Note: Descriptions are shown in the official language in which they were submitted.
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COMPOSITIONS CONTAINING CATIONICALLY SURFACE-MODIFIED
MICROPARTICULATE CARRIER FOR BENEFIT AGENTS
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of the filing dates of U.S. Patent
Application
Nos. 12/028,685, filed February 8, 2008, which is a continuation-in-part of
U.S. Pat. Appl.
No. 11/331,248, filed January 12, 2006, which claims the benefit of U.S.
Provisional Pat.
Appl. No. 60/643,430, filed January 12, 2005; 12/152,364, filed May 14, 2008,
which is a
continuation-in-part of U.S. Pat. Appl. No. 11/331,248; 12/327,570, filed
December 3, 2008,
which is a continuation-in-part of U.S. Pat. Appl. Nos. 12/152,364,
12/028,685, and
11/331,248; U.S. Provisional Patent Application Nos. 61/044,381, filed April
11, 2008; and
61/101,336, filed September 30, 2008, each incorporated herein by reference in
their entirety.
FIELD OF THE INVENTION
[0002] The present invention is directed to carrier materials containing one
or more benefit
agents, e.g., a liquid fragrance, that have increased deposition onto
substrates as a result of a
plurality of cationic coating materials.
BACKGROUND OF THE INVENTION
[0003] The consumer products industry has long searched for ways to enhance
the
performance of fabric care products, like a fabric softener, and to make the
products more
esthetically pleasing to consumers. For example, fragrance is an important
ingredient in
successful commercial fabric care products because, in addition to imparting
an esthetically
pleasing odor, a fragrance conveys a positive image of product performance to
the consumer,
e.g., the fabric is clean and fresh.
[0004] Fragrances typically are added to fabric care products to provide a
fresh, clean
impression for the product itself, as well as to the fabric treated with the
product. Although
the fragrance does not enhance the performance of a fabric care product, the
fragrance makes
these products more esthetically pleasing, and consumers expect and demand a
pleasing odor
for such products.
[0005] A fragrance plays an important, and often a determining, role when the
consumer
selects and purchases a fabric care product. Many consumers desire the
fragrance to be
deposited on the fabric and remain on the fabric for an extended time in order
to convey a
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continuing impression of freshness. Consumers also desire fabric care products
that impart a
sufficient fi a~~rance level to the fabric, and, in some embodiments, release
the fragrance when
the fabric is ironed.
[0006] Introduction of a fragrance into a fabric care product is restricted by
considerations
such as availability and cost, and also by an inability of the fragrance to
sufficiently deposit
onto a fabric, and then remain on the fabric during the wash, rinse, and
drying cycles. For
example, a substantial amount of the fragrance deposited on a fabric is
removed from the
fabric during the drying process, even when the treated fabrics are line
dried. It also has been
demonstrated that a substantial amount of the fragrance in currently available
fabric care
products is lost during rinse cycles. This fragrance loss is attributed to the
water solubility of
various fragrance ingredients, to the volatility of fragrance ingredients that
deposit on the
fabric, and the wash-off of the fragrance from the fabric.
[0007] Typical fabric care products, such as laundry detergent compositions
and fabric
softener compositions, contain about 0.1% to about 1%, by weight, of a
fragrance. U.S. Pat.
No. 6,051,540 discloses that in the course of the washing clothes with a
standard powdered
laundry detergent, or a fabric softener rinse, only a small fraction of the
fragrance present in
these fabric care products is actually transferred to the fabric, i.e., as low
as 1% of the
original amount of fragrance present in these products.
[0008] Attempts have been made to increase fragrance deposition onto fabric,
and to
hinder or delay the release of the fragrance from the fabric, such that the
laundered fabric
remains esthetically pleasing for an extended length of time. One approach
uses a carrier to
introduce the fragrance to the fabric. The carrier is formulated to contain a
fragrance and to
adhere to the fabric during a washing cycle through particle entrainment or
chemical change.
[0009] Fragrances have been adsorbed onto various materials, such as silica
and clay, for
delivery of the fragrance from detergents and fabric softeners to fabrics.
U.S. Pat. No.
4,954,285 discloses fragrance particles especially for use with dryer-released
fabric
softening/antistatic agents. The fragrance particles are formed by adsorbing
the fragrance
onto silica particles having a diameter of greater than about one micron. The
fragrance
particles are included in dryer-activated solid fabric softener compositions
including coated
particles of fabric softener. The compositions release softener to fabrics in
the dryer, and the
fragrance particles improve the esthetic character of the fabric softener
deposited on the
fabric. The fragrance particles also can be admixed with detergent granules
and can be coated
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or uncoitcd. This system has a drawback in that the fragrance is not
sufficiently protected,
and frequcntly is lost or destabilized during processing.
[0010] Another problem often associated with perfumed fabric care products is
excessive
odor intensity. A need therefore exists for a fragrance delivery system that
provides
satisfactory fragrance both during use and from the dry laundered fabric, and
also provides
prolonged storage benefits and an acceptable odor intensity of the fabric care
product.
[0011] U.S. Patent No. 6,790,814 discloses that a fragrance loaded into a
porous carrier,
such as zeolite particles, can be effectively protected from premature release
of the fragrance
by coating the loaded carrier particles with a hydrophobic oil, then
encapsulating the resulting
carrier particles with a water-soluble or water-dispersible, but oil-
insoluble, material, such as
a starch or modified starch.
[0012] U.S. Pat. Nos. 4,946,624; 5,112,688; and 5,126,061 disclose
microcapsules
prepared by a coacervation process. The microcapsules have a complex
structure, with a large
central core of encapsulated material, preferably a fragrance, and walls that
contain small
wall inclusion particles of either the core material or another material that
can be activated to
disrupt the wall. The microcapsules are incorporated into a fabric softener
composition
having a pH of about 7 or less and which further contains a cationic fabric
softener. The
encapsulated fragrance preferably is free of large amounts of water-soluble
ingredients. The
microcapsules are added separately to the fabric softener compositions.
Ingredients that have
high and low volatilities, compared to desired fragrance, either can be added
to or removed
from the fragrance to achieve the desired volatility. This type of controlled
release system
cannot be used with all types of fragrance ingredients, in particular, with
fragrance
ingredients that are relatively water soluble and/or are incapable of
depositing onto a fabric.
[0013] U.S. Pat. No. 4,402,856 discloses a coacervation technique to provide
fragrance
particles for fabric care products containing gelatin or a mixture of gelatin
with gum arabic,
carboxymethylcellulose, and/or anionic polymers. The gelatin is hardened with
a natural
and/or synthetic tanning agent and a carbonyl compound. The particles adhere
to the fabric
during rinse cycles, and are carried over to the dryer. Diffusion of the
fragrance from the
capsules occurs only in the heat-elevated conditions of a dryer.
[0014] U.S. Pat. No. 4,152,272 discloses incorporating a fragrance into wax
particles to
protect the fragrance during storage and through the laundry process. The
fragrance/wax
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particles are incorporated into an aqueous fabric conditioner composition. The
fragrance
diffuses from the particles onto the fabric in the heat-elevated conditions of
the dryer.
[0015] U.S. Pat. Nos. 4,446,032 and 4,464,271 disclose liquid or solid fabric
softener
compositions comprising microencapsulated fragrance suspensions. The
compositions
contain sustained release fragrances prepared by combining nonconfined
fragrance oils with
encapsulated or physically entrapped fragrance oils. These combinations are
designed such
that the nonconfined fragrance oil is bound in a network of physically
entrapped fragrance oil
and suspending agent. The controlled release system comprises a mixture of (i)
a nonconfined
fragrance composition, (ii) one or more fragrance oils which are physically
entrapped in one
or more types of solid particles, and (iii) a suspending agent such as
hydroxypropyl cellulose,
silica, xanthan gum, ethyl cellulose, or combinations thereof. The nonconfined
fragrance, the
entrapped fragrance, and the suspending agent are premixed prior to
preparation of the liquid
or solid fabric softener compositions.
