Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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FABRIC COLOR CARE METHOD
TECHNICAL FIELD
The present invention relates to methods and articles for treating fabrics to
improve fabric appearance, especially with regards to color of fabrics,
especially those
that have been worn and having a faded appearance.
BACKGROUND OF THE INVENTION
There is a continuous need for improved compositions, products, and methods
that provide useful benefits to :fabrics, especially clothing, such as
maintaining and/or
improving a good appearance, especially fabric color, especially for fabric
that have been
worn, through a simple and convenient application of a product.
Consumer commonly judges the desirability and wearability of a garment by
many appearance criteria, such a.s, absence of color fading, absence of
wrinkles, absence
of soiling and staining, absence oi~ damage such as pilling, and the like. It
is preferable
that these benefits are provided via simple and convenient consumer
compositions,
methods and products, to be applied in the consumer's home. These consumer
compositions and products are preferably safe, and do not involve complicated
and/or
unsafe treatments and/or applications. Desirably they comprise treatments that
are
familiar to the consumers, such as spraying, soaking, adding to the wash
cycle, adding to
the rinse cycle, and/or adding to the drying cycle.
Many published fabric care compositions methods try to provide fabric
maintenance benefits, e.g., keep fabric from, e.g., fading, wear, pilling,
soiling, staining,
shrinkage, and the like. However, fabric articles, such as clothing, that are
worn and
used will get damaged via, e.g., mechanical abrasion in use and in the laundry
washing
processes. The resulting worn., damaged fabric can have loosened fabric weave
and
pilling. Worn, damaged color fabric especially has a undesirable faded
appearance. A
common method that the consumer can practice to improve and/or restore the
color of
such worn, faded fabric is the use of fabric dyes. However, dyeing process
done at home
tend to result in color bleeding in the subsequent washes that can discolor
other fabrics in
the same wash. Furthermore, when the fabric color is not uniform, such as when
the
fabric has design with different colors and,%or different tones of the same
color, the use of
fabric dyes is not desirable.
The present invention comprises methods that can be used to improve color
fidelity, i.e., recover, restore, rejuvenate color of worn, damaged clothing
upon a single
application.
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The present invention optionally can provide other fabric care benefits, such
as
wrinkle removal, pill prevention, anti-shrinkage, and fabuic shape retention.
SUM1VIARY OF THE INVENTION
The present invention relates to methods for treating fabrics by direct
application, .
primarily to the surface of the fabrics, of certain preferred fabric color
care actives and
compositions, and to articles o>i manufacture that facilitate the use such
fabric color care
compositions and other known fabric care compositions to restore and/or
rejuvenate
color of worn, faded color fabrics. The present invention also relates to the
use fabric
color care active and composition comprising said fabric color care active to
restore
and/or rejuvenate color of worn, faded color fabrics.
The fabric color care .active that can provide the unobvious color restoration
and/or rejuvenation benefit to the worn, faded fabric is characterized by its
ability to
reduce the three following properties of said fabric, namely, its reflectance,
its Hunter L
value, and its pill number.
Preferred fabric color care composition comprises an effective amount of
fabric
color care active preferably being; selected from the group consisting of:
(A) water soluble andlor water dispersible polymer; said polymer is selected
from the group consisting of: natural polymer; synthetic polymer;
substituted materials thereof; derivatised materials thereof; and mixtures
thereo f;
(B) surfactant capable of forming a bilayer structure; and
(C) mixtures thereof;
said composition optionally being essentially free of any material that would
soil or
discernible when dried on thc~ fabric surface; and said composition optionally
being
substantially removed during subsequent cleaning cycles to prevent undesirable
build-up
of the active on the fabrics; and said composition additionally being
essentially free of
any material that would cause the treated fabric to feel unduly sticky, or
"tacky" to the
touch.
Said composition is applied to fabric in a positive step, e.g., spraying,
dipping,
and/or soaking processes, followed by a drying step to maximize the
application and ,
retention of the active to the surface of the fibers. Preferably the treatment
is by spray
and/or roller so that the active is primarily applied to the visible surface
of the fabric. ,
The present invention also preferably relates to the fabric care compositions
incorporated
into a spray dispenser, to create an article of manufacture that can
facilitate treatment of
fabric articles and/or surfaces with said compositions containing fabric color
care active
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and other optional ingredients at a level that is effective, yet is preferably
not discernible
when dried on the surfaces.
Also, concentrated aqueous or solid, preferably powder, fabric color care
compositions can be used to prepare such compositions for treating worn, faded
and/or
damaged fabric.
It is especially important that said article, or any container containing said
composition, or concentrate used to prepare said composition have a set of
instructions
associated therewith to inform the consumer that the composition can provide
the color
restoration benefit for worn, damaged and faded color fabric. Without
knowledge of the
unobvious benefit that can be c>btained, a consumer would be highly unlikely
to treat the
visible surface of the fabric, especially older fabrics, and might even
discard the fabric
when it could be substantially restored to near-new condition.
DETAIII>5:D DESCRIPTION Or THE INVENT10N
The present invention relates to methods for treating fabrics by direct
application,
primarily to the surface of the fabrics, of certain preferred fabric color
care actives and
compositions, and to articles of manufacture that facilitate the use such
fabric color care
compositions and other known fabric care compositions to restore and/or
rejuvenate
color of worn, faded color fabrics. The present invention also relates to the
use fabric
color care active and composition comprising said fabric color care active to
restore
and/or rejuvenate color of worn, faded calor fabrics.
The unobvious color restoration and/or rejuvenation benefit to the worn, faded
fabric is characterized by the ability of the fabric color care active to
change the three
following properties of worn, faded black cotton (chino) twill test fabric (as
defined
hereinbelow) resulting in:
(A) a percentage reflectance reduction 0R of at least about 3%, preferably at
least about 5°~0, more preferably at least about 8%, and even more
preferably at least about 10%;
(B) a Hunter L value reduction OL of at least about 0.5, preferably at least
about 1.0, more preferably at least about 1.5; and even more preferably at
' least about 2.0; and
(C) a percentage pill number reduction ~P of at least about 10%, preferably at
' least about 20'%x, more preferably at least about 40%, and even more
preferably at least about 80%.
The preferred fabric color care composition of the present invention
comprises:
(A) an effective amount of fabric color care active for restoring and/or
rejuvenating the color of worn, faded color fabric, said fabric color care
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active is preferably selected from the group consisting of water soluble and
or dispersible polymer; substituted materials thereof; derivatised materials
thereof; and mixtures thereof; surfactant capable of forming a bilayer
structure; and mixtures thereof; ,
(B) optionally, an effective amount to provide olfactory effects of perfume;
(C) optionally, to reduce surface tension, and/or to improve performance and
formulatability, an effective amount of surfactant;
(D) optionally, an effective amount to absorb malodor, of odor control agent;
(E) optionally, an effective amount, to kill, or reduce the growth of
microbes, of
antimicrobial active;
(F) optionally, an effective amount to provide improved antimicrobial action
of
aminocarboxylate chelator;
(G) optionally, an effective amount of antimicrobial preservative; and
(H) optionally, an aqueous carrier;
said composition optionally being essentially free of any material that would
soil or
discernible when dried on the surfaces, and said composition optionally being
substantially removed during subsequent cleaning cycles to prevent undesirable
build-up
of the active on the fabrics; and said composition additionally being
essentially free of
any material that would cause the treated fabric to feel unduly sticky, or
"tacky" to the
touch.
The preferred polymer is colorless, to minimize the change of hue and to
improve
the color fidelity.
The present invention relates to the application of an effective amount of a
fabric
color care active and/or fabric color care composition to fabric to modify the
following
fabric properties, namely, a reduction of reflectance, a lowering of the L
value, and a
reduction of the microfibril number, to reduce the loss of fabric color and/or
to recover
fabric color. It has not previously been recognized that the use of the above
compositions can provide good color restoration and/or recovery.
Methods For Determinin the Observed Color Restoration Benefit
The utility of a fabric color care active can be determined by the following
simple
screening test procedures. The desired fabric properties are determined using
worn black
chino (cotton) twill test fabric that is available from TESTFABRICS, Inc.,
West Pittston,
PA. Worn black cotton twill test fabric is obtained by treating new fabric
through eight
treatment cycles, each washing/drying treatment cycle comprises of one
washing/rinsing
cycle with the AATCC powder detergent, followed by two washing/rinsing cycles
with
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clear water (without detergent), all cycles using 90°C water in a
Kenmore automatic
clothes washer Model 110, followed by a drying cycle in a Kenmore automatic
electric
tumble dryer Model 110. The r.°sulting test fabric is visibly worn and
faded. Some worn
fabric samples are retained for use as control worn fabrics. Other worn fabric
samples
are treated using the method of the present invention. The control and treated
fabrics are
examined visually and their properties are determined by the following three
test
procedures.
Reflectance
The reduction of reflecaance of a fabric is determined using the optical
measurement from the LabScanOXE instrument from Hunter Associates Laboratory,
Inc,
Reston, Virginia. The LabScan~XE is a full-scanning spectrophotometer with a
wavelength range from 400 to ?00 nanometer. The sample is illuminated by a
xenon
flash lamp and reflected light is collected by a 15-station fiber optic ring.
For reflectance
measurements, the diameter of opening in port is 50 mm. The illumination angle
is 0°
(normal) to the specimen. The viewing angle is 45° from normal via
fiber optic; ring.
The reflectance of the whole range of wavelength from about 420 nm to about
620 nm is measured for the black cotton twill test fabrics. For each
wavelength in an
increment of about 10 nm, the reflectance of the treated fabric (Rt) and that
of the wom,
untreated fabric (Ru) are measured. The percentage reduction of the
reflectance for each
wavelength is
OR == 100 x f (~Ru-y Rt) / ~Ru
For a noticeable improvement and/or restoration of fabric color, aR should be
a
positive number and having a value of at least about 3%, preferably at least
about 5%,
more preferably at least about f>°,%, and even more preferably at least
about 10°/>.
Hunter L Value
The rejuvenation/restoration of color of the worn/faded color fabric is found
to
correlate with a reduction in the Hunter L value as defined below . The
reduction of the
Hunter L value of a fabric is determined by also using the LabScan~XE
instrument from
the Hunter Associates Laboratory, Inc. According to its manual, the
0°/45° geometry of
this instrument 'sees' the color the way the human eye sees color, its
circumferential
. viewing reduces the effect of sample directionality by detecting light
evenly from the
entire measured surface, and i~a specular excluded mode measures the entire
appearance
of samples, including the color component and the geometric component (gloss
and
texture). In a cylindrical space all color sensations can be arranged
according to the
attributes lightness, hue, and chroma. L,lghtness (the L value) is an
attribute :having end
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points white (L value of 100) and black (L value of 0) and a continuous scale
of greys
between them. The internationally agreed upon system (Commision Internationale
de .
I'Eclairage, CIE Publication No. I5, E-1.3.1, 1971) for converting instrument
data into
color data is the CIE system. The CIELAB formula and its associated color
space are
based on a coordinate system with coordinates L* for lightness, a* for redness-
greenness
and b* for yellowness-blueness.
Unlike normal color measurement, where all three values "L", "a" and "b" are
measured, in the deternlination of the color restoration benefit of the
current invention,
only the "L" values are determined, without a consideration of the "a" and "b"
values.
The L values for the treated black cotton twill fabric, Lt, and that of the
worn, untreated
black cotton twill fabric, Lu, are measured. The reduction of the L value
4L=Lu-Lt
should be a positive number, and for an appreciable improvement of color, OL
should
have a value of at least about 0.5, preferably at least about 1.0, more
preferably at least
about 1.5.
Microfibril Number.
An image analysis system is used to estimate the number of pills on the
untreated
and treated black cotton twill fabrics that are used to define the observed
color restoration
benefit. The general setup and procedure are described in "Efforts to Control
Pilling in
Wool/Cotton Fabrics", Jeanette M. Cardamone, Textile Chemist and Colorist, 31,
27-31
(1999), incorporated herein by reference. The image analysis system that we
used
utilizes a light booth with a circular fluorescent light bulb. The bulb is
just above the
plane of the fabric. The fabric is put into the light booth via a drawer. To
remove any
wrinkle the fabric is held down at the edges by a Plexiglas clamp (imagine a
Plexiglas
book with a hole in the cover where the fabric shows tluough). The pills rise
above the
fabric and reflect light to the monochrome camera, which is mounted above. The
camera
and video frame grabber are adjusted so that the pills show up as bright, and
the plane of
the fabric shows up as dark. Then the image is thresholded, and the bright
blobs (pills)
are counted and sized. The image analysis is done using a custom macro written
in the
OPTIMAS image analysis software package, available at the Meyer Instruments,
Inc.,
Houston, Texas. The "pill number" (Pt) for the treated black cotton twill
fabric and that
of the worn, untreated fabric (Pu) are determined. The percentage reduction of
the pill
number OP is
OP = 100 x (Pu-Pt)/Pu
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It is found that for an appreciable color restoration benefit provided by a
fabric
. color care composition, DP should be a positive number and having a value of
at least
about 10%, preferably at least by about 20%, more preferably at least about
40%, and
even more preferably at least about 80%.
It is highly desirable to use actives that provide other benefits such as
reduction of
wrinkles, maintenance of garment shape, soil release, etc., since the process
used herein
requires substantially complete treatment of the visible portions of the
fabric with
relatively high levels of active and a consumer will normally be reluctant to
invest the
time, money, and effort requirf;d to make sure that all areas are properly
covered. It is
known that the color restoration benefit can be achieved by use of rinse-added
and dryer-
added fabric softeners as taught by the applicants herein. However, the total
of active
required in the rinse is much greater since the active is applied to the
fabric in depth, and
even with the best dryer-added fabric softeners that are released from a
carrier such as a
flexible substrate, the distribution can be less than perfect the first time.
A preferred fabric color care active of the present invention comprises of
water
dispersible, preferably water soluble polymers. They can be natural, or
synthetic
polymers and can act by forming a film, and/or by providing adhesive
properties. E.g.,
the present invention can optionally use film-forming and/or adhesive polymer
to also
impart shape retention to fabric, particularly clothing. By "adhesive" it is
meant that
when applied as a solution or a dispersion io a fiber surface and dried, the
polymer can
attach to the surface. The poly~rner can form a film on the surface, or when
residing
between two fibers and in contact with the two fibers, it can bond the two
fibers together.
Natural Polymers
A preferred fabric color care active of the present invention include water
soluble
and/or water dispersible natural polymers which are derived from natural
sources,
preferably polysaccharides, oligosaccharides, proteins; substituted versions
of said
polymers; derivatised versions of said polymers; and mixtures thereof. The
preferred
polymer is colorless, to minimize the change of hue and to improve the color
fidelity.
A preferred active is selected from the group consisting of polysaccharides;
proteins; glycoproteins; glycolipids; substituted versions of said polymers;
dcrivatised
versions of said polymers; and mixtures thereof.
Synthetic Po~mers
Another preferred fabric color care active of the present invention include
water
soluble and/or water dispersible synthetic polymers. The preferred polymer is
colorless,
to minimize the change of hue. and to improve the color fidelity. Fabric color
care
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synthetic polymer includes: homopolymer and copolymer containing hydrophilic
monomers and/or hydrophobic monomers. .
Another preferred fabric color care synthetic polymer includes:
dimethylsiloxane
silicones and their derivatives. A class of silicone derivatives that is also
preferred in the
present invention is silicone copolyols.
Surfactant Ca able of Forming a Bilaver Structure
Surfactants capable of forming a bilayer structure are those that can form a
vesicle or liposome. Surfactant capable of forming a bilayer structure is
useful fabric
color care active in the spray composition of the present invention. Said
surfactant
comprises natural and synthetic materials. An example of natural surfactant
include the
phospholipids. Nonlimiting examples of synthetic surfactants include fabric
softening
actives and sorbitan esters of long chain (C, ~-C, g) fatty acids.
A preferred fabric color care composition for treating worn and/or faded
fabric
comprises an effective amount of said fabric color care active, and
optionally, at least one
adjunct ingredients selected from the group consisting of: perfume, odor
control agent
including cyclodextrin, antimicrobial active and/or preservative, surfactant,
optical
brightener, antioxidant, chelating agent including aminocarboxylate chelating
agent,
antistatic agent, dye transfer inhibiting agent, fabric softening active,
static control agent,
or mixtures thereof.
Cationic dye fixing agents are not preferred in the composition of the present
invention, because these materials are based on quaternized nitrogen compound
or on
nitrogen compounds having a strong cationic charge which is formed in situ
under the
conditions of usage. These materials arc often substantive to the fabric and
attract the
fugitive dyes in the subsequent wash and rinse cycles, and can discolor and/or
change the
color and/or hue of the treated color fabric. Enzymes are also not preferred
in the
composition of the present invention, specially in the spray compositions,
because
aerosolized particles containing enzymes often constitute a health lzazard.
