The oil or mixture of oils is generally included in the
concentrate formulas at a level of from about 5% to about 45%, by
weight of the concentrate. This viscosity ranges noted above in
connection with the different classes of oil can facilitate desired
spray rates and patterns, and can help minimize nozzle clogging. To
provide desired skin feel, minimal nozzle clogging, and good
concentrate stability, the ratio of alcohol to volatile silicone
oil is preferably greater than 1.0, 1.35, or 1.5. And in examples
having both a volatile silicone oil and an organic emollient oil,
the ratio of alcohol to total oil is preferably greater than or
equal to about 0.90. The oils in certain examples are miscible with
the alcohol and antiperspirant active solution. Although various
levels of miscibility are acceptable, the oils are preferably
miscible enough with the alcohol and antiperspirant active solution
to yield a concentrate having a clear appearance.
[0317] The antiperspirant compositions can also include
residue-masking agents and propellants as discussed above.
[0318] Additional Consumer Product Ingredients/Adjunct
Materials
[0319] While not essential for the purposes of the present
invention, the non-limiting list of consumer product
ingredients/adjuncts illustrated hereinafter are suitable for use
in the instant compositions and may be desirably incorporated in
certain aspects of the invention, for example to assist or enhance
cleaning 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. 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 fabric treatment operation for which it is to be used.
[0320] Suitable adjunct materials include, but are not limited to,
surfactants, builders, chelating agents, dye transfer inhibiting
agents, dispersants, enzymes, and enzyme stabilizers, catalytic
materials, bleach activators, hydrogen peroxide, sources of
hydrogen peroxide, preformed peracids, polymeric dispersing agents,
clay soil removal/anti-redeposition agents, brighteners, suds
suppressors, dyes, hueing dyes, perfumes, perfume delivery systems,
structure elasticizing agents, carriers, structurants, hydrotropes,
processing aids, solvents, pigments and/or fabric softener actives
and clothes softening agents compatible with detergents,
anti-bacterials, anti-microbials, and anti-fungals.
[0321] As stated, the adjunct ingredients are not essential to
Applicants' compositions. Thus, certain aspects of Applicants'
compositions do not contain one or more of the following adjuncts
materials: surfactants, builders, chelating agents, dye transfer
inhibiting agents, dispersants, enzymes, and enzyme stabilizers,
catalytic materials, bleach activators, hydrogen peroxide, sources
of hydrogen peroxide, preformed peracids, polymeric dispersing
agents, clay soil removal/anti-redeposition agents, brighteners,
suds suppressors, dyes, hueing dyes, perfumes, perfume delivery
systems structure elasticizing agents, carriers, hydrotropes,
processing aids, solvents, pigments and/or fabric softener actives,
anti-bacterial/microbial. However, when one or more adjuncts are
present, such one or more adjuncts may be present as detailed
below.
[0322] Rheology Modifier--
[0323] The liquid compositions of the present invention may
comprise a rheology modifier. The rheology modifier may be selected
from the group consisting of non-polymeric crystalline,
hydroxy-functional materials, polymeric rheology modifiers which
impart shear thinning characteristics to the aqueous liquid matrix
of the composition. In one aspect, such rheology modifiers impart
to the aqueous liquid composition a high shear viscosity, at 20
sec.sup.-1 shear rate and at 21.degree. C., of from 1 to 7000 cps
and a viscosity at low shear (0.5 sec.sup.-1 shear rate at
21.degree. C.) of greater than 1000 cps, or even 1000 cps to
200,000 cps. In one aspect, for cleaning and treatment
compositions, such rheology modifiers impart to the aqueous liquid
composition a high shear viscosity, at 20 sec.sup.-1 and at
21.degree. C., of from 50 to 3000 cps and a viscosity at low shear
(0.5 sec.sup.-1 shear rate at 21.degree. C.) of greater than 1000
cps, or even 1000 cps to 200,000 cps. Viscosity according to the
present invention is measured using an AR 2000 rheometer from TA
instruments using a plate steel spindle having a plate diameter of
40 mm and a gap size of 500 .mu.m. The high shear viscosity at 20
sec.sup.-1 and low shear viscosity at 0.5 sec.sup.-1 can be
obtained from a logarithmic shear rate sweep from 0.1 sec.sup.-1 to
25 sec.sup.-1 in 3 minutes time at 21.degree. C. Crystalline
hydroxyl functional materials are rheology modifiers which form
thread-like structuring systems throughout the matrix of the
composition upon in situ crystallization in the matrix. Polymeric
rheology modifiers are preferably selected from polyacrylates,
polymeric gums, other non-gum polysaccharides, and combinations of
these polymeric materials. Generally the rheology modifier will
comprise from 0.01% to 1% by weight, preferably from 0.05% to 0.75%
by weight, more preferably from 0.1% to 0.5% by weight, of the
compositions herein.
[0324] Structuring agents which are especially useful in the
compositions of the present invention may comprise non-polymeric
(except for conventional alkoxylation), crystalline
hydroxy-functional materials which can form thread-like structuring
systems throughout the liquid matrix when they are crystallized
within the matrix in situ. Such materials can be generally
characterized as crystalline, hydroxyl-containing fatty acids,
fatty esters or fatty waxes. In one aspect, rheology modifiers
include crystalline, hydroxyl-containing rheology modifiers include
castor oil and its derivatives. In one aspect, rheology modifiers
include hydrogenated castor oil derivatives such as hydrogenated
castor oil and hydrogenated castor wax. Commercially available,
castor oil-based, crystalline, hydroxyl-containing rheology
modifiers include THIXCIN.TM. from Rheox, Inc. (now Elementis).
[0325] Other types of rheology modifiers, besides the
non-polymeric, crystalline, hydroxyl-containing rheology modifiers
described heretofore, may be utilized in the liquid detergent
compositions herein. Polymeric materials which provide
shear-thinning characteristics to the aqueous liquid matrix may
also be employed. Suitable polymeric rheology modifiers include
those of the polyacrylate, polysaccharide or polysaccharide
derivative type. Polysaccharide derivatives typically used as
rheology modifiers comprise polymeric gum materials. Such gums
include pectine, alginate, arabinogalactan (gum Arabic),
carrageenan, gellan gum, xanthan gum and guar gum. If polymeric
rheology modifiers are employed herein, a preferred material of
this type is gellan gum. Gellan gum is a heteropolysaccharide
prepared by fermentation of Pseudomonaselodea ATCC 31461. Gellan
gum is commercially marketed by CP Kelco U.S., Inc. under the
KELCOGEL tradename.
[0326] A further alternative and suitable rheology modifier include
a combination of a solvent and a polycarboxylate polymer. More
specifically the solvent may be an alkylene glycol. In one aspect,
the solvent may comprise dipropylene glycol. In one aspect, the
polycarboxylate polymer may comprise a polyacrylate,
polymethacrylate or mixtures thereof. In one aspect, solvent may be
present, based on total composition weight, at a level of from 0.5%
to 15%, or from 2% to 9% of the composition. In one aspect,
polycarboxylate polymer may be present, based on total composition
weight, at a level of from 0.1% to 10%, or from 2% to 5%. In one
aspect, the solvent component may comprise mixture of dipropylene
glycol and 1,2-propanediol. In one aspect, the ratio of dipropylene
glycol to 1,2-propanediol may be 3:1 to 1:3, or even 1:1. In one
aspect, the polyacrylate may comprise a copolymer of unsaturated
mono- or di-carbonic acid and C.sub.1-C.sub.30 alkyl ester of the
(meth) acrylic acid. In another aspect, the rheology modifier may
comprise a polyacrylate of unsaturated mono- or di-carbonic acid
and C.sub.1-C.sub.30 alkyl ester of the (meth) acrylic acid. Such
copolymers are available from Noveon Inc under the tradename
Carbopol Aqua 30.RTM..
[0327] In the absence of rheology modifier and in order to impart
the desired shear thinning characteristics to the liquid
composition, the liquid composition can be internally structured
through surfactant phase chemistry or gel phases.
[0328] Hueing Dye--
[0329] The liquid laundry detergent composition may comprise a
hueing dye. The hueing dyes employed in the present laundry care
compositions may comprise polymeric or non-polymeric dyes, organic
or inorganic pigments, or mixtures thereof. Preferably the hueing
dye comprises a polymeric dye, comprising a chromophore constituent
and a polymeric constituent. The chromophore constituent is
characterized in that it absorbs light in the wavelength range of
blue, red, violet, purple, or combinations thereof upon exposure to
light. In one aspect, the chromophore constituent exhibits an
absorbance spectrum maximum from about 520 nanometers to about 640
nanometers in water and/or methanol, and in another aspect, from
about 560 nanometers to about 610 nanometers in water and/or
methanol.
[0330] Although any suitable chromophore may be used, the dye
chromophore is preferably selected from benzodifuranes, methine,
triphenylmethanes, napthalimides, pyrazole, naptho-quinone,
anthraquinone, azo, oxazine, azine, xanthene, triphenodioxazine and
phthalocyanine dye chromophores. Mono and di-azo dye chromophores
are may be preferred.
[0331] The hueing dye may comprise a dye polymer comprising a
chromophore covalently bound to one or more of at least three
consecutive repeat units. It should be understood that the repeat
units themselves do not need to comprise a chromophore. The dye
polymer may comprise at least 5, or at least 10, or even at least
20 consecutive repeat units. The repeat unit can be derived from an
organic ester such as phenyl dicarboxylate in combination with an
oxyalkyleneoxy and a polyoxyalkyleneoxy. Repeat units can be
derived from alkenes, epoxides, aziridine, carbohydrate including
the units that comprise modified celluloses such as
hydroxyalkylcellulose; hydroxypropyl cellulose; hydroxypropyl
methylcellulose; hydroxybutyl cellulose; and, hydroxybutyl
methylcellulose or mixtures thereof. The repeat units may be
derived from alkenes, or epoxides or mixtures thereof. The repeat
units may be C.sub.2-C.sub.4 alkyleneoxy groups, sometimes called
alkoxy groups, preferably derived from C.sub.2-C.sub.4 alkylene
oxide. The repeat units may be C.sub.2-C.sub.4 alkoxy groups,
preferably ethoxy groups. For the purposes of the present
invention, the at least three consecutive repeat units form a
polymeric constituent. The polymeric constituent may be covalently
bound to the chromophore group, directly or indirectly via a
linking group. Examples of suitable polymeric constituents include
polyoxyalkylene chains having multiple repeating units. In one
aspect, the polymeric constituents include polyoxyalkylene chains
having from 2 to about 30 repeating units, from 2 to about 20
repeating units, from 2 to about 10 repeating units or even from
about 3 or 4 to about 6 repeating units. Non-limiting examples of
polyoxyalkylene chains include ethylene oxide, propylene oxide,
glycidol oxide, butylene oxide and mixtures thereof.
[0332] Surfactants--
[0333] The compositions according to the present invention may
comprise a surfactant or surfactant system wherein the surfactant
can be selected from nonionic surfactants, anionic surfactants,
cationic surfactants, ampholytic surfactants, zwitterionic
surfactants, semi-polar nonionic surfactants and mixtures thereof.
The surfactant is typically present at a level of from about 0.1%
to about 60%, from about 1% to about 50% or even from about 5% to
about 40% by weight of the subject composition.
[0334] Chelating Agents--
[0335] The compositions herein may contain a chelating agent.
Suitable chelating agents include copper, iron and/or manganese
chelating agents and mixtures thereof. When a chelating agent is
used, the composition may comprise from about 0.1% to about 15% or
even from about 3.0% to about 10% chelating agent by weight of the
subject composition.
[0336] Dye Transfer Inhibiting Agents--
[0337] The compositions of the present invention may also include
one or more dye transfer inhibiting agents. Suitable polymeric dye
transfer inhibiting agents include, but are not limited to,
polyvinylpyrrolidone polymers, polyamine N-oxide polymers,
copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.
When present in a subject composition, the dye transfer inhibiting
agents may be present at levels from about 0.0001% to about 10%,
from about 0.01% to about 5% or even from about 0.1% to about 3% by
weight of the composition.
[0338] Dispersants--
[0339] The compositions of the present invention can also contain
dispersants. Suitable water-soluble organic materials include the
homo- or co-polymeric acids or their salts, in which the
polycarboxylic acid comprises at least two carboxyl radicals
separated from each other by not more than two carbon atoms.
[0340] Perfumes--
[0341] The consumer product may comprise, either in neat form or
via a delivery system, a perfume raw materials selected from the
group consisting of perfumes such as 3-(4-t-butylphenyl)-2-methyl
propanal, 3-(4-t-butylphenyl)-propanal,
3-(4-isopropylphenyl)-2-methylpropanal,
3-(3,4-methylenedioxyphenyl)-2-methylpropanal, and
2,6-dimethyl-5-heptenal, .alpha.-damascone, .beta.-damascone,
.DELTA.-damascone, .gamma.-damascenone,
6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone,
methyl-7,3-dihydro-2H-1,5-benzodioxepine-3-one,
2-[2-(4-methyl-3-cyclohexenyl-1-yl)propyl]cyclopentan-2-one,
2-sec-butylcyclohexanone, and .beta.-dihydro ionone, linalool,
ethyllinalool, tetrahydrolinalool, and dihydromyrcenol.
[0342] Additional Perfume Delivery Technologies--
[0343] The compositions of the present invention may comprise one
or more perfume delivery technologies that stabilize and enhance
the deposition and release of perfume ingredients from treated
substrate. Such perfume delivery technologies can also be used to
increase the longevity of perfume release from the treated
substrate. Perfume delivery technologies, methods of making certain
perfume delivery technologies and the uses of such perfume delivery
technologies are disclosed in US 2007/0275866 A1.
[0344] In one aspect, the compositions of the present invention may
comprise from about 0.001% to about 20%, preferably from about
0.01% to about 10%, more preferably from about 0.05% to about 5%,
most preferably from about 0.1% to about 0.5% by weight of the
perfume delivery technology. In one aspect, said perfume delivery
technologies may be selected from the group consisting of:
pro-perfumes, polymer particles, functionalized silicones, polymer
assisted delivery, molecule assisted delivery, fiber assisted
delivery, amine assisted delivery, cyclodextrins, starch
encapsulated accord, zeolite and inorganic carrier, additional
perfume microcapsules, and mixtures thereof:
[0345] In one aspect, said perfume delivery technology may comprise
an additional encapsulated perfume such as additional perfume
microcapsules formed by at least partially surrounding a benefit
agent with a wall material. Said benefit agent may include
materials selected from the group consisting of perfumes such as
3-(4-t-butylphenyl)-2-methyl propanal,
3-(4-t-butylphenyl)-propanal, 3-(4-isopropylphenyl)-2-methylprop
anal, 3-(3,4-methylenedioxyphenyl)-2-methylpropanal, and
2,6-dimethyl-5-heptenal, a-damascone, B-damascone, A-damascone,
.gamma.-damascenone, 6,7-dihydro-1,1,2,3,3-pentamethyl-4
(5H)-indanone, methyl-7,3-dihydro-2H-1,5-benzodioxepine-3-one,
2-[2-(4-methyl-3-cyclohexenyl-1-yl)propyl]cyclopentan-2-one,
2-sec-butylcyclohexanone, and B-dihydro ionone, linalool,
ethyllinalool, tetrahydrolinalool, and dihydromyrcenol. Suitable
perfume materials can be obtained from Givaudan Corp. of Mount
Olive, N.J., USA, International Flavors & Fragrances Corp. of
South Brunswick, N.J., USA, or Quest Corp. of Naarden, Netherlands.