[0016] U.S. Pat. Nos. 4,973,422 and 5,137,646 disclose fragrance particles for
use in
cleaning and conditioning compositions. The particles comprise a fragrance
dispersed within
a wax material. The particles further can be coated with a material that
renders the particles
more substantive to the surface being treated, for example, a fabric in a
laundry process. Such
materials help deliver the particles to the fabric and maximize fragrance
release directly on
the fabric. In general, the coating materials are water-insoluble cationic
materials.
[0017] U.S. Pat. No. 6,024,943 discloses particles containing absorbed liquids
and methods
of making the particles. A fragrance is absorbed within organic polymer
particles, which
further have a polymer at their exterior. The external polymer has free
hydroxyl groups,
which promote deposition of the particles from a wash or rinse liquor. The
external polymer
can be a component of an encapsulating shell, but typically is used as a
stabilizer during
polymerization of the particles. A highly hydrolyzed polyvinyl alcohol is a
preferred external
polymer.
[0018] U.S. Pat. No. 6,740,631 discloses a free-flowing powder formed from
solid
hydrophobic, positively-charged nanospheres containing an active ingredient,
such as a
fragrance, encapsulated in a moisture sensitive microsphere. To maximize
deposition of the
nanospheres on a fabric, particle size is optimized to ensure entrainment of
the particles
within the fabric fibers, and a sufficiently high cationic charge density on
the particle surface
is provided to maximize an ionic interaction between the particles and the
fabric.
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[00191 U.S. Pat. No. 7,119,057 discloses a polymeric encapsulated fragrance
where the
fragrance encapsulating polymer is coated with one cationic polymer. The
cationic polymer
aids in the deposition and stability of the polymeric encapsulated fragrance.
The load of the
cationic polymer is preferably from about 10% to about 500% of the fragrance
containing
composition, based on a ratio with the fragrance on a dry basis.
[00201 U.S. Pat. No. 7,119,060 discloses solid spheres comprising a
crystallized waxy
material. The waxy material may have a fragrance or other active agent
incorporated therein,
together with a cationic, hydrophobic charge-enhancing agent and a cationic
softening agent.
The spheres adhere to a fabric because of the cationic charge, and when
ironing a dried
fabric, a burst of fragrance occurs. The load of fragrance or other active
agent is limited to
about 30%, by weight, of the waxy material.
[00211 U.S. Pat. App. No. 11/231,082 discloses the delivery of a benefit agent
that is
introduced into a formulation after admixture with a carrier. The agent and
carrier
composition requires a viscosity of at least 400 cps.
[00221 Generally, the prior art does not sufficiently teach or suggest a
composition having
a microparticulate material coated with one or more layers of two different
cationic polymers
for increased deposition of the microparticulate onto a substrate, such as a
fabric. Moreover,
the prior art does not teach or suggest a methodology for making a
micropartieulate material
containing a benefit agent, such as a fragrance, coated with layers of two
different cationic
polymers.
SUMMARY OF THE INVENTION
[00231 The present disclosure relates to compositions comprising a
cationically surface-
modified microparticulate material, containing at least one benefit agent.
Benefit agents
include flavors, fragrances, insect repellents, silicone oils, fabric
softening agents, anti-static
agents, anti-wrinkle agents, stain-resistant agents, emollients, moisturizing
agents, waxes,
ultraviolet (UV) ray absorbers, antimicrobial agents, antioxidants, pigments,
film-forming
agents, skin-care agents, hair-care agents, scalp-care agents, anti-dandruff
agents, hair-
coloring agents, hair-conditioning agents, and the like. The cationic surface
modification
comprises two different cationic coating materials which increase the
deposition and
retention of the benefit agent-containing microparticulate material on a
substrate, for example
fabric, hair, skin, teeth, and hard surfaces. The disclosed compositions can
further include
additives, for example water, organic solvents, and surfactants, to formulate
commercial
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products. Examples of compositions employing the disclosed benefit agent-
containing
microparticulate materials having a plurality of deposition-enhancing cationic
coating
materials include cleansing products, such as shampoos, conditioners, body
washes,
moisturizing agents, creams, shower gels, soaps, detergents, toothpastes,
surface cleansing
agents, and surface-conditioning agents, such as fabric softeners.
[0024] The microparticulate material can be a mixture of the benefit agent and
a carrier
agent or can be entirely composed of one or more benefit agents. One example
is a
microparticulate that is a porous solid carrier loaded with a benefit agent.
The carrier can be a
polymer (including film-forming polymers, phase-separated or coacervated
polymers, and
water-insoluble polymers, copolymers, and cross-polymers), wax, water-
insoluble organic
solid or liquid, and/or water-insoluble inorganic solid. Additionally, the
microparticulates can
be emulsion droplets formed, for example, from one or more benefit agents
dispersed in two
immiscible liquids. The microparticulate can further be a mixture of a benefit
agent and a
clay, such as a smectite clay, an organoclay, a water-insoluble inorganic
microparticulate
solid, hydrophilic liquid, hydrophobic liquid, gel, gum, solid including
hydrocarbon solid,
ester and/or ether solvent, silicone fluid, elastomer, wax, polymer, and/or
mixtures, or the
like.
[0025] The present disclosure additionally relates to the cationic surface
modification of
the microparticulate with two different polymers, a Type-1 Polymer and a Type-
2 Polymer.
The Type-1 Polymer is a polymer having a cationic atom content in the range of
about 3 to
about 20 wt. % and a weight average molecular weight in the range of about
300,000 to
800,000 Dalton. The Type-2 Polymer is a polymer having a cationic atom content
of about
0.1 to about 3 wt. % and a weight average molecular weight greater than about
1,000,000
Dalton.
[0026] Importantly, the present improved characteristics of the disclosed
composition are
not obtained if the microparticulate is coated with only the Type-1 Polymer or
coated with
only the Type-2 Polymer, if the microparticulate is only coated with less than
about 10%,
more often less than about 60% of the Type-2 Polymer, or if the
microparticulate is coated
with two polymers where one or both do not meet weight average molecular
weight and/or
cationic atom content requirements.
[0027] The herein disclosed compositions and methods provide compositions with
improved characteristics and use much lower amounts of cationic polymer(s)
than previously
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employed in the prior art, making the disclosed compositions more commercially
and
industrially applicable. One important aspect of compositions that employ
significantly lower
amounts of cationic polymer(s) is that the resulting compositions can have a
much higher
concentration of benefit agent(s). Raising the concentration of the benefit
agent in benefit
agent containing compositions, with the herein defined improved
characteristics, decreases
the costs and formulation problems associated with the inclusion of benefit
agent containing
compositions in commercial products. The improved characteristics of the
disclosed
composition include stability against strong coagulation, enhanced deposition,
and enhanced
retention on a substrate. Herein, strong coagulation means the average
particle size in a
dispersion of agglomerated particles is at least three times greater than the
average particle
size in a dispersion of unagglomerated particle. Additional scope and
description can be
found below.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0028] The compositions and methods described herein have microparticulates as
an
integral component. As used herein, microparticulates are a plurality of
different types of
individual particulates having an average particle diameter that varies from
about one to
about 500 pm, preferably from about three to about 100 pm, more preferably
from about six
to about 50 m, and still more preferably from about eight to about ten
microns. Herein,
microparticulates have at least one benefit agent. Microparticulates can be
entirely made of
one or more benefit agents or can be combinations of benefit agent(s) and
particulate
carrier(s).