The composition is typically applied to fabric via a positive step, e.g.,
spraying,
dipping, soaking and/or padding process to treat substantially all of the
visible surface
followed by a drying step, including the process comprising a step of treating
or spraying
the fabric with the fabric care composition either outside or inside an
automatic clothes
dryer followed by, or concurrently with, the drying step in said clothes
dryer. The
application can be done industrially by large scale processes on textiles
and/or finished
garments and clothing, or, preferably, in the consumer's home by the use of
commercial
product.
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The fabric color care spray composition contains fabric color care active at a
level
of from about 0.01 % to about 20~%, typically from about 0.05% to about 10%,
preferably
from about 0.1% to about 5%, more preferably from about 0.2% to about 3%, even
more
preferably from about 0.3% to about 2%, by weight of the usage composition.
The present invention also relates to concentrated liquid or solid fabric
color care
compositions, which are diluted to form compositions with the usage
concentrations, as
given hereinabove, for use in the "usage conditions". Concentrated
compositions
comprise a higher level of fabric. color care active, typically from about 1%
to about 99%,
preferably from about 2% to about 65%, more preferably from about 3% to about
25%,
by weight of the concentrated fabric color care composition. Concentrated
compositions
are used in order to provide a less expensive' product per use. When a
concentrated
product is used, i.e., when the fabric color care active is from about 1 % to
about 99%, by
weight of the concentrated composition, it is preferable to dilute the
composition before
treating fabric. Preferably, the concentrated fabric care is diluted with
about 50% to
about 10,000%, more preferably from about 50% to about 8,000%, and even more
preferably from about SO% to about 5,000%, by weight of the composition, of
water.
The present invention preferably comprises articles of manufacture that use
such
fabric color care compositions. Thus the present invention relates to the
compositions
incorporated into a spray dispenser to create an article of manufacture that
can facilitate
treatment of fabric surfaces with said fabric care compositions containing a
fabric color
care active and other optional ingredients at a level that is effective, yet
is not discernible
when dried on the surfaces. Tlue; spray dispenser comprises manually activated
and non-
manual powered (operated) spray means and a container containing the fabric
color care
composition. For a non-manually operated sprayer, preferably battery powered
for safety
reasons in the home, the container is preferably the one sold in the store
containing the
fabric color care composition that is applied to the fabric, adapted to be
used with the
particular sprayer. The invention also comprises containers that are adapted
far use with
spray dispensers.
Preferably the articles of manufacture are in association with a set of
instructions
for how to use the composition to treat fabrics correctly, to obtain the
desirable fabric
care results, viz, color renewal, and, preferably, other additional fabric
care benefits, such
as wrinkle removal, wrinkle resistance, fiber strengthcning/anti-wear, pill
prevention,
anti-shrinkage, soiling prevention and/or reduction, and/or fabric shape
retention,
including, e.g., the manner and~'or amount of composition to used, and the
preferred ways
of checking for completeness of application, stretching and/or smoothing of
the fabrics.
Ironing and/or smoothing C1I7 help distribute the active over the surface and
partially
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compensate for incomplete distribution. As used herein, the phrase "in
association with"
means the instructions are either directly printed on the container itself or
presented in a
different manner including, but not limited to, a brochure, print
advertisement, electronic
advertisement, and/or verbal communication, so as to communicate the set of
instructions
to a consumer of the article of manufacture. It is important that the
instructions be as
simple and clear as possible, so that using pictures and/or icons is
desirable.
I. COMPOSITION
FABRIC COLOR CARE ACTIVE
The fabric color care spray composition contains fabric color care active at a
level
of from about 0.01 % to about 20%, typically from about 0.05% to about 10%,
preferably
from about 0.1% to about 5%, more preferably from about 0.2°/, to about
3%, even more
preferably from about 0.3% to about 2%, by weight of the usage composition.
The present invention also relates to concentrated liquid or solid fabric
color care
compositions, which are diluted to form compositions with the usage
concentrations, as
given hereinabove, for use in the "usage conditions". Concentrated
compositions
comprise a higher level of fabric color care active, typically from about 1 %
to about 99%,
preferably from about 2% to about GS%, more preferably from about 3% to about
25%,
by weight of the concentrated fabric color care composition. Concentrated
compositions
are used in order to provide a less expensive product per use. When a
concentrated
product is used, i.e., when the fabric color care active is from about 1% to
about 99%, by
weight of the concentrated composition, it is preferable to dilute the
composition before
treating fabric. Preferably, the concentrated fabric care is diluted with
about 50% to
about 10,000%, more preferably from about 50°ro to about 8,000%, and
even more
preferably from about 50% to about 5,000%, by weight of the composition, of
water.
Typical rinse additive compositions contain a level of fabric color care
active of
from 0.05% to about 50%, preferably from about 1 % to about 35%, more
preferably from
about 2% to about 18%, and even more preferably from about 3% to about 10%,by
weight of the rinse added compositions.
Preferred color care active includes polymers which can act by forming a film,
and/or by providing adhesive properties. By "adhesive" it is meant that when
applied as
a solution or a dispersion to a fiber surface and dried, the polymer can
attach to the
surface. The polymer can form a film on the surface, or when residing between
two
fibers and in contact with the two fibers, it can bond the two fibers
together. E.g., the
present invention can use film-forming and/or adhesive polymer to provide
color
restoration to worn, faded fabric. The present invention can optionally use
film-forming
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and/or adhesive polymer to also impart shape retention to fabric, particularly
clothing.
Useful polymers include natural polymers, synthetic polymers, and mixtures
thereof.
These polymers are preferably colorless, to minimize the change of hue and to
improve
the color fidelity.
Water Soluble and Water Dispersible Natural Polymers
A fabric color c;ire active useful in the present invention comprises water
soluble and/or water dispersible polymers derived from natural sources,
preferably
selected from the ,~noup consisting of polysaccharides; proteins;
glycoproteins;
glycolipids; substituted versions thereof; derivatised versions thereof; and
mixtures
thereof.
Preferably the fabric color rare active is selected from the group consisting
of
polysaccharides and proteins. Preferably, said polysaccharides have a
molecular weight
of from about 1,000 to about ',000,000, more preferably from about 5,000 to
about
1,000,000, and even more preferably from about 10,000 to about 300,000.
Nonlimiting
examples of water soluble/dispersible polysaccharides useful in the present
invention
includes the following:
(i) Heteropolysaccharides derived from the bark, seeds, roots and leaves of
plants,
which arc divided into two distinct groups, namely, acidic polysaccharides
described as gums, mucilages and pectins, and the neutral polysaccharides
known
as hemicelluloses,
(ii j Algal polysaccharides including food-reserve polysaccharides (e.g.,
iarninaran),
structural polysaccharides (e.g., D-xylans, D-mannans), sulphated
polysaccharides that are isolated from algae (e.g., carrageenan, agar}, other
algal
mucilages which have similar properties and usually contain L-rhamnose, D-
xylose, D-glucuronic acid, D- and L-galactose and D-mannose,
(iii) Microbial polysaccharides, such as teichoic acids, cell wall
peptidoglycans
(mureins}, extracellular polysaccharides, gram-positive bacterial capsular
polysaccharides and gram-negative bacterial capsular polysaccharides.
(iv) Lipopolysaccharides,
(v) Fungal polysaccharides, and
( vi ) Animal polysaccharides (e.g., glycogen, chitin).
A preferred fabric color care polysaccharide is hemicelluloses selected from
the
group consisting of L-arabmo-D-galactan; D-gluco-D-mannan, D-galacto-D-gluco-D-
mannan, partly acetylated (4-O-methyl-D-glucurono)-D-xylan, L-arabino-(4-o-
methyl-D-
glucurono)-D-xylan; substituted versions thereof; derivatised versions
thereof; and
mixtures thereof; and more preferably, arabinogalactan. Arabinogalactans are
long,
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densely branched high-molecular weight polysaccharides. Arabinogalactan that
is useful
in the composition of the present invention has a molecular weight range of
from about
5,000 to about 500,000, preferably from about 6,000 to about 250,000, more
preferably
from about 10,000 to about 150,000. These polysaccharides are highly branched,
consisting of a galactan backbone with side-chains of galactose and arabinose
units.
Most commercial arabinogalactan is produced from western larch, through a
counter-
current extraction process. Larch arabinogalactan is water soluble and is
composed of
arabinose and galactose units in about a 1:6 ratio, with a trace of uronic
acid. The
molecular weights of the preferred fractions of larch arabinogaiactan include
one fraction
in the range of from about 14,000 to about 22,000, mainly from about 16,000 to
about
21,000, and the other in the range of from about 60,000 to about 500,000,
mainly from
about 80,000 to about 120,000. The fraction that has the average molecular
weight of
from about 16,000 to about 20,000 is highly preferred for use in direct
applications to
fabric, such as in spray-on products.
Cationic polysaccharides such as chitins are also useful in the present
invention.
Chitin, a linear polysaccharide consisting of N-acetyl-D-glucosamine, is
widely
distributed in nature, e.g., in the shells of crustaceans and insects, and in
the cell wall of
bacteria. Chemically, chitin is very similar to cellulose, differing only in
the fact that
chitin has an aminoacetyl group instead of hydroxyl group at C-2. In spite of
the
similarity in structure with cellulose, the chemical and physical properties
of chitin are
significantly different from those of cellulose.
Water Soluble/Dispersible Proteins
Nonlimiting examples of water soluble/dispersible proteins useful in the
present
invention includes: globular proteins, such as albumins, globulins,
protamines, histones,
prolamines and glutelins; low levels of fibrous proteins, such as elastin,
fibroin and
sericin; and conjugated proteins with one or more non-protein moieties such as
carbohydrates, lipids, and phosphate residues. The proteins useful herein
preferably do
not include enzymes, specially in the spray compositions, because aerosolized
particles
containing enzymes often constitute a health hazard.
Water Soluble and Water Dispersible Synthetic Polymers
Water soluble and water dispersible synthetic polymers useful in the present
invention are comprised of monomers. Some nonlimiting examples of monomers
which
can be used to form the synthetic polymers of the present invention include:
low
molecular weight C1-C6 unsaturated organic mono-carboxylic and polycarboxylic
acids,
such as acrylic acid, mcthacrylic acid. crotonic acid, malefic acid and its
half esters,
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13
itaconic acid, and mixtures thereof; esters of said acids with C I -C 12
alcohols, such as
methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-I-propanol, 1~-
pentanol,
2-pentanol, 3-pentanol, 2-methyl-1-butanol, 1-methyl-I -butanol, 3-methyl-1-
butanol, 1-
methyl-1-pentanol, 2-methyl-I-pc.ntanol, 3-methyl-I-pentanol, t-butanol,
cyclohexanol,
2-ethyl-1-butanol, neodecanol, 3-heptanol, benzyl alcohol, 2-octanol, 6-methyl-
1-
heptanol, 2-ethyl-1-hexanol, 3,5-dimethyl-I-hexanol, 3,5,5-trimethyl-I-
hexanol, 1-
decanol, 1-dodecanol, and the li:k~°, and mixtures thereof. Nonlimiting
examples of said
esters are methyl acrylate, ethyl acrylate, t-butyl acrylate, methyl
methacrylate,
hydroxyethyl methacrylate, methoxy ethyl methacrylate, and mixtures thereof;
amides
and imides of said acids, such as N,:N-dimethylacrylamide, N-t-butyl
acrylamide,
maleimides; low molecular weight unsaturated alcohols such as vinyl alcohol
(produced
by the hydrolysis of vinyl acetate after polymerization), allyl alcohol;
esters of said
alcohols with low molecular weight carboxylic acids, such as, vinyl acetate,
vinyl
propionate; ethers of said alcohols such as methyl vinyl ether; aromatic vinyl
such as
styrene, alpha-methylstyrene, t-~~utylstyrene, vinyl toluene, polystyrene
macromer, and
the like; polar vinyl heterocyclica, such as vinyl pyrrolidone, vinyl
caprolactam, vinyl
pyridine, vinyl imidazole, and mixtures thereof; other unsaturated amines and
amides,
such as vinyl amine, diethylen~ triamine, dimethylaminoethyl methacrylate,
ethenyl
formamide; vinyl sulfonate; salts of acids and amines listed above; low
molecular weight
unsaturated hydrocarbons and derivatives such as ethylene, propylene,
butadiene,
cyclohexadiene, vinyl chloride; vinylidene chloride; and mixtures thereof and
alkyl
quaternized derivatives thereof, and mixtures thereof. Preferably, said
monomers are
selected from the group consistins; of vinyl alcohol; acrylic acid;
methacrylic acid; methyl
acrylate; ethyl acrylate; methyl methacrylate; t-butyl acrylate; t-butyl
methacrylate; n-
butyl acrylate; n-butyl methacrylate; isobutyl methacrylate; 2-ethylhexyl
methacrylate;
dimethylaminoethyl methacrylate; N,N-dimethyl acrylamide; N,N-dimethyl
methacrylamide; N-t-butyl acryl;3mide; vinylpyrrolidone; vinyl pyridine;
adipic acid;
diethylenetriamine; salts thereof and alkyl quaternized derivatives thereof,
and mixtures
thereof.
Preferably, said monomers form homopolyrners and/or copolymers that are water
soluble or dispersible in water and have a molecular weight of at least about
500,
preferably from about 1,000 to about 2,000,000, more preferably from about
4,000 to
about 1,000,000, and even more preferably from about 10,000 to about 300,000
for some
polymers.
Polymers useful in the present invention can comprise homopolymers and
copolymers of hydrophilic monomers and hydrophobic monomers. The copolymer can
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14
be linear random or block copolymers, and mixtures thereof. The
hydrophobic/hydrophilic copolymers typically have a hydrophobic
monomer/hydrophilic
monomer ratio of from about 5:95 to about 95:5, preferably from about 15:85 to
about
85:15, more preferably from about 30:70 to about 75:25, by weight of the
copolymer.
The hydrophobic monomer can comprise a single hydrophobic monomer or a mixture
of
hydrophobic monomers, and the hydrophilic monomer can comprise a single
hydrophilic
monomer or a mixture of hydrophilic monomers. The term "hydrophobic" is used
herein
consistent with its standard meaning of lacking affinity for water, whereas
"hydrophilic"
is used herein consistent with its standard meaning of having affinity for
water. As used
herein in relation to monomer units and polymeric materials, including the
copolymers,
"hydrophobic" means substantially water insoluble; "hydrophilic" means
substantially
water soluble. In this regard, "substantially water insoluble" shall refer to
a material that
is not soluble in distilled (or equivalent) water, at 25°C., at a
concentration of about 0.2%
by weight, and preferably not soluble at about 0.1 % by weight (calculated on
a water plus
monomer or polymer weight basis). "Substantially water soluble" shall refer to
a
material that is soluble in distilled (or equivalent) water, at 25°C.,
at a concentration of
about 0.2% by weight, and are preferably soluble at about 1 % by weight. The
terms
"soluble", "solubility" and the like, for purposes hereof, corresponds to the
maximum
concentration of monomer or polymer, as applicable, that can dissolve in water
or other
solvents to forn~ a homogeneous solution, as is well understood to those
skilled in the art.
Nonlimiting examples of useful hydrophilic monomers are unsaturated organic
mono-carboxylic and polycarboxylic acids, such as acrylic acid, methacrylic
acid,
crotonic acid, malefic acid and its half esters, itaconic acid; unsaturated
alcohols, such as
vinyl alcohol, allyl alcohol; polar vinyl heterocyclics, such as vinyl
pyrrolidone, vinyl
caprolactam, vinyl pyridine, vinyl imidazole; vinyl amine; vinyl sulfonatc;
unsaturated
amides, such as acrylamides, e.g., N,N-dimethylacrylamide, N-t-butyl
acrylamide;
hydroxyethyl methacrylate; dimethyiaminoethyl methacrylate; salts of acids and
amines
listed above; and the like; and mixtures thereof. Some preferred hydrophilic
monomers
are acrylic acid, methacrylic acid, N,N-dimethyl acryIamide, N,N-dimethyl
methacrylamide, N-t-butyl acrylamidc, dimethylamino ethyl methacrylate, vinyl
pyrrolidone, salts thereof and alkyl quaternized derivatives thereof, and
mixtures thereof.
Nonlimiting examples of useful hydrophobic monomers are acrylic acid C1-Clg
alkyl esters, such as methyl acrylate, ethyl acrylate, t-butyl acrylate;
methacrylic C1-Clg
alkyl esters, such as methyl methacrylate, 2-ethyl hexyl methacrylate, methoxy
ethyl
methacrylate; vinyl alcohol esters of carboxylic acids, such as, vinyl
acetate, vinyl
propionate, vinyl neodecanoate; aromatic vinyls, such as styrene, t-butyl
styrene, vinyl
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toluene; vinyl ethers, such as methyl vinyl ether; vinyl chloride; vinylidene
chloride;
ethylene, propylene and other unsaturated hydrocarbons; and the like; and
mixtures
thereof. Some preferred hydrophobic monomers are methyl acrylate, methyl
methacrylate, t-butyl acrylate, t-butyl methacrylate, n-butyl acrylate, n-
butyl
methacrylate, and mixtures thereof.