In one aspect, the microcapsule wall material may comprise:
melamine, polyacrylamide, silicones, silica, polystyrene, polyurea,
polyurethanes, polyacrylate based materials, gelatin, styrene malic
anhydride, polyamides, and mixtures thereof. In one aspect, said
melamine wall material may comprise melamine crosslinked with
formaldehyde, melamine-dimethoxyethanol crosslinked with
formaldehyde, and mixtures thereof. In one aspect, said polystyrene
wall material may comprise polyestyrene cross-linked with
divinylbenzene. In one aspect, said polyurea wall material may
comprise urea crosslinked with formaldehyde, urea crosslinked with
gluteraldehyde, and mixtures thereof. In one aspect, said
polyacrylate based materials may comprise polyacrylate formed from
methylmethacrylate/dimethylaminomethyl methacrylate, polyacrylate
formed from amine acrylate and/or methacrylate and strong acid,
polyacrylate formed from carboxylic acid acrylate and/or
methacrylate monomer and strong base, polyacrylate formed from an
amine acrylate and/or methacrylate monomer and a carboxylic acid
acrylate and/or carboxylic acid methacrylate monomer, and mixtures
thereof. In one aspect, the perfume microcapsule may be coated with
a deposition aid, a cationic polymer, a non-ionic polymer, an
anionic polymer, or mixtures thereof. Suitable polymers may be
selected from the group consisting of: polyvinylformaldehyde,
partially hydroxylated polyvinylformaldehyde, polyvinylamine,
polyethyleneimine, ethoxylated polyethyleneimine, polyvinylalcohol,
polyacrylates, and combinations thereof. In one aspect, the
microcapsule may be a perfume microcapsule. In one aspect, one or
more types of microcapsules, for example two microcapsules types
having different benefit agents may be used.
[0346] In one aspect, said perfume delivery technology may comprise
an amine reaction product (ARP) or a thio reaction product. One may
also use "reactive" polymeric amines and or polymeric thiols in
which the amine and/or thiol functionality is pre-reacted with one
or more PRMs to form a reaction product. Typically the reactive
amines are primary and/or secondary amines, and may be part of a
polymer or a monomer (non-polymer). Such ARPs may also be mixed
with additional PRMs to provide benefits of polymer-assisted
delivery and/or amine-assisted delivery. Non-limiting examples of
polymeric amines include polymers based on polyalkylimines, such as
polyethyleneimine (PEI), or polyvinylamine (PVAm). Non-limiting
examples of monomeric (non-polymeric) amines include hydroxyl
amines, such as 2-aminoethanol and its alkyl substituted
derivatives, and aromatic amines such as anthranilates. The ARPs
may be premixed with perfume or added separately in leave-on or
rinse-off applications. In another aspect, a material that contains
a heteroatom other than nitrogen and/or sulfur, for example oxygen,
phosphorus or selenium, may be used as an alternative to amine
compounds. In yet another aspect, the aforementioned alternative
compounds can be used in combination with amine compounds. In yet
another aspect, a single molecule may comprise an amine moiety and
one or more of the alternative heteroatom moieties, for example,
thiols, phosphines and selenols. The benefit may include improved
delivery of perfume as well as controlled perfume release. Suitable
ARPs as well as methods of making same can be found in USPA
2005/0003980 A1 and U.S. Pat. No. 6,413,920 B1.
[0347] Suitable Fabric Softening Actives
[0348] The fluid fabric enhancer compositions disclosed herein
comprise a fabric softening active ("FSA"). Suitable fabric
softening actives, include, but are not limited to, materials
selected from the group consisting of quaternary ammonium
compounds, amines, fatty esters, sucrose esters, silicones,
dispersible polyolefins, clays, polysaccharides, fatty acids,
softening oils, polymer latexes and mixtures thereof.
[0349] Non-limiting examples of water insoluble fabric care benefit
agents include dispersible polyethylene and polymer latexes. These
agents can be in the form of emulsions, latexes, dispersions,
suspensions, and the like. In one aspect, they are in the form of
an emulsion or a latex. Dispersible polyethylenes and polymer
latexes can have a wide range of particle size diameters
(.chi..sub.50) including but not limited to from about 1 nm to
about 100 .mu.m; alternatively from about 10 nm to about 10 .mu.m.
As such, the particle sizes of dispersible polyethylenes and
polymer latexes are generally, but without limitation, smaller than
silicones or other fatty oils.
[0350] Generally, any surfactant suitable for making polymer
emulsions or emulsion polymerizations of polymer latexes can be
used to make the water insoluble fabric care benefit agents of the
present invention. Suitable surfactants consist of emulsifiers for
polymer emulsions and latexes, dispersing agents for polymer
dispersions and suspension agents for polymer suspensions. Suitable
surfactants include anionic, cationic, and nonionic surfactants, or
combinations thereof. In one aspect, such surfactants are nonionic
and/or anionic surfactants. In one aspect, the ratio of surfactant
to polymer in the water insoluble fabric care benefit agent is
about 1:100 to about 1:2; alternatively from about 1:50 to about
1:5, respectively. Suitable water insoluble fabric care benefit
agents include but are not limited to the examples described
below.
[0351] Quats--Suitable quats include but are not limited to,
materials selected from the group consisting of ester quats, amide
quats, imidazoline quats, alkyl quats, amidoester quats and
mixtures thereof. Suitable ester quats include but are not limited
to, materials selected from the group consisting of monoester
quats, diester quats, triester quats and mixtures thereof. In one
aspect, a suitable ester quat is
bis-(2-hydroxypropyl)-dimethylammonium methylsulfate fatty acid
ester having a molar ratio of fatty acid moieties to amine moieties
of from 1.85 to 1.99, an average chain length of the fatty acid
moieties of from 16 to 18 carbon atoms and an iodine value of the
fatty acid moieties, calculated for the free fatty acid, which has
an Iodine Value of between 0-140, preferably 5-100, more preferably
10-80, even more preferably 15-70, even more preferably 18-55, most
preferably 18-25. When a soft tallow quaternary ammonium compound
softener is used, most preferably range is 25-60. In one aspect,
the cis-trans-ratio of double bonds of unsaturated fatty acid
moieties of the bis (2 hydroxypropyl)-dimethylammonium
methylsulfate fatty acid ester is from 55:45 to 75:25,
respectively. Suitable amide quats include but are not limited to,
materials selected from the group consisting of monoamide quats,
diamide quats and mixtures thereof. Suitable alkyl quats include
but are not limited to, materials selected from the group
consisting of mono alkyl quats, dialkyl quats quats, trialkyl
quats, tetraalkyl quats and mixtures thereof.
[0352] Amines--Suitable amines include but are not limited to,
materials selected from the group consisting of amidoesteramines,
amidoamines, imidazoline amines, alkyl amines, amidoester amines
and mixtures thereof. Suitable ester amines include but are not
limited to, materials selected from the group consisting of
monoester amines, diester amines, triester amines and mixtures
thereof. Suitable amido quats include but are not limited to,
materials selected from the group consisting of monoamido amines,
diamido amines and mixtures thereof. Suitable alkyl amines include
but are not limited to, materials selected from the group
consisting of mono alkylamines, dialkyl amines quats, trialkyl
amines, and mixtures thereof.
[0353] Silicone--
[0354] In one embodiment, the fabric softening composition
comprises a silicone. Suitable levels of silicone may comprise from
about 0.1% to about 70%, alternatively from about 0.3% to about
40%, alternatively from about 0.5% to about 30%, alternatively from
about 1% to about 20% by weight of the composition. Useful
silicones can be any silicone comprising compound. In one
embodiment, the silicone polymer is selected from the group
consisting of cyclic silicones, polydimethylsiloxanes,
aminosilicones, cationic silicones, silicone polyethers, silicone
resins, silicone urethanes, and mixtures thereof. In one
embodiment, the silicone is a polydialkylsilicone, alternatively a
polydimethyl silicone (polydimethyl siloxane or "PDMS"), or a
derivative thereof. In another embodiment, the silicone is chosen
from an aminofunctional silicone, amino-polyether silicone,
alkyloxylated silicone, cationic silicone, ethoxylated silicone,
propoxylated silicone, ethoxylated/propoxylated silicone,
quaternary silicone, or combinations thereof.
[0355] In another embodiment, the silicone may be chosen from a
random or blocky organosilicone polymer having the following
formula:
[R.sub.1R.sub.2R.sub.3SiO.sub.1/2].sub.(j+2)[(R.sub.4Si(X--Z)O.sub.2/2].-
sub.k[R.sub.4R.sub.4SiO.sub.2/2].sub.m[R.sub.4SiO.sub.3/2].sub.j
wherein:
[0356] j is an integer from 0 to about 98; in one aspect j is an
integer from 0 to about 48; in one aspect, j is 0;
[0357] k is an integer from 0 to about 200, in one aspect k is an
integer from 0 to about 50;
[0358] when k=0, at least one of R.sub.1, R.sub.2 or R.sub.3 is
--X--Z;
[0359] m is an integer from 4 to about 5,000; in one aspect m is an
integer from about 10 to about 4,000; in another aspect m is an
integer from about 50 to about 2,000;
[0360] R.sub.1, R.sub.2 and R.sub.3 are each independently selected
from the group consisting of H, OH, C.sub.1-C.sub.32 alkyl,
C.sub.1-C.sub.32 substituted alkyl, C.sub.5-C.sub.32 or
C.sub.6-C.sub.32 aryl, C.sub.5-C.sub.32 or C.sub.6-C.sub.32
substituted aryl, C.sub.6-C.sub.32 alkylaryl, C.sub.6-C.sub.32
substituted alkylaryl, C.sub.1-C.sub.32 alkoxy, C.sub.1-C.sub.32
substituted alkoxy and X--Z;
[0361] each R.sub.4 is independently selected from the group
consisting of H, OH, C.sub.1-C.sub.32 alkyl, C.sub.1-C.sub.32
substituted alkyl, C.sub.5-C.sub.32 or C.sub.6-C.sub.32 aryl,
C.sub.5-C.sub.32 or C.sub.6-C.sub.32 substituted aryl,
C.sub.6-C.sub.32 alkylaryl, C.sub.6-C.sub.32 substituted alkylaryl,
C.sub.1-C.sub.32 alkoxy and C.sub.1-C.sub.32 substituted alkoxy;
each X in said alkyl siloxane polymer comprises a substituted or
unsubsitituted divalent alkylene radical comprising 2-12 carbon
atoms, in one aspect each divalent alkylene radical is
independently selected from the group consisting of
--(CH.sub.2).sub.s-- wherein s is an integer from about 2 to about
8, from about 2 to about 4; in one aspect, each X in said alkyl
siloxane polymer comprises a substituted divalent alkylene radical
selected from the group consisting of:
--CH.sub.2--CH(OH)--CH.sub.2--; --CH.sub.2--CH.sub.2--CH(OH)--;
and
##STR00007##
[0362] each Z is selected independently from the group consisting
of
##STR00008##
with the proviso that when Z is a quat, Q cannot be an amide,
imine, or urea moiety and if Q is an amide, imine, or urea moiety,
then any additional Q bonded to the same nitrogen as said amide,
imine, or urea moiety must be H or a C.sub.1-C.sub.6 alkyl.
[0363] In one aspect, said additional Q is H. For Z, A.sup.n- is a
suitable charge balancing anion. In one aspect A.sup.n- is selected
from the group consisting of Cl.sup.-, Br.sup.-, I.sup.-,
methylsulfate, toluene sulfonate, carboxylate and phosphate; and at
least one Q in said organosilicone is independently selected from
--CH.sub.2--CH(OH)--CH.sub.2--R.sub.5;
##STR00009##
and each additional Q in said organosilicone is independently
selected from the group comprising of H, C.sub.1-C.sub.32 alkyl,
C.sub.1-C.sub.32 substituted alkyl, C.sub.5-C.sub.32 or
C.sub.6-C.sub.32 aryl, C.sub.5-C.sub.32 or C.sub.6-C.sub.32
substituted aryl, C.sub.6-C.sub.32 alkylaryl, C.sub.6-C.sub.32
substituted alkylaryl, --CH.sub.2--CH(OH)--CH.sub.2--R.sub.5;
##STR00010##
[0364] wherein each R.sub.5 is independently selected from the
group consisting of H, C.sub.1-C.sub.32 alkyl, C.sub.1-C.sub.32
substituted alkyl, C.sub.5-C.sub.32 or C.sub.6-C.sub.32 aryl,
C.sub.5-C.sub.32 or C.sub.6-C.sub.32 substituted aryl,
C.sub.6-C.sub.32 alkylaryl, C.sub.6-C.sub.32 substituted alkylaryl,
--(CHR.sub.6--CHR.sub.6--O--).sub.w-L and a siloxyl residue;
[0365] each R.sub.6 is independently selected from H,
C.sub.1-C.sub.18 alkyl
[0366] each L is independently selected from --C(O)--R.sub.7 or
R.sub.7;
[0367] w is an integer from 0 to about 500, in one aspect w is an
integer from about 1 to about 200; in one aspect w is an integer
from about 1 to about 50;
[0368] each R.sub.7 is selected independently from the group
consisting of H; C.sub.1-C.sub.32 alkyl; C.sub.1-C.sub.32
substituted alkyl, C.sub.5-C.sub.32 or C.sub.6-C.sub.32 aryl,
C.sub.5-C.sub.32 or C.sub.6-C.sub.32 substituted aryl,
C.sub.6-C.sub.32 alkylaryl; C.sub.6-C.sub.32 substituted alkylaryl
and a siloxyl residue;
[0369] each T is independently selected from H, and
##STR00011##
and [0370] wherein each v in said organosilicone is an integer from
1 to about 10, in one aspect, v is an integer from 1 to about 5 and
the sum of all v indices in each Q in the said organosilicone is an
integer from 1 to about 30 or from 1 to about 20 or even from 1 to
about 10.