[0029] Benefit agents are those compositions, chemicals, and formulations that
impart a
desired effect on a substrate whether the benefit agent or substrate is solid,
liquid, gas, or
combination. Examples of substrates include teeth, hair, skin, fabric,
plastic, polymer, glass,
metal, insects, plants, fungus, yeast, foods, drinks, and the like. A benefit
agent can itself be a
solid, liquid, gas, or mixture. Benefit agents include volatile and non-
volatile compounds
and/or compositions. Examples of volatile compounds include fragrances, insect
repellants,
therapeutic agents, and the like.
[0030] Suitable fragrances include but are not limited to fruits such as
almond, apple,
cherry, grape, pear, pineapple, orange, strawberry, raspberry, musk, and
flower scents such as
lavender-like, rose-like, iris-like, and carnation-like. Other fragrances
include herbal scents
such as rosemary, thyme, and sage; and woodland scents derived from pine,
spruce and other
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forest smells. Fragrances may also be derived from various oils, such as
essential oils, or
from plant materials such as peppermint, spearmint and the like. Fragrances
can be familiar
and popular smells such as baby powder, popcorn, pizza, cotton candy and the
like.
Applicable fragrances can be found in U.S. Pat. Nos. 4,534,891, 5,112,688,
5,145,842,
6,844,302 and Perfumes Cosmetics and Soaps, Second Edition, edited by W. A.
Poucher,
1959, all hereby incorporated by reference. The fragrances included in these
references
include acacia, cassie, chypre, cylamen, fern, gardenia, hawthorn, heliotrope,
honeysuckle,
hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cut hay,
orange blossom,
orchids, reseda, sweet pea, trefle, tuberose, vanilla, violet, wallflower, and
the like.
[00311 Applicable insect repellant benefit agents include dichlorvos,
pyrethrin, allethrin,
paled and/or fenthion pesticides disclosed in the U.S. Pat. No. 4,664,064,
incorporated herein
by reference. Preferable insect repellants are citronella) (3,7-dimethyl-6-
octanal), N,N-
diethyl-3-methylbenzamide (DEET), vanillin, and the volatile oils extracted
from turmeric
(Curcuma Tonga), kaffir lime (Citrus hystrix), citronella grass (Cymbopogon
winterianus) and
hairy basil (Ocimum americanum). Moreover, applicable insect repellants can be
mixtures of
insect repellants.
[0032] Examples of therapeutic benefit agents include creams or lotions,
pharmaceuticals,
neutraceuticals, homeopathic agents, and/or other materials.
[00331 Examples of non-volatile benefit agents include silicone oils, resins,
and
modifications thereof such as linear and/or cyclic polydimethylsiloxanes,
amino-modified,
alkyl, aryl, and alkylaryl silicone oils, which preferably have a viscosity
greater than about
50,000 centistokes; organic and inorganic sunscreen actives, for example,
octylmethoxy
cinnamate; antimicrobial agents, for example, 2-hydroxy-2,4,4-
trichlorodiphenylether; ester
solvents, for example, isopropyl myristate; lipids and lipid like substance,
for example,
cholesterol; hydrocarbons such as paraffins, petrolatum, and mineral oil; fish
and vegetable
oils; hydrophobic plant extracts; therapeutic and skin-care reagents, for
example, salicylic
acid, benzoyl peroxide, and retinol; various waxes and soft solids; organic
and inorganic
fabric softening agents; and pigments including inorganic compounds with
hydrophobically
modified surface and/or dispersed in an oil or a hydrophobic liquid.
[00341 Particulate carriers include those materials for encapsulating a
benefit agent.
Particulate carriers can be porous polymeric or solid state materials,
encapsulating shells, and
the like. Examples of encapsulated benefit agents include those described in
U.S. Pat. App.
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No. 10/823,033, incorporated herein by reference, where the fragrances were
encapsulated in
substituted or un-substituted acrylic acid polymer or copolymer cross-linked
with a
melamine- formaldehyde pre-condensate or a urea-formaldehyde pre-condensate.
[0035] Examples of porous particulate carriers for holding benefit agents
include various
adsorbent polymeric microparticles available from AMCOL Int'l Corp., as noted
below. One
class of adsorbent polymeric microparticles is prepared by suspension
polymerization
techniques, as set forth in U.S. Pat. Nos. 5,677,407; 5,712,358; 5,777,054;
5,830,967;
5,834,577; 5,955,552; and 6,107,429, each incorporated herein by reference
(available
commercially under the tradename of POLY-PORE E200, INCI name, ally
methacrylates
crosspolymer, from AMCOL Int'l, Arlington Heights, IL).
[0036] Another class of adsorbent polymeric microparticle is prepared by a
precipitation
polymerization technique, as set forth in U.S. Patent Nos. 5,830,960;
5,837,790; 6,248,849;
and 6,387,995, each incorporated herein by reference (available commercially
under the trade
name of POLY-PORE L200 from AMCOL Int'l).
[0037] Yet another class of adsorbent polymeric microparticle is prepared by a
precipitation polymerization technique as disclosed in U.S. Pat. Nos.
4,962,170; 4,948,818;
and 4,962,133, each incorporated herein by reference. Examples of this class
of absorbent
polymeric microparticle are available commercially under the trade name of
POLYTRAP by
AMCOL Int'l (INCI name of lauryl methacrylate / glycol dimethacrylate cross
polymer).
[0038] Additional adsorbent polymeric microparticles have been developed, for
example
those disclosed in U.S. Pat. Re. 33,429, incorporated herein by reference, and
sold under the
trade name of MACROBEAD by AMCOL Int'l (INCI name of lauryl methacrylate /
glycol
dimethacrylate cross polymer). Other adsorbent polymeric microparticles that
are
commercially available include, for example, MICROSPONGEO (INCI name of methyl
methacrylate / glycol dimethylacrylate crosspolymer), as disclosed in U.S.
Pat. No.
4,690,825, incorporated herein by reference, available from AMCOL Int'l, and
the Poly-
HIPE polymer (e.g., a copolymer of 2-ethylhexyl acrylate, styrene, and
divinylbenzene)
available from BIOPORE Corp., Mountain View, CA.
[0039] In an other embodiment, particulate carriers include combinations of
porous
polymeric or solid state materials, encapsulating shells, absorbent polymeric
microparticles,
adsorbent polymers, and the like. One example of a microparticulate having a
plurality of
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particulate carriers is an absorbent polymeric microparticle including a
benefit agent and
within an encapsulating shell.
[0040] The amount of the particulate carrier may range from about 10% to about
99% by
weight of the microparticulate. One or more of the foregoing benefit agents is
included in the
compositions described herein in an amount varying from about 0.01 to about
80%,
preferably from about 0.1 to about 40%, and most preferably from about 0.5 to
about 20% of
the total weight of the composition.
[0041] Methods for the general encapsulation of fragrances is known in the
art, see for
example U.S. Pat. Nos. 2,800,457, 3,870,542, 3,516,941, 3,415,758, 3,041,288,
5,112,688,
6,329,057, and 6,261,483, each incorporated herein by reference. Preferred
encapsulating
polymers include those formed from melamine-formaldehyde or urea-formaldehyde
condensates, as well as similar types of aminoplasts. Additionally, capsules
made by the
simple or complex coacervation of gelatin are also preferred for use with the
coating.
Capsules having shell walls comprised of polyurethane, polyamide, polyolefin,
polysaccaharide, protein, silicone, lipid, modified cellulose, gums,
polyacrylate,
polyphosphazines, polystyrene, and polyesters or combinations of these
materials are also
applicable.