Some nor.-limiting e~:amples of water soluble and water dispersible
homopolymers include polyacrylic acid, polyacrylamidc; polymethacrylic acid;
polymethacrylamide; polyvinyl alcohol; polyvinyl acetate;
polyvinylpyrrolidone;
polyvinyloxazolidone; polyvinylmethyloxazolidonc; polyethylene oxide;
polypropylene
oxide; polyvinylpyridine n-oxide;,; polyquaternary amine resins;
poly(ethenylfonnamide);
poly(vinylamine) hydrochloride; and mixtures thereof. Many of these polymers
are
described with more details ire "Water-Soluble Synthetic Polymers: Properties
and
Behavior, Volume I, Philip Molyneux, published byCRC Press, 1983, incorporated
herein by reference. Preferably said homopolymers are selected from the group
consisting of polyvinyl alcohol; polyvinyl acetate; polyacrylic acid;
polyacrylamide;
polymethacrylic acid; polymethacrylamide; polyinylpyrrolidone;
polyvinyloxazolidone;
polyethylene oxide; polypropylene oxide; polyvinylpyridine n-oxide; and
mixtures
thereof.
Some non-limiting examples of copolymers which can be used as fabric color
care active of the present invention are: adipic acid/
dimethylaminohydro~;ypropyl
diethylenetriamine copolymer; adipic acid/ epoxypropyl diethylenetriamine
copolymer;
poly(vinylpyrrolidone/ dimcth;ylaminoethyl methacrylate); methacryloyl ethyl
betaine/methacrylates copolymer; ethyl acrylate/methyl
methacrylate/methacrylic
acid/acrylic acid copolymer; polyvinyl alcohol-co-6% vinylamine); polyvinyl
alcohol-
co-12% vinylaminc); polyvinyl alcohol-co-G% vinyiamine hydrochloride); and
polyvinyl alcohol-co-12% vinylatnine hydrochloride). Preferably, said
copolymer are
selected from the group consisting of adipic acid/dimethylaminohydroxypropyl
diethylenetriamine copolymer; poly(vinylpyrrolidone/dimethylaminoethyl
methacrylate);
ethyl acrylate/methyl methacrylatc~/methacrylic acid/acrylic acid copolymer;
methacryloyl
ethyl betaine/methacrylates copolymer; polyquaternary amine resins;
poly(ethenylfonnamide); poly(vinylamine) hydrochloride; polyvinyl alcohol-co-
6%
vinylamine); polyvinyl alcohol-co-12°/> vinylamine); polyvinyl alcohol-
co-6%
vinylamine hydrochloride); and polyvinyl alcohol-co-12% vinylamine
hydrochloride).
Nonlimiting examples of the preferred polymer that are commercially available
are: polyvinylpyrrolidone/dimethylaminoethyl methacrylate copolymer, such as
Copolymer 958~, molecular weight of about 100,000 and Copolymer 937, molecular
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WO 00/24858 ~ PCT/US99/
16
weight of about 1,000,000, available from GAF Chemicals Corporation; adipic
acid/dimethylaminohydroxypropyl diethylenetriamine copolymer, such as
Cartaretin F-
4~ and F-23, available from Sandoz Chemicals Corporation; methacryloyl ethyl
betaine/methacrylates copolymer, such as Diaformer Z-SM~, available from
Mitsubishi
Chemicals Corporation; polyvinyl alcohol copolymer resin, such as Vinex 2019~,
available from Air Products and Chemicals or Moweol~, available from Clariant;
adipic
acid/epoxypropyl diethylenetriamine copolymer, such as Delsette I OI ~,
available from
1-lercules Incorporated; and polyvinylpyrrolidone/acrylic acid, such as
Sokalan EG 310,
available from BASF.
Non limiting examples of polymers for use in the present invention include the
following, where the composition of the copolymer is given as approximate
weight
percentage of each monomer used in the polymerization reaction used to prepare
the
polymer: vinyl pyrrolidone/vinyl acetate copolymers (at ratios of up to about
30% by
weight of vinyl pyrrolidone); dimethyl acrylamide/ t-butyl acrylate/ethyl
hexyl
methacrylate copolymer ( 10/45/45); vinyl pyrrolidone/vinyl acetate/butyl
acrylate
copolymer (10/78/12 and 10/70/20); vinyl pyrrolidone/vinyl propionate
copolymer
(5/95); vinyl caprolactam/vinyl acetate copolymer (5/95); acrylic acid/t-butyl
acrylate
(25/75) and styling resins sold under the trade names Ultrahold CA 8~ by Ciba
Geigy
(ethyl acrylate/ acrylic acid,~N-t-butyl acrylamide copolymer); Resyn 28-1310~
by
National Starch and Luviset CA 66~ by BASF (vinyl acetate/crotonic acid
copolymer
90/10); Luviset CAP~ by BASF (vinyl acetate/vinyl propionate/crotonic acid
50/40/10);
Resyn 28-2930 by National Starch (vinyl acetate/vinyl neodecanoate/crotonic
acid
copolymer), Amerhold DR-25G by Union Carbide (ethyl acrylate/methacrylic
acid/methyl methacrylate/acrylic acid copolymer), and Poligen A~ by BASF
(polyacrylate dispersion).
A preferred fabric color care active comprises copolymers contain hydrophobic
monomers and hydrophilic monomers which comprise unsaturated organic mono-
carboxylic and polycarboxylic acid monomers, such as acrylic acid, methacrylic
acid,
crotonic acid, malefic acid and its half esters, itaconic acid, and salts
thereof, and mixtures
thereof; and optionally other hydrophilic monomers. Examples of the
hydrophilic
unsaturated organic mono-carboxylic and polycarboxylic acid monomers are
acrylic acid,
methacrylic acid, crotonic acid, malefic acid and its half esters, itaconic
acid, and mixtures
thereof. Nonlimiting examples of the hydrophobic monomers are esters of the
unsaturated organic mono-carboxylic and polycarboxylic acids cited hercinabove
with
C1-C12 alcohols, such as methanol, ethanol, I-propanol, 2-propanol, 1-butanol,
2-
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17
methyl-1-propanol, 1-pentanol, '?-pentanol, 3-pentanol, 2-methyl-1-butanol, 1-
methyl-1-
butanol, 3-methyl-1-butanol, 1-methyl-1-pentanol, 2-methyl-1-pentanol, 3-
methyl-1-
pentanol, t-butanol, cyclohexanol, 2-ethyl-1-butanol, and mixtures thereof,
preferably
methanol, ethanol, 1-propanol, 2-propanol, 1--butanol, 2-methyl-1-propanol, t-
butanol,
and mixtures thereof. One preferred copolymer contains acrylic acid and t-
butyl acrylate
monomeric units, preferably with acrylic acid/t-butyl acrylate ratios of from
about 90:10
to about 10:90, preferably from about 70:30 to about 1 S:BS, more preferably
from about
40:60 to about 20:80. Nonlimiting examples of acrylic acid/tert-butyl acrylate
copolymers useful in the present invention are those typically with a
molecular weight of
from about 1,000 to about 2,000,000, preferably from about 5,000 to about
1,000,000,
and more preferably from abo:at 30,000 to about 300,000, and with an
approximate
acrylic acid/tert-butyl acrylate weight ratio of about 2S:7S and an average
molecular
weight of from about 70,000 to about 100,000, and those with an approximate
acrylic
acid/tert-butyl acrylate weight ratio of about 3S:6S and an average molecular
weight of
from about 60,000 to about 90,000.
A class of water-soluble pol5~ners containing nitrogen and oxygen atoms useful
in
the present invention for fabric color restoration/rcjuvenation can also be
used as dye
transfer inhibiting agents. These; polymers have the ability to complex or
adsorb the
fugitive dyes washed out of dyed fabrics before the dyes have the opportunity
to become
attached to other articles in the wash or the rinse. Nonlimiting examples of
these actives
are polyvinylpyrrolidone polymers, poly(4-vinylpyridine-N-oxide), polyamine N-
oxide
polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Examples of
such
dye transfer inhibiting agents ar~° disclosed in U.S. Pat. No.
5,804,219, issued Sept. 8,
1998 to T. Trinh, S. L.-L. Sung, f1. B. Tordil, and P. A. Wendland, and in
U.S. Patent
Nos. 5,707,950 and S,7(>7,951, all are incorporated herein by reference.
Polyalkyleneterephthlate Co~olym~ers
Another fabric color care active suitable in the present invention comprises
block
copolymers of polyalkylene terephthaiate and polyoxycthylene terephthalate,
and block
copolymers of polyalkylene terephthalate and polyethylene glycol. The
polyalkylene
terephthalate blacks preferably comprise ethylene and/or propylene groups.
Many such
polymers are nonionic.
A preferred nonionic polymer has the following average structure:
CH30(CH~CH20)4~~ ~-[C{O)-C6H4-C{O)-OCH2CH(CH3)O -)S
-C(O)-Cf~H4-C(O)-(OCH2CH~-)40OCH.1 .
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Such polymers are described in U.S. Pat. No. 4,849,257, Borcher, Trinh and
Bolich, issued July 18, 1989. Another preferred nonionic polymer is described
in New
Zealand Pat. No. 242,150, issued Aug. 7, 1995 to Pan, Gosselink, and Honsa,
said
patents are incorporated herein by reference.
Other suitable polymers that are useful in the present invention comprise
anionic
and cationic polymers. Suitable anionic polymers or oligomers are disclosed in
U.S. Pat.
No. 4,018,569, Trinh, Gosselink and Rattinger, issued April 4, 1989. Suitable
cationic
polymers are described in U.S. Pat. No. 4,956,447, Gossclink, Hardy, and
Trinh, issued
Sept. 11, 1990. Other suitable polymers are disclosed in U.S. Pat. No.
4,808,086, Evans,
Huntington, Stewart, Wolf, and Zimmerer, issued Feb. 24, 1989. All said
patents are
incorporated herein by reference.
The above polyalkylene terephthalate copolymers can be used in the composition
of the present invention to additionally provide a soil release benefit.
Silicones
Another preferred fabric color care active comprises silicones and their
derivatives. Nonlimiting examples of useful silicones in the composition of
the present
invention include noneurablc silicones such as polydimethylsilieone, and
curable
silicones such as aminosilicones, phenylsilicones and hydroxysilicones. The
word
"silicone" as used herein preferably refers to emulsified silicones, including
those that are
commercially available and those that are emulsified in the composition,
unless
otherwise described..
The silicones that are preferred in the composition of the present invention
is
polyalkyl and/or phcnylsilicones silicone fluids and gums with the following
structure:
A-Si~R2> -c~-(si~R2) -O-~q-si~R2) -A
The alkyl groups substituted on the siloxane chain (R) or at the ends of the
siloxane chains (A) can have any structure as long as the resulting silicones
remain fluid
at room temperature.
Each R group preferably can be alkyl, aryl, hydroxy, or hydroxyalkyl group,
and
mixtures thereof, more preferably, each R is methyl, ethyl, propyl or phenyl
group, most
preferably R is methyl. Each A group which blocks the ends of the silicone
chain can be
hydrogen, methyl, methoxy, ethoxy, hydroxy, propoxy, and aryloxy group,
preferably
methyl. Suitable A groups include hydrogen, methyl, methoxy, ethoxy, hydroxy,
and
propoxy. q is preferably an integer from about 7 to about 8,000. The preferred
silicones
are polydimethyl siloxanes; more preferred silicones are polydimethyl
siloxanes having a
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19
viscosity of from about 50 to about 5,000 centistokes at 25°C. Suitable
examples include
silicones offered by Dow Corning Corporation and General Electric Company.
Other useful silicone materials, but less preferred than polydimethyl
siloxanes,
include materials of the formula:
HO-[Si(CH3)2-O]x-__ ~Si(OH)[(CH2)3-~-(CH2)2-~2]O) y-H
wherein x and y are integers which depend on the molecular weight of the
silicone,
preferably having a viscosity of from about 10,000 cst to about 500,000 cst at
25°C. This
material is also known as "amodimethicone". These aminofunctional silicones
are highly
substantive to fabrics.
When the composition of this invention is to be dispensed from a spray
dispenser
m a consumer household setting, the noncurable silicones such as
polydimethylsiIicone,
are preferred. Curable and/or reactive silicones such as aminofunctionaI
silicones and
silicones with reactive groups such as Si-OH, Si-H, silanes, and the like, are
not preferred
in this situation, because the povrtion of the composition that is sprayed but
misses the
garment, and falls instead on flooring surfaces, such as rug, carpet, concrete
floor, tiled
floor, linoleum floor, bathtub floor, can leave a silicone layer that is cured
and/or bonded
to the flooring surfaces. Such silicones that are bonded to surfaces are
difficult to be
removed from the flooring surfaces. Flooring surfaces thus become slippery and
can
present a safety hazard to the household members. The curable and reactive
silicones can
be used in compositions specifically designed for use in enclosed areas such
as in a
dewrinkling cabinet. Many types of amino functional silicones also cause
fabric
yellowing. Thus, the silicones th~~t cause fabric discoloration are also not
preferred.
Another silicone material which can be used, but is less preferred than
polydimethyl siloxanes, has the formula:
(CH3)3Si-[O-Si(CH3)2]n-~OSi(CH3)[(CH2)3-NH-(CH2)2-NH2] ) m-OSi(CH3)3
wherein the sum of n + m is a number from 2 to about 1,000. The preferred
silicones of
this type are those which do not cause fabric discoloration.
The fabric color care silicones can also impart a lubricating property, and
are
useful in the composition to provide fabric wrinkle control benefit
A preferred class of silicono derivatives that are useful in the present
invention are
the silicone copolyols. Nonlimiting examples of silicone copolyols are the
polyalkylene
oxide polysiloxanes having a dimethyl polysiloxane hydrophobic moiety and one;
or more
hydrophilic polyalkylene side chains, and having the general formula:
Rl-(CH3)2Si0-[(CH3)2Si0]a-[(CH~)(Rl )Si0]b-Si(CH3)2-R1
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wherein a + b are from about I to about 50, preferably from about 3 to about
30 , more
preferably from about 10 to about 25, and each R1 is the same or different and
is selected
from the group consisting of methyl and a poly(ethyleneoxide/propyleneoxide)
copolymer
group having the general formula:
-(CH2)n O(C2 H4 O)c (C3 H6 O)d R2
with at least one R1 being a poly(cthyleneoxy/propyleneoxy) copolymer group,
and
wherein n is 3 or 4, preferably 3; total c (for all polyalkylcneoxy side
groups) has a value
of from 1 to about 100, preferably from about 6 to about I00; total d is from
0 to about 14,
preferably from 0 to about 3; and more preferably d is 0; total c+d has a
value of from
about ~ to about 150, preferably from about 9 to about 100 and each R2 is the
same or
different and is selected from the group consisting of hydrogen, an alkyl
having 1 to 4
carbon atoms, and an acetyl group, preferably hydrogen and methyl group. Each
polyalkylene oxide polysiloxane has at least one RI group being a
poly(ethyleneoxide/propyleneoxide) copolymer group.
Nonlimiting examples of this type of silicone copolyols are the Silwet~
surfactants
which are available from Witco Corporation. Representative Silwet surfactants
which
contain only ethyleneoxy (C2H40) groups are as follows.
Name Average MW Average a+b Average total c
L-7607 1,000 2 17
L-7605 6,000 20 99
L-7604 4,000 21 53
L-7600 4,000 11 68
L-7657 5,000 20 76
L-7602 3,000 20 29
L-7622 I 0,000 88 75
Nonlim iting examples ontain both ethyleneoxy
of surfactants (C2 H4 O)
which c
and propyleneoxy
(C3 H6
O) groups
are as
follows.
Name Average MW EO/PO ratio
Silwet 12,000 50/50
L-720
Silwet 20,000 40/60
L-7001
Siiwet 8,000 50/50
L-7002
Silwet 13,000 20/80
L-7210
Silwet 19,000 75/25
L-7200
Silwet 17,000 20/80
L-7220
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The molecular weight of the polyalkyleneoxy group (R1) is less than or equal
to
about 10,000. Preferably, the molecular weight of the polyalkyleneoxy group
:is less than
or equal to about 8,000, and most preferably ranges from about 300 to about
5,000. Thus,
the values of c and d can be those numbers which provide molecular weights
within these
ranges. However, the number of ethyleneoxy units (-C2H40) in the polyether
chain (R1)
must be sufficient to render the polyalkylene oxide polysiloxane water
dispersible or water
soluble. If propyleneoxy groups arc present in the polyalkylenoxy chain, they
can be
distributed randomly in the chain or exist as blocks. Surfactants which
contain only
propyleneoxy groups without ethyleneoxy groups are less preferred.