[0371] In another embodiment, the silicone may be chosen from a
random or blocky organosilicone polymer having the following
formula:
[R.sub.1R.sub.2R.sub.3SiO.sub.1/2].sub.(j+2)[(R.sub.4Si(X--Z)O.sub.2/2].-
sub.k[R.sub.4R.sub.4SiO.sub.2/2].sub.m[R.sub.4SiO.sub.3/2].sub.j
[0372] wherein
[0373] j is an integer from 0 to about 98; in one aspect j is an
integer from 0 to about 48; in one aspect, j is 0;
[0374] k is an integer from 0 to about 200; when k=0, at least one
of R.sub.1, R.sub.2 or R.sub.3=--X--Z, in one aspect, k is an
integer from 0 to about 50
[0375] m is an integer from 4 to about 5,000; in one aspect m is an
integer from about 10 to about 4,000; in another aspect m is an
integer from about 50 to about 2,000;
[0376] R.sub.1, R.sub.2 and R.sub.3 are each independently selected
from the group consisting of H, OH, C.sub.1-C.sub.32 alkyl,
C.sub.1-C.sub.32 substituted alkyl, C.sub.5-C.sub.32 or
C.sub.6-C.sub.32 aryl, C.sub.5-C.sub.32 or C.sub.6-C.sub.32
substituted aryl, C.sub.6-C.sub.32 alkylaryl, C.sub.6-C.sub.32
substituted alkylaryl, C.sub.1-C.sub.32 alkoxy, C.sub.1-C.sub.32
substituted alkoxy and X--Z;
[0377] each R.sub.4 is independently selected from the group
consisting of H, OH, C.sub.1-C.sub.32 alkyl, C.sub.1-C.sub.32
substituted alkyl, C.sub.5-C.sub.32 or C.sub.6-C.sub.32 aryl,
C.sub.5-C.sub.32 or C.sub.6-C.sub.32 substituted aryl,
C.sub.6-C.sub.32 alkylaryl, C.sub.6-C.sub.32 substituted alkylaryl,
C.sub.1-C.sub.32 alkoxy and C.sub.1-C.sub.32 substituted
alkoxy;
[0378] each X comprises of a substituted or unsubstituted divalent
alkylene radical comprising 2-12 carbon atoms; in one aspect each X
is independently selected from the group consisting of
--(CH.sub.2).sub.s--O--; --CH.sub.2--CH(OH)--CH.sub.2--O--;
##STR00012##
wherein each s independently is an integer from about 2 to about 8,
in one aspect s is an integer from about 2 to about 4;
[0379] At least one Z in the said organosiloxane is selected from
the group consisting of R.sub.5;
##STR00013##
provided that when X is
##STR00014##
then Z=--OR.sub.5 or
##STR00015##
[0380] wherein A.sup.- is a suitable charge balancing anion. In one
aspect A.sup.- is selected from the group consisting of Cl.sup.-,
Br.sup.-, I.sup.-, methylsulfate, toluene sulfonate, carboxylate
and phosphate and each additional Z in said organosilicone is
independently selected from the group comprising of H,
C.sub.1-C.sub.32 alkyl, C.sub.1-C.sub.32 substituted alkyl,
C.sub.5-C.sub.32 or C.sub.6-C.sub.32 aryl, C.sub.5-C.sub.32 or
C.sub.6-C.sub.32 substituted aryl, C.sub.6-C.sub.32 alkylaryl,
C.sub.6-C.sub.32 substituted alkylaryl, R.sub.5,
##STR00016##
--C(R.sub.5).sub.2O--R.sub.5; --C(R.sub.5).sub.2S--R.sub.5 and
##STR00017##
provided that when X is
##STR00018##
then Z=--OR.sub.5 or
##STR00019##
[0381] each R.sub.5 is independently selected from the group
consisting of H; C.sub.1-C.sub.32 alkyl; C.sub.1-C.sub.32
substituted alkyl, C.sub.5-C.sub.32 or C.sub.6-C.sub.32 aryl,
C.sub.5-C.sub.32 or C.sub.6-C.sub.32 substituted aryl or
C.sub.6-C.sub.32 alkylaryl, or C.sub.6-C.sub.32 substituted
alkylaryl,
--(CHR.sub.6--CHR.sub.6--O--).sub.w--CHR.sub.6--CHR.sub.6-L and
siloxyl residue wherein each L is independently selected from
--O--C(O)--R.sub.7 or --O--R.sub.7;
##STR00020##
[0382] w is an integer from 0 to about 500, in one aspect w is an
integer from 0 to about 200, one aspect w is an integer from 0 to
about 50;
[0383] each R.sub.6 is independently selected from H or
C.sub.1-C.sub.18 alkyl;
[0384] each R.sub.7 is independently selected from the group
consisting of H; C.sub.1-C.sub.32 alkyl; C.sub.1-C.sub.32
substituted alkyl, C.sub.5-C.sub.32 or C.sub.6-C.sub.32 aryl,
C.sub.5-C.sub.32 or C.sub.6-C.sub.32 substituted aryl,
C.sub.6-C.sub.32 alkylaryl, and C.sub.6-C.sub.32 substituted aryl,
and a siloxyl residue;
[0385] each T is independently selected from H;
##STR00021##
[0386] wherein each v in said organosilicone is an integer from 1
to about 10, in one aspect, v is an integer from 1 to about 5 and
the sum of all v indices in each Z in the said organosilicone is an
integer from 1 to about 30 or from 1 to about 20 or even from 1 to
about 10.
[0387] In one embodiment, the silicone is one comprising a
relatively high molecular weight. A suitable way to describe the
molecular weight of a silicone includes describing its viscosity. A
high molecular weight silicone is one having a viscosity of from
about 10 cSt to about 3,000,000 cSt, or from about 100 cSt to about
1,000,000 cSt, or from about 1,000 cSt to about 600,000 cSt, or
even from about 6,000 cSt to about 300,000 cSt.
[0388] In one embodiment, the silicone comprises a blocky cationic
organopolysiloxane having the formula:
M.sub.wD.sub.xT.sub.yQ.sub.z
wherein:
[0389] M=[SiR.sub.1R.sub.2R.sub.3O.sub.1/2],
[SiR.sub.1R.sub.2G.sub.1O.sub.1/2],
[SiR.sub.1G.sub.1G.sub.2O.sub.1/2],
[SiG.sub.1G.sub.2G.sub.3O.sub.1/2], or combinations thereof;
[0390] D=[SiR.sub.1R.sub.2O.sub.2/2], [SiR.sub.1G.sub.1O.sub.2/2],
[SiG.sub.1G.sub.2O.sub.2/2] or combinations thereof;
[0391] T=[SiR.sub.1O.sub.3/2], [SiG.sub.1O.sub.3/2] or combinations
thereof;
[0392] Q=[SiO.sub.4/2];
[0393] w=is an integer from 1 to (2+y+2z);
[0394] x=is an integer from 5 to 15,000;
[0395] y=is an integer from 0 to 98;
[0396] z=is an integer from 0 to 98;
[0397] R.sub.1, R.sub.2 and R.sub.3 are each independently selected
from the group consisting of H, OH, C.sub.1-C.sub.32 alkyl,
C.sub.1-C.sub.32 substituted alkyl, C.sub.5-C.sub.32 or
C.sub.6-C.sub.32 aryl, C.sub.5-C.sub.32 or C.sub.6-C.sub.32
substituted aryl, C.sub.6-C.sub.32 alkylaryl, C.sub.6-C.sub.32
substituted alkylaryl, C.sub.1-C.sub.32 alkoxy, C.sub.1-C.sub.32
substituted alkoxy, C.sub.1-C.sub.32 alkylamino, and
C.sub.1-C.sub.32 substituted alkylamino;
[0398] at least one of M, D, or T incorporates at least one moiety
G.sub.1, G.sub.2 or G.sub.3, and G.sub.1, G.sub.2, and G.sub.3 are
each independently selected from the formula:
##STR00022##
wherein:
[0399] X comprises a divalent radical selected from the group
consisting of C.sub.1-C.sub.32 alkylene, C.sub.1-C.sub.32
substituted alkylene, C.sub.5-C.sub.32 or C.sub.6-C.sub.32 arylene,
C.sub.5-C.sub.32 or C.sub.6-C.sub.32 substituted arylene,
C.sub.6-C.sub.32 arylalkylene, C.sub.6-C.sub.32 substituted
arylalkylene, C.sub.1-C.sub.32 alkoxy, C.sub.1-C.sub.32 substituted
alkoxy, C.sub.1-C.sub.32 alkyleneamino, C.sub.1-C.sub.32
substituted alkyleneamino, ring-opened epoxide, and ring-opened
glycidyl, with the proviso that if X does not comprise a repeating
alkylene oxide moiety then X can further comprise a heteroatom
selected from the group consisting of P, N and 0;
[0400] each R.sub.4 comprises identical or different monovalent
radicals selected from the group consisting of H, C.sub.1-C.sub.32
alkyl, C.sub.1-C.sub.32 substituted alkyl, C.sub.5-C.sub.32 or
C.sub.6-C.sub.32 aryl, C.sub.5-C.sub.32 or C.sub.6-C.sub.32
substituted aryl, C.sub.6-C.sub.32 alkylaryl, and C.sub.6-C.sub.32
substituted alkylaryl;
[0401] E comprises a divalent radical selected from the group
consisting of C.sub.1-C.sub.32 alkylene, C.sub.1-C.sub.32
substituted alkylene, C.sub.5-C.sub.32 or C.sub.6-C.sub.32 arylene,
C.sub.5-C.sub.32 or C.sub.6-C.sub.32 substituted arylene,
C.sub.6-C.sub.32 arylalkylene, C.sub.6-C.sub.32 substituted
arylalkylene, C.sub.1-C.sub.32 alkoxy, C.sub.1-C.sub.32 substituted
alkoxy, C.sub.1-C.sub.32 alkyleneamino, C.sub.1-C.sub.32
substituted alkyleneamino, ring-opened epoxide and ring-opened
glycidyl, with the proviso that if E does not comprise a repeating
alkylene oxide moiety then E can further comprise a heteroatom
selected from the group consisting of P, N, and 0;
[0402] E' comprises a divalent radical selected from the group
consisting of C.sub.1-C.sub.32 alkylene, C.sub.1-C.sub.32
substituted alkylene, C.sub.5-C.sub.32 or C.sub.6-C.sub.32 arylene,
C.sub.5-C.sub.32 or C.sub.6-C.sub.32 substituted arylene,
C.sub.6-C.sub.32 arylalkylene, C.sub.6-C.sub.32 substituted
arylalkylene, C.sub.1-C.sub.32 alkoxy, C.sub.1-C.sub.32 substituted
alkoxy, C.sub.1-C.sub.32 alkyleneamino, C.sub.1-C.sub.32
substituted alkyleneamino, ring-opened epoxide and ring-opened
glycidyl, with the proviso that if E' does not comprise a repeating
alkylene oxide moiety then E' can further comprise a heteroatom
selected from the group consisting of P, N, and 0;
[0403] p is an integer independently selected from 1 to 50;
[0404] n is an integer independently selected from 1 or 2;
[0405] when at least one of G.sub.1, G.sub.2, or G.sub.3 is
positively charged, A.sup.-t is a suitable charge balancing anion
or anions such that the total charge, k, of the charge-balancing
anion or anions is equal to and opposite from the net charge on the
moiety G.sub.1, G.sub.2 or G.sub.3; wherein t is an integer
independently selected from 1, 2, or 3; and k.ltoreq.(p*2/t)+1;
such that the total number of cationic charges balances the total
number of anionic charges in the organopolysiloxane molecule;
[0406] and wherein at least one E does not comprise an ethylene
moiety.
[0407] Particularly Preferred Adjuncts for Freshening
Compositions
[0408] Buffering Agent--
[0409] The freshening composition of the present invention may
include a buffering agent which may be a carboxylic acid, or a
dicarboxylic acid like maleic acid, or a polybasic acid such as
citric acid or polyacrylic acid. The acid may be sterically stable,
and used in this composition for maintaining the desired pH. The
buffering agent may also comprise a base such as triethanolamine,
or the salt of an organic acid such as sodium citrate.
[0410] The freshening composition may have a pH from about 3 to
about 8, alternatively from about 4 to about 7, alternatively from
about 5 to about 8, alternatively from about 6 to about 8,
alternatively about 6 to about 7, alternatively about 7,
alternatively about 6.5. Carboxylic acids such as citric acid may
act as metal ion chelants and can form metallic salts with low
water solubility. As such, in some embodiments, the freshening
composition is essentially free of citric acids. The buffer can be
alkaline, acidic or neutral.
[0411] Other suitable buffering agents for freshening compositions
of the present invention include biological buffering agents. Some
examples are nitrogen-containing materials, sulfonic acid buffers
like 3-(N-morpholino)propanesulfonic acid (MOPS) or
N-(2-Acetamido)-2-aminoethanesulfonic acid (ACES), which have a
near neutral 6.2 to 7.5 pKa and provide adequate buffering capacity
at a neutral pH. Other examples are amino acids such as lysine or
lower alcohol amines like mono-, di-, and tri-ethanolamine. Other
nitrogen-containing buffering agents are tri(hydroxymethyl)amino
methane (HOCH2)3CNH3 (TRIS), 2-amino-2-ethyl-1,3-propanediol,
2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanol, disodium
glutamate, N-methyl diethanolamide,
2-dimethylamino-2-methylpropanol (DMAMP),
1,3-bis(methylamine)-cyclohexane, 1,3-diamino-propanol
N,N'-tetra-methyl-1,3-diamino-2-propanol,
N,N-bis(2-hydroxyethyl)glycine (bicine) and N-tris
(hydroxymethyl)methyl glycine (tricine). Mixtures of any of the
above are also acceptable.
[0412] The freshening compositions may contain at least about 0%,
alternatively at least about 0.001%, alternatively at least about
0.01%, by weight of the composition, of a buffering agent. The
composition may also contain no more than about 1%, alternatively
no more than about 0.75%, alternatively no more than about 0.5%, by
weight of the composition, of a buffering agent.
[0413] Solubilizer--
[0414] The freshening composition of the present invention may
contain a solubilizing aid to solubilize any excess hydrophobic
organic materials, particularly some malodor reduction materials of
the current invention, perfume materials, and also optional
ingredients (e.g., insect repelling agent, antioxidant, etc.) which
can be added to the composition, that are not readily soluble in
the composition, to form a clear translucent solution. A suitable
solubilizing aid is a surfactant, such as a no-foaming or
low-foaming surfactant. Suitable surfactants are nonionic
surfactants, cationic surfactants, amphoteric surfactants,
zwitterionic surfactants, and mixtures thereof.
[0415] In some embodiments, the freshening composition contains
nonionic surfactants, cationic surfactants, and mixtures thereof.
In one embodiment, the freshening composition contains ethoxylated
hydrogenated castor oil. One type of suitable hydrogenated castor
oil that may be used in the present composition is sold as
Basophor.TM., available from BASF.
[0416] Freshening compositions containing anionic surfactants
and/or detergent surfactants may make fabrics susceptible to
soiling and/or leave unacceptable visible stains on fabrics as the
solution evaporates off of the fabric. In some embodiments, the
freshening composition is free of anionic surfactants and/or
detergent surfactants.
[0417] When the solubilizing agent is present, it is typically
present at a level of from about 0.01% to about 3%, alternatively
from about 0.05% to about 1%, alternatively from about 0.01% to
about 0.05%, by weight of the freshening composition.
[0418] Antimicrobial Compounds--
[0419] The freshening composition of the present invention may
include an effective amount of a compound for reducing microbes in
the air or on inanimate surfaces. Antimicrobial compounds are
effective on gram negative and gram positive bacteria and fungi
typically found on indoor surfaces that have contacted human skin
or pets such as couches, pillows, pet bedding, and carpets. Such
microbial species include Klebsiella pneumoniae, Staphylococcus
aureus, Aspergillus niger, Klebsiella pneumoniae, Streptococcus
pyogenes, Salmonella choleraesuis, Escherichia coli, Trichophyton
mentagrophytes, and Pseudomonas aeruginosa. In some embodiments,
the antimicrobial compounds are also effective on viruses such
H1-N1, Rhinovirus, Respiratory Syncytial, Poliovirus Type 1,
Rotavirus, Influenza A, Herpes simplex types 1 & 2, Hepatitis
A, and Human Coronavirus.
[0420] Antimicrobial compounds suitable in the freshening
composition of the present invention can be any organic material
which will not cause damage to fabric appearance (e.g.,
discoloration, coloration such as yellowing, bleaching).
Water-soluble antimicrobial compounds include organic sulfur
compounds, halogenated compounds, cyclic organic nitrogen
compounds, low molecular weight aldehydes, quaternary compounds,
dehydroacetic acid, phenyl and phenoxy compounds, or mixtures
thereof.
[0421] In one embodiment, a quaternary compound is used. Examples
of commercially available quaternary compounds suitable for use in
the freshening composition are Barquat available from Lonza
Corporation; and didecyl dimethyl ammonium chloride quat under the
trade name Bardac.RTM. 2250 from Lonza Corporation.
[0422] The antimicrobial compound may be present in an amount from
about 500 ppm to about 7000 ppm, alternatively about 1000 ppm to
about 5000 ppm, alternatively about 1000 ppm to about 3000 ppm,
alternatively about 1400 ppm to about 2500 ppm, by weight of the
freshening composition.