[0042] Although many variations of materials and process steps are possible,
representative methods used for aminoplast encapsulation and gelatin
encapsulation are
disclosed in U.S. Pat. Nos. 3,516,941 and 2,800,457, respectively, each
incorporated herein
by reference. Both of these processes are discussed in the context of
fragrance encapsulation
and for use in consumer products in U.S. Pat. Nos. 4,145,184 and 5,112,688,
respectively,
each incorporated herein by reference.
[0043] Preferably, the microparticulate has a neutral or anionic surface
charge. The surface
charge on the microparticulate can often be determined by a measurement of the
zeta (c)-
potential and/or electrophoretic mobility. When the microparticulate has a
neutral or cationic
surface charge the microparticulate is often treated with an anionic polymer.
According to
one embodiment of the cationically surface-modified benefit agent-containing
microparticulate materials and methods described herein, the microparticulate
material may
be surface-treated with an anionic polymer or an anionic surfactant or
mixtures thereof
(herein termed anionic treatment agents), prior to the claimed surface-
modification. The
resulting anionic microparticulate material has approximately one monolayer of
the anionic
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polymer and/or surfactant on the surface and is subsequently further surface-
treated as
described below for achieving the claimed cationic surface-modification. In
this case, the
anionic polymer and cationic polymer are not pre-mixed in the solution phase
prior to adding
to the microparticulate. Importantly, the anionic polymer and/or surfactant on
the surface of
the microparticulate is coated with the cationic polymer(s) disclosed herein
and is neither
entangled nor quaternized with the cationic polymer coating. The required
amount of an
anionic polymer or surfactant that may be used for the aforementioned anionic
pre-treatment
of the microparticulate material is such that the anionic surface charge
resulting from the pre-
treatment is relatively low, wherein the 4-potential of the microparticulate
material in a dilute,
approximately 0.1 wt. %, aqueous dispersion is preferably less than about -50
mV, while the
conductivity of the dispersion is in the range of about 0.01 to about 0.5
mS/cm.
[00441 Applicable anionic polymers include water-soluble anionic polymers and
water-
insoluble anionic polymers. By way of non-limiting example, applicable water-
soluble
anionic polymers include polyphosphate, polysulfonates (e.g., polyvinyl
sulfonate,
lignosulfonates), polycarboxylates (e.g. sodium polyacrylate), polysulfates
(e.g., polyvinyl
sulfate), and silicone polymers with a pendant anionic group selected from
carboxylate,
sulfate, and phosphate groups. One example of a water-insoluble anionic
polymer is the
copolymer of castor oil phosphate and 3-isocyanato-methyl-3,5,5-trimethyl
cyclohexyl
isocyanate, referred to herein as castor oil phosphate/IPDI copolymer.
100451 An important aspect of the microparticulate materials and methods
described herein
is the coating of the benefit agent-containing microparticulate material with
two different
cationic polymers. As used herein, coating means the polymer deposits onto the
surface of the
microparticulate and is not incorporated into the core of the
microparticulate. Effectively,
coating means the creation of an encapsulating layer of cationic polymer. This
is distinct and
significantly different from the entanglement or quaterization of a cationic
polymer and an
anionic polymer forming a particulate, known in the art, therein the
particulate is not coated
with the cationic polymer but encompasses the cationic polymer. Herein, these
polymers are
termed Type-1 Polymer and Type-2 Polymer. The Type-I Polymer can be a
homopolymer or
a copolymer including an amphiphilic polymer or copolymer, a hydrophobically-
modified
polymer or copolymer, and the like. The preferred Type-1 cationic polymer is
poly(diallyldimethyl ammonium halide), poly(DADMAC). The Type-2 Polymer can be
a
cationic guar gum, a cationic cellulose, a cationic starch, a hydrophobically-
modified thereof,
or the like.
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WO 2009/100464 PCT/US2009/035871
100461 Type-1 Polymers are selected from the cationic polymers that have a
high cationic
charge content. As used herein a high cationic charge content is measured by
the cationic
atom content. The cationic atom content is a measure of the total atomic
weight of the atoms
bearing cationic charge in/on the polymer chain divided by the molecular
weight of the
polymer, times 100, expressed as a weight percentage. By way of descriptive
example, all of
the cationic nitrogen atoms in the polymer poly(DADMAC) are quaternary
ammonium ions,
thereby the cationic atom content (here, the cationic nitrogen content) can be
determined
either by elemental analysis of a sample of the poly(DADMAC) or by the weight
average
molecular weight of the polymer. The elemental analysis would provide the
weight
percentage of nitrogen atoms in a sample of polymer, that is the cationic atom
content.
Preferably, a Type-1 Polymer has a cationic atom content in the range of about
3 wt. % to
about 20 wt. %. More preferably, a Type-1 Polymer has a cationic atom content
in the range
of about 5 to about 15 wt. %, and still more preferably this polymer has a
cationic atom
content in the range of about 8 wt. % to about 10 wt. %. Even more preferably,
a Type-1
Polymer has a cationic nitrogen content of at least 3 wt. %. Additionally,
Type-1 Polymers,
preferably, have a weight average molecular weight in the range of about
300,000 to about
800,000 Dalton, more preferably in the range of about 350,000 to about 600,000
Dalton, and
still more preferably in the range of about 400,000 to about 550,000 Dalton.
[00471 The preferred Type-1 Polymer should have a solubility of less than 2
wt. % in a
solution of anionic surfactant(s) containing 3 wt. % of an anionic surfactant.
More preferably,
the solubility of the Type-1 Polymer is less than about 1 wt. %, and even more
preferably the
solubility is less than about 0.5 wt. % in a 3 wt. % solution of an anionic
surfactant, e.g.,
sodium laurylsulfate.
[00481 The preferred Type-1 Polymer is poly(diallyl dimethyl ammonium
chloride),
referred to herein as Poly(DADMAC), that has a cationic nitrogen content of
about 8.7 wt. %.
Other useful Type-1 Polymers include polyacrylates and polyolefins with
pendant quaternary
ammonium groups. For example, polymers that meet the above referenced weight
average
molecular weight, solubility, and cationic nitrogen content and also having
the following
compositions: polyquaterium 1 (CAS#: 68518-54-7); polyquaterium-2 (CAS#: 63451-
27-
1); polyquatemium-4 (copolymer of hydroxyethylcellulose and diallyldimethyl
ammonium
chloride); polyquatemium-5 (CAS#: 26006-22-4); polyquatemium-6
(polyallyldimethylammonium chloride (CAS#: 26062-79-3); polyquaternium-7
(CAS#:
26590-05-6); polyquaternium-8 (poly((methyl, stearyl) dimethylaminoethyl
methacrylate),
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polvgiiaitci niurn-9 (polydimetliy1,-t Itiocthylmethacrylate brnrrnitlc):
polyquaternium-l0
(CASis: 53568-66-4, 55353-19-0, 54351-50-7, 81859-24-7; 6~010-92-4, 81859-24-
7);
polyquaternium-11 (polyvinyl-N-ethyl-methylpyrrolidonium);
poly(ethyldimethylammonium
eth;linc[1iucrylate) sulfate copolymer), polyquaternium-12 (CAS#: 68877-50-9);
polyquaternium-13 (CAS#: 68877-47-4); polyquaternium-14 (CAS#: 27103-90-8);
polyquaternium- 15 (CAS#: 35429-19-7); polyquaternium-16 (quaternary ammonium
salt of
methyl-vinylimidazolium chloride and vinylpyrrolidone) (CAS#: 95144-24-4);
polyquaternium-17 (adipic acid - dimethylaminopropylamine polymer (CAS#: 90624-
75-2);
polyquaternium-18 (azelaic acid, dimethylaminopropylamine, dicholorethylether
polymer,
CAS#: 113784-58-0); polyquaternium-19 (polyvinyl alcohol, 2,3-epoxypropylamine
polymer
(CAS#: 110736-85-1); polyquaternium-20 (polyvinyl octadecylether, 2,3-
epoxypropylamine
polymer (CAS#: 110736-86-2); polyquatemium-22 (CAS#: 53694-17-0);
polyquatemium-24
(hydroxyethylcellulose, lauryl dimethylammonium epoxide polymer);
polyquatemium-27
(copolymer of polyquaternium-2 and polyquaternium-17, CAS#: 131954-48-4);
polyquatemium-28 (vinylpyrrolidone, dimethylaminopropylmethacrylamide
copolymer,
CAS#: 131954-48-8), polyquatemium-29 (chitosan, CAS#: 9012-76-4); propylene
oxide
polymer reacted with epichlorohydrin); polyquaternium-30 (methylmethacrylate,
methyl(dimethylacetylammonium ethyl)acrylate copolymer, (CAS#: 147398-77-4);
polyquaternium-33 (CAS#: 69418-26-4); poly(ethylene(dialkyl)ammonium)
polymethacrylamidopropyltrimonium chloride (CAS#: 68039-13-4); and poly(2-
acryloyloxyethyl)trimethylammonium) are applicable Type-1 Polymers.