Other useful silicone derivatives are those having a hydrophobic moiety and
hydrophilic ionic groups, including, e.g., anionic, cationic, and amphoteric
groups.
Nonlimiting examples of anionic silicone surfactants are silicone
sulfosuccinates,
silicone sulfates, silicone phosphates, silicone carboxylates, and mixtures
thereof, as
disclosed respectively in U.S. Pat. Nos, 4,717,498, 4,960,845, 5,149,765, and
5,296,434.
Nonlimiting examples of cationic silicone surfactants are silicone alkyl quats
(quaternary
ammoniums), silicone amido quats, silicone imidazoline quats, and mixtures
thereof, as
disclosed respectively in U.S. Pat. Nos. 5,098,979, 5,135,294, and 5,196,499.
Nonlimiting examples of amphoteric silicone surfactants are silicone betaines,
silicone
amino proprionates, silicone phosphobetaines, and mixtures thereof, as
disclosed
respectively in U.S. Pat. Nos. 4,654,161, 5,073,~.i19, and 5,237,035. All of
these patents
are incorporated herein by reference.
A special type of synthetic fabric color care polymer useful in the present
invention comprises graft and block copolymers of silicone with moieties
containing
hydrophilic and/or hydrophobic; monomers described hereinbefore. The silicone-
containing copolymers in the spray composition of the present invention
provide color
rejuvenation, and in addition, other fabric care benefits such as shape
retention, body,
and/or good, soft fabric feel. Preferred silicone-containing copolymers
contain
hydrophobic monomers and hydrophilic monomers which comprise unsaturated
organic
mono-carboxylic and/or polycarboxylic acid monomers, such as acrylic acid,
methacrylic
acid, crotonic acid, malefic acid and its half esters, itaconic acid; and
salts thereof; and
mixtures thereof; and optionally other hydrophilic monomers.
Surfactant Capable Of Forming A Bilayer Structure
Surfactants capable of forming a bilayer structure are those that can form a
vesicle or liposome. Suitable surfactants include phospholipids such as
phosphatidyl
choline, phosphatidylethanolamine, phosphatidylinositol, lecithin, cephalin,
plasmalogen,
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22
and mixtures thereof, glycolipids such as cerbroside, sorbitan esters of long
chain (C»-
C1g) fatty acids, lactic acid esters of long chain (Cl~-C~g) fatty acid
monoglycerides (e.g.,
Lactem), diacetyl tartaric acid esters of long chain (C,~-C,8) fatty acid
monoglycerides
(e.g., Panodan FDPK), and mixtures thereof:
A preferred class of surfactants capable of forming a bilayer structure are
the
fabric softening actives. These materials are traditionally used in rinse-
added and dryer-
added fabric softener compositions. In the current invention, the fabric
softening actives
are preferably used in fabric color care compositions that are applied
directly to the worn,
faded fabrics, such as by spraying, soaking, dipping, or padding, preferably
spraying,
which are very efficient. The treatment using said fabric softening actives in
the rinse for
fabric color restoration benefit is less efficient, and requires a high level
of fabric
softening active, and thus is less preferred. The method of using a dryer-
added fabric
softener sheet in the dryer is also not preferred, because it can provide a
patchy, non-
uniform coverage of the fabric visible surface, resulting in a poor fabric
appearance.
Any fabric softening active, including quaternary and non-quaternary softening
actives, with saturated, partially saturated, unsaturated an/or highly
unsaturated, with
straight, linear alkyl chains and/or branched alkyl gn-oups, can be used in
the fabric color
care composition of the present invention, to be applied directly to the worn,
faded fabric,
preferably via a spraying mechanism. Biodegradable fabric softening actives
are
preferred.
A preferred fabric color care composition herein uses fabric softening active
with
highly unsaturated and/or branched hydrophobic chains, preferably
biodegradable,
selected from the highly unsaturated and/or branched fabric softening actives,
and
mixtures thereof.
Preferred fabric softening actives of the invention comprise a majority of
compounds as follows:
Diester uaternary Ammonium Fabric Softening Active Compound (DEQA)
(1) The first type of DEQA preferably comprises, as the principal active,
compounds of the formula
{R4_m - N+ - [(CH2)n - ~' - Rljm~
wherein each R substituent is either hydrogen, a short chain Cl-Cb, preferably
Cl-C3
alkyl or hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl,
hydroxyethyl,
and the like, poly (C2_3alkoxy) preferably polyethoxy group, benzyl, or
mixtures thereof;
each m is 2 or 3; each n is from 1 to about 4; each Y is -O-(O)C-, -C(O)-O-, -
NR-C(O)-
or -C(O)-IVR-; the sum of carbons in each R1, plus one when ~' is -O-(O)C- or -
NR-
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C(O) -, is C12-C22, preferably C14-C20, with each R1 being a hydrocarbyl, or
substituted hydrocarbyl group, and A- can be any softener-compatible anion,
preferably,
chloride, bromide, methylsulfate, ethylsulfate, sulfate, and nitrate, more
preferably
chloride or methyl sulfate. (As used herein, the "percent of softening active"
containing a
given R1 group is based upon taking a percentage of the total active based
upon the
percentage that the given R1 group is, of the total R1 groups present.)
(2) A second type of DE'sQA active has the general formula:
[R3N+CH2CH(YR1)(CH2YR1)] A-
wherein each Y, R, R1, and A- have the same meanings as before. Such compounds
include those having the formula:
[CH3]3 N(+)[CH2CH{CH20(O)CRl)O(O)CR1] C1(-)
where each R is a methyl or ethyl ~noup and preferably each R1 is in the range
of C15 to
C19
These types of agents and general methods of making them are disclosed in U.S.
Pat. No. 4,137,180, Naik et al., issued Jan. 30, 1979, which is incorporated
herein by
reference. An example of a preferred DEQA of formula (2) is the "propyl" ester
quaternary ammonium fabric softening active having the formula 1,2-di(acyloxy)-
3-
trimethylammoniopropane chloride, where the acyl is the same as that of FA1
mixture
disclosed hereinafter.
These biodegradable quaternary ammonium fabric softening compounds preferably
contain the group C(O)R1 which is preferably derived from partially
hydrogenated fatty
acids from natural sources, e.g., derived from animal fat, such as tallow
fatty acids. More
preferred are unsaturated fatty acids, e.g., oleic acid, and polyunsaturated
fatty acids, such
as those derived from vegetables oils, such as, canola oil, safflower oil,
peanut oil,
sunflower oil, corn oil, soybean oil, tall oil. rice bran oil, etc. Non-
limiting examples of
fatty acids (FA) are listed in U.S. Pat. No. 5,759,990 at column 4, lines 45-
66. Fabric
softening actives containing unsaturated and polyunsaturated fatty acids are
preferred in
formulating the fabric color care compositions of the present invention.
Iodine Value (referred to as ''ly"' herein) is used to define the level of
unsaturation
of a fatty acid. As used herein, Iodine Value of the "parent" fatty acid, or
"corresponding" fatty acid that th~~ R1 group is derived from, is also used to
define the
level of unsaturation of a fabric softening active. 'The IV of the parent
fatty acids of these
R1 group is from about 0 to about 140, more preferably from about 40 to about
130, on
the average. For concentrate, clear compositions, The IV is preferably from
about 70 to
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about 140, more preferably from about 80 to about 130, and even more
preferably from
about 90 to about I 15, on the average.
It is preferred that at least a majority of the fatty acyl groups are
unsaturated, e.g.,
from about 50% to 100%, preferably from about 55% to about 100%, more
preferably
from about 60% to about 100%.
Another DEQA softening active that is suitable for the formulation of the
fabric
color care compositions of the present invention, has the above formula ( 1 )
wherein one
R group is a C1-4 hydroxy alkyl group, or polyalkoxy group, preferably hydroxy
alkyl,
more preferably hydroxyethyl, group. An example of such a hydroxyethyl ester
active is
di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate, where the acyl
is
derived from the fatty acids described hereinbefore, e.g., oleic acid and
other highly
unsaturated fatty acids.
Polyquaternary Ammonium Softening Actives. Fabric softening actives carrying
more than one positive quaternary ammonium charge are also useful in the
fabric color
care compositions of the present invention. An example of this type of
softening active
is that having the formula:
R R
\N-R2-N
N~ N 2A0
R~ R~
wherein each R is H or a short chain Cl-C~, preferably C1-C3 alkyl or
hydroxyalkyl
group, e.g., methyl (most preferred), ethyl, propyl, hydroxycthyl, and the
like, benzyl, or
(R2 O)2-4H; each Rl is a C6-C2~. preferably C14-C20 hydrocarbyl, or
substituted
hydrocarbyl substituent, preferably C10-C20 alkyl or alkenyl (unsaturated
alkyl,
including polyunsaturated alkyl, also referred to sometimes as "alkylene"),
most
preferably C 12-C 1 g alkyl or alkenyl; each R2 is a C 1 _6 alkylene group,
preferably an
ethylene group; and A- are defined as below. Fabric softening actives having
the
following formula:
CHI CH~~
N-CH~CH2-N I 2CH3S040
N~ ~_ N
R~ R~
wherein R1 is derived from oleic acid is available from Witco Company.
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2S
Softening active having the formula:
R4_m - N(+) - IZ 1 m A_
wherein each m is 2 or 3, each R I is a C6-C22, preferably C I 4-C20, but no
more than
one being less than about C 12 and then the other is at least about 16,
hydrocarbyl, or
substituted hydrocarbyl substituent, preferably C10-C2p alkyl or alkenyl, most
preferably
C12-Clg alkyl or alkenyl, and where the Iodine Value of a fatty acid
containing this RI
group is from C) to about 140, more preferably from about 40 to about 130;
with a
cis/trans ratio of from about l :l to about 50:1, the minimum being 1:1,
preferably from
about 2:1 to about 40:1, more preferably from about 3:1 to about 30:1, and
even more
preferably from about 4:1 to about 20:1; each R 1 can also be a branched chain
C 14-C22
alkyl group, preferably a branched chain C16-C18 group; each R is H or a short
chain
C I -C6, preferably C 1-C3 alkyl or hydroxyalkyl group, e.g., methyl (most
preferred),
ethyl, propyl, hydroxyethyl, and the like, benzyl, or (R2 O)2-4H; and A- is a
softening
active compatible anion, preferably, chloride, bromide, methylsulfate,
ethylsulfate,
sulfate, and nitrate, more preferably chloride and methyl sulfate.
Other fabric softening actives that can be used herein are disclosed, at least
generically for the basic structures, in U.S. Pat. Nos.: 3,408,361,
Mannheimer, issued
Oct. 29, 1968; 4,709,045; Kubo et al., issued Nov. 24, 1987; 4,233,451, Pracht
et al.,
issued Nov. 11, 1980; 4,127,489, Pracht et al., issued Nov. 28, 1979;
3,689,424, Berg et
al., issued Sept. 5, 1972; 4,128,485, Baumann et al., issued Dec. S, 1978;
4,161,604,
Elster et al., issued July 17, I ~~ 79; 4,18>,593, Wechsler et al., issued
Feb. 19, 1980;
4,339,391, Hoffinan et al., issued July 13, 1982 3,861,870, Edwards and Diehl;
4,308,151, Cambre; 3,886,075, Bernardino; 4,233,164, Davis; 4,401,578,
Verbruggen;
3,974,076, Wiersema and Riekc; 4,237,016, Rudkin, Clint, and Young; 4,885,102,
Yamamura et al., issued Dec. >, 1989; 4,937,008, Yamamura et al., issued Jun.
26, 1990;
and 5,133,885, Contor et al., issued Jul. 28, 1992; Case 4768C, Trinh et al.;
and
European patent applications 91/3:36,267, Rutzen et a.l. and 91/423,894,
Contor et al. and
International Patent WO 91/01295, Trius et al., published Feb. 7, 1991, all of
said patents
and applications being incorporated herein by reference.
Other useful fabric softening actives are disclosed in U.S. Pat. No.
4,fi61,269,
issued April 28, 1987, to T. Trinh, E. H. Wahl, D. M. Swartley and R. L.
Hemingway.
Biodegradable ester and/or amide linked fabric softening actives are
disclosed, e.g., in
U.S. Pat. No. S,54S,340, issued Aug. 13, 1996, to Wahl et al. Biodegradable
unsaturated
ester and/or amide linked fabric softening actives in concentrated clear
compositions are
disclosed in U. S. Pat. No. S,7S9,990, issued Jun. 2, 1998 in the names of
Wahl, Tordil,
Trinh, Carr, Keys, and Meyer, and in U. S. Pat. No. 5,747,443, issued May 5,
1998 in the
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26
names of Wahl, Trinh, Gosselink, Letton, and Sivik. All said patents are
incorporated
herein by reference.
OPTIONAL INGREDIENTS
The fabric care composition of the present invention can optionally contain
surfactant, perfume, brightener, odor-controlling agent, antimicrobial active
and/or
preservative, antistatic agent, antioxidant, insect and moth repelling agent,
and mixtures
thereof. The total level of optional ingredients is low, preferably less than
about 5%,
more preferably less than about 3%, and even more preferably less than about
2%, by
weight of the usage composition. These optional ingredients exclude the other
ingredients specifically mentioned hereinbefore.
Surfactant
Surfactant is an optional but highly preferred ingredient of the present
invention.
Surfactant is especially useful in the composition to facilitate the
dispersion and/or
solubilization of color improvement agents such as silicones and/or perfume.
Such
surfactant is preferably included when the composition is used in a spray
dispenser in
order to enhance the spray characteristics of the composition and allow the
composition,
including the fabric color care active, to distribute more evenly, and to
prevent clogging
of the spray apparatus. The spreading of the composition can also allow it to
dry faster,
so that the treated material is ready to use sooner. For concentrated
compositions, the
surfactant facilitates the dispersion of many actives such as antimicrobial
actives and
perfumes in the concentrated aqueous compositions. Suitable surfactant useful
in the
present invention is nonionic surfactant, anionic surfactant, cationic
surfactant,
amphoteric surfactant, and mixtures thereof.
When surfactant is used in the composition of the present invention, it is
added at
an effective amount to provide one, or more of the benefits described herein,
typically
from about 0.01% to about 5%, preferably from about 0.05% to about 3%, more
preferably from about 0.1 % to about 2%, and even more preferably, from about
0.2% to
about 1 %, by weight of the usage composition.
A preferred type of surfactant is ethoxylated surfactant, such as addition
products
of ethylene oxide with fatty alcohols, fatty acids, fatty amines, etc.
Optionally, addition
products of mixtures of ethylene oxide and propylene oxide with fatty
alcohols, fatty
acids, fatty amines can be used. The ethoxylated surfactant includes compounds
having
the general formula:
Rg-Z-(CH~CH20)sB
wherein Rg is an alkyl group or an alkyl aryl group, selected from the group
consisting of
primary, secondary and branched chain alkyl hydrocarbyl groups, primary,
secondary and
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branched chain alkenyl hydrocarbyl groups, and/or primary, secondary and
branched
chain alkyl- and alkenyl-substituted phenolic hydrocarbyl groups having from
about 6 to
about 20 carbon atoms, preferably from about 8 to about 18, more preferably
from about
to about 15 carbon atoms; s is an integer from about 2 to about 45, preferably
from
about 2 to about 20, more preferably from about 2 to about 15; B is a
hydrogen, a
carboxylate group, or a sulfate group; and linking group Z is -O-, -C(O)O-, -
C(O)N(R)-,
or -C(O)N(R)-, and mixtures thereof in which R, when present, is R8 or
hydrogen.
The nonionic surfactants herein are characterized by an HLB (hydrophilic-
Iipophilic balance) of from 5 to 20, preferably from 6 to 15.
Nonlimiting examples of preferred ethoxylated surfactant are:
- straight-chain, primary alcohol ethoxylates, with R8 being Cg-C1 g alkyl
and/or
alkenyl group, more preferably C10-C14, and s being from about 2 to about 8,
preferably
from about 2 to about 6;
- straight-chain, secondary alcohol ethoxylates, with R8 being Cg-Clg alkyl
and/or
alkenyl, e.g., 3-hexadecyl, 2-octadecyl, 4-cicosanyl, and 5-eicosanyl, and s
being from
about 2 to about 10;
- alkyl phenol ethoxylates wherein the alkyl phenols having an alkyl or
alkenyl
group containing from 3 to 20 carbon atoms in a primary, secondary or branched
chain
configuration, preferably from 6 to 12 carbon atoms, and s is from about 2 to
about 12,
preferably from about 2 to about 8;
- branched chain alcohol ethoxylates, wherein branched chain primary and
secondary alcohols (or Guerbet alcohols) which are available, e.g., from the
well-known
"OXO" process or modification thereof are ethoxylated.