[0423] Preservatives--
[0424] The freshening composition of the present invention may
include a preservative. The preservative is included in the present
invention in an amount sufficient to prevent spoilage or prevent
growth of inadvertently added microorganisms for a specific period
of time, but not sufficient enough to contribute to the odor
neutralizing performance of the freshening composition. In other
words, the preservative is not being used as the antimicrobial
compound to kill microorganisms on the surface onto which the
composition is deposited in order to eliminate odors produced by
microorganisms. Instead, it is being used to prevent spoilage of
the freshening composition in order to increase the shelf-life of
the composition.
[0425] The preservative can be any organic preservative material
which will not cause damage to fabric appearance, e.g.,
discoloration, coloration, bleaching. Suitable water-soluble
preservatives include organic sulfur compounds, halogenated
compounds, cyclic organic nitrogen compounds, low molecular weight
aldehydes, parabens, propane diol materials, isothiazolinones,
quaternary compounds, benzoates, low molecular weight alcohols,
dehydroacetic acid, phenyl and phenoxy compounds, or mixtures
thereof. Non-limiting examples of commercially available
water-soluble preservatives for use in the present invention
include a mixture of about 77%
5-chloro-2-methyl-4-isothiazolin-3-one and about 23%
2-methyl-4-isothiazolin-3-one, a broad spectrum preservative
available as a 1.5% aqueous solution under the trade name
Kathon.RTM. CG by Rohm and Haas Co.; 5-bromo-5-nitro-1,3-dioxane,
available under the tradename Bronidox L.RTM. from Henkel;
2-bromo-2-nitropropane-1,3-diol, available under the trade name
Bronopol.RTM. from Inolex; 1,1'-hexamethylene
bis(5-(p-chlorophenyl)biguanide), commonly known as chlorhexidine,
and its salts, e.g., with acetic and digluconic acids; a 95:5
mixture of
1,3-bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione and
3-butyl-2-iodopropynyl carbamate, available under the trade name
Glydant Plus.RTM. from Lonza;
N-[1,3-bis(hydroxymethyl)2,5-dioxo-4-imidazolidinyl]-N,N'-bis(hydroxy-met-
hyl) urea, commonly known as diazolidinyl urea, available under the
trade name Germall.RTM. II from Sutton Laboratories, Inc.;
N,N''-methylenebis
{N'-[1-(hydroxymethyl)-2,5-dioxo-4-imidazolidinyl]urea}, commonly
known as imidazolidinyl urea, available, e.g., under the trade name
Abiol.RTM. from 3V-Sigma, Unicide U-13.RTM. from Induchem, Germall
115.RTM. from Sutton Laboratories, Inc.; polymethoxy bicyclic
oxazolidine, available under the trade name Nuosept.RTM. C from
Hills America; formaldehyde; glutaraldehyde; polyaminopropyl
biguanide, available under the trade name Cosmocil CQ.RTM. from ICI
Americas, Inc., or under the trade name Mikrokill.RTM. from Brooks,
Inc; dehydroacetic acid; and benzsiothiazolinone available under
the trade name Koralone.TM. B-119 from Rohm and Hass
Corporation.
[0426] Suitable levels of preservative are from about 0.0001% to
about 0.5%, alternatively from about 0.0002% to about 0.2%,
alternatively from about 0.0003% to about 0.1%, by weight of the
freshening composition.
[0427] Wetting Agents--
[0428] The freshening composition may include a wetting agent that
provides a low surface tension that permits the composition to
spread readily and more uniformly on hydrophobic surfaces like
polyester and nylon. It has been found that the aqueous solution,
without such a wetting agent will not spread satisfactorily. The
spreading of the composition also allows it to dry faster, so that
the treated material is ready to use sooner. Furthermore, a
composition containing a wetting agent may penetrate hydrophobic,
oily soil better for improved malodor neutralization. A composition
containing a wetting agent may also provide improved "in-wear"
electrostatic control. For concentrated compositions, the wetting
agent facilitates the dispersion of many actives such as
antimicrobial actives and perfumes in the concentrated aqueous
compositions.
[0429] Non-limiting examples of wetting agents include block
copolymers of ethylene oxide and propylene oxide. Suitable block
polyoxyethylene-polyoxypropylene polymeric surfactants include
those based on ethylene glycol, propylene glycol, glycerol,
trimethylolpropane and ethylenediamine as the initial reactive
hydrogen compound. Polymeric compounds made from a sequential
ethoxylation and propoxylation of initial compounds with a single
reactive hydrogen atom, such as C12-18 aliphatic alcohols, are not
generally compatible with the cyclodextrin. Certain of the block
polymer surfactant compounds designated Pluronic.RTM. and
Tetronic.RTM. by the BASF-Wyandotte Corp., Wyandotte, Mich., are
readily available. Nonlimiting examples of wetting agents of this
type are described in U.S. Pat. No. 5,714,137 and include the
Silwet.RTM. surfactants available from Momentive Performance
Chemical, Albany, N.Y. Exemplary Silwet surfactants are as
presented in Table 5 which may be used alone or in combinations of
one another.
TABLE-US-00005 TABLE 5 Name L-7608 L-7607 L-77 L-7605 L-7604 L-7600
L-7657 L-7602 Average MW 600 1000 600 6000 4000 4000 5000 3000
[0430] In another aspect of the invention freshening fabric is a
restoration of the fabric such as its surface appearance (reduction
of wrinkling, improved color appearance, improved or restored
fabric shape). Adjunct ingredients that help restore fabric
appearance are selected from: water soluble or miscible quaternary
ammonium surfactants and water insoluble oil components together
with surfactants, emulsifiers, and solvents needed to form a
composition that is stable and does not separate. Some non-limiting
preferred emulsifiers are sorbitan esters and sorbitan esters
modified with alkylene oxides, such as Tween.RTM. 20
(polyoxyethylene (20)sorbitan monolaurate, branched surfactants,
like Guerbet alcohols or alkylene oxide modified Guerget alcohols
such as Lutensol.RTM. XL 70 (Oxirane, 2-methyl-, polymer with
oxirane, mono(2-propylheptyl) ether, BASF). It is optional but
preferred to have a wetting agent in this aspect of the invention.
Wetting agents aid in spreading components and in reducing foaming
of the composition during spraying. Some preferred wetting agents
include the class of wetting agents known in the art as
superwetters. Not to be bound by theory, superwetters pack very
efficiently at surfaces resulting in an extremely low equilibrium
surface tension. Non-limiting examples of such surfactants include
Surfynols.RTM. like Surfynol.RTM. 465 and Surfynol.RTM. 104PG 50
(Dow Chemicals).
[0431] Water soluble or miscible quaternary ammonium
surfactant:
[0432] Typically, minimum levels of the water soluble quat included
in the compositions of the present invention are at least about
0.01%, preferably at least about 0.05%, more preferably at least
about 0.1% even more preferably at least about 0.2% by weight,
based on the total weight of the composition. Typically maximum
levels of water soluble quaternary agent included in the
composition are up to about 20%, preferably less than about 10%,
and more preferably less than about 3% based on the total weight of
the composition. Typically, the agent is present in the composition
in an amount of about 0.2% to about 1.0%.
[0433] Specifically, the preferred water soluble quaternary
compounds are dialkly quaternary surfactant compounds. Suitable
quaternary surfactants include, but are not limited to, quaternary
ammonium surfactants having the formula:
##STR00023##
wherein R.sub.1 and R.sub.2 are individually selected from the
group consisting of C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 hydroxy
alkyl, benzyl, and --(C.sub.2H.sub.4O).sub.xH where x has a value
from about 2 to about 5; X is an anion; and (1) R.sub.3 and R.sub.4
are each a C.sub.6-C.sub.14 alkyl or (2) R.sub.3 is a
C.sub.6-C.sub.18 alkyl, and R.sub.4 is selected from the group
consisting of C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 hydroxy
alkyl, benzyl, and --(C.sub.2H.sub.4O).sub.xH where x has a value
from 2 to 5. A preferred asymmetric quaternary compounds for this
invention are compounds where R3 and R4 are not identical, and
preferably one is branched and the other one is linear.
[0434] An example of a preferred asymmetric quaternary compound is
ARQUAD HTL8-MS where X is a methyl sulfate ion, R1 and R2 are
methyl groups, R3 is a hydrogenated tallow group with <5% mono
unsaturation, and R4 is a 2-ethylhexyl group. ARQUAD HTL8-MS is
available from Akzo Nobel Chemical of Arnhem, Netherlands.
[0435] An example of a suitable symmetric quaternary compound is
UNIQUAT 22c50 where X is a carbonate and bicarbonate, R1 and R2 are
methyl groups, R3 and R4 are C10 alkyl groups. UNIQUAT 22c50 is a
registered trademark of Lonza and in North America is available
thru Lonza Incorporated of Allendale, N.J.
[0436] Another example of a suitable water soluble quaternary
compound is BARQUAT CME-35 which is N-Cetyl Ethyl Morpholinium
Ethosulfate available from Lonza and having the following
structure:
##STR00024##
[0437] Oil Component--
[0438] The oil component of the present invention represents a
substantially water insoluble material that is incorporated into
the composition by way of a microemulsion. The said oil component
is a non-perfume raw material and a non-malodor reduction material.
Typically the minimum levels of the oil component included in the
composition are at least about 0.001%, preferably at least about
0.005%, more preferably at least about 0.01%, and typically maximum
levels of oil components are up to about 5%, preferably less than
about 3%, more preferably less than 1.5; with typical levels being
in the range of about 0.05% to about 1%. The oil component can be a
single component or a mixture and usually represents the
incorporation of some benefit agent into the composition such as
the nonlimiting example benefits softness or wrinkle
reduction/release. Typically the oil component comprises
substituted or unsubstituted hydrocarbon(s) and the like. For spray
products it is preferred that the oil component or mix be a liquid
at room temperature for ease of incorporation into the composition
and less potential for nozzle clogging on drying.
[0439] The oil components of the present invention are
substantially water insoluble and form a microemulsion.
Substantially water insoluble means the log P of the ingredients
are greater than about 1. A log P of about 1 indicates that the
component would tend to partition into octanol about 10 times more
than water. Some preferred, but non-limiting, components in the oil
mixture are branched hydrocarbons and perfumes when perfumes are
used.
[0440] Aqueous Carrier--
[0441] The freshening composition of the present invention may
include an aqueous carrier. The aqueous carrier which is used may
be distilled, deionized, or tap water. Water may be present in any
amount for the composition to be an aqueous solution. In some
embodiments, water may be present in an amount of about 85% to
99.5%, alternatively about 90% to about 99.5%, alternatively about
92% to about 99.5%, alternatively about 95%, by weight of said
freshening composition. Water containing a small amount of low
molecular weight monohydric alcohols, e.g., ethanol, methanol, and
isopropanol, or polyols, such as ethylene glycol and propylene
glycol, can also be useful. However, the volatile low molecular
weight monohydric alcohols such as ethanol and/or isopropanol
should be limited since these volatile organic compounds will
contribute both to flammability problems and environmental
pollution problems. If small amounts of low molecular weight
monohydric alcohols are present in the composition of the present
invention due to the addition of these alcohols to such things as
perfumes and as stabilizers for some preservatives, the level of
monohydric alcohol may about 1% to about 5%, alternatively less
than about 6%, alternatively less than about 3%, alternatively less
than about 1%, by weight of the freshening composition.
[0442] Other Ingredients--
[0443] The freshening composition may include perfume raw materials
that solely provide a hedonic benefit (i.e. that do not neutralize
malodors yet provide a pleasant fragrance). Suitable perfumes are
disclosed in U.S. Pat. No. 6,248,135, which is incorporated in its
entirety by reference. For example, the freshening composition may
include a mixture of volatile aldehydes for neutralizing a malodor
and hedonic perfume aldehydes. Where perfumes, other than the
volatile aldehydes in the malodor control component, are formulated
into the freshening composition of the present invention, the total
amount of perfumes and volatile aldehydes in the malodor control
component may be from about 0.015% to about 1%, alternatively from
about 0.01% to about 0.5%, alternatively from about 0.015% to about
0.3%, by weight of the freshening composition.
[0444] The freshening composition may also include diluents.
Exemplary diluents include dipropylene glycol methyl ether, and
3-methoxy-3-methyl-1-butanol, and mixtures thereof.
[0445] Optionally, adjuvants can be added to the freshening
composition herein for their known purposes. Such adjuvants
include, but are not limited to, water soluble metallic salts,
including zinc salts, copper salts, and mixtures thereof;
antistatic agents; insect and moth repelling agents; colorants;
antioxidants; aromatherapy agents and mixtures thereof.
[0446] The freshening composition may include other malodor
reducing technologies in addition to the malodor reduction
composition of the current invention. This may include, without
limitation, amine functional polymers, metal ions, cyclodextrins,
cyclodextrin derivatives, polyols, oxidizing agents, activated
carbon, and combinations thereof.
[0447] Particularly Preferred Adjuncts for Personal Care
Compositions
[0448] While not essential for the purposes of the present
invention, the non-limiting list of adjuncts illustrated
hereinafter are suitable for use in the instant compositions and
may be desirably incorporated in certain aspects of the invention,
for example to assist or enhance performance.
[0449] A variety of optional ingredients can also be added to
personal care compositions. Optional ingredients can include, but
are not limited to, structurants, humectants, fatty acids,
inorganic salts, and other antimicrobial agents or actives.
[0450] A personal care composition can also include hydrophilic
structurants such as carbohydrate structurants and gums. Some
suitable carbohydrate structurants include raw starch (corn, rice,
potato, wheat, and the like) and pregelatinized starch. Some
suitable gums include carrageenan and xanthan gum. A personal care
composition can include from about 0.1% to about 30%, from about 2%
to about 25%, or from about 4% to about 20%, by weight of the
personal care composition, of a carbohydrate structurant.
[0451] A personal care composition can also include one or more
humectants. Examples of such humectants can include polyhydric
alcohols. Further, humectants such as glycerin can be included the
personal care composition as a result of production or as an
additional ingredient. For example, glycerin can be a by-product
after saponification of the personal care composition. Including
additional humectant can result in a number of benefits such as
improvement in hardness of the personal care composition, decreased
water activity of the personal care composition, and reduction of a
weight loss rate of the personal care composition over time due to
water evaporation.
[0452] A personal care composition can include inorganic salts.
Inorganic salts can help to maintain a particular water content or
level of the personal care composition and improve hardness of the
personal care composition. The inorganic salts can also help to
bind the water in the personal care composition to prevent water
loss by evaporation or other means. A personal care composition can
optionally include from about 0.01% to about 15%, from about 1% to
about 12%, or from about 2.5% to about 10.5%, by weight of the
personal care composition, of inorganic salt. Examples of suitable
inorganic salts can include magnesium nitrate, trimagnesium
phosphate, calcium chloride, sodium carbonate, sodium aluminum
sulfate, disodium phosphate, sodium polymetaphosphate, sodium
magnesium succinate, sodium tripolyphosphate, aluminum sulfate,
aluminum chloride, aluminum chlorohydrate, aluminum-zirconium
trichlorohydrate, aluminum-zirconium trichlorohydrate glycine
complex, zinc sulfate, ammonium chloride, ammonium phosphate,
calcium acetate, calcium nitrate, calcium phosphate, calcium
sulfate, ferric sulfate, magnesium chloride, magnesium sulfate, and
tetrasodium pyrophosphate.
[0453] A personal care composition can include one or more
additional antibacterial agents that can serve to further enhance
antimicrobial effectiveness of the personal care composition. A
personal care composition can include, for example, from about
0.001% to about 2%, from about 0.01% to about 1.5%, or from about
0.1% to about 1%, by weight of the personal care composition, of
additional antibacterial agent(s). Examples of suitable
antibacterial agents can include carbanilides, triclocarban (also
known as trichlorocarbanilide), triclosan, a halogenated
diphenylether available as DP-300 from Ciba-Geigy, hexachlorophene,
3,4,5-tribromosalicylanilide, and salts of 2-pyridinethiol-1-oxide,
salicylic acid, and other organic acids. Other suitable
antibacterial agents are described in U.S. Pat. No. 6,488,943.