[0049] Type-2 Polymers are the cationic polymers that have a moderate to low
cationic
charge content. As used herein a moderate to low cationic charge content is
measured by the
cationic atom content, as defined above. Preferably, a Type-2 Polymer has a
cationic atom
content less than about 3 wt. %. More preferably, the Type-2 Polymer has a
cationic atom
content in the range of about 0.01 wt. % to about 3 wt. %, still more
preferably in the range of
about 0.1 wt. % to about 2 wt. %, and even more preferably in the range of
about 0.5 wt. % to
about 1 wt. %. Additionally, Type-2 Polymers, preferably, have a weight
average molecular
weight in the range of about 1,000,000 to about 15,000,000 Dalton, more
preferably in the
range of about 1,000,000 to about 10,000,000 Dalton, and still more preferably
in the range
of about 1,000,000 to about 5,000,000 Dalton.
[00501 Some useful Type-2 Polymers are those cationic polymers disclosed in
U.S. Pat.
No. 7,119,057, incorporated herein by reference, though herein used in
significantly lower
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WO 2009/100464 PCT/US2009/035871
Preferable Type-2 Polymers include cationic copolymers of acrylamide,
and cationic derivatives of natural polymers such as cellulose ether polymers,
guar gum, and
starch. Preferred Type-2 Polymers are those cationic derivatives of guar,
cellulose, and/or
starch that satisfy the above defined weight average molecular weight, and
cationic weight
percentage.
[0051] Another aspect of the cationically-modified benefit agent-containing
microparticulate materials, compositions and methods described herein is the
relative
amounts of the Type-1 Polymer and Type-2 Polymer, in specific weight ratios,
that are coated
onto the benefit agent-containing microparticulate. Generally, the ratio of
the weight of the
Type-1 Polymer to the weight of the Type-2 Polymer should be in the range of
about 0.1 to
about 100. Preferably the weight ratio of the Type-I Polymer to the Type-2
Polymer should
be in the range of about 1 to 20, more preferably in the range of about 2 to
about 20, and even
more preferably in the range of about 2 to about 10, and most preferably about
3 to about 7.
As expressed as weight percentages, the weight percentage of the Type-I
Polymer to the
combined weight of the Type-1 and Type-2 polymer is in the range of about 50
to less than
100 wt. %, preferably in the range of about 60 to about 95 wt. %, and more
preferably in the
range of about 70 to about 90 wt. %. Correspondingly, the weight percentage of
the Type-2
Polymer to the combined weight of the Type-i and Type-2 polymer is in the
range of about
one to about 50 wt. %, preferably in the range of about 5 to about 40 wt. %,
and more
preferably in the range of about 10 to about 30 wt. %.
[0052] Yet another aspect of the cationically-modified benefit agent-
containing
microparticulate materials, compositions and methods described herein is the
addition of the
Type-1 Polymer and Type-2 Polymer (the cationic polymers) to the
microparticulate in a
specific weight ratio, irrespective of other materials, water, solvents, or
items in the
composition. Generally, the ratio of the weight of the cationic polymers to
the weight of the
microparticulate is in the range of about 0.01 to about 10. Preferably the
ratio is in the range
of about 0.05 to about 5, more preferably in the range of about 0.1 to about
1, and most
preferably about 0.1 to about 0.3.
[0053] Additionally, the Type-1 Polymer and Type-2 Polymer are combined with
the
microparticulate to form a composition where the weight percentage of the
microparticulate
in the coated microparticulate composition is in the range of about 1 to about
99.9 wt. %,
preferably in the range of about 35 to about 99.5 wt. %, and more preferably
in the range of
about 50 to about 99.0 wt. %, irrespective of other materials, water,
solvents, or items in the
14
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WO 2009/100464 PCT/US2009/035871
composition. In one preferred coated microparticulate composition, the weight
percentage of
the Type-I Polymer in the total composition is in the range of about 5 to
about 20 wt. % and
the weight percentage of the Type-2 Polymer is in the range of about 0.1 to
about 5 wt. %,
irrespective of other materials, water, solvents, or items in the composition.
[0054] The cationically-modified benefit agent-containing microparticulate
materials,
compositions and methods described herein can be made by any of a plurality of
methods.
The first involves the admixing of the Type-1 Polymer with the benefit agent-
containing
microparticulate followed by the admixing of the product from the addition of
the Type-I
Polymer to the microparticulate with the Type-2 Polymer. One embodiment of
this method is
the surface-modification, surface-treatment, or coating of the
microparticulate with the Type-
1 Polymer, then the surface-modification, surface-treatment, or coating with
the Type-2
Polymer. It is believed that this method yields a composition having the Type-
1 Polymer
bound to the surface of the microparticulate and having the Type-2 Polymer
bound to the
Type-I Polymer and/or any of the microparticulate's surface area that is not
coated with the
Type-I Polymer. A second method involves the admixing of the Type-1 Polymer
with the
Type-2 Polymer followed by the admixing of this cationic polymer mixture with
the benefit
agent-containing microparticulate to coat the benefit agent-containing
microparticulate with
both cationic polymers simultaneously. It is believed that this method yields
a composition
having the Type-I Polymer preferentially bound to the microparticulate surface
and the Type-
2 Polymer bound to the Type-i Polymer, in a layered structure similar to the
structure
produced from the sequential addition of Type-i then Type-2 Polymers. The
higher
concentration, higher cationic atom content, and lower molecular weight of the
Type-I
Polymer theoretically allow the Type-1 Polymer to more rapidly (based on
relative reaction
rates) add to the anionic microparticulate; such that the Type-I Polymer coats
greater than
50% of the microparticulate's surface area, preferably greater than 70%, more
preferably
greater than 90, and even more preferably greater than 95% of the
microparticulate's surface
area. A third method involves the admixing of the Type-I Polymer with the Type-
2 Polymer,
followed by the admixing of this cationic polymer mixture with the benefit
agent-containing
microparticulate to coat the benefit agent-containing microparticulate with
both cationic
polymers simultaneously, followed by the admixing of this coated
microparticulate with
additional Type-2 Polymer. It is believed that this method yields a
composition having an
outer coating layer that is greater than 95% Type-2 Polymer, theoretically
this method assures
that the outer coating layer is 100% Type-2 Polymer.
CA 02725814 2010-11-25
WO 2009/100464 PCT/US2009/035871
[0055] The surface-modification, surface-treatment, or coating of the
microparticulate
material may be carried out by repeatedly adding the microparticulate
material, either in a
powder-form (generally, with a moisture content of less than 30% by weight) or
as an
aqueous dispersion, to an aqueous solution or dispersion containing a cationic
polymer, and
subsequently shearing the resulting dispersion. Alternatively, the
microparticulate material in
a powder-form may be blended with a mixture of a Type-1 Polymer and a Type-2
Polymer,
wherein the two cationic polymers are used, respectively, in a form selected
from a powder, a
solution, a dispersion, and/or mixtures thereof.