Especially preferred are alkyl ethoxylate surfactants with each R8 being Cg-
C16
straight chain and/or branch chain alkyl and the number of ethyleneoxy groups
s being
from about 2 to about 6, preferably from about 2 to about 4, more preferably
with R8
being Cg-C15 alkyl and s being from about 2.25 to about 3.5. These nonionic
surfactants
are characterized by an HLB of from 6 to about 1 i , preferably from about 6.5
to about
9.5, and more preferably from about 7 to about 9. Nonlimiting examples of
commercially available preferred surfactants are Neodol 91-2.5 (C9-C10, s =
2.7, HLB =
8.5), Neodol 23-3 (C12-C13, s = %.9, HLB = 7.9) and Neodol 25-3 (C12-C15, s =
2.8,
HLB = 7.5). It is found, very surprisingly, that these preferred surfactants
which are
themselves not very water soluble (0.1% aqueous solutions of these surfactants
are not
clear), can at low levels, effectively dissolve and/or disperse shape
retention polymers
such as copolymers containing acrylic acid and tert-butyl acrylate and
silicone-containing
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28
copolymers into clear compositions, even without the presence of a low
molecular weight
alcohol.
Also preferred is a nonionic surfactant selected from the group consisting of
fatty
acid (C12_1g) esters of ethoxylated (EOS_,oo) sorbitans. More preferably said
surfactant is
selected from the group consisting of mixtures of laurate esters of sorbitol
and sorbitol
anhydrides; mixtures of stearate esters of sorbitol and sorbitol anhydrides;
and mixtures
of oleate esters of sorbitol and sorbitol anhydrides. Even more preferably
said surfactant
is selected from the group consisting of Polysorbate 20, which is a mixture of
laurate
esters of sorbitol and sorbitol anhydrides consisting predominantly of the
monoester,
condensed with about 20 moles of ethylene oxide; Polysorbate 60 which is a
mixture of
stearate esters of sorbitol and sorbitol anhydride, consisting predominantly
of the
monoester, condensed with about 20 moles of ethylene oxide; Polysorbate 80
which is a
mixture of oleate esters of sorbitol and sorbitol anhydrides, consisting
predominantly of
the monoester, condensed with about 20 moles of ethylene oxide; and mixtures
thereof.
Most preferably, said surfactant is Polysorbate 60.
Other examples of preferred ethoxylated surfactant include carboxylated
alcohol
ethoxylate, also known as ether carboxylate, with R8 having from about I2 to
about 16
carbon atoms and s being from about 5 to about 13; ethoxylated quaternary
ammonium
surfactants, such as PEG-5 cocomonium methosulfate, PEG-I S cocomonium
chloride,
PEG-15 oleammonium chloride and bis{polyethoxyethanol)tallow ammonium
chloride.
Other suitable nonionic ethoxylated surfactants are ethoxylated alkyl amines
derived from the condensation of ethylene oxide with hydrophobic alkyl amines,
with R8
having from about 8 to about 22 carbon atoms and s being from about 3 to about
30.
Also suitable nonionic ethoxylated surfactants for use herein are
alkylpolysaccharides which are disclosed in U.S. Patent 4,565,647, Llenado,
issued
January 21, 1986, incorporated herein by reference, having a hydrophobic group
containing from about 8 to about 30 carbon atoms, preferably from about 10 to
about 16
carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group
containing
from about 1.3 to about 10, preferably from about I.3 to about 3, most
preferably from
about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5
or 6
carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can
be
substituted for the glucosyl moieties. The intersaccharide bonds can be, e.g.,
between the
one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6-
positions on
the preceding saccharide units. The preferred alkylpolyglycosides have the
formula
R~O(CnH2n0)t(glycosyl)x
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wherein Rz is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain
from 10 to
18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably from about
1.3 to
about 3, most preferably from about 1.3 to about 2.7. The glycosyl is
preferably derived
from glucose.
Odor Control Agent
The agents for odor control are of the type disclosed in U:S. Pats. 5,534,165;
x,578,563; 5,663, I 34; 5,668,097; 5,670,475; and 5,714, I 37, Trinh et al.
issued Jul. 9,
1996; Nov. 26, 1996; Sep. 2, 1!97; Sep. 16, 1997; Sep. 23, 1997; and Feb. 3,
1998
respectively, all of said patents being incorporated herein by reference.
Fabric care
compositions of the present invention can contain several different optional
odor control
agents, preferably cyclodextrins, water soluble zinc salts, water soluble
copper salts, and
mixtures thereof.
(a). 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-c:yclodextrin consists of six
glucose units,
the beta-cyclodextrin consists of seven glucose units, and the gamma-
cyclodextrin
consists of eight glucose units arranged in donut-shaped rings. The specific
coupling and
conformation of the glucose units give the cyclodextrins a rigid, conical
molecular
structures with hollow interiors of specific volumes. The "lining" of each
internal cavity
is formed by hydrogen atoms and glycosidic bridging oxygen atoms; therefore,
this
surface is fairly hydrophobic. The unique shape and physical-chemical
properties 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
odorous molecules can fit into the cavity including many malodorous molecules
and
perfume molecules. Therefore, cyclodextrins, and especially mixtures of
cyclodextrins
with different size cavities, can be used to control odors caused by a broad
spectrum of
organic odoriferous materials, wr~ich may, or may not, contain reactive
functional groups.
The complexation between cycLodextrin and odorous molecules occurs rapidly in
the
presence of water. However, the extent of the complex formation also depends
on the
polarity of the absorbed molecules. In an aqueous solution, strongly
hydrophilic
molecules (those which are highly water-soluble) are only partially absorbed,
if at all.
Therefore, cyclodextrin does not complex effectively with some very low
molecular
weight organic amines and acids when they are present at low levels on wet
fabrics. As
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the water is being removed however, e.g., the fabric is being dried off, some
low
molecular weight organic amines and acids have more affinity and will complex
with the
cyclodextrins more readily.
The cavities within the cyclodextrin in the solution of the present invention
should remain essentially unfilled (the cyclodextrin remains uncomplexed)
while in
solution, in order to allow the cyclodextrin to absorb various odor molecules
when the
solution is applied to a surface. Non-derivatised (normal) beta-cyclodextrin
can be
present at a level up to its solubility limit of about 1.85% (about 1.85g in
100 grams of
water) at room temperature. Beta-cyclodextrin is not preferred in compositions
which
call for a level of cyclodextrin higher than its water solubility limit. Non-
derivatised
beta-cyclodextrin is generally not preferred when the composition contains
surfactant
since it affects the surface activity of most of the preferred surfactants
that are compatible
with the derivatised cyclodextrins.
Preferably, the odor absorbing solution of the present invention is clear. The
term
"clear" as defined herein means transparent or translucent, preferably
transparent, as in
"water clear," when observed through a layer having a thickness of less than
about 10 cm.
Preferably, the cyclodextrins used in the present invention are highly water-
soluble such as, alpha-cyclodextrin and/or derivatives thereof, gamma-
cyclodextrin
and/or derivatives thereof, derivatised beta-cyclodextrins, and/or mixtures
thereof. The
derivatives of cyclodextrin consist mainly of molecules wherein some of the OH
groups
are converted to OR groups. Cyclodextrin derivatives include, e.g., those with
short
chain alkyl groups such as methylated cyclodextrins, and ethylated
cyclodextrins,
wherein R is a methyl or an ethyl group; those with hydroxyalkyl substituted
groups,
such as hydroxypropyl cyclodextrins and/or hydroxyethyl cyclodextrins, wherein
R is a -
CH2-CH(OH)-CH3 or a -CH~CH~-OH group; branched cyclodcxtrins such as maltose-
bonded cyclodextrins; cationic cyclodextrins such as those containing 2-
hydroxy-3-
(dimethylamino)propyl ether, wherein R is CHI-CH(OH)-CHI-N(CH3)~ which is
cationic at low pH; quaternary ammonium, e.g., 2-hydroxy-3-
(trimethylammonio)propyl
ether chloride groups, wherein R is CHI-CH(OH)-CH2-N+(CH3)3C1-; anionic
cyclodextrins such as carboxymethyl cyclodextrins, cyclodextrin sulfates, and
cyclodextrin succinylates; amphoteric cyclodextrins such as
carboxymcthyl/quaternary
ammonium cyclodextrins; cyclodextrins wherein at least one glucopyranosc unit
has a 3-
6-anhydro-cyclomalto structure, e.g., the mono-3-G-anhydrocyclodextrins, as
disclosed in
"Optimal Performances with Minimal Chemical Modification of Cyclodextrins", F.
Diedaini-Pilard and B. Perly, The 7th International Cyclodextrin Symposium
Abstracts,
April 1994, p. 49, said references being incorporated herein by reference; and
mixtures
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31
thereof. Other cyclodextrin derivatives are disclosed in U.S. Pat. Nos.:
3,426,011,
Parmerter et al., issued Feb. 4, 1969; 3,453,257; 3,453,258; 3,453,259; and
3,453,260, all
in the names of Parmerter et al., and all issued July l, 1969; 3,459,731,
Gramera et al.,
issued Aug. 5, 1969; 3,553,1'~l, Parmerter et al., issued Jan. 5, 1971;
3,565,887,
Parmerter et al., issued Feb. 23, l~>71; 4,535,152, Szejtli et al., issued
Aug. 13, 1985;
4,616,008, Hirai et al., issued Oct. 7, 1986; 4,678,598, Ogino et al., issued
Jul.. 7, 1987;
4,638,058, Brandt et al., issued Jan. 20, 1987; and 4,746,734, Tsuchiyama et
al., issued
May 24, 1988; all of said patents being incorporated herein by reference.
Highly water-soluble cyclodextrins are those having water solubility of at
least
about 10 g in 100 ml of water at room temperature, preferably at least about
20 g in 100
ml of water, more preferably at least about 25 g in 100 ml of water at room
temperature.
The availability of solubilized, uncomplexed cyclodextrins is essential for
effective and
efficient odor control performance. Solubilized, water-soluble cyclodextrin
can exhibit
more efficient odor control performance than non-water-soluble cyclodextrin
when
deposited onto surfaces, especially fabric.
Examples of preferred water-soluble cyclodextrin derivatives suitable for use
herein are hydroxypropyl alpha-cyclodextrin, methylated alpha-cyclodextrin,
methylated
beta-cyclodextrin, hydroxyethyl beta-cyclodextrin, and hydroxypropyl beta-
cyclodextrin.
Hydroxyalkyl cyclodextrin derivatives preferably have a degree of substitution
of from
about 1 to about 14, more preferably from about 1.5 to about 7, wherein the
total number
of OR groups per cyclodextrin is defined as the degree of substitution.
Methylated
cyclodextrin derivatives typicall~~ have a degree of substitution of from
about 1 to about
18, preferably from about 3 to about 16. A known methylatcd beta-cyclodextrin
is
heptakis-2,6-di-O-methyl-~3-cyclodextrin, commonly known as DIMEB, in which
each
glucose unit has about 2 methyl ,groups with a degree of substitution of about
14. A
preferred, more commercially available, methylated beta-cyclodextrin is a
randomly
methylated beta-cyclodextrin, commonly known as RAMEB, having different
degrees of
substitution, normally of about 1:Z.6. RAMEB is more preferred than DIMEB,
since
DIMEB affects the surface activity of the preferred surfactants more than
RAMEB. The
preferred cyclodextrins are available, e.g., from Cerestar USA, Inc. and
blacker
Chemicals (USA), Inc.
It is also preferable to use a mixture of cyclodextrins. Such mixtures absorb
odors more broadly by complexing; with a wider range of odoriferous molecules
having a
wider range of molecular sizes. Preferably at least a portion of the
cyclodextrins is alpha-
cyclodextrin and its derivatives thereof, gamma-cyclodextrin and its
derivatives thereof,
and/or derivatised beta-cyclodextrin, more preferably a mixture of alpha-
cyclodextrin, or
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32
an alpha-cyclodextrin derivative, and derivatised beta-cyclodextrin, even more
preferably
a mixture of derivatised alpha-cyclodextrin and derivatised beta-cyclodextrin,
most
preferably a mixture of hydroxypropyl alpha-cyclodextrin and hydroxypropyl
beta-
eyclodextrin, and/or a mixture of methylated alpha-cyclodextrin and methylated
beta-
cyclodextrin.
For controlling odor on fabrics, the composition is preferably used as a
spray. It
is preferable that the usage compositions of the present invention contain low
levels of
cyclodextrin so that a visible stain does not appear on the fabric at normal
usage levels.
Preferably, the solution used to treat the surface under usage conditions is
virtually not
discernible when dry. Typical levels of cyclodextrin in usage compositions for
usage
conditions are from about 0.01 °/> to about 5%, preferably from about
0.1 % to about 4%,
more preferably from about 0.5'% to about 2°,% by weight of the
composition.
Compositions with higher concentrations can leave unacceptable visible stains
on fabrics
as the solution evaporates off of the fabric. This is especially a problem on
thin, colored,
synthetic fabrics. In order to avoid or minimize the occurrence of fabric
staining, it is
preferable that the fabric be treated at a level of less than about 5 mg of
cyclodextrin per
gram of fabric, more preferably less than about 2 mg of cyclodextrin per gram
of fabric.
The presence of the surfactant can improve appearance by minimizing localized
spotting.
When the optiona3 cyclodextrin is present in the composition, the polymer
active
in the composition of the present invention should be cyclodextrin-compatible,
that is it
should not substantially fom complexes with cyclodextrin so as to diminish
performance
of the cyclodextrin and/or the polymer. Complex formation affects both the
ability of the
cyclodextrin to absorb odors and the ability of the polymer to impart color
renewal and/or
shape retention to fabric. In this case, the monomers having pendant groups
that can
complex with cyclodextrin are not preferred because they can form complexes
with
cyclodextrin. Examples of such monomers are acrylic or methacrylic acid esters
of C~-
Clg alcohols, such as neodecanol, 3-heptanol, benzyl alcohol, 2-octanol, 6-
methyl-1-
heptanol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-
hexanol, and 1-
decanol; aromatic vinyls, such as styrene; t-butyl styrene; vinyl toluene; and
the like.
Low Molecular Weight Polyols
Low molecular weight polyols with relatively high boiling points, as compared
to
water, such as ethylene glycol, propylene glycol and/or glycerol are preferred
optional
ingredients for improving odor control performance of the composition of the
present
invention when cyclodextrin is present. Not to be bound by theory, it is
believed that the
incorporation of a small amount of low molecular weight glycols into the
composition of
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33
the present invention enhances the formation of the cyclodextrin inclusion
complexes as
the fabric dries.
It is believed that the pol~~ols' ability to remain on the fabric for a longer
period of
time than water, as the fabric dries allows it to form ternary complexes with
the
cyclodextrin and some malodorous molecules. The addition of the glycols is
believed to
fill up void space in the cyclode:xtrin cavity that is unable to be filled by
some malodor
molecules of relatively smaller aizes. Preferably the glycol used is glycerin,
ethylene
glycol, propylene glycol, diethylene glycol, dipropylene glycol or mixtures
thereof, more
preferably ethylene glycol and/or propylene glycol. Cyclodextrins prepared by
processes
that result in a level of such polyols are highly desirable, since they can be
used without
removal of the polyols.
Some polyols, e.g., dipropylene glycol, are also useful to facilitate the
solubilization of some perfume ingredients in the composition of the present
invention.
Typically, glycol is added to the composition of the present invention at a
level of
from about 0.01% to about 3'%, by weight of the composition, preferably from
about
0.05% to about 1 %, more preferably from about 0.1 % to about 0.5%, by weight
of the
composition. The preferred weight ratio of low molecular weight polyol to
cyclodextrin
is from about 2:1,000 to about 20:100, more preferably from about 3:1,000 to
about
15:100, even more preferably from about 5:1,000 to about 10:100, and most
preferably
from about 1:100 to about 7:100.
(b). Metal Salts
Optionally, but highly preferred, the present invention can include metallic
salts
for added odor absorption and/or antimicrobial benefit for the cyclodextrin
solution when
cyclodextrin is present. The mcaallic salts are selected from the group
consisting of
copper salts, zinc salts, and mixtures thereof:
Copper salts have some a:ntimicrobial benefits. Specifically, cupric abietate
acts
as a fungicide, copper acetate acts as a mildew inhibitor, cupric chloride
acts as a
fungicide, copper lactate acts as a fungicide, and copper sulfate acts as a
germicide.
Copper salts also possess some malodor control abilities. See U. S. Pat. No.
3,172,817,
Leupold, et al., which discloses deodorizing compositions for treating
disposable articles,
comprising at least slightly water-soluble salts of acylacetone, including
copper salts and
zinc salts, all of said patents are incorporated herein by reference.
The preferred zinc salts possess malodor control abilities. Zinc has been used
most often for its ability to ameliorate malodor, e.g., in mouth wash
products, as
disclosed in U.S. Pat. Nos. 4,325,939, issued Apr. 20, 1982 and 4,469,674,
issued Sept.