[0454] Scalp Active Material--
[0455] In an embodiment of the present invention, the personal care
composition may comprise a scalp active material, which may be an
anti-dandruff active. In an embodiment, the anti-dandruff active is
selected from the group consisting of: pyridinethione salts; zinc
carbonate; azoles, such as ketoconazole, econazole, and elubiol;
selenium sulfide; particulate sulfur; keratolytic agents such as
salicylic acid; and mixtures thereof. In a further embodiment, the
anti-dandruff active may be an anti-dandruff particulate. In an
embodiment, the anti-dandruff particulate is a pyridinethione salt.
Such anti-dandruff particulate should be physically and chemically
compatible with the components of the composition, and should not
otherwise unduly impair product stability, aesthetics or
performance.
[0456] Pyridinethione particulates are suitable particulate
anti-dandruff actives for use in composition of the present
invention. In an embodiment, the anti-dandruff active is a
1-hydroxy-2-pyridinethione salt and is in particulate form. In an
embodiment, the concentration of pyridinethione anti-dandruff
particulate ranges from about 0.01% to about 5%, by weight of the
composition, or from about 0.1% to about 3%, or from about 0.1% to
about 2%. In an embodiment, the pyridinethione salts are those
formed from heavy metals such as zinc, tin, cadmium, magnesium,
aluminium and zirconium, generally zinc, typically the zinc salt of
1-hydroxy-2-pyridinethione (known as "zinc pyridinethione" or
"ZPT"; zinc pyrithione), commonly 1-hydroxy-2-pyridinethione salts
in platelet particle form. In an embodiment, the
1-hydroxy-2-pyridinethione salts in platelet particle form have an
average particle size of up to about 20 microns, or up to about 5
microns, or up to about 2.5 microns. Salts formed from other
cations, such as sodium, may also be suitable.
[0457] In an embodiment, in addition to the anti-dandruff active
selected from polyvalent metal salts of pyrithione, the composition
further comprises one or more anti-fungal and/or anti-microbial
actives. In an embodiment, the anti-microbial active is selected
from the group consisting of: coal tar, sulfur, fcharcoal,
whitfield's ointment, castellani's paint, aluminum chloride,
gentian violet, octopirox (piroctone olamine), ciclopirox olamine,
undecylenic acid and its metal salts, potassium permanganate,
selenium sulfide, sodium thiosulfate, propylene glycol, oil of
bitter orange, urea preparations, griseofulvin, 8-hydroxyquinoline
ciloquinol, thiobendazole, thiocarbamates, haloprogin, polyenes,
hydroxypyridone, morpholine, benzylamine, allylamines (such as
terbinafine), tea tree oil, clove leaf oil, coriander, palmarosa,
berberine, thyme red, cinnamon oil, cinnamic aldehyde, citronellic
acid, hinokitol, ichthyol pale, Sensiva SC-50, Elestab HP-100,
azelaic acid, lyticase, iodopropynyl butylcarbamate (IPBC),
isothiazalinones such as octyl isothiazalinone, and azoles, and
mixtures thereof. In an embodiment, the anti-microbial is selected
from the group consisting of: itraconazole, ketoconazole, selenium
sulfide, coal tar, and mixtures thereof.
[0458] In an embodiment, the azole anti-microbials is an imidazole
selected from the group consisting of: benzimidazole,
benzothiazole, bifonazole, butaconazole nitrate, climbazole,
clotrimazole, croconazole, eberconazole, econazole, elubiol,
fenticonazole, fluconazole, flutimazole, isoconazole, ketoconazole,
lanoconazole, metronidazole, miconazole, neticonazole, omoconazole,
oxiconazole nitrate, sertaconazole, sulconazole nitrate,
tioconazole, thiazole, and mixtures thereof, or the azole
anti-microbials is a triazole selected from the group consisting
of: terconazole, itraconazole, and mixtures thereof. When present
in the composition, the azole anti-microbial active is included in
an amount of from about 0.01% to about 5%, or from about 0.1% to
about 3%, or from about 0.3% to about 2%, by total weight of the
composition. In an embodiment, the azole anti-microbial active is
ketoconazole. In an embodiment, the sole anti-microbial active is
ketoconazole.
[0459] The present invention may also comprise a combination of
anti-microbial actives. In an embodiment, the combination of
anti-microbial active is selected from the group of combinations
consisting of: octopirox and zinc pyrithione, pine tar and sulfur,
salicylic acid and zinc pyrithione, salicylic acid and elubiol,
zinc pyrithione and elubiol, zinc pyrithione and climbasole,
octopirox and climbasole, salicylic acid and octopirox, and
mixtures thereof.
[0460] In an embodiment, the composition comprises an effective
amount of a zinc-containing layered material. In an embodiment, the
composition comprises from about 0.001% to about 10%, or from about
0.01% to about 7%, or from about 0.1% to about 5% of a
zinc-containing layered material, by total weight of the
composition. Zinc-containing layered materials may be those with
crystal growth primarily occurring in two dimensions. It is
conventional to describe layer structures as not only those in
which all the atoms are incorporated in well-defined layers, but
also those in which there are ions or molecules between the layers,
called gallery ions (A. F. Wells "Structural Inorganic Chemistry"
Clarendon Press, 1975). Zinc-containing layered materials (ZLMs)
may have zinc incorporated in the layers and/or be components of
the gallery ions. The following classes of ZLMs represent
relatively common examples of the general category and are not
intended to be limiting as to the broader scope of materials which
fit this definition.
[0461] Many ZLMs occur naturally as minerals. In an embodiment, the
ZLM is selected from the group consisting of: hydrozincite (zinc
carbonate hydroxide), basic zinc carbonate, aurichalcite (zinc
copper carbonate hydroxide), rosasite (copper zinc carbonate
hydroxide), and mixtures thereof. Related minerals that are
zinc-containing may also be included in the composition. Natural
ZLMs can also occur wherein anionic layer species such as clay-type
minerals (e.g., phyllosilicates) contain ion-exchanged zinc gallery
ions. All of these natural materials can also be obtained
synthetically or formed in situ in a composition or during a
production process.
[0462] Another common class of ZLMs, which are often, but not
always, synthetic, is layered double hydroxides. In an embodiment,
the ZLM is a layered double hydroxide conforming to the formula
[M.sup.2+.sub.1-xM.sup.3+.sub.x(OH).sub.2].sup.x+A.sup.m-.sub.x/m.nH.sub.-
2O wherein some or all of the divalent ions (M.sup.2+) are zinc
ions. Yet another class of ZLMs can be prepared called hydroxy
double salts
[0463] In an embodiment, the ZLM is a hydroxy double salt
conforming to the formula
[M.sup.2+.sub.1-xM.sup.2+.sub.1+x(OH).sub.3(1-y)].sup.+A.sup.n-.sub.(1=3y-
)/n.nH.sub.2O where the two metal ions (M.sup.2+) may be the same
or different. If they are the same and represented by zinc, the
formula simplifies to
[Zn.sub.1+x(OH).sub.2].sup.2x+2.times.A.sup.-.nH.sub.2O. This
latter formula represents (where x=0.4) materials such as zinc
hydroxychloride and zinc hydroxynitrate. In an embodiment, the ZLM
is zinc hydroxychloride and/or zinc hydroxynitrate. These are
related to hydrozincite as well wherein a divalent anion replace
the monovalent anion. These materials can also be formed in situ in
a composition or in or during a production process.
[0464] In an embodiment, the composition comprises basic zinc
carbonate. Commercially available sources of basic zinc carbonate
include Zinc Carbonate Basic (Cater Chemicals: Bensenville, Ill.,
USA), Zinc Carbonate (Shepherd Chemicals: Norwood, Ohio, USA), Zinc
Carbonate (CPS Union Corp.: New York, N.Y., USA), Zinc Carbonate
(Elementis Pigments: Durham, UK), and Zinc Carbonate AC (Bruggemann
Chemical: Newtown Square, Pa., USA). Basic zinc carbonate, which
also may be referred to commercially as "Zinc Carbonate" or "Zinc
Carbonate Basic" or "Zinc Hydroxy Carbonate", is a synthetic
version consisting of materials similar to naturally occurring
hydrozincite. The idealized stoichiometry is represented by
Zn.sub.5(OH).sub.6(CO.sub.3).sub.2 but the actual stoichiometric
ratios can vary slightly and other impurities may be incorporated
in the crystal lattice.
[0465] In embodiments having a zinc-containing layered material and
a pyrithione or polyvalent metal salt of pyrithione, the ratio of
zinc-containing layered material to pyrithione or a polyvalent
metal salt of pyrithione is from about 5:100 to about 10:1, or from
about 2:10 to about 5:1, or from about 1:2 to about 3:1.
[0466] Liquid Personal Care Compositions
[0467] Exemplary liquid rinse-off personal care compositions can
include an aqueous carrier, which can be present at a level of from
about 5% to about 95%, or from about 60% to about 85%. The aqueous
carrier may comprise water, or a miscible mixture of water and
organic solvent. Non-aqueous carrier materials can also be
employed.
[0468] Such rinse-off personal care compositions can include one or
more detersive surfactants. The detersive surfactant component can
be included to provide cleaning performance to the product. The
detersive surfactant component in turn comprises anionic detersive
surfactant, zwitterionic or amphoteric detersive surfactant, or a
combination thereof. A representative, non-limiting, list of
anionic surfactants includes anionic detersive surfactants for use
in the compositions can include ammonium lauryl sulfate, ammonium
laureth sulfate, triethylamine lauryl sulfate, triethylamine
laureth sulfate, triethanolamine lauryl sulfate, triethanolamine
laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine
laureth sulfate, diethanolamine lauryl sulfate, diethanolamine
laureth sulfate, lauric monoglyceride sodium sulfate, sodium lauryl
sulfate, sodium laureth sulfate, potassium lauryl sulfate,
potassium laureth sulfate, sodium lauryl sarcosinate, sodium
lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium
cocoyl sulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate,
sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauryl
sulfate, triethanolamine lauryl sulfate, triethanolamine lauryl
sulfate, monoethanolamine cocoyl sulfate, monoethanolamine lauryl
sulfate, sodium tridecyl benzene sulfonate, sodium dodecyl benzene
sulfonate, sodium cocoyl isethionate and combinations thereof. In
one example, the anionic surfactant can be sodium lauryl sulfate or
sodium laureth sulfate. The concentration of the anionic surfactant
component in the product can be sufficient to provide a desired
cleaning and/or lather performance, and generally ranges from about
2% to about 50%.
[0469] Amphoteric detersive surfactants suitable for use in the
rinse-off personal care compositions are well known in the art, and
include those surfactants broadly described as derivatives of
aliphatic secondary and tertiary amines in which an aliphatic
radical can be straight or branched chain and wherein an aliphatic
substituent can contain from about 8 to about 18 carbon atoms such
that one carbon atom can contain an anionic water solubilizing
group, e.g., carboxy, sulfonate, sulfate, phosphate, or
phosphonate. Examples of compounds falling within this definition
can be sodium 3-dodecyl-aminopropionate, sodium
3-dodecylaminopropane sulfonate, sodium lauryl sarcosinate,
N-alkyltaurines such as the one prepared by reacting dodecylamine
with sodium isethionate according to the teaching of U.S. Pat. No.
2,658,072, N-higher alkyl aspartic acids such as those produced
according to the teaching of U.S. Pat. No. 2,438,091, and products
described in U.S. Pat. No. 2,528,378. Other examples of amphoteric
surfactants can include sodium lauroamphoacetate, sodium
cocoamphoactetate, disodium lauroamphoacetate disodium
cocodiamphoacetate, and mixtures thereof. Amphoacetates and
diamphoacetates can also be used.
[0470] Zwitterionic detersive surfactants suitable for use in the
rinse-off personal care compositions are well known in the art, and
include those surfactants broadly described as derivatives of
aliphatic quaternary ammonium, phosphonium, and sulfonium
compounds, in which aliphatic radicals can be straight or branched
chains, and wherein an aliphatic substituent can contain from about
8 to about 18 carbon atoms such that one carbon atom can contain an
anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or
phosphonate. Other zwitterionic surfactants can include betaines,
including cocoamidopropyl betaine.
[0471] The liquid rinse off personal care composition can comprise
one or more phases. Such personal care compositions can include a
cleansing phase and/or a benefit phase (i.e., a single- or
multi-phase composition). Each of a cleansing phase or a benefit
phase can include various components. The cleansing phase and the
benefit phase can be blended, separate, or a combination thereof.
The cleansing phase and the benefit phase can also be patterned
(e.g. striped).
[0472] The cleansing phase of a personal care composition can
include at least one surfactant. The cleansing phase can be an
aqueous structured surfactant phase and constitute from about 5% to
about 20%, by weight of the personal care composition. Such a
structured surfactant phase can include sodium trideceth(n)
sulfate, hereinafter STnS, wherein n can define average moles of
ethoxylation. n can range, for example, from about 0 to about 3;
from about 0.5 to about 2.7, from about 1.1 to about 2.5, from
about 1.8 to about 2.2, or n can be about 2. When n can be less
than 3, STnS can provide improved stability, improved compatibility
of benefit agents within the personal care compositions, and
increased mildness of the personal care compositions as disclosed
in U.S. Pre-Grant Publication No. 2010/009285 A1.
[0473] The cleansing phase can also comprise at least one of an
amphoteric surfactant and a zwitterionic surfactant. Suitable
amphoteric or zwitterionic surfactants (in addition to those cited
herein) can include, for example, those described in U.S. Pat. No.
5,104,646 and U.S. Pat. No. 5,106,609.
[0474] A cleansing phase can comprise a structuring system. A
structuring system can comprise, optionally, a non-ionic
emulsifier, optionally, from about 0.05% to about 5%, by weight of
the personal care composition, of an associative polymer; and an
electrolyte.
[0475] The personal care composition can optionally be free of
sodium lauryl sulfate, hereinafter SLS, and can comprise at least a
70% lamellar structure. However, the cleansing phase could comprise
at least one surfactant, wherein the at least one surfactant
includes SLS. Suitable examples of SLS are described in U.S.
Pre-Grant Publication No. 2010/0322878 A1.
[0476] Rinse-off personal care compositions can also include a
benefit phase. The benefit phase can be hydrophobic and/or
anhydrous. The benefit phase can also be substantially free of
surfactant. A benefit phase can also include a benefit agent. In
particular, a benefit phase can comprise from about 0.1% to about
50% benefit agent by weight of the personal care composition. The
benefit phase can alternatively comprise less benefit agent, for
example, from about 0.5% to about 20% benefit agent, by weight of
the personal care composition. Examples of suitable benefit agents
can include petrolatum, glyceryl monooleate, mineral oil, natural
oils, and mixtures thereof. Additional examples of benefit agents
can include water insoluble or hydrophobic benefit agents. Other
suitable benefit agents are described in U.S. Pre-Grant Publication
No. 2012/0009285 A1.
[0477] Non-limiting examples of glycerides suitable for use as
hydrophobic skin benefit agents herein can include castor oil,
safflower oil, corn oil, walnut oil, peanut oil, olive oil, cod
liver oil, almond oil, avocado oil, palm oil, sesame oil, vegetable
oils, sunflower seed oil, soybean oil, vegetable oil derivatives,
coconut oil and derivatized coconut oil, cottonseed oil and
derivatized cottonseed oil, jojoba oil, cocoa butter, and
combinations thereof.