[0056] For a microparticulate material having an anionic surface charge prior
to the
cationic surface-modification, the surface-modification, surface-treatment, or
coating of the
benefit agent-containing microparticulate material with the Type-1 Polymer is
preferably
carried out by adding the benefit agent-containing microparticulate material
to an aqueous
solution/dispersion of the polymer under high-shear agitation. The required
amount of the
Type-1 Polymer is such that the anionic surface-charge of the microparticulate
material is
partially or fully neutralized by the cationic charge of the Type-1 Polymer,
inasmuch as the
net surface-charge of the modified microparticulate-surface is cationic, and
is sufficiently
high for preventing strong coagulation amongst or between the dispersed
particles of the
microparticulate material, due to what is known in the art as the electrical
double layer
repulsion between electrically charged particles in a dispersion.
[0057] For any microparticulate material having a given anionic surface charge
prior to the
claimed surface-modification, an optimum dosage (amount added to the
microparticulate
material) of the Type-1 cationic polymer maybe determined by a two step
process. First, by
measuring the minimum dosage at which the ~-potential of the microparticulate
material in a
dilute aqueous dispersion (generally about 0.02 to about 0.1 wt. % of the
microparticulate
material in water) is greater than about 65 mV, preferably greater than about
70 mV, and
more preferably greater than about 75 mV, while the conductivity of the
dispersion is in the
range of about 0.01 to about 0.5 mS/cm. And second, by measuring the minimum
dosage at
which the sample does not strongly coagulate in a dilute, 0.1 wt. %, aqueous
dispersion as
measured by particle size analysis. The optimum dosage is when both steps are
satisfied.
[0058] Yet another aspect of the cationically-modified microparticulate
materials,
compositions and methods described herein is the incorporation of the
cationically-modified
benefit agent-containing microparticulate materials in commercial products.
The cationically-
modified benefit agent-containing microparticulate materials can be used in
products such as
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WO 2009/100464 PCT/US2009/035871
shampoo, liquid soap, bodywash, laundry detergent, fabric softener,
toothpaste, and antiseptic
ointments. These commercial products that contain cationically-modified
benefit agent-
containing microparticulate materials can further include solvents and/or
other ingredients for
the coated cationically-modified microparticulates. Examples of solvents
and/or added
ingredients include fatty alcohols, opacifiers, pearlescers, viscosity
modifiers, rheology
modifiers, inorganic oxides, buffering or pH adjusting chemicals, foam-
boosters, perfumes,
dyes, coloring agents or pigments, herb extracts, preservatives, hydrotopes,
enzymes,
bleaches, fabric conditioners, optical brighteners, antioxidants, stabilizers,
thickeners,
dispersants, soil release agents, anti-wrinkle agents, polymers, chelants,
anti-corrosion agents,
teeth cleansing and whitening agents, polymers, coplyrners, cross-polymers,
smectite clays,
silica, silicate minerals, and the like. Generally, these products employ
surfactant and
emulsifying systems that are well known. For example, fabric softener systems
are described
in U.S. Pat. Nos. 6,335,315, 5,674,832, 5,759,990, 5,877,145, 5,574,179;
5,562,849,
5,545,350, 5,545,340, 5,411,671, 5,403,499, 5,288,417, 4,767,547, 4,424,134,
each hereby
incorporated by reference. Liquid dish detergents are described in U.S. Pat.
Nos. 6,069,122
and 5,990,065; automatic dish detergent products are described in U.S. Pat.
Nos. 6,020,294,
6,017,871, 5,968,881, 5,962,386, 5,939,373, 5,914,307, 5,902,781, 5,705,464,
5,703,034,
5,703,030, 5,679,630, 5,597,936, 5,581,005, 5,559,261, 4,515,705, 5,169,552,
and 4,714,562,
each hereby incorporated by reference. Liquid laundry detergents which can use
the present
invention include those systems described in U.S. Pat. Nos. 5,929,022,
5,916,862, 5,731,278,
5,565,145, 5,470,507, 5,466,802, 5,460,752, 5,458,810, 5,458,809,
5,288,431,5,194,639,
4,968,451, 4,597,898, 4,561,998, 4,550,862, 4,537,707, 4,537,706, 4,515,705,
4,446,042, and
4,318,818, each hereby incorporated by reference. Shampoo and conditioners
that can
employ the present invention include U.S. Pat. Nos. 6,162,423, 5,968,286,
5,935,561,
5,932,203, 5,837,661, 5,776,443, 5,756,436, 5,661,118, 5,618,523, 5,275,755,
5,085,857,
4,673,568, 4,387,090, 4,705,681, each hereby incorporated by reference.
[00591 Non-limiting examples of suitable anionic surfactants that can be
combined with
the herein described microparticulate composition are the sodium, ammonium,
and mono-,
di-, and tri-ethanolamine salts of alkyl sulfates, alkyl ether sulfates,
alkaryl sulfonates, alkyl
succinates, alkyl sulfosuccinate, N-alkoyl sarcosinates, alkyl phosphates,
alkyl ether
phosphates, alkyl ether carboxylates, and ct-olefin sulfonates. The alkyl
groups generally
contain from 8 to 18 carbon atoms and may be unsaturated. The alkyl ether
sulfates, alkyl
ether phosphates, and alkyl ether carboxylates may contain from 1 to 10
ethylene oxide or
17
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WO 2009/100464 PCT/US2009/035871
propylene oxide units per molecule, and prc fCrahly contain 2 to 3 ethylene
oxide units per
molecule. Non-limiting examples ofnonionic surfactants that can be combined
with the
herein described microparticulate composition include, but are not limited to,
aliphatic,
primary or secondary linear or branched chain alcohols or phenols with
alkylene oxides,
generally ethylene oxide and generally 6-30 ethylene oxide groups. Other
suitable nonionic
surfactants include mono- or di-alkyl alkanolamides, alkyl polyglucosides, and
polyhydroxy
fatty acid amides. Non-limiting examples of amphoteric surfactants that can be
combined
with the herein described microparticulate composition include alkyl amine
oxides, alkyl
betaines, alkyl amidopropyl betaines, alkyl sulfobetaines, alkyl glycinates,
alkyl
carboxyglycinates, alkyl amphopropionates, alkyl amidopropyl hydroxysultaines,
acyl
taurates, and acyl glutamates wherein the alkyl and acyl groups have from 8 to
18 carbon
atoms. Nonlimiting examples of suitable cationic surfactants that can be
combined with the
herein described microparticulate composition include water-soluble or water-
dispersible or
water-insoluble compounds containing at least one amine group which is
preferably a
quaternary amine group, and at least one hydrocarbon group which is preferably
a long-chain
hydrocarbon group. The hydrocarbon group may be hydroxylated and/or
alkoxylated and
may comprise ester- and/or amido- and/or aromatic-groups. The hydrocarbon
group may be
fully saturated or unsaturated. Generally, the surfactant is combined with the
microparticulate
composition in a range from about 1 to about 95%, preferably from about 2 to
about 90%,
and most preferably from 3 to 90% by weight of the total compositions.
[0060] Alternatively the microparticulate composition can be formed into a
commercial
product by admixing the microparticulate composition with a hydrophilic
solvent. Suitable
hydrophilic solvents include water, glycerol, ethanol, isopropanol, propylene
glycol, butylene
glycol, hexylene glycol, polyethylene glycol and mixtures thereof. Generally,
the solvent is
combined with the microparticulate composition in a range from about 0.1 to
about 95%,
preferably from 1 to 90%, and most preferably from 3 to 90% by weight of the
total
compositions.