4, 1983, to N. B. Shah, et al., all of~ which are incorporated herein by
reference. ~Iighly-
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34
ionized and soluble zinc salts such as zinc chloride, provide the best source
of zinc ions.
Zinc borate functions as a fungistat and a mildew inhibitor, zinc caprylate
functions as a
fungicide, zinc chloride provides antiseptic and deodorant benefits, zinc
ricinoleate
functions as a fungicide, zinc sulfate heptahydrate functions as a fungicide
and zinc
undecylenate functions as a fungistat.
Preferably the metallic salts are water-soluble zinc salts, copper salts or
mixtures
thereof, and more preferably zinc salts, especially ZnCl2. These salts are
preferably
present in the present invention primarily to absorb amine and sulfur-
containing
compounds that have molecular sizes too small to be effectively complexed with
the
cyclodextrin molecules. Low molecular weight sulfur-containing materials,
e.g., sulfide
and mercaptans, are components of many types of malodors, e.g., food odors
(garlic,
onion), body/perspiration odor, breath odor, etc. Low molecular weight amines
are also
components of many malodors, e.g., food odors, body odors, urine, etc.
When metallic salts are added to the composition of the present invention they
arc
typically present at a level of from about 0.1 % to about 10%, preferably from
about 0.2%
to about 8%, more preferably from about 0.3% to about 5% by weight of the
usage
composition. When zinc salts are used as the metallic salt, and a clear
solution is
desired, it is preferable that the pH of the solution is adjusted to less than
about 7, more
preferably less than about 6, most preferably, less than about 5, in order to
keep the
solution clear.
(c). Soluble Carbonate and/or Bicarbonate Salts
Water-soluble alkali metal carbonate and/or bicarbonate salts, such as sodium
bicarbonate, potassium bicarbonate, potassium carbonate, cesium carbonate,
sodium
carbonate, and mixtures thereof can be added to the composition of the present
invention
in order to help to control certain acid-type odors. Preferred salts are
sodium carbonate
monohydrate, potassium carbonate, sodium bicarbonate, potassium bicarbonate,
and
mixtures thereof. When these salts are added to the composition of the present
invention,
they are typically present at a level of from about 0.1 % to about 5%,
preferably from
about 0.2% to about 3%, more preferably from about 0.3% to about 2%, by weight
of the
composition. When these salts are added to the composition of the present
invention it is
preferably that incompatible metal salts not be present in the invention.
Preferably, when
these salts are used the composition should be essentially free of zinc and
other
incompatible metal ions, e.g., Ca, Fe, Ba, ctc. which form water-insoluble
salts.
(d). Mixtures Thereof
Mixtures of the above materials are desirable, especially when the mixture
provides control over a broader range of odors.
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Perfu me
The composition of the present invention can also optionally provide a "scent
signal" in the form of a pleasant odor which provides a freshness impression
to the
treated fabrics. The scene sib ial can be designed to provide a fleeting
perfume scent.
When perfume is added as a scent signal, it is added only at very low levels,
e.g., from
about 0.001 % to about 0.5°r, preferably from about 0.003% to about
0.3%, more
preferably from about 0.005% to about 0.2%, by weight of the usage
composition.
Perfume can also be added as a more intense odor in product and on fabrics.
When stronger levels of perfume°, .are preferred, relatively higher
levels of perfume can be
added.
Any type of perfume can be incorporated into the composition of the present
invention. The preferred perfume ingredients are those suitable for use to
apply on
fabrics and garments. Typical examples of such preferred ingredients are given
in U.S.
Pat. 5,445,747, issued Aug. 29, 1995 to Kvietok et al., incorporated herein by
reference.
When long lasting fragrance odor on fabrics is desired, it is preferred to use
at
least an effective amount of perfume ingredients which have a boiling point of
about
240°C or higher, preferably of about 250°C or higher.
Nonlimiting examples of such
preferred ingredients are given in U.S. Pat. 5,500,138, issued Mar. 19, 1996
to Bacon et
al., incorporated herein by reference. It is also preferred to use materials
that can slowly
release perfume ingredients after the fabric is treated by the color
improvement
composition of this invention. Examples of materials of this type are given in
1J.S. Pat.
5,531,910, Severns et al., issued :luly 2, 1996, said patent being
incorporated herein by
reference.
When cyclodextrin is present, it is essential that the perfume be added at a
level
wherein even if all of the perfume in the composition were to complex with the
cyclodextrin molecules when cyclodextrin is present, there will still be an
effective level
of uncomplexed cyclodextrin molecules present in the solution to provide
adequate odor
control. In order to reserve an effective amount of cyclodextrin molecules for
odor
control when cyclodextrin is present, perfume is typically present at a level
wherein less
than about 90% of the cyclodextrin complexes with the perfume, preferably less
than
about 50% of the cyclodextrin complexes with the perfume, more preferably,
less than
about 30% of the cyclodextrin complexes with the perfume, and most preferably,
less
than about 10% of the cyclodextrin complexes with the perfume. The
cyclodextrin to
perfume weight ratio should be greater than about 8:1, preferably greater than
about 10:1,
more preferably greater than about 20:1, even more preferably greater than
40:1 and most
preferably greater than about 70:1.
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36
Preferably the perfume is hydrophilic and is composed predominantly of
ingredients selected from two groups of ingredients, namely, (a) hydrophilic
ingredients
having a ClogP of less than about 3.5, more preferably less than about 3.0,
and (b)
ingredients having significant low detection threshold, and mixtures thereof.
Typically,
at least about 50%, preferably at least about 60%, more preferably at least
about 70%,
and most preferably at least about 80% by weight of the perfume is composed of
perfume
ingredients of the above groups (a) and (b). For these preferred perfumes, the
cyclodextrin to perfume weight ratio is typically of from about 2:1 to about
200:1;
preferably from about 4:1 to about l 00:1, more preferably from about 6:1 to
about 50:1,
and even more preferably from about 8:1 to about 30:1.
(a). Hydrophilic Perfume Ingredients
The hydrophilic perfume ingredients are more soluble in water, have less of a
tendency to complex with the cyclodextrins, and are more available in the odor
absorbing
composition than the ingredients of conventional perfumes. The degree of
hydrophobicity of a perfume ingredient can be correlated with its
octanollwater partition
coefficient P. The octanol/watcr partition coefficient of a perfume ingredient
is the ratio
between its equilibrium concentration in octanol and in water. A perfume
ingredient
with a greater partition coefficient P is considered to be more hydrophobic.
Conversely,
a perfume ingredient with a smaller partition coefficient P is considered to
be more
hydrophilic. Since the partition coefficients of the perfume ingredients
normally have
high values, they are more conveniently given in the form of their logarithm
to the base
10, loge. Thus the preferred perfume hydrophilic perfume ingredients of this
invention
have IogP of about 3.5 or smaller. preferably of about 3.0 or smaller.
The IogP of many perfume ingredients have been reported; for example, the
Pomona92 database, available from Daylight Chemical Information Systems, Inc.
(Daylight CIS), Irvine, California, contains many, along with citations to the
original
literature. However, the loge values arc most conveniently calculated by the
"CLOGP"
program, also available from Daylight CIS. This program also lists
experimental loge
values when they are available in the Pomona92 database. The "calculated loge"
(ClogP)
is determined by the fragment approach of Hansch and Leo (cf., A. Leo, in
Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B.
Taylor
and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990, incorporated herein by
reference). The fragment approach is based on the chemical structure of each
perfume
ingredient, and takes into account the numbers and types of atoms, the atom
connectivity,
and chemical bonding. The ClogP values, which are the most reliable and widely
used
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37
estimates for this physicochemical property, are used instead of the
experimental loge
values in the selection of perfume ingredients which are useful in the present
invention.
Non-limiting examples o:f the more preferred hydrophilic perfume ingredients
are
allyl amyl glycolate, allyl caproate, amyl acetate, amyl propionate, anisic
aldehyde, anisyl
acetate, anisole, benzaldehyde, benzyl acetate, benzyl acetone, benzyl
alcohol, benzyl
formate, benzyl iso valerate, bf:nzyl propionate, beta gamma hexenol, calone,
camphor
gum, laevo-carveol, d-carvone, laevo-carvone, cinnamic alcohol; cinnamyl
acetate,
cinnamic alcohol, cinnamyl fonnate, cinnamyl propionate, cis-jasmone, cis-3-
hexenyl
acetate, coumarin, cuminic alcohol, cuminic aldehyde, Cyclal C,
cyclogalbanate,
dihydroeuginol, dihydro isoja:smonate, dimethyl benzyl carbinol, dimethyl
benzyl
carbinyl acetate, ethyl acetate, ethyl aceto acetate, ethyl amyl ketone, ethyl
anthraniIate,
ethyl benzoate, ethyl butyrate, ethyl cinnamate, ethyl hexyl ketone, ethyl
maltol, ethyl-2-
methyl butyrate, ethyl methylphenyl glycidate, ethyl phenyl acetate, ethyl
salicylate, ethyl
vanillin, eucalyptol, eugenol, eugenyl acetate, eugenyl formate, eugenyl
methyl ether,
fenchyl alcohol, flor acetate (tricycle decenyl acetate), fructone, frutene
(tricycle decenyl
propionate), geraniol, geranyl oxyacetaldehyde, heliotropin, hexenol, hexenyl
acetate,
hexyl acetate, hexyl formate, hinokitiol, hydrotropic alcohol,
hydroxycitronellal,
hydroxycitronellal diethyl acetal, hydroxycitronellol, indole, isoamyl
alcohol, iso cycle
citral, isoeugenol, isoeugenyl ;acetate, isomenthone, isopulegyl acetate,
isoquinoline,
keone, ligustral, linalool, linalool oxide, linalyl formate, lyral, menthone,
methyl
acetophenone, methyl amyl ketone, methyl anthranilate, methyl benzoate, methyl
benzyl
acetate, methyl cinnamate, methyl dihydrojasmonate, methyl eugenol, methyl
heptenone,
methyl heptine carbonate, methyl heptyl ketone, methyl hexyl ketone, methyl
isobutenyl
tetrahydropyran, methyl-N-methyl anthranilatc. methyl beta naphthyl ketone,
methyl
phenyl carbinyl acetate, methyl salicylate, nerol, nonalactone, octalactone,
octyl alcohol
(octanol-2), para-anisic aldehyde, para-cresol, para-cresyl methyl ether, para
hydroxy
phenyl butanone, para-methox:~ aceiopl~enone, para-methyl acetophenone,
phenoxy
ethanol, phenoxyethyl propionate, phenyl acetaldehyde, phenylacetaldehyde
diethyl ether,
phenylethyl oxyacetaldehyde, phenyl ethyl acetate, phenyl ethyl alcohol,
phenyl ethyl
dimethyl carbinol, prenyl acetate, propyl butyrate, pulegone, rose oxide,
safrole,
terpineol, vanillin, viridine, and rnixtures thereof.
Nonlimiting examples of other preferred hydrophilic perfume ingredients which
can be used in perfume compositions of this invention are allyl heptoate, amyl
benzoate,
anethole, benzophenone, carvacrol, citral, citronellol, citronellyl nitrile,
cyclohexyl ethyl
acetate, cymal, 4-decenal, dihydro isojasmonate, dihydro myrcenol, ethyl
methyl phenyl
glycidate, fenchyl acetate, florhydral, gamma-nonalactone, geranyl formate,
geranyl
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38
nitrite, hexenyl isobutyrate, alpha-ionone, isobornyl acetate, isobutyl
benzoate, isononyl
alcohol, isomenthol, para-isopropyl phenylacetaldehyde, isopulegol, linalyl
acetate, 2-
methoxy naphthalene, menthyl acetate, methyl chavicol, musk ketone, beta
naphthol
methyl ether, neral, nonyl aldehyde, phenyl heptanol, phenyl hexanol, terpinyl
acetate,
Veratrol, yara-yara, and mixtures thereof.
The preferred perfume compositions used in the present invention contain at
least
4 different hydrophilic perfume ingredients, preferably at least 5 different
hydrophilic
perfume ingredients, more preferably at least 6 different hydrophilic perfume
ingredients,
and even more preferably at least 7 different hydrophilic perfume ingredients.
Most
common perfume ingredients which are derived from natural sources are composed
of a
multitude of components. When each such material is used in the formulation of
the
preferred perfume compositions of the present invention, it is counted as one
single
ingredient, for the purpose of defining the invention.
(b). Low Odor Detection Threshold Perfume Ingredients
The odor detection threshold of an odorous material is the lowest vapor
concentration of that material which can be olfactorily detected. The odor
detection
threshold and some odor detection threshold values are discussed in, e.g.,
"Standardized
Human Olfactory Thresholds", M. Devos et al, IRL Press at Oxford University
Press,
1990, and "Compilation of Odor and Taste Threshold Values Data", F. A.
Fazzalari,
editor, ASTM Data Series DS 48A, American Society for Testing and Materials,
1978,
both of said publications being incorporated by reference. The use of small
amounts of
perfume ingredients that have low odor detection threshold values can improve
perfume
odor character, even though they are not as hydrophilic as perfume ingredients
of group
(a) which are given hereinabove. Perfume ingredients that do not belong to
group (a)
above, but have a significantly low detection threshold, useful in the
composition of the
present invention, are selected from the group consisting of ambrox, bacdanol,
benzyl
salicylate, butyl anthranilate, cetalox, damascenone, alpha-damascone, gamma-
dodecalactone, ebanol, herbavert, cis-3-hexenyl salicylate, alpha-ionone, beta-
ionone,
alpha-isomethylionone, filial, methyl nonyl ketone, gamma-undecalactone,
undecylenic
aldehyde, and mixtures thereof. These materials are preferably present at low
levels in
addition to the hydrophilic ingredients of group (a), typically less than
about 20%,
preferably less than about 15%, more preferably less than about 10%, by weight
of the
total perfume compositions of the present invention. However, only low levels
are
required to provide an effect.
There are also hydrophilic ingredients of group (a) that have a significantly
low
detection threshold, and are especially useful in the composition of the
present invention.
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39
Examples of these ingredients a.re allyl amyl glycolate, anethole, benzyl
acetone, calone,
cinnamic alcohol, coumarin, cyclogalbanate, Cyclal C, cymal, 4-decenal,
dihydro
isojasmonate, ethyl anthranilate, ethyl-2-methyl butyrate, ethyl methylphenyl
glycidate,
ethyl vanillin, eugenol, flor acetate, florhydral, fructone, frutene,
heliotropin, keone,
indole, iso cyclo citral, isoeugenol, lyral, methyl heptine carbonate,
linaloal, methyl
anthranilate, methyl dihydrojasmonate, methyl isobutenyl tetrahydropyran,
methyl beta
naphthyl ketone, beta naphthol methyl ether, nerol, para-anisic aldehyde, para
hydroxy
phenyl butanone, phenyl acetaldehyde, vanillin, and mixtures thereof. Use of
low odor
detection threshold perfume in g;redients minimizes the level of organic
material that is
released into the atmosphere.
Antimicrobial Active
Optionally, the color improvement composition of the present invention
comprise
an effective amount, to kill, or reduce the growth of microbes, of
antimicrobial active;
preferably from about 0.001 % to about ?°/~, more preferably from about
0.00?% to about
1 %, even more preferably from about 0.003% to about 0.3%, by weight of the
usage
composition. The effective anti:microbial active can function as
disinfectants/sanitizers,
and is useful in providing protection against organisms that become attached
to the
fabrics.