[0478] Non-limiting examples of alkyl esters suitable for use as
hydrophobic skin benefit agents herein can include isopropyl esters
of fatty acids and long chain esters of long chain (i.e. C10-C24)
fatty acids, e.g., cetyl ricinoleate, non-limiting examples of
which can include isopropyl palmitate, isopropyl myristate, cetyl
riconoleate, and stearyl riconoleate. Other example can include
hexyl laurate, isohexyl laurate, myristyl myristate, isohexyl
palmitate, decyl oleate, isodecyl oleate, hexadecyl stearate, decyl
stearate, isopropyl isostearate, diisopropyl adipate, diisohexyl
adipate, dihexyldecyl adipate, diisopropyl sebacate, acyl
isononanoate lauryl lactate, myristyl lactate, cetyl lactate, and
combinations thereof.
[0479] Non-limiting examples of polyglycerin fatty acid esters
suitable for use as hydrophobic skin benefit agents herein can
include decaglyceryl distearate, decaglyceryl diisostearate,
decaglyceryl monomyriate, decaglyceryl monolaurate, hexaglyceryl
monooleate, and combinations thereof.
[0480] The rinse-off personal care composition can be applied by a
variety of means, including by rubbing, wiping or dabbing with
hands or fingers, or by means of an implement and/or delivery
enhancement device. Non-limiting examples of implements include a
sponge or sponge-tipped applicator, a mesh shower puff, a swab, a
brush, a wipe (e.g., wash cloth), a loofah, and combinations
thereof. Non-limiting examples of delivery enhancement devices
include mechanical, electrical, ultrasonic and/or other energy
devices. Employment of an implement or device can help delivery of
the particulate antimicrobial agent to target regions, such as, for
example, hair follicles and undulations that can exist in the
underarm. The rinse-off care product can be sold together with such
an implement or device. Alternatively, an implement or device can
be sold separately but contain indicium to indicate usage with a
rinse-off care product. Implements and delivery devices can employ
replaceable portions (e.g., the skin interaction portions), which
can be sold separately or sold together with the rinse-off care
product in a kit.
[0481] Solid Personal Care Compositions
[0482] As noted herein, personal care compositions can take on
numerous forms. One suitable form is that of a solid personal care
composition. Solid compositions can take many forms like powder,
pellets, bars, etc. These forms will generally be described herein
as bar soap, but it should be understood that the solid composition
could be in another form or shape. One example of a bar soap
personal care composition can include from about 0.1% to about 35%,
by weight of the personal care composition, of water, from about
45% to about 99%, by weight of the personal care composition, of
soap, and from about 0.01% to about 5%, by weight of the personal
care composition, of a particulate antimicrobial agent. Another
suitable antimicrobial bar soap can include, for example, from
about 0.1% to about 30%, by weight of the personal care
composition, of water, from about 40% to about 99%, by weight of
the personal care composition, of soap, and from about 0.25% to
about 3%, by weight of the personal care composition, of a
particulate antimicrobial agent.
[0483] Bar soap compositions can be referred to as conventional
solid (i.e. non-flowing) bar soap compositions. Some bar soap
composition can comprise convention soap, while others can contain
synthetic surfactants, and still others can contain a mix of soap
and synthetic surfactant. Bar compositions can include, for
example, from about 0% to about 45% of a synthetic anionic
surfactant. An example of a suitable conventional soap can include
milled toilet bars that are unbuilt (i.e. include about 5% or less
of a water-soluble surfactancy builder).
[0484] A personal care bar composition can include soap. By weight,
the soap can be, for example, from about 45% to about 99%, or from
about 50% to about 75%, by weight of the personal care composition.
Such soaps can include a typical soap, i.e., an alkali metal or
alkanol ammonium salt of an alkane- or alkene monocarboxylic acid.
Sodium, magnesium, potassium, calcium, mono-, di- and tri-ethanol
ammonium cations, or combinations thereof, can be suitable for a
personal care composition. The soap included in a personal care
composition can include sodium soaps or a combination of sodium
soaps with from about 1% to about 25% ammonium, potassium,
magnesium, calcium, or a mixture of these soaps. Additionally, the
soap can be well-known alkali metal salts of alkanoic or alkenoic
acids having from about 12 to about 22 carbon atoms or from about
12 to about 18 carbon atoms. Another suitable soap can be alkali
metal carboxylates of alkyl or alkene hydrocarbons having from
about 12 to about 22 carbon atoms. Additional suitable soap
compositions are described in U.S. Pre-Grant Publication No.
2012/0219610 A1.
[0485] A personal care composition can also include soaps having a
fatty acid. For example, one bar soap composition could contain
from about 40% to about 95% of a soluble alkali metal soap of
C.sub.8-C.sub.24 or C.sub.10-C.sub.20 fatty acids. The fatty acid
can, for example, have a distribution of coconut oil that can
provide a lower end of a broad molecular weight range or can have a
fatty acid distribution of peanut or rapeseed oil, or their
hydrogenated derivatives, which can provide an upper end of the
broad molecular weight range. Other such compositions can include a
fatty acid distribution of tallow and/or vegetable oil. The tallow
can include fatty acid mixtures that can typically have an
approximate carbon chain length distribution of 2.5% C.sub.14, 29%
C.sub.16, 23% C.sub.18, 2% palmitoleic, 41.5% oleic, and 3%
linoleic. The tallow can also include other mixtures with a similar
distribution, such as fatty acids derived from various animal
tallows and/or lard. In one example, the tallow can also be
hardened (i.e., hydrogenated) such that some or all unsaturated
fatty acid moieties can be converted to saturated fatty acid
moieties.
[0486] Suitable examples of vegetable oil include palm oil, coconut
oil, palm kernel oil, palm oil stearine, soybean oil, and
hydrogenated rice bran oil, or mixtures thereof, since such oils
can be among more readily available fats. One example of a suitable
coconut oil can include a proportion of fatty acids having at least
12 carbon atoms of about 85%. Such a proportion can be greater when
mixtures of coconut oil and fats such as tallow, palm oil, or
non-tropical nut oils or fats can be used where principle chain
lengths can be C.sub.16 and higher. The soap included in a personal
care composition can be, for example, a sodium soap having a
mixture of about 67-68% tallow, about 16-17% coconut oil, about 2%
glycerin, and about 14% water.
[0487] Soap included in a personal care composition can also be
unsaturated in accordance with commercially acceptable standards.
For example, a soap included in a personal care composition can
include from about 37% to about 45% unsaturated saponified
material.
[0488] Soaps included in a personal care composition can be made,
for example, by a classic kettle boiling process or modern
continuous soap manufacturing processes wherein natural fats and
oils such as tallow or coconut oil or their equivalents can be
saponified with an alkali metal hydroxide using procedures well
known to those skilled in the art. Soap can also be made by
neutralizing fatty acids such as lauric (C.sub.12), myristic
(C.sub.14), palmitic (C.sub.16), or stearic (C.sub.18) acids, with
an alkali metal hydroxide or carbonate.
[0489] Soap included in a personal care composition could also be
made by a continuous soap manufacturing process. The soap could be
processed into soap noodles via a vacuum flash drying process. One
example of a suitable soap noodle comprises about 67.2% tallow
soap, about 16.8% coconut soap, about 2% glycerin, and about 14%
water, by weight of the soap noodle. The soap noodles can then be
utilized in a milling process to finalize a personal care
composition.
[0490] Test Methods for the Commercial Products/Formulations
[0491] Viscosity Test Method
[0492] Viscosity is measured using an AR 550 rheometer/viscometer
from TA instruments (New Castle, Del., USA), using parallel steel
plates of 40 mm diameter and a gap size of 500 .mu.m. The high
shear viscosity at 20 s.sup.-1 is obtained from a logarithmic shear
rate sweep from 0.1 s.sup.-1 to 25 s.sup.-1 in 3 minutes time at
21.degree. C.
[0493] Test Method for Determining the Logarithm of the
Octanol/Water Partition Coefficient (log P)
[0494] The value of the log of the Octanol/Water Partition
Coefficient (log P) is computed for each PRM in the perfume mixture
being tested. The log P of an individual PRM is calculated using
the Consensus log P Computational Model, version 14.02 (Linux)
available from Advanced Chemistry Development Inc. (ACD/Labs)
(Toronto, Canada) to provide the unitless log P value. The
ACD/Labs' Consensus log P Computational Model is part of the
ACD/Labs model suite.
CLEANING AND/OR TREATMENT COMPOSITION EXAMPLES
[0495] A series of cleaning and/or treatment compositions are
prepared and evaluated as follows: the examples being designated
with the letters CL followed by the sequence to distinguish from
the microcapsule examples, noted above. In each example and table
below, the amounts of each ingredient is presented as a wt %.
Example CL1--Light Cleaning/Additive Composition
[0496] A liquid composition for very light cleaning or additive to
the laundry process is prepared with microcapsules of the present
invention by combining the microcapsules with the additional
ingredients presented in Table 6.
TABLE-US-00006 TABLE 6 Ingredients Amount Nonionic Surfactant (1)
0-10 Emulsifier (2) 0-10 Cationic surfactant 0-10 Anti-bac 0-5 Free
(Neat) Perfume 0-10 Microcapsules (3) 0-10 Structurant 0-0.3
Aesthetics Dye 0.015 Water Balance (1) Alkyl ethoxylate with alkyl
chain length between C8 and C18, preferably C12 to C16 and mixtures
thereof with 3 to 12 ethoxylate groups, preferably 5 to 9. (2)
Emulsifier description, including Cremophor, Basophor, Spans and
Tweens, etc. (3) Microcapsules made in accordance with the examples
of the present specification
Example CL 2--Liquid Detergent Compositions
[0497] A HDL-Heavy Duty Liquid composition is prepared with
microcapsules of the present invention by combining the
microcapsules with the additional ingredients presented in Table 7.
The exemplified space is meant to represent dilute to concentrated
detergent products. The resulting detergent liquid product when
used to wash articles of clothing is effective at freshening washed
clothing.
TABLE-US-00007 TABLE 7 Ingredient % wt Active Alkyl (ethoxy)
sulfate (1) 0-30 Linear alkyl benzene sulfonic acid (2) 0-30 HSAS
(3) 0-30 Nonionic Surfactant (4) 0-15 Amine Oxide 0-8 Citric Acid
0-10 Lactic Acid 0-10 C.sub.12-C.sub.18 Fatty Acid 0-5 Protease
(55.3 mg/g) 0-3 Amylase (25.4 mg/g) 0-2 Borax 0-5 Calcium Formate
0-0.5 Polyethyleneimine 600, EO20 (5) 0-5 Polyethyleneimine 600,
EO24, PO16 (6) 0-5 DTPA (7) 0-5 Optical Brightener (8) 0-1 NaOH As
needed Na Cumene Sulfonate 0-5 Na Formate 0-1 MEA hydrogenated
castor oil 0-0.5 Aesthetics Dye 0-1.0 Free (Neat) Perfume 0-3.0
Microcapsules (9) 0-5 Water and Solvent To 100 pH 3.5-8.5 (1)
Typically the alkyl group has about 12 to about 18 carbons and with
0 to about 3 ethoxylate groups. (2) Typically the alkyl group has
about 10 to about 16 carbons. (3) HSAS is secondary alkyl sulfate,
acid form (4) Alkyl ethoxylate with about 12 to about 18 carbons
and about 5 to about 9 moles ethoxylation. (5) Polyethyleneimine at
about 600 molecular weight reacted with about 20 moles of ethylene
oxide. (6) Polyethyleneimine at about 600 molecular weight reacted
with about 24 moles of ethylene oxide and about 16 moles of
propylene oxide. (7) Select optical brighteners from one or more of
the following, Brightener 14, Brightener 36, Brightener 49. (8)
Select chelant from one or a combination of the following
non-limiting list DTPA is diethylene triamine pentaacetic acid,
Tiron .RTM. is 4,5-Dihydroxy-1,3-benzenedisulfonic acid disodium
salt monohydrate, EDTA ethylene diamine tetra acetate, HEDP
1-Hydroxyethylidene-1,1-diphosphonic Acid, Octapirox
1-Hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)-pyridone
Ethanolamine, EDDS Ethylenediamine-N,N'-disuccinic acid. (9)
Microcapsules made in accordance with the examples of the present
specification
Example CL3--Liquid Fabric Enhancer Composition
[0498] Examples of liquid fabric enhancer compositions are prepared
with microcapsules of the present invention by combining the
microcapsules of the present invention with the additional
ingredients as presented in Table 8.
TABLE-US-00008 TABLE 8 Ingredient A B C D FSA.sup.1 12 21 18 14 Low
MW alcohol 1.95 3.0 3.0 2.28 Structurant 1.25.sup.2 NIL 0.2.sup.3
NIL Free (Neat) Perfume 1.50 1.8 2.0 1.50 Microcapsules.sup.4 4.0
1.85 1.85 3.7 Calcium Chloride 0.10 0.12 0.1 0.45 DTPA.sup.6 0.005
0.005 0.005 0.005 Preservative (ppm).sup.7 5 5 5 5 Antifoam.sup.8
0.015 0.15 0.11 0.011 Polyethylene imines.sup.9 0.15 0.05 NIL 0.1
PDMS emulsion.sup.10 NIL 0.5 1 2.0 Dispersant.sup.11 NIL NIL 0.5
0.2 Organosiloxane.sup.12 5 NIL NIL NIL Front-end Stability Aid
0.06.sup.13 0.63.sup.14 0.36.sup.13 0.14.sup.14 Dye (parts per
million ppm) 40 11 30 40 Ammonium Chloride 0-0.1 0-0.1 0-0.1 0.10
Hydrochloric Acid 0.010 0.01 0.10 0.010 Water Balance Balance
Balance Balance
.sup.1N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride.
.sup.2Cationic high amylose maize starch-available from National
Starch under the trade name HYLON VII .RTM.. .sup.3Cationic polymer
available from BASF .RTM. under the name Rheovis .RTM. CDE.
.sup.4Microcapsules made in accordance with the examples of the
present specification .sup.5Diethylene triamine pentaacetic acid
.sup.619% active aqueous solution of 1,2 Benzisothiazolin-3-one
(BIT) in dipropylene glycol and water available from Dow Chemical
under the trade name Koralone B-119 .sup.7Silicone antifoam agent
available from Dow Corning .RTM. under the trade name DC2310.
.sup.8Polyethylene imines available from BASF under the trade name
Lupasol .RTM.. .sup.9Polydimethylsiloxane emulsion from Dow Corning
.RTM. under the trade name DC346. .sup.10Non-ionic such as TWEEN 20
.TM. or cationic surfactant as Berol 648 and Ethoquad .RTM. C 25
from Akzo Nobel. .sup.11Organosiloxane polymer condensate made by
reacting hexamethylenediisocyanate (HDI), and a, w silicone diol
and 1,3-propanediamine, N'-(3-(dimethylamino)propyl)-
N,N-dimethyl-Jeffcat Z130) or
N-(3-dimethylaminopropyl)-N,Ndiisopropanolamine (Jeffcat ZR50)
commercially available from Wacker Silicones, Munich, Germany.
.sup.12Fineoxocol .RTM. 1.80 from Nissan Chemical Co. .sup.13Isofol
.RTM. 16 from Sasol. **For example PGE
[0499] Liquid fabric enhancer compositions in EXAMPLE CL3 are made
by combining the molten fabric softener active with the front-end
stability agent to form a first mixture. This first mixture is
combined with water and hydrochloric acid using a high shear mixing
device to form a second mixture. The adjunct ingredients are
combined with the second mixture using low shear mixing to form the
fabric enhancing formula.