EXAMPLES
[0061] The following examples will more fully illustrate the preferred
embodiments within
the scope of the present invention. These examples are solely for the purpose
of illustration
and are not to be construed as limitations of the present invention as many
variations thereof
are possible without departing from the purview and spirit of the compositions
and methods
described herein. As used in the examples, given polymer weight percentages in
tables 1-6
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WO 2009/100464 PCT/US2009/035871
correspond to the relative weight percentage of the polymer to the
microparticulate,
irrespective of other possibly materials, water, solvents, or items in the
compositions.
[00621 The cationic surface-treatment of the microparticulate material may be
carried out
by adding the microparticulate material, either in a powder-form (with a
moisture content of
less than 30% by weight) or as an aqueous dispersion, to an aqueous solution
or dispersion
containing the Type-1 Polymer and then adding the Type-1 coated
microparticulate material
to a solution or dispersion containing the Type-2 Polymer, and respectively
shearing the
resulting dispersions. Alternatively, the microparticulate material in a
powder-form may be
blended with a mixture of a Type-I Polymer and a Type-2 Polymer, wherein the
two
polymers are used, respectively, in a form selected from a powder, a solution
or a dispersion,
and mixtures thereof.
[00631 For a microparticulate material having an anionic surface charge prior
to the
claimed surface-modification, the adsorption of the Type-1 Polymer onto the
surface of the
microparticulate material (coating step) is preferably carried out by adding
the
microparticulate material to an aqueous solution/dispersion of the polymer
under high-shear
agitation.
[00641 The general procedure for the preparation of the cationically surface-
treated
microparticulates can be understood through the herein disclosed
representative examples.
Table 1 provides the general formulations, as weight percents of the entire
composition, of a
number of prepared samples. These samples can be prepared through the
adaptation of the
representative examples through augmentation of the amounts of reagents added.
Example 3
was prepared as follows: 60 g of a poly(DADMAC) solution (Zetag 7122, also
called
Magnafloc LT-7992, available from Ciba Specialty Chemicals, with 20% active)
and 60 g of
deionized water were added to a suitable flask. The batch was mixed for 6
minutes at a
mixing speed of 200 rpm using a caframo mixer fitted with a dispersion blade
agitator. After
increasing the speed to 1,000 rpm, 300 g of an aqueous dispersion of an
encapsulated
fragrance (BL-AWAY-478A from International Flavors & Fragrances, Inc. (IFF,
Inc.) New
York, NY, with 40% encapsulated solids, including a fragrance) was added to
the batch. The
mixing speed was increased to at least 1,500 rpm, once about half of the
dispersion-amount
was added to the batch. Then a 1 g aliquot of a 50% (w/w) solution of sodium
hydroxide was
added to the batch within one minute after the completion of addition of the
above dispersion,
while the batch remained under agitation at a mixing speed of 1,500 rpm. The
batch was
mixed for 30 minutes at 1,500 rpm, counted from the time of completion of
addition of the
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WO 2009/100464 PCT/US2009/035871
foregoing dispersion. The above dosage of the poly(DADMAC) solution
corresponds to 10%
poly(DADMAC), based on the weight of encapsulated solids, including a
fragrance.
[0065] Table I shows examples of compositions of microparticulates coated with
Type-]
Polymer, specifically poly(DADMAC) as prepared in the above described example
3. These
samples became the starting materials for those samples shown in Table 2.
[0066] TABLE 1.
Ex. Weight Percent Microparticulate material
of Type-1 Polymer
}poly(DADMAC)}
1 5 BL-AWAY-478A
2 7.5 BL-AWAY-478A
3 10 BL-AWAY-478A
4 12.5 BL-AWAY-478A
15 BL-AWAY-478A
[0067] Example 7 was prepared as follows: to 124 g of the resulting dispersion
from
Example 3 was added 26 g of a 2.5% (w/w) solution of a cationic guar (Jaguar C-
14S from
Rhodia), Type-2 Polymer, in a suitable vessel. The resulting mixture was mixed
at a mixing
speed of 1,000 rpm for 2.5 minutes, using a caframo mixer fitted with a
dispersion blade
agitator. The mixing speed was then increased to 1,500 rpm, and the batch was
mixed for an
additional 27.5 minutes. The amount of Type-1 Polymer and Type-2 Polymer
correspond to
wt. % and 1.8 wt. %, respectively, based on the weight of encapsulated solids,
including a
fragrance.
[0068] Table 2 shows examples of microparticulate compositions corresponding
to the
present disclosure. The samples were prepared from the samples shown in Table
1 as
described in the procedure for Example 7, above. For the purpose of these
examples three
Type-2 Polymers were employed. These are Jaguar C-17 (INCI Name: Guar
hydroxypropyltrimonium chloride; CAS: 65497-29-2) available from Rhodia Inc.
Cranberry
NJ; Jaguar C-14S (INCI Name: Guar hydroxypropyltrimonium chloride; CAS: 65497-
29-2)
available from Rhodia Inc.; and Soft-Cat SL-30 (INCI Name: Polyquatemium-67)
available
from Dow Chemical Co., Midland, MI.
CA 02725814 2010-11-25
WO 2009/100464 PCT/US2009/035871
100691 TABLE 2.
Ex. Weight Percent of Weight Percent of Name of Type-2 Microparticulate
"Type-1 Polymer Type-2 Polymer Polymer material
{poly(DADMAC)
6 10 1.8 Jaguar C-17 ex. 3 + type 2 BL-AWAY-478A
7 10 1.8 Jaguar C-14S ex. 3 + type 2 BL-AWAY-478A
8 10 1.8 Soft-Cat SL-30 ex. 3 + type 2 BL-AWAY-478A
9 12.5 1.8 Jaguar C-17 ex. 4 + type 2 BL-AWAY-478A
12.5 1.8 Jaguar C-14S ex. 4 + type 2 BL-AWAY-478A
11 12.5 1.8 Soft-Cat SL-30 ex. 4 + type 2 BL-AWAY-478A
12 15 1.8 Jaguar C-17 ex. 5 + type 2 BL-AWAY-478A
13 15 1.8 Jaguar C-14S ex. 5 + type 2 BL-AWAY-478A
14 15 1.8 Soft-Cat SL-30 ex. 5 + type 2 BL-AWAY-478A
10 3.8 Jaguar C-17 ex. 6 + type 2 BL-AWAY-478A
16 12.5 3.8 Jaguar C-17 ex. 9+ type 2 BL-AWAY-478A
17 15 3.8 Jaguar C-17 ex. 12 type 2 BL-AWAY-478A
18 10 3.8 Jaguar C-14S ex. 7 + type 2 BL-AWAY-478A
19 I 12.5 3.8 Jaguar C-14S ex. 10 + type 2 BL-AWAY-478A
15 3.8 Jaguar C-14S ex. 13 + type 2 BL-AWAY-478A
[00701 Table 3 shows examples of microparticulate compositions corresponding
to the
present disclosures. Example 21 was prepared by the method described for
example 3 but no
NaOH solution was added to the dispersion. Examples 22, 23, and 24 were
prepared as
described for example 7 but example 21 was used as the precursor sample.
Example 25 was
prepared by the sequential treatment of the microparticulate material with the
Type-i
Polymer and the Type-2 Polymer.
[00711 TABLE 3.