Given below arc nonlimiting examples of antimicrobial actives which are useful
in the present invention:
Pyrithiones, especially the zinc complex (ZPT); Octopirox; parabens, including
methylparaben, propylparaben, butylparaben, ethylparaben, isopropylparaben,
isobutylparaben, benzylparabcn, sodium methylparaben, and sodium
propylparaben;
DMDM hydantoin (Glydant):; methylchloroisothiazoIinone/methylisothiazolinone
(Kathon CG); sodium sulfite; sodium bisulfate; imidazolidinyl urea;
diazolidinyl urea
(Germail 2); sorbic acid/potassiurn sorbate; dehydroacetic acid/sodium
dehydroacetate;
benzyl alcohol; sodium borate; 2-bromo-'?-nitropropane-1,3-diol (Bronopol);
formalin;
iodopropynyl butylcarbamate; boric acid; chloroacetamide; methenamine;
methyldibromo glutaronitrile; glutaraldehyde; hexamidine isethionate; 5-bromo-
5-nitro-
1,3-dioxane; phenethyl alcohol:. o-phenylphenol/sodium o-phenylphenol; sodium
hydroxyrnethylglycinate; polymethoxy bicyclic oxazolidine; dimethoxane;
thimersol;
dichlorobenzyl alcohol; capta.n; chlorphenenesin; dichlorophene; chlorbutanol;
phenoxyethanol; phenoxyisopropanol; halogenated diphenyl ethers; 2,4,4'-
tricluloro-2'-
hydroxy-diphenyl ether (Triclosan); 2,2'-dihydroxy-S,5'-dibromo-diphenyl
ether;
Phenolic Compounds - (including phenol and its homologs, mono- and poly-alkyl
and
aromatic halophenols, resorcinol and its derivatives, bisphenolic compounds
and
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halogenated salicylanilides); phenol and its homologs including phenol, 2-
methyl phenol,
3-methyl phenol, 4-methyl phenol, 4-ethyl phenol, 2,4-dimethyl phenol, 2,5-
dimethyl
phenol, 3,4-dimethyl phenol, 2,6-dimethyl phenol, 4-n-propyl phenol, 4-n-butyl
phenol,
4-n-amyl phenol, 4-tert-amyl phenol, 4-n-hexyl phenol, and 4-n-heptyl phenol;
mono-
and poly-alkyl and aromatic halophenols including p-chlorophenol, methyl p-
chlorophenol, ethyl p-chlorophenol, n-propyl p-chlorophenol, n-butyl p-
chlorophenol, n-
amyl p-chlorophenol, sec-amyl p-chlorophenol, n-hexyl p-chlorophenol,
cyclohexyl p-
chlorophenol, n-heptyl p-chlorophenol, n-octyl p-chlorophenol, o-chlorophenol,
methyl
o-chlorophenol, ethyl o-chlorophenol, n-propyl o-chlorophenol, n-butyl o-
chlorophenol,
n-amyl o-chlorophenol, tert-amyl o-chlorophenol, n-hexyi o-chlorophenol, n-
heptyl
o-chlorophenol, o-benzyl p-chlorophenol, o-bcnzyl-m-methyl p-chlorophenoi, o-
benzyl-
m, m-dimethyl p-chlorophenol, o-phenylethyl p-chlorophenol, o-phenylethyl-m-
methyl
p-chlorophenol, 3-methyl p-chlorophenol, 3,>-dimcthyl p-chlorophenol, 6-ethyl-
3-methyl
p-chlorophenol, 6-n-propyl-3-methyl p-chlorophenol, 6-iso-propyl-3-methyl p-
chlorophenol, 2-ethyl-3,5-dimethyl p-chlorophenol, 6-sec-butyl-3-methyl p-
chlorophenol, 2-iso-propyl-3,5-dimethyl p-chlorophenol, 6-diethylmethyl-3-
methyl p-
chlorophenol, 6-iso-propyl-2-ethyl-3-methyl p-chlorophenol, 2-sec-amyl-3,5-
dimethyl p-
chlorophenol, 2-diethylmethyl-3,5-dimethyl p-chlorophenol, 6-sec-octyl-3-
methyl p-
chlorophenol, p-chloro-m-cresol, p-bromophenol, methyl p-bromophenol, ethyl p-
bromophenol, n-propyl p-bromophenol, n-butyl p-bromophenol, n-amyl p-
bromophenol,
sec-amyl p-bromophenol, n-hexyl p-bromophenol, cyclohexyl p-bromophenol, o-
bromophenol, tent-amyl o-bromophenol, n-hexyl o-bromophenol, n-propyl-m,m-
dimethyl
o-bromophenol, 2-phenyl phenol, 4-chloro-2-methyl phenol, 4-chloro-3-methyl
phenol, 4-chloro-3,5-dimethyl phenol, 2,4-dichloro-3,5-dimethylphenol, 3,4,5,6-
terabromo-2-methylphenol, ~-methyl-2-pentylphenol, 4-isopropyl-3-methylphenol,
para-
chloro-meta-xylenol (pcmx), 5-chloro-2-hydroxydiphenyhnethane; resorcinol and
its
derivatives including resorcinol, methyl resorcinol, ethyl resorcinol, n-
propyl resorcinol,
n-butyl resorcinol, n-amyl resorcinol, n-hexyl resorcinol, n-heptyl
resorcinol, n-octyl
resorcinol, n-nonyl resorcinol, phenyl resorcinol, benzyl resorcinol,
phenylethyl
resorcinol, phenylpropyl resorcinol, p-chlorobenzyl resorcinol, 5-chloro 2,4-
dihydroxydiphenyl methane, 4'-chloro 2,4-dihydroxydiphenyl methane, 5-bromo
2,4-
dihydroxydiphenyl methane, and 4' -bromo 2,4-dihydroxydiphenyl methane;
bisphenolic
compounds including 2,2'-, methylene bis (4-chlorophenol), 2,2'-methyIene bis
(3,4,6-
trichlorophenol), 2,2'-methylene bis (4-chloro-6-bromophenol), bis (2-hydroxy-
3,5-
dichlorophenyl) sulphide, and bis (2-hydroxy-5-chlorobenzyl)sulphide; benzoic
esters
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including p-hydroxybenzoic acid, methyl p-hydroxybenzoic acid, ethyl p-
hydroxybenzoic
acid, propyl p-hydroxybenzoic acid, and butyl p-hydroxybenzoic acid.
Another class of antibacterial agents, which are useful in the present
invention, are
the so-called "natural" antibacterial actives, referred to as natural
essential oils. These
actives derive their names from their natural occurrence in plants. Typical
natural
essential oil antibacterial activea include oils of anise, lemon, orange,
rosemary,
wintergreen, thyme, lavender, cloves, hops, tea tree, citronella, wheat,
barley,
lemongrass, cedar leaf, cedarwood, cinnamon, fleagrass, geranium, sandalwood,
violet,
cranberry, eucalyptus, vervain, peppermint, gum benzoin, I~vdastis
carr°adensis,
Berberidaceae. daceae, Ratanhiac and Ca~rcuma Tonga. Also included in this
class of
natural essential oils are the key chemical components of the plant oils which
have been
found to provide the antimicrobial benefit. These chemicals include, but are
not limited
to anethol, catechole, camphen~e, thymol, eugenol, eucalyptol, ferulic acid,
:farnesol,
hinokitiol, tropolone, limonene, menthol, methyl salicylate, salicylic acid,
thymol,
terpineol, verbenone, berberine, ratanhiae extract, caryophellene oxide,
citronellic acid,
curcumin, nerolidol, geraniol and benzoic acid.
Additional active agents arcs antibacterial metal salts. This class generally
includes
salts of metals in groups 3b-7b, 8 and 3a-Sa. Specifically are the salts of
aluminum,
zirconium, zinc, silver, gold, copper, lanthanum, tin, mercury, bismuth,
selenium,
strontium, scandium, yttrium, cerium, praseodymium neodymium, promethum,
samarium, europium, gadolinium., terbium, dysprosium, holmium, erbium,
thulium,
ytterbium, lutetium and mixtures thereof.
Preferred antimicrobial agents for use herein are the broad spectrum actives
selected from the group consisting of Triclosan, phenoxyisopropanol,
phenoxyethanol,
PCMX, natural essential oils and their key ingredients, and mixtures thereof.
The most
preferred antimicrobial active for use in the present invention is Triclosan.
Quaternary Compounds.
A wide range of quaternary compounds can also be used as antimicrobial
actives,
in conjunction with the preferred surfactants, for compositions of the present
invention.
Non-limiting examples of useful quaternary compounds include: ( 1 )
benzalkonium
chlorides and/or substituted benzalkonium chlorides such as commercially
available
Barquat~ (available from Lonza), Maquat~ (available from Mason), Variquat~
(available from WitcoiSherex), and Hyamine~R' (available from Lonza); (2)
di(C6-
C 14)alkyl di-short chain (C 1-4 aik:yl and/or hydroxyalkyl) quaternary such
as Bardac~
products of Lonza. These quaternary compounds contain two relatively short
chains,
e.g., C 1 _4 alkyl and/or hydroxy alkyl ,~noups and two C~-1 ~, preferably C(-
l p, and more
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42
preferably Cg, alkyl groups,(3) N-(3-chloroallyl) hexaminium chlorides such as
Dowicide~ and DowicilG available from Dow; (4) benzethonium chloride such as
Hyamine~ 1622 from Rohm & Haas; (5) methylbenzethonium chloride represented by
Hyamine~ l OX supplied by Rohm & Haas, (6) cetylpyridinium chloride such as
Cepaeol
chloride available from of Merrell Labs. Examples of the preferred dialkyl
quaternary
compounds are di(Cg-C12)dialkyl dimethyl ammonium chloride, such as
didecyldimethylammonium chloride (Bardac 22), and dioctyldimethylammonium
chloride (Bardac 2050). Typical concentrations for biocidal effectiveness of
these
quaternary compounds range from about 0.001 % to about 0.8%, preferably from
about
0.005% to about 0.3%, more prcfcrably from about 0.01 % to 0.2%, by weight of
the
usage composition. The corresponding concentrations for the concentrated
compositions
are from about 0.003°/~ to about 2°'0, preferably from about
0.006% to about 1.2%, and
more preferably from about 0. l °ro to about 0.8% by weight of the
concentrated
compositions.
When cyclodextrin is present, the solubilized, water-soluble antimicrobial
active
is useful in providing protection against organisms that become attached to
the treated
fabrics. The antimicrobial should be cyclodextrin-compatible, e.g., not
substantially
forming complexes with the cyclodextrin in the odor absorbing composition when
cyclodextrin is present. The free, uncomplexed antimicrobial, e.g.,
antibacterial, active
provides an optimum antibacterial performance.
Sanitization of fabrics can be achieved by the compositions of the present
invention containing, antimicrobial materials, e.g., antibacterial halogenated
compounds,
quaternary compounds, and phenolic compounds. Some of the more robust
cyclodextrin-
compatible antimicrobial halogenated compounds which can function as
disinfectants/sanitizers as well as finish product preservatives (vide infra),
and are useful
in the compositions of the present invention include 1,1'-hexamethylene bis(5-
(p-
chlorophenyl)biguanide), commonly known as chlorhexidine, and its salts, e.g.,
with
hydrochloric, acetic and gluconic acids. The digluconate salt is highly water-
soluble,
about 70% in water, and the diacetate salt has a solubility of about 1.8% in
water. When
chlorhexidine is used as a sanitizer in the present invention it is typically
present at a
level of from about 0.001 % to about 0.4%, preferably from about 0.002% to
about 0.3%,
and more preferably from about 0.05% to about 0.2%, by weight of the usage
composition. In some cases, a level of from about 1 % to about 2% may be
needed for
virucidal activity.
Aminocarboxylate Chelators
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Chelators, e.g., ethylenediaminetetraacetic acid (EDTA), hydroxyethylene-
diaminetriacetic acid, diethylenetriaminepentaacetic acid, and other
aminocarboxylate
chelators, and mixtures thereof, and their salts, and mixtures thereof, can
optionally be
used to increase antimicrobial and preservative effectiveness against Gram-
negative
bacteria, especially Pseudomonas species. Although sensitivity to EDTA and
other
aminocarboxylate chelators is mainly a characteristic of Pseudomonas species,
other
bacterial species highly susceptible to chelators include Achromobacter,
Alcaligenes,
Azotobacter, Escherichia, Salmonella, Spirillum, and Vibrio. Other groups of
organisms
also show increased sensitivities to these chelators, including fungi and
yeasts.
Furthermore, aminocarboxylate chelators can help, e.g., maintaining product
clarity,
protecting fragrance and perfume components, and preventing rancidity and off
odors.
Although these aminocarboxylate chelators may not be potent biocides in their
own right, they function as potentiators for improving the performance of
other
antimicrobials/preservativcs in the compositions of the present invention.
Aminocarboxylate chelators can potentiate the performance of many of the
cationic,
anionic, and nonionic antimic:robials/preservatives, phenolic compounds, and
isothiazolinones, that are used as antimicrobials/prescrvativcs in the
composition of the
present invention. Nonlimiting examples of cationic
antimicrobials/preservatives
potentiated by aminocarboxylate chelators in solutions are chlorhexidine salts
(including
digluconate, diacetate, and dihydrochloride salts), and Quaternium-15, also
known as
Dowicil 200, Dowicide Q, Preventol Dl, benzalkonium chloride, cetrimonium,
myristalkonium chloride, cetylpyridinium chloride, lauryl pyridinium chloride,
and the
like. Nonlimiting examples of useful anionic antimicrobials/preservatives
which are
enhanced by aminocarboxylate c:helators are sorbic acid and potassium sorbate.
Nonlimiting examples of useful nonionic antimicrobials/prescrvatives which are
potentiated by aminocarboxylate chelators are DMDM hydantoin, phenethyl
alcohol,
monolaurin, imidazolidinyl urea, and Bronopol (2-bromo-2-nitropropane-1,3-
diol).
Examples of useful phenolic antimicrobials/preservatives potentiated by these
chelators are chloroxylenol, phenol, tert-butyl hydroxyanisole, salicylic
acid, resorcinol,
and sodium o-phenyl phenate:. Nonlimiting examples of isothiazolinone
antimicrobials/preservatives which are enhanced by aminocarboxylate chelators
are
Kathon, Proxel and Promexal.
The optional chelators are present in the compositions of this invention at
levels
of, typically, from about 0.01 % to about 0.3%, more preferably from about
0.02% to
about 0.1 %, most preferably from about 0.02% to about 0.05°/« by
weight of the usage
compositions to provide antimicrobial efficacy in this invention.
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44
Free, uncomplexed aminocarboxylate chelators are required to potentiate the
efficacy of the antimicrobials. Thus, when excess alkaline earth (especially
calcium and
magnesium) and transitional metals (iron, manganese, copper, and others) are
present,
free chelators are not available and antimicrobial potentiation is not
observed. In the case
where significant water hardness or transitional metals are available or where
product
esthetics require a specified chelator level, higher levels may be required to
allow for the
availability of free, uncomplexed aminocarboxylate chelators to function as
antimicrobial/preservative potentiators.
Antimicrobial Preservative
Optionally, but preferably, an antimicrobial preservative can be added to the
composition of the present invention, preferably solubiIized, water-soluble,
antimicrobial
preservative, to protect the fabric color care active andior other easily
degradable organic
ingredients such as natural polysaccharides, because these molecules are made
up, e.g.,
of varying numbers of glucose units which can make them a prime breeding
ground for
certain microorganisms, especially when in aqueous compositions. This drawback
can
lead to the problem of storage stability of fabric care solutions for any
significant length
of time. Contamination by certain microorganisms with subsequent microbial
growth
can result in an unsightly and/or malodorous solution. Because microbial
growth in the
fabric care solutions is highly objectionable when it occurs, it is highly
preferable to
include an antimicrobial preservative, preferably solubilized, water-soluble,
antimicrobial
preservative, which is effective for inhibiting and/or regulating microbial
growth in order
to increase storage stability of the preferably clear, aqueous odor-absorbing
solution
containing the fabric color care active.
It is preferable to use a broad spectrum preservative, e.g., one that is
effective on
both bacteria (both gram positive and gram negative) and fungi. A limited
spectrum
preservative, e.g., one that is only effective on a single group of
microorganisms, e.g.,
fungi, can be used in combination with a broad spectrum preservative or other
limited
spectrum preservatives with complimentary and/or supplementary activity. A
mixture of
broad spectrum preservatives can also be used. In some cases where a specific
group of
microbial contaminants is problematic (such as Gram negatives),
aminocarboxylate
chelators can be used alone or as potentiators in conjunction with other
preservatives.
These chelators which include, e.g., ethylenediaminetetraacetic acid (EDTA),
hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and
other
aminocarboxylate chelators, and mixtures thereof, and their salts, and
mixtures thereof,
can increase preservative effectiveness against Gram-negative bacteria,
especially
Pseudotnonas species.
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Antimicrobial preservatives useful in the present invention include biocidal
compounds, i.e., substances that kill microorganisms, or biostatic compounds,
i.e.,
substances that inhibit and/or regulate the growth of microorganisms. Suitable
preservatives are disclosed in I.J.S. Pats. 5,534,165; 5,578,563; 5,663,134;
5,668,097;
5,670,475; and 5,714,137, Trinl-i et al. issued Jul. 9, 1996; Nov. 26, 1996;
Sep. 2, 1997;
Sep. 16, 1997; Sep. 23, 1997; and Feb. :3, 1998 respectively, all of said
patents being
incorporated hereinbefore by reference. Many antimicrobial preservatives are
given
under the section on Antimicrobial Active given herein above. Water insoluble
antimicrobial preservatives such as paraben and triclosan are useful in the
fabric care
compositions of the present invention, but they require the use of a
solubilizer, an
emulsifier, a dispersing agent, or the like, such as a surfactant and/or
cyclodextrin to
effectively distribute said preservative in the liquid composition. Preferred
antirnicrobial
preservatives are those that are water-soluble and are effective at low
levels. Water-
solubie preservatives useful in the present invention are those that have a
solubility in
water of at least about 0.3 g per 100 ml of water, i.e., greater than about
0.3% at room
temperature, preferably greater than about 0.5% at room temperature.