[0500] Liquid fabric enhancer compositions in EXAMPLE CL3 are used
by dosing 10 to 60 g of the formula into the rinse liquor for
example via dispensing into a clothes washing machine. Clothes are
dried on a line or in an automated clothes dryer. The fabrics
treated with these formulas have improved feel and scent.
Example CL4--Liquid Fabric Enhancer Composition
[0501] Examples of liquid fabric enhancer compositions are prepared
with microcapsules of the present invention by combining the
microcapsules with the additional ingredients as presented in Table
9.
TABLE-US-00009 TABLE 9 Ingredients A B C D E F G H I DEEDMAC.sup.1
16 9 9 12 4 NIL NIL NIL NIL Dialkyl NIL NIL NIL NIL NIL 7 2.5 9 11
esterdimethyl ammonium methyl sulfate.sup.2 HCl 0.02 0.01 0.01 0.01
NIL 0.01 NIL 0.01 0.01 Fromic Acid 0.05 0.05 0.05 0.05 0.05 0.05
0.025 0.05 0.05 Proxel .RTM..sup.3 0.02 0.02 0.02 0.02 0.02 0.02
0.02 0.02 0.02 CaCl2 1 0.3 0.3 0.4 NIL 0.3 NIL 0.1 0.1 Antifoam 0.2
0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 MP10.sup.4 Rheovis 0.1 NIL NIL NIL
0.4 0.1 0.2 NIL 0.2 CDE .RTM..sup.5 Flosoft .RTM..sup.6 NIL 0.1 0.1
0.05 NIL NIL NIL 0.3 NIL Bardac 2250 .RTM..sup.7 NIL NIL 0.5 NIL
NIL NIL NIL NIL 0.5 NaHEDP.sup.8 0.03 0.03 0.03 0.03 0.03 0.03 0.03
0.03 0.03 Genapol NIL NIL NIL NIL NIL NIL NIL 0.6 0.8 T680
.RTM..sup.9 CAE10.sup.10 NIL 0.6 NIL NIL NIL NIL NIL NIL NIL
Glycerol NIL 10 NIL NIL NIL NIL NIL NIL 5 Perfume 0-2 0-1 0-1.5 0-3
0-2.3 0-1.5 0-3 0-0.8 0-0.5 Encapsulated 0-0.25 0-0.5 0-1 0-0.6
0-1.5 0-3 0-0.5 0-1 0-5 perfume Water To 100 To 100 To 100 To 100
To 100 To 100 To 100 To 100 To 100 .sup.191% activity, 9%
isopropanol, supplied by Evonik .sup.2Reaction product of
triethanolamine and alkyl and/or fatty acids followed by
methylation. .sup.3Proxel GXL, 20% activity, supplied by Lonza
.sup.4MP10, 8% activity, supplied by Dow Corning .sup.5Rheovis CDE,
supplied by BASF .sup.6Flosoft 222, supplied by SNF .sup.7Bardac
2250, 50% activity, supplied by Lonza .sup.820% activity
.sup.9Genapol T680, supplied by Clariant .sup.10C12-14 ALCOHOL
ETHOXYLATE AE 10 (24E10)
Example CL5--Soluble Uni-Dose Heavy Duty Liquid Composition
[0502] Examples of Soluble Uni-dose heavy duty liquid composition
are prepared with microcapsules of the present invention by
combining the microcapsules with the additional ingredients as
presented in Table 10. The resulting Unidose pouch product when
used to wash articles of clothing is effective at freshening
garments.
TABLE-US-00010 TABLE 10 F 3 compartments A B C D E pouched product
Form liquid liquid liquid Liquid gel liq liq liq Compartment # 1 1
1 1 1 1 2 3 Dosage (g) 36.0 38.0 32.0 36.0 40.0 34.0 25 35
Alkylbenzene 14.5 13.8 16.0 14.5 13.5 14.5 20.0 NIL sulfonic acid
C.sub.12-14 alkyl ethoxy 8.5 16.4 10.0 8.5 15.0 8.5 NIL NIL 3
sulfate C.sub.12-13 alkyl 3- NIL NIL NIL 13.0 NIL NIL NIL NIL
ethoxylate C.sub.12-14 alkyl 7- 12.5 9.0 14.0 NIL 4.0 12.5 17.0 NIL
ethoxylate C12-18 Fatty acid 14.5 8.5 16.0 15.0 7.2 14.5 13.0 NIL
Citric acid NIL NIL NIL 2.0 4.1 NIL NIL NIL Enzymes 0-3 0-3 0-3 NIL
0-3 0-3 0-3 NIL PAP granule.sup.1 NIL NIL NIL NIL NIL NIL NIL 50.0
Ethoxysulfated NIL 3.0 NIL NIL NIL NIL 2.2 NIL Hexamethylene
Diamine Dimethyl Quat Ethoxylated 4.0 1.0 NIL 4.0 3.0 2.0 NIL NIL
Polyethylenimine Hydroxyethane 1.0 1.0 NIL NIL 1.6 0.6 0.6 NIL
diphosphonic acid Ethylene diamine NIL NIL NIL 1.0 NIL NIL NIL NIL
tetra(methylene phosphonic) acid Brightener 0.2 0.2 0.3 0.3 0.2 0.2
0.2 NIL Polydimethyl NIL NIL 3.0 NIL NIL NIL NIL NIL Siloxane
Hueing dye.sup.2 NIL NIL NIL NIL NIL NIL 0.05 NIL Perfume 0-3.0
0-3.0 0-3.0 0-3.0 0-3.0 0-3.0 NIL NIL Microcapsules of 0-5 0-5 0-5
0-5 0-5 0-5 NIL NIL the present invention Water and minors To 100%
Buffers (sodium To pH 8.0 carbonate, monoethanolamine) Solvents To
100% (1,2 propanediol, ethanol), Sulfate
.sup.1.epsilon.-Phthalimido-peroxy-hexanoic acid particles made by
Solvay Chemicals International, Brussels, Belgium.
Example CL 6--Dish Cleaning Composition
[0503] Examples of Dish cleaning compositions are prepared with
microcapsules of the present invention by combining the
microcapsules with the additional ingredients presented in Table
11.
TABLE-US-00011 TABLE 11 EXAMPLES A B C D E F G Alkyl C.sub.10-14
Ethoxy Sulphate 26.9 NIL NIL 25.7 NIL 11.1 21.0 (AE0.6S) Alkyl
C.sub.10-14 Ethoxy Sulphate NIL 18.7 26.9 NIL 18.7 NIL NIL (AE2S)
Sodium alkyl benzene sulfonate NIL 8.0 NIL NIL NIL NIL NIL Sodium
paraffin sulfonate NIL NIL NIL NIL 8.0 NIL NIL C12-14 dimethyl
amine oxide 6.1 NIL NIL 4.1 NIL 3.7 10.0 Cocamido propyl betaine
NIL 4.5 6.8 3.2 6.0 NIL NIL C12-13 EO7 nonionic NIL NIL NIL NIL NIL
1.0 2.0 Branched Nonionic: 3-propyl 1.0 0.8 NIL NIL NIL NIL 1.0
heptanol EO8 PEI600-EO10-PO7 block NIL NIL 0.8 NIL NIL 0.4 0.8
polymer Perfume 0-2 0-2 0-2 0-2 0-2 0-2 0-2 Perfume microcapsule of
the 0-1 0-0.5 0-0.5 0-1.5 0-0.5 0-0.8 0-2 present invention Ethanol
4.0 5.0 3.0 3.0 2.0 NIL 3.0 Polypropylene glycol MW2000 1.1 0.8 1.1
1.1 1.1 0.5 1.1 Sodium Chloride 1.3 0.8 1.3 0.5 0.8 1.3 1.3 Minors*
and water to balance up to 100%
Example CL7--Compositions for Use in Cleaning in an Automatic
Dishwashing Machine
[0504] Automatic dish washing compositions are prepared with
microcapsules of the present invention by combining the
microcapsules with the additional ingredients presented in Table
12. Some aspects of the present invention have at least one water
soluble compartment, preferably composed of Monosol 660 mm M8630K
Water Soluble Film. In other aspects of the present invention the
unit dose composition has more than one compartment and at least
one of the compartments comprises powder as in EXAMPLE CL7 A.
TABLE-US-00012 TABLE 12 % wt Active A B C Ingredients POWDER LIQUID
LIQUID Sodium sulfate 0-15 2-7 NIL Soda ash 20-50 NIL NIL Zinc
carbonate NIL 0.1-0.2 NIL Zinc sulfate NIL NIL 0.3-0.7 Sodium
silicate 0-2 3-15 1-2 Sodium bicarbonate NIL NIL 15-25 Glutamic
acid-N,N-diacetic acid, NIL NIL 3-7 tetra sodium salt. Citric acid
NIL NIL 1-2 NaOH (preferably low iron) NIL 0-1.5 Carboxylate
polymer, GT101 2.5-7 NIL 1.25 Plurafac SLF 180 0.2-1.5 NIL 0.25-0.6
MDGA 5-15 NIL NIL Polyacrylate thickener Polygel NIL 0.7-2.3 NIL
DKP Acrylic/sulfonic dispersant Acusol 2-10 NIL NIL 588 Acrylic
acid polymer Acusol NIL 1-3 NIL 425 N Sodium hypochlorite bleach
0-30 0.3-1.5 NIL Ultimase 0-2 NIL NIL Stainzyme 0-1 NIL NIL
Savinase Ultra 16XL NIL NIL 0.2-0.5 Termamyl Ultra 300 L NIL NIL
0.1-0.15 Calcium Chloride NIL NIL 0.3-0.4 Dipropylene Glycol NIL
NIL NIL Nonionic Surfactant NIL 9-50 NIL Plurafac SLF 180 NIL 25-60
NIL Glycerine NIL 0-1 NIL Dye NIL 0-0.1 NIL Nitric acid NIL
0.005-0.05 NIL Preservative sodium benzoate NIL 0.25-0.8 0.2-0.8
Perfume 0-1 0-1 0-1 Microcapsules of the present 0-2 0-2 0-2
invention Balance Water To 100 To 100 To 100 Fatty acid has C12 to
C14 alkyl groups and mixtures thereof Rheovis .RTM. AT 120 is a
methacrylate/acrylic acid copolymer.
Example CL8--Spray for Cleaning Hard Surfaces
[0505] A spray for cleaning hard surfaces is prepared with
microcapsules of the present invention by combining the
microcapsules with the additional ingredients presented in Table
13.
TABLE-US-00013 TABLE 13 Ingredients % wt Active C.sub.13-15 alkyl
ethoxylate (30) 0-0.5 C.sub.9-11 alkyl ethoxylate (8) 0-0.5
C.sub.12/14 Amine-oxide 0-3 Barquat 4280-Z 0-3 Ethylene glycol
monohexyl ether 0-1 Phenoxyethanol 0-1 Dense Soda ash 0-0.3
Pentasodum diethylene triamine (DTPA) 0-0.4 Tartaric acid 0-0.1 Dye
0-1.2 1,2-Benzisothioazolin-3-one 0-0.1 Perfume 0-1 Microcapsules
of the present invention 0-0.5 Balance Water To 100
Solid Consumer Products Examples
Example CL9--Free Flowing Particles
[0506] Free flowing particles are prepared with microcapsules of
the present invention by combining the microcapsules with the
additional ingredients presented in Table 14.
TABLE-US-00014 TABLE 14 % wt Active Ingredients A B C D
Polyethylene 70-99 0-20 0-29 0-40 glycol Clay 0-29 0-20 0-20 0-10
NaCl 0-29 50-99 0-29 0-40 Na2SO4 0-10 0-10 0-10 0-5 Urea 0-29 0-29
0-99 0-40 Polysaccharide 0-29 0-29 0-29 0-5 Zeolite 0-29 0-29 0-29
0-5 Plasticizers/ Solvents Starch/Zeolite 0-29 0-29 0-29 0-5 Silica
0-5 0-5 0-5 0-5 Metal oxide 0-29 0-29 0-29 0-29 Metal catalyst
0.001-0.5 0.001-0.5 0.001-0.5 0.001-0.5 Opacifier 0-5 0-5 0-1 0-1
Water 0-2 0-2 0-5 0-5 Perfume 0-5 0-5 0-5 0-5 Microcapsules 0-10
0-4.5 0-3 0-7.5 made in accordance with the examples of the present
specification
Example CL10--Spray-Dried Laundry Detergent Powder Composition
[0507] Spray-Dried Laundry Detergent Powder compositions are
prepared with microcapsules of the present invention by combining
the microcapsules with the additional ingredients as presented in
Table 15.
TABLE-US-00015 TABLE 15 Ingredients wt. % Active Slurry A B C D
Linear alkyl benzene sulfonate 10.6 15.8 21.3 35.7 Acrylate/maleate
copolymer 4.6 6.8 9.4 14.2 Ethylenediame disuccinic acid 1.4 2.1
1.7 7.9 and/or Hydroxyethane dimethylene phosphonic acid Sodium
carbonate 19.4 26.5 18.8 29.9 Sodium sulfate 28.6 42.4 -- --
Carboxy methyl cellulose polymer -- -- 4.3 7.1 Carboxy methyl
cellulose polymer -- -- 4.3 7.1 Miscellaneous, such as magnesium
1.4 2.2 2.5 4.2 sulfate, brightener and one or more stabilizers
Perfume 0-3 0-2 0-2 0-3 Microcapsules made in accordance 0-5 0-5
0-5 0-5 with the examples of the present specification Water
Balance Balance Balance Balance
[0508] A first spray-dried laundry detergent powder is formed from
an aqueous slurry, slurry A from Table 15, which is prepared having
a moisture content of 34.0%. Any ingredient added above in liquid
form is heated to 70.degree. C., such that the aqueous slurry is
never at a temperature below 70.degree. C. At the end of
preparation, the aqueous slurry is heated to 80'' C. and pumped
under pressure (5.times.10.sup.6 Nm.sup.-2) into a counter current
spray-drying tower with an air inlet temperature of from
290.degree. C. The aqueous slurry is atomized and the atomized
slurry is dried to produce a solid mixture, which is then cooled
and sieved to remove oversize material (>1.8 mm) to form a
spray-dried powder, which is free-flowing. Fine material (<0.15
mm) is elutriated with the exhaust the exhaust air in the
spray-drying tower and collected in a post tower containment
system. The spray-dried powder has a moisture content of 2.0 wt %,
a bulk density of 310 g/l and a particle size distribution such
that greater than 90 wt % of the spray-dried powder has a particle
size of from 1.50 to 710 micrometers. The composition of the
spray-dried powder A is listed in the Table 15. Perfume and
microcapsules are sprayed onto the composition following the spray
dry procedure.
[0509] A second spray-dried laundry detergent powder is formed from
an aqueous slurry, slurry B from Table 15, having a moisture
content of 42.0%. Any ingredient added above in liquid form is
heated to 70.degree. C., such that the aqueous slurry is never at a
temperature below 70.degree. C. At the end of preparation, the
aqueous slurry is heated to 85.degree. C. and pumped under pressure
(from 6.5.times.1.0.sup.6 Nm.sup.-2), into a counter current
spray-drying tower with an air inlet temperature of from
275.degree. C. The aqueous slurry is atomized and the atomized
slurry is dried to produce a solid mixture, which is then cooled
and sieved to remove oversize material (>1.8 mm) to form a
spray-dried powder B, which is free-flowing. Fine material
(<0.15 mm) is elutriated with the exhaust the exhaust air in the
spray-drying tower and collected in a post tower containment
system. The spray-dried powder has a moisture content of 3.0 wt %,
a bulk density of 250 g/l and a particle size distribution such
that greater than 90 wt % of the spray-dried powder has a particle
size of from 150 to 710 micrometers. The composition of the
spray-dried powder is given in Table 15. Perfume and microcapsules
are sprayed onto the composition after the spray dry process.