Weight Percent of Weight Percent of Name of Microparticulate
Ex. Type-1 Polymer Type-2 Polymer Type-2 material
f poly(DADMAC) } Polymer
21 15 NaOH free BL-AWAY-478A
22 15 1.8 Jaguar C-17 ex. 21 + type 2 BL-AWAY-478A
23 15 3.8 Jaguar C-17 ex. 21 + type 2 BL-AW\Y-478A
24 15 1.8 Jaguar C-14S ex. 21 + type 2 BL-AWAY-478A
10 1.8 Jaguar C-17 NaOH free BL-AWAY-478A
[00721 Table 4 shows examples of microparticulate compositions corresponding
to the
present disclosures. Example 26 was prepared by the method described for
example 3 but no
NaOH solution was added to the dispersion and SN-SBOO- 100 1 AE from IFF,
Inc., with 40%
encapsulated solids, including a fragrance was used. Examples 27 and 28 were
prepared as
described for example 7 but example 26 was used at the precursor sample.
Example 29 was
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WO 2009/100464 PCT/US2009/035871
prepared by the sequential treatment of the microparticulate material with the
Type-1
Polymer and the Type-2 Polymer.
[0073] TABLE 4.
Weight Percent of Weight Percent of Name of Microparticulate
Ex. Type-1 Polymer Type-2 Polymer Type-2 material
{poly(DADMAC) }) Polymer
26 15 --- --- NaOH FREE SN-SBOO-1001AE
27 15 2.5 Jaguar C-17 ex. 26 + type 2 SN-SBOO-1001AE
28 15 1.8 Jaguar C-17 ex. 26 + type 2 SN-SBOO-1001AE
29 15 1.8 Jaguar G NaOH free SN-SBOO-1001AE
14S
[0074] Table 5 shows examples of microparticulate compositions corresponding
to the
present disclosures. Example 30 was prepared by the method described for
example 3 but no
NaOH solution was added to the dispersion and a galaxolide containing melamine
capsule
("encapsulated galaxolide") dispersion from IFF, Inc., with 40% encapsulated
solids,
including the fragrance was used. Examples 31, 32, and 33 were prepared as
described for
example 7 but example 30 was used at the precursor sample. Example 34 was
prepared by the
method described for example 3 but an encapsulated galaxolide dispersion from
IFF, Inc.,
with 40% encapsulated solids, including the fragrance was used. Examples 35,
36, and 37
were prepared as described for example 7 but example 34 was used at the
precursor sample.
Examples 38 and 39 were prepared by the sequential treatment of the
microparticulate
material with the Type-1 Polymer and the Type-2 Polymer without the addition
of NaOH.
Example 40 was prepared by the sequential treatment of the microparticulate
material with
the Type- 1, then a NaOH solution, then the Type-2 polymer. Example 41 was
prepared by the
addition of the microparticulate material to a premixed sample of the Type-I
Polymer and the
Type-2 Polymer. Example 42 was prepared by the subsequent addition of
additional Type-2
polymer to the product of example 41.
[0075] TABLE 5.
Weight Percent of Weight Percent of Name of Type-2 Microparticulate
Ex. Type-1 Polymer Type-2 Polymer Polymer material
{poly(DADMAC)}
30 15 --- --- NaOH FREE Encapsulated
galaxolide
31 15 1.8 Jaguar C-17 ex. 30 + type 2 Encapsulated
galaxolide
32 15 3.8 Jaguar C-17 ex. 30 + type 2 Encapsulated
galaxolide
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WO 2009/100464 PCT/US2009/035871
Weight Pcrccnt of Weight Percent of Name ofTyhc-2 Microparticulate
Fx. Type-l Polviucr
of DA f~?E 1.1( ) } Type 2 Polymer Polymer material
s
APO(
33 13 1.8 Jaguar C-14S ex. 30 + type 2 Encapsulated
galaxolide
34 15 --- --- NaOH Encapsulated
galaxolide
35 15 3.8 Jaguar C-17 ex. 34 + type 2 Encapsulated
galaxolide
36 15 1.8 Soft-Cat SL-30 ex. 34 + type 2 Encapsulated
galaxolide
37 15 3.8 Jaguar C-14S ex. 34 + type 2 Encapsulated
galaxolide
38 10 1.8 Jaguar C-14S sequential Encapsulated
treatment galaxolide
NaOH free
39 10 1.8 Jaguar C-17 sequential Encapsulated
treatment galaxolide
NaOH free
40 10 3.8 Jaguar C-14S sequential Encapsulated
treatment galaxolide
41 10 1.8 Jaguar C-14S Type 1 Type 2 Encapsulated
Preblend galaxolide
42 10 3.8 Jaguar C-14S ex. 41 + C-14S Encapsulated
galaxolide
[00761 Table 6 shows examples compositions comparing the ~-potential and
electrophoretic mobility of coated microparticulate materials. The results
show the
importance of the weight average molecular weight of the Type-1 Polymer; the
comparison is
between two different poly(DADMAC) polymers, a non-Type-1 Polymer: Zetag 7131
(Mw =
75,000 - 125,000 Dalton) and a Type-1 Polymer: Zetag 7122 (Mw = 400,000 -
450,000
Dalton), both from Ciba Specialty Chemicals. The sample with the Type-1
Polymer, that is
the polymer that has a weight average molecular weight between about 300,000
and about
800,000 Dalton, shows significantly higher ~-potential and electrophoretic
mobility
indicating higher charge on the microparticulate and very limited to no
coagulation in a
dispersion.
[00771 TABLE 6.
Ex. Weight Percent of Name of Polymer Microparticulate
Polymer material
43 20 Zetag 7131 BL-AWAY-478A
43A 20 Zetag 7122 BL-AWAY-478A
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WO 2009/100464 PCT/US2009/035871
Ex. Zeta-potential, mV Electrophoretic
Mobility, tm/V's-'
43 58.35 4.601
55.86 4.404
57.24 4.513
Mean: 57.15 Mean: 4.506
43A 79.61 6.277
78.00 6.149
79.94 6.303
Mean: 79.18 Mean: 6.243
[0078] Tables 7 shows examples of shower gel compositions employing the herein
described microparticulate compositions.
[0079] TABLE 7
Ingredients Weight %, Weight %, Weight %, Weight %,
Shower Gel 1 Shower Gel 2 Shower Gel 3 Shower Gel 4
Deionized Water 35 35 33.5 33.5
Ammonium Lauryl
Sulfate
(Stepanol AMV, 28% 50 50 50 50
active, from Stepan
Company)
Cocamidopropyl Betaine
(Amphosol CG, 30% 12 12 12 12
active, Stepan Company)
Composition of 3
EXAMPLE 28
Composition of 3
EXAMPLE 29
Composition of
EXAMPLE 31 4.5
Composition of
EXAMPLE 36 4.5
[0080] Tables 8 shows examples of shampoo compositions employing the herein
described
microparticulate compositions.
[0081] TABLE 8
Ingredients Weight %, Weight %, Weight %, Weight %,
Shampoo 1 Shampoo 2 Shampoo 3 Shampoo 4
Deionized Water 6.87 6.87 5.37 5.37
Disodium Laureth
Sulfosuccinate
(Stepan-Mild SL3, 38 38 38 38
32.5% active, from
Stepan Company)
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WO 2009/100464 PCT/US2009/035871
Ingredients VN ei,;ht /%, Weight 'lo, Weight %, Weight
Shampoo 1 Shampoo 2 Shampoo 3 Shampoo 4
Sodium I aureth Sulfate
(Steol CS-330, 28.5% 35 35 35 35
active, from Stepan
Company)
Cocamidopropyl Betaine
(Amphosol CG, 30% 16.5 16.5 16.5 16.5
active, Stepan Company)
50% Sodium Hydroxide 0.63 0.63 0.63 0.63
Composition of 3
EXAMPLE 28
Composition of 3
EXAMPLE 29
Composition of
EXAMPLE 31 4'S
Composition of
EXAMPLE 36 4.5