Example CL11--Freshening Composition
[0510] Liquid fabric spray fabric freshening compositions are
prepared with microcapsules of the present invention by combining
the microcapsules with the additional ingredients as presented in
Table 16 The resulting fabric refreshing spray product when used to
treat fabric surfaces is effective at freshening a treated
fabric.
TABLE-US-00016 TABLE 16 Ingredient A B C D E Deionized Water
Balance Balance Balance Balance Balance Ethanol 3.0 3.0 3.0 3.0 3.0
Lupasol HF.sup.1 NIL NIL NIL NIL NIL Hydroxypropyl b-CD NIL NIL NIL
NIL NIL Diethylene Glycol NIL NIL NIL NIL NIL Silwet L-7600 0.1 0.1
0.1 0.100 0.100 Basophor EL60.sup.2 NIL 0.05 0.05 0.05 0.05 Maleic
Acid and/or Citric As As As As As Acid.sup.3 needed needed needed
needed needed Koralone B-119 0.015 0.015 0.015 0.015 0.015
Hydroxypropyl .beta.- NIL NIL NIL NIL NIL cyclodextrin Sodium
Hydroxide.sup.3 As As As As As needed needed needed needed needed
Microcapsules made in 1 2 0.1 5 0.05 accordance with the examples
of the present specification Fragrance 0 0 0 0 0 Target pH 6.8 6.8
6.8 6.8 6.8 Total 100 100 100 100 100
Example CL12--Dryer Added Fabric Softener Sheet Composition
[0511] A series of dryer added fabric softener sheet compositions
are prepared with microcapsules of the present invention by
combining the microcapsules with the additional ingredients as
presented in Table 17. The compositions A-D of this example are
mixed homogeneously and impregnated onto a non-woven polyester
sheet having dimensions of about 6% in .times.12'' about 17.1
cm.times.30.5 cm) and weighing about 1 gram. The resulting dryer
added fabric softener sheet product when added to an automatic
dryer is effective at softening, freshening and reducing the static
on clothing that contact the sheet.
TABLE-US-00017 TABLE 17 B A Wt % C D Ingredient Wt % Active Active
Wt % Active Wt % Active DEQA.sup.1 0-50 50 -- -- DEQA.sup.2 0-50 --
-- 30 DTDMAMS.sup.3 0-50 -- 50 -- 7018FA.sup.4 0-50 -- 50 --
TS-20.sup.5 0-15 -- -- 15 SMS.sup.6 0-15 -- -- 15 SDASA.sup.7 0-19
25 -- 19 TPED.sup.8 -- 3 -- -- Complex.sup.9 0-16.5 16.5 -- 8.0
Clay.sup.10 Balance Balance Balance Balance Free (Neat) Perfume 0-4
0-1.5 0-3 0-1.5 Microcapsules.sup.11 0-4 0-4 0-2 0-2 Active Weight
2.4 2.4 1.9 2.4 (g/sheet) .sup.1DEQA.sup.1: Di(soft
tallowoyloxyethyl)dimethylammonium methyl sulfate with 25%> 7018
FA, as described below, as solvent .sup.2DEQA.sup.2: Di(soft
tallowoyloxyethyl)hydroxyethylmethylammoniun methyl sulfate with
18% partially hydrogenated tallow fatty acid solvent .sup.3DTDMAMS:
Di(hydrogenated tallowalkyl)dimethylammonium methyl sulfate
.sup.47018FA: 70:30 Stearic Acid:Palmitic Acid (IV = 0) Industrene
7018 sold by Witco .sup.5TS-20: Polyoxyethylene-20 Sorbitan
Tristearate (Glycosperse TS-20, sold by Lonza .sup.6SMS: Sorbitan
Mono Stearate .sup.7SDASA: 1:2 ratio of stearyl dimethyl
amine:triple pressed stearic acid .sup.8TPED:
N,N,N',N'-Tetrakis(2-hydroxypropyl)ethylenediamine (Quadrol, sold
by BASF) .sup.9Complex: Beta-Cyclodextrin/Perfume Complex
.sup.10Clay: Calcium Bentonite Clay (Bentonite L sold by Southern
Clay Products Free (Neat) Perfume .sup.11Microcapsules made in
accordance with the examples of the present specification
Examples CL13-CL15--Absorbent Articles
Example CL13--Pads for Menstrual Odor Control
[0512] The microcapsules of the present invention are added into
the core of an Always Ultra Thin Unscented menstrual pad.
Optionally, a neat fragrance is preferably added beneath the core
of the article.
Example CL14--Heavy AI Pants for Urine Odor Control
[0513] The microcapsules of the present invention are added into
the core of an Always Discreet Adult Incontinence Underwear,
moderate absorbency. Optionally, a neat fragrance is preferably
added beneath the core of the article.
Example CL15--Diapers for Odor Control
[0514] The microcapsules of the present invention are added into
the core of an Pampers Cruisers Baby Diaper. Optionally, a neat
fragrance is preferably added beneath the core of the article.
Examples CL16-CL17--Personal Care Compositions
Example CL16--Body Wash
[0515] Body Wash compositions are prepared with microcapsules of
the present invention by combining the microcapsules with the
additional ingredients as presented in Table 18.
TABLE-US-00018 TABLE 18 Body Wash A B C Sodium Laureth-3 Sulfate
(as 28% active) 27.85% 27.85% 27.85% Water Q.S. Q.S. Q.S. Sodium
Lauryl Sulfate (as 29% active) 10.34 10.34 10.34 Cocamidopropyl
Betaine B (30% active) 4.01 4.01 4.01 Citric Acid 0.18 0.18 0.18
Sodium Benzoate 0.3 0.3 0.3 Disodium EDTA 0.12 0.12 0.12
Methylchloroisothiazolinone/ 0.04 0.04 0.04 Methylisothiazolinone
Sodium Chloride 2.35 1.7 1.6 Neat Perfume 1.25 1 2 Microcapsules
made in accordance with the 0.25 0.175 0.25 examples of the present
specification QS - indicates that this material is used to bring
the total to 100%
Example CL17--Shampoos
[0516] Shampoo compositions are prepared with microcapsules of the
present invention by combining the microcapsules with the
additional ingredients as presented in Table 19.
TABLE-US-00019 TABLE 19 A B C Ingredient Wt % D E F Ammonium
Laureth Sulfate.sup.1 14.1 14.1 14.1 14.1 14.1 14.1 Ammonium Lauryl
Sulfate.sup.2 3.1 3.1 3.1 3.1 3.1 3.1 Ammonium
Xylenesulfonate.sup.3 0.45 0.45 0.45 0.45 0.45 0.45 TWEEN 60.sup.4
3.0 3.0 3.0 3.0 3.0 3.0 Polyquaternium-10.sup.5 0.35 0.35 0.35 0.35
0.35 0.35 Cetrimonium Chloride.sup.6 0.5 0.5 0.5 0.5 0.5 0.5
Selenium Sulfide.sup.7 1.0 1.0 1.0 1.0 0.2 0.2 Dimethicone.sup.8
0.60 0.60 0.60 0.60 0.60 0.60 Ethylene Glycol Distearate.sup.9 3.0
3.0 3.0 3.0 3.0 3.0 Cocamide MEA.sup.10 3.0 3.0 3.0 3.0 3.0 3.0
Zinc Pyrithione.sup.11 -- 0.2 0.2 -- 1.0 1.0 Zinc Carbonate.sup.12
-- -- 1.61 -- -- 1.61 Neat Fragrance 1.1 0.75 0.75 0.65 0.85 1.0
Microcapsules made in 0.25 0.25 0.175 0.175 0.175 0.175 accordance
with the examples of the present specification Cetyl Alcohol.sup.13
0.42 0.42 0.42 0.42 0.42 0.42 DMDM Hydantoin 0.40 0.40 0.40 0.40
0.40 0.40 Sodium Chloride 0.30 0.30 0.30 0.30 0.30 0.30 Stearyl
Alcohol.sup.14 0.20 0.20 0.20 0.20 0.20 0.20 Hydroxypropyl 0.02
0.02 0.02 0.02 0.02 0.02 Methylcellulose.sup.15 Water Q.S. Q.S.
Q.S. Q.S. Q.S. Q.S. .sup.1Ammonium Laureth Sulfate at 25% active,
supplier: P&G .sup.2Ammonium Lauryl Sulfate at 25% active,
supplier: P&G .sup.3Ammonium Xylene Sulfonate 40% active,
supplier: Stepan .sup.4Polysorbate 60, upplier: Croda .sup.5UCARE
Polymer LR400, supplier - Dow Chemical .sup.6cetrimonium chloride,
supplier - Croda .sup.7Selenium disulfide, supplier Eskay
.sup.8Viscasil 330M from Momentive Performance Materials with a
viscosity of 330,000 cSt (centistokes). .sup.9Ethylene Glycol
Disterate, supplier: Stepan .sup.10Ninol COMF from the Stepan
Company .sup.11Zinc Pyrithione, supplier Lonza .sup.12Zinc
Carbonate Basic, supplier Pan Continental Chemical .sup.13Cetyl
Alcohol, supplier P&G .sup.14Stearyl Alcohol, supplier P&G
.sup.15Methocel, supplier Dow Chemical
Examples CL18-CL20--Antiperspirant and/or Deodorant
Compositions
Example CL18--Deodorants
[0517] Deodorants are prepared with microcapsules of the present
invention by combining the microcapsules with the additional
ingredients as presented in Table 20.
TABLE-US-00020 TABLE 20 Ingredient A B C D E Product Form Solid
Solid Solid Solid Aerosol Deo- Deo- Deo- Deodorant Deodorant dorant
dorant dorant or Body Spray dipropylene glycol 48 48 20 30 20
propylene glycol 19.3 19.3 22 -- -- tripopylene glycol -- -- 25 --
-- Glycerine -- -- -- 10 -- PEG-8 -- -- -- 20 -- Propylene Glycol
1.4 1.4 -- -- -- 3 Myristyl Ether ethanol -- -- -- -- QS Water QS
QS QS QS -- sodium stearate 5.4 5.4 5.5 5.5 -- tetra sodium 0.5 0.5
0.05 0.05 -- EDTA sodium hydroxide -- -- 0.04 0.04 -- triclosan --
-- 0.3 0.3 -- Neat Perfume 2.8 2.8 2 1.5 1.5 Microcapsules 3 0.7
1.0 0.5 0.35 made in accordance with the examples of the present
specification Blue 1 0.0009 0.0009 -- -- -- Propellant (1,1 -- --
-- -- 40 difluoroethane) QS - Indicates that this material is used
to bring the total to 100%.
Example CL19--Antiperspirants
[0518] Antiperspirant compositions are prepared with microcapsules
of the present invention by combining the microcapsules with the
additional ingredients as presented in Table 21.
TABLE-US-00021 TABLE 21 Form Invisible Invisible Invisible Soft
Soft Soft Solid Solid Solid Solid Solid Solid Ingredient A B C D E
F Aluminum Zirconium 24 24 24 26.5 26.5 26.5 Trichlorohydrex
Glycine Powder Cyclopentasiloxane Q.S. Q.S. Q.S. Q.S. Q.S. Q.S.
Dimethicone -- -- -- 5 5 5 CO-1897 Stearyl Alcohol NF 14 14 14 --
-- -- Hydrogenated Castor Oil 3.85 3.85 3.85 -- -- -- MP80
Deodorized Behenyl Alcohol 0.2 0.2 0.2 -- -- -- Tribehenin -- -- --
4.5 4.5 4.5 C18-36 acid triglyceride -- -- -- 1.125 1.125 1.125
C12-15 Alkyl Benzoate 9.5 9.5 5 -- -- -- PPG-14 Butyl Ether 6.5 6.5
-- 0.5 0.5 0.5 Phenyl Trimethicone 3 -- 3 -- -- -- White Petrolatum
3 -- -- 3 3 3 Mineral Oil 1.0 1.0 1.0 -- -- -- Free (Neat) Perfume
1.0 0.75 2.0 0.75 1.0 1.25 Microcapsules made in 0.25 3 0.35 0.175
0.25 0.1 accordance with the examples of the present specification
Beta-Cyclodextrin -- 3.0 -- -- -- 3.0 complexed with Malodor
reducing composition Talc Imperial 250 USP 3.0 3.0 3.0 -- -- -- QS
- indicates that this material is used to bring the total to
100%.
Example CL20--Clear Gel Antiperspirant
[0519] Clear gel antiperspirants are prepared with microcapsules of
the present invention by combining the microcapsules with the
additional ingredients as presented in Table 22.
TABLE-US-00022 TABLE 22 3.1 3.2 3.3 3.4 3.5 Clear Gel Clear Gel
Clear Gel Clear Gel Clear Gel Antiperspirant Antiperspirant
Antiperspirant Antiperspirant Antiperspirant Aluminum 20 18.5 20 18
10 Zirconium Octachlorohydrex Gly Water Q.S Q.S. Q.S. Q.S. Q.S.
Ethanol 5.5 8 6 6.5 5 Propylene Glycol 5.3 5 7 5.5 8 DC 5225c- 7.8
9 6.5 7 8 Cyclopentasiloxane & PEG/PPG- 18/18 Dimethicone
Dimethicone 5.6 4.5 5.8 5 4.1 Cyclopentasiloxane 2.6 3 1 3 2.5 Free
(Neat) 1.0 0.75 2.0 0.75 1.0 Perfume Microcapsules 0.25 -- 0.35
0.175 0.25 made in accordance with the examples of the present
specification QS - indicates that this material is used to bring
the total to 100%.
[0520] For avoidance of doubt and to preclude any unintentional
omission of an embodiment, it is to be appreciated that the present
teaching also pertains to and by this reference incorporates any
and all consumer products and methods of making consumer products
containing or made using, respectively, the microcapsules embraced
by the appended claims as well as the microcapsules resulting from
the methods of the appended claims in combination with at least one
consumer product ingredient. In general, these compositions and
methods will contain or employ, as appropriate, a sufficient amount
of said microcapsules to provide, based on the total consumer
product weight, said consumer product with from 0.001% about to
about 25%, preferably from about 0.01% to about 10%, more
preferably from about 0.05% to about 5%, most preferably from about
0.1% to about 0.5% of said microcapsules.
[0521] The dimensions and values disclosed herein are not to be
understood as being strictly limited to the exact numerical values
recited. Instead, unless otherwise specified, each such dimension
is intended to mean both the recited value and a functionally
equivalent range surrounding that value. For example, a dimension
disclosed as "40 mm" is intended to mean "about 40 mm"
[0522] Every document cited herein, including any cross referenced
or related patent or application is hereby incorporated herein by
reference in its entirety unless expressly excluded or otherwise
limited. The citation of any document is not an admission that it
is prior art with respect to any invention disclosed or claimed
herein or that it alone, or in any combination with any other
reference or references, teaches, suggests, or discloses any such
invention. Further, to the extent that any meaning or definition of
a term in this document conflicts with any meaning or definition of
the same term in a document incorporated by reference, the meaning
or definition assigned to that term in this document shall
govern.
[0523] Although the process and prepared microcapsules of the
present specification as well as various commercial and consumer
products containing/comprising the same have been described with
respect to specific embodiments and examples, it should be
appreciated that the present teachings are not limited thereto and
other embodiments utilizing the concepts expressed herein are
intended and contemplated without departing from the scope of the
present teaching as intended in the true spirit and scope of the
invention. It is therefore intended any and all modifications,
variations, or equivalents that fall within the spirit and scope of
the underlying principles are within the scope of this invention
and are covered by the appended claims.
* * * * *