The water-soluble antimicrobial preservative in the present invention is
included
at an effective amount. The term "effective amount" as herein defined means a
level
sufficient to prevent spoilage, or prevent growth of inadvertently added
microorganisms,
for a specific period of time. In other words, the preservative is not being
used to kill
microorganisms on the surface onto which thc; composition is deposited in
order to
eliminate odors produced by microorganisms. Instead, it is preferably being
used to
prevent spoilage of the fabric color care active solution in order to increase
the shelf life
of the composition. Preferred levels of preservative are ii-om about 0.0001 %
to about
0.5%, more preferably from about 0.0002'% to about 0.2%, most preferably from
about
0.0003% to about 0.1 %, by weight of the usage composition.
The preservative can be any organic preservative material which will not cause
damage to fabric appearance, e.~,., discoloration, coloration, bleaching.
Preferred water-
soluble preservatives include organic sulfur compounds, halogenated compounds,
cyclic
organic nitrogen compounds, low molecular weight aldehydes, quaternary
ammonium
compounds, dehydroacetic acid, phenyl and phenolic compounds, and mixtures
thereof.
The preservatives of the present invention can be used in mixtures in order to
control a broad range of microar~;anisms.
Bacteriostatic effects can sometimes be obtained for aqueous compositions by
adjusting the composition pH to an acid pH, e.~., less than about pH 4,
preferably less
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46
than about pH 3, or a basic pH, e.g., greater than about 10, preferably
greater than about
11.
Antistatic Agents
The composition of the present invention can optionally contain an effective
amount of antistatic agent to provide the treated clothes with in-wear static.
Preferred
antistatic agents are those that are water soluble in at least an effective
amount, such that
the composition remains a clear solution. Examples of these antistatic agents
are
monoalkyl cationic quaternary ammonium compounds, e.g., mono(C10-C14
alkyl)trimethyl ammonium halide, such as monolauryl trimethyl ammonium
chloride,
hydroxycetyl hydroxyethyl dimethyl ammonium chloride, available under the
trade name
Dehyquart E~ from Henl:el, and ethyl bis(polyethoxy ethanol) alkylammonium
ethylsulfate, available under the trade name Variquat 66~ from Witco Corp.,
polyethylene glycols, polymeric quaternary ammonium salts, such as polymers
conforming to the general formula:
-[N(CH3)2-(CH2)3-NH-CO-NH-(CH2)3-N(CH3)~+-CH2CH20CH?CH?]-x ~+ 2x[C1-]
available under the trade name Mirapol A-15~ from Rhone-Poulenc, and
-[N(CH3)2-(CHI)3-NH-CO-(CHI)4-CO-NH-(CH~)3-N(CH3)~-(CH~CH~OCH~CH2]
x+ x[Cl-],
available under the trade name Mirapol AD-1 'z from Rhone-Poulenc, quaternized
polyethyleneimines, vinylpvrrolidone/methacrylamidopropyltrimethylammonium
chloride copolymer, available under the trade name Gafquat I-IS-100 from GAF;
triethonium hydrolyzed collagen ethosulfate, available under the trade name
Quat-Pro E
~ from Maybrook; and mixtures thereof.
It is preferred that a no foaming, or low foaming, agent is used, to avoid
foam
formation during fabric treatment. It is also preferred that polyethoxylated
agents such as
polyethylene glycol or Variquat 66~ are not used when alpha-cyclodextrin is
used. The
polyethoxylate groups have a strong affinity to, and readily complex with,
alpha-
cyclodextrin which in turn depletes the uncomplexed cyclodextrin available for
odor
control.
When an antistatic agent is used it is typically present at a level of from
about
0.05% to about 10%, preferably from about 0.1% to about 5%, more preferably
from
about 0.3% to about 3%, by weight of the usage composition.
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Insect and/or Moth Repelling Agent
The composition of the present invention can optionally contain an effective
amount of insect and/or moth repelling agents. Typical insect and moth
repelling agents
are pheromones, such as anti-aggregation pheromones, and other natural and/or
synthetic
ingredients. Preferred insect and moth repellent agents useful in the
composition of the
present invention are perfume ingredients, such as citronellol, citronellal,
citral, linalool,
cedar extract, geranium oil, sandalwood oil, 2-(diethylphenoxy)ethanol, 1-
dodecene, etc.
Other examples of insect and/or rr~oth repellents useful in the composition of
the present
invention are disclosed in U.S. Pat. Nos. 4,440,987, 4,693,890, 4,696,676,
4,933,371,
5,030,660, 5,196,200, and in "'Semio Activity of Flavor and Fragrance
Molecules on
Various Insect Species", B.D. Mookherjee et al., published in Bioactive
Volatile
Compounds from Plants, ASC Symposium Series 525, R.. Teranishi, R.G. Buttery,
and
H. Sugisawa, 1993, pp. 35-48, all of said patents and publications being
incorporated
herein by reference. When an insect and/or moth repellent is used it is
typically present
at a level of from about 0.005°/; to about 3°~0, by weight of
the usage composition.
Optional Anti-Clo~~in~ Agent
Optional anti-clogging agent which enhances the wetting and anti-clogging
properties of the composition, especially when starch is present, is chosen
from the group
of polymeric glycols of alkanes and olefins having from 2 to about 6,
preferably :? carbon
atoms. The anti-clogging agent inhibits the formation of "plugs" in the spray
nozzle. An
example of the preferred anti-clod,=grog agent is polyethylene glycol having
an average
molecular weight of from about 800 to about 12,000, more preferably from about
1,400
to about 8,000. When used, the anti-clogging agent is present at a level of
from about
0.01 % to about 1 %, preferably from about 0.05"o to about 0.5°/>, more
preferably, from
about 0.1 % to about 0.3'% by wei~,ht of the usage composition.
Agueous Carrier
The preferred carrier of the present invention is water. The water which is
used
can be distilled, deionizcd, or tap water. . Water is the main liquid carrier
due to its low
cost, availability, safety, and environmental compatibility. Water serves as
the liquid
carrier for the fabric color care active and other soluble and/or dispersible
optional
ingredients.
The level of liquid carrier in the compositions of the present invention is
typically
greater than about 80%, preferably greater than about 90%, more preferably
greater than
about 95%, by weight of the composition. When a concentrated composition is
used, the
level of liquid carrier is typically from about 2% to about 98%, by weight of
the
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WO 00/24858 PCT/US99/24925
48
composition, preferably from about 35% to about 97%, more preferably from
about 60%
to about 95%, by weight of the composition.
Optionally, in addition to water, the carrier can contain a low molecular
weight
organic solvent that is highly soluble in water, e.g., ethanol, propanol,
isopropanol, and
the Like, and mixtures thereof. Low molecular weight aicohols can help the
treated fabric
to dry faster. The optional solvent is also useful in the solubilization of
some shape
retention polymers described hereinbefore. The optional water soluble low
molecular
weight solvent can be used at a level of up to about 50%, typically from about
0.1 % to
about 25%, preferably from about 2% to about 15%, more preferably from about
5% to
about 10%, by weight of the total composition. Factors that need to consider
when a
high level of solvent is used in the composition are odor, flammability, and
environment
impact.
II. ARTICLE OF MANUFACTURE
The present invention can also be comprise an article of manufacture
comprising
said composition plus a spray dispenser. Preferably the articles of
manufacture are in
association with a set of instructions for how to use the composition to treat
fabrics
correctly so as to provide good color, especially one step color restoration,
including,
e.g., the manner and/or amount of composition to spray, and the preferred ways
of
handling of the fabrics, as will be described with more detailed herein below
where
wrinkle control is also desired. It is important that the instructions be as
simple and clear
as possible, so that using pictures and/or icons is desirable.
SPRAY DISPENSER
The article of manufacture herein comprises a spray dispenser. The fabric
color
care composition is placed into a spray dispenser in order to be distributed
onto the
fabric. Said spray dispenser for producing a spray of liquid droplets can be
any of the
manually activated means as is known in the art, c.g. trigger-type, pump-type,
non-
aerosol self pressurized, and aerosol-type spray means, for adding the fabric
color care
composition to small fabric surface areas and/or a small number of garments,
as well as
non-manually operated, powered sprayers for conveniently adding the fabric
color care
composition to large fabric surface areas and/or a large number of garments.
The spray
dispenser herein does not normally include those that will substantially foam
the clear,
aqueous fabric color care composition. It has been found that the performance
is
improved by providing smaller particle droplets. Desirably, the Sauter mean
particle
diameter is from about 10 pm to about 120 Vim, more preferably, from about 20
pm to
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49
about 100 Vim. Dewrinkling benefits are improved by providing small particles
(droplets), as discussed hereinbefore, especially when the surfactant is
present.
The spray dispenser can be an aerosol dispenser. Said aerosol dispenser
comprises a container which can be constructed of any of the conventional
materials
employed in fabricating aerosol containers. The dispenser must be capable of
withstanding internal pressure in the range of from about 20 to about 110
p.s..i.g., more
preferably from about 20 to about 70 p.s.i.g. The one important requirement
concerning
the dispenser is that it be provided with a valve member which will permit the
clear,
aqueous de-wrinkle composition contained in the dispenser to be dispensed in
the form
of a spray of very fine, or finely divided, particles or droplets. The aerosol
dispenser
utilizes a pressurized sealed container from which the clear, aqueous de-
wrinkle
composition is dispensed through a special actuator/valve assembly under
pressure. The
aerosol dispenser is pressurized by incorporating therein a gaseous component
generally
known as a propellant. Common aerosol propellants, e.g., gaseous hydrocarbons
such as
isobutane, and mixed halogenated hydrocarbons, can be used. Halogenated
hydrocarbon
propellants such as chlorofluoro hydrocarbons have been alleged to contribute
to
environmental problems, and are not preferred. When cyclodextrin is present
hydrocarbon propellants are not preferred, because they can form complexes
with the
cyclodextrin molecules thereby reducing the availability of uncomplexed
cyclodextrin
molecules for odor absorption. Preferred propellants are compressed air,
nitrogen, inert
gases, carbon dioxide, etc. A more complete description of commercially
available
aerosol-spray dispensers appears in U.S. Pat. Nos.: 3,436,772, Stebbins,
issued April 8,
1969; and 3,600,325, Kaufman ea al., issued August 17, 1971; both of said
references are
incorporated herein by reference
Preferably the spray dispenser can be a self pressurized non-aerosol container
having a convoluted liner and ar.~ elastomcric sleeve. Said self pressurized
dispenser
comprises a liner/sleeve assembly containing a chin, flexible radially
expandable
convoluted plastic liner of from about 0.010 to about 0.020 inch thick, inside
an
essentially cylindrical elastomeric sleeve. The liner/sleeve is capable of
holding a
substantial quantity of fabric color care composition product and of causing
said product
to be dispensed. A more complete description of self pressurized spray
dispensers can be
found in U.S. Pat. Nos. 5,111,971, Winer, issued May 12, 1992, and 5,232,126,
Winer,
issued Aug. 3, 1993; both of said references are herein incorporated by
reference.
Another type of aerosol spray dispenser is one wherein a barrier separates the
fabric color
care composition from the propellant preferably compressed air or nitrogen),
as
disclosed in U.S. Pat. No. 4,260,! 10, issued April 7, 1981, and incorporated
herein by
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WO 00/24858 PCT/US99/24925
reference. Such a dispenser is available from EP Spray Systems, East Hanover,
New
Jersey.
More preferably, the spray dispenser is a non-aerosol, manually activated,
pump-
spray dispenser. Said pump-spray dispenser comprises a container and a pump
mechanism which securely screws or snaps onto the container. The container
comprises
a vessel for containing the aqueous fabric color care composition to be
dispensed.
The pump mechanism comprises a pump chamber of substantially fixed volume,
having an opening at the inner end thereof. Within the pump chamber is located
a pump
stem having a piston on the end thereof disposed for reciprocal motion in the
pump
chamber. The pump stem has a passageway there through with a dispensing outlet
at the
outer end of the passageway and an axial inlet port located inwardly thereof.
The container and the pump mechanism can be constructed of any conventional
material employed in fabricating pump-spray dispensers, including, but not
limited to:
polyethylene; polypropylene; polyethyleneterephthalate; blends of
polyethylene, vinyl
acetate, and rubber elastomer. A preferred container is made of clear, e.g.,
polyethylene
terephthalate. Other materials can include stainless steel. A more complete
disclosure of
commercially available dispensing devices appears in: U.S. Pat. Nos.:
4,895,279,
Schultz, issued January 23, 1990; 4,735,347, Schultz et al., issued April 5,
1988; and
4,274,560, Carter, issued June 23, 1981; all of said references are herein
incorporated by
reference.
Most preferably, the spray dispenser is a manually activated trigger-spray
dispenser. Said trigger-spray dispenser comprises a container and a trigger
both of which
can be constructed of any of the conventional material employed in fabricating
trigger-
spray dispensers, including, but not limited to: polyethylene; polypropylene;
polyacetal;
polycarbonate; polyethyleneterephthalate; polyvinyl chloride; polystyrene;
blends of
polyethylene, vinyl acetate, and rubber elastomcr. Other materials can include
stainless
steel and glass. A preferred container is made of clear, e.g. polyethylene
terephthalate.
The trigger-spray dispenser does not incorporate a propellant gas into the
odor-absorbing
composition, and preferably it does not include those that will foam the
fabric color care
composition. The trigger-spray dispenser herein is typically one which acts
upon a
discrete amount of the fabric color care composition itself, typically by
means of a piston
or a collapsing bellows that displaces the composition through a nozzle to
create a spray
of thin liquid. Said trigger-spray dispenser typically comprises a pump
chamber having
either a piston or bellows which is movable through a limited stroke response
to the
trigger for varying the volume of said pump chamber. This pump chamber or
bellows
chamber collects and holds the product for dispensing. The trigger spray
dispenser
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Sl
typically has an outlet check valve for blocking communication and flow of
fluid through
the nozzle and is responsive to the pressure inside the chamber. For the
piston type
trigger sprayers, as the trigger is compressed, it acts on the fluid in the
chamber and the
spring, increasing the pressure on the fluid. For the bellows spray dispenser,
as the
bellows is compressed, the pressure increases on the fluid. The increase in
fluid pressure
in either trigger spray dispenser acts to open the top outlet check valve. The
top valve
allows the product to be forced tluough the swirl chamber and out the nozzle
to form a
discharge pattern. An adjustable nozzle cap can be used to vary the pattern of
the fluid
dispensed.
For the piston spray dispenser, as the trigger is released, the spring acts on
the
piston to return it to its original position. For the bellows spray dispenser,
the bellows
acts as the spring to return to its. original position. This action causes a
vacuum in the
chamber. The responding fluid acts to close the outlet valve while opening the
inlet
valve drawing product up to the chamber from the reservoir.
A more complete disclosure of commercially available dispensing devices
appears in U.S. Pat. Nos. 4.,082,223, Nozawa, issued Apr. 4, 1978; 4,I61, 288,
McKinney, issued Jul. I7, 1985; 4,434,917, Saito et al., issued Mar. 6, 1984;
and
4,819,835, Tasaki, issued Apr. I 1, 1989; 5,303,867, Peterson, issued Apr. 19,
1994; all
of said references are incorporal:ed herein by reference.
A broad array of trigger sprayers or finger pump sprayers are suitable for use
with
the compositions of this invention. These are readily available from suppliers
such as
Calmar, Inc., City of Industry, California; CSI (Continental Sprayers, lnc.),
St. Peters,
Missouri; Berry Plastics Corp., I:vansville, Indiana, a distributor of Guala~
sprayers; or
Seaqucst Dispensing, Cary, Illinois.
The preferred trigger sprayers are the blue inserted Guala~ sprayer, available
from Berry Plastics Corp., or the Calmar TS800-lA~ , TS1300~, and TS-800-2~,
available from Calmar Inc., because of the line uniform spray characteristics,
spray
volume, and pattern size. More preferred are sprayers with precompression
features and
finer spray characteristics and even distribution, such as Yoshino sprayers
from Japan.
Any suitable bottle or container can be used with the trigger sprayer, the
preferred bottle
is a 17 fl-oz. bottle (about 5()0 rnl} of good ergonomics similar in shape to
the Cinches
bottle. It can be made of any materials such as high density polyethylene,
polypropylene,
polyvinyl chloride, polystyrene, polyethylene terephthalate, glass, or any
other material
that forms bottles. Preferably, it is made of high density polyethylene or
clear
polyethylene terephthalate.
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52
For smaller fluid ounce sizes ( such as 1 to 8 ounces), a finger pump can be
used
with canister or cylindrical bottle. The preferred pump for this application
is the
cylindrical Euromist IIU from Seaquest Dispensing. More preferred are those
with
precompression features.
The article of manufacture herein preferably can also comprise a non-manually
operated spray dispenser. By "non-manually operated" it is meant that the
spray
dispenser can be manually activated, but the force required to dispense the
fabric color
care composition is provided by another, non-manual means. Non-manually
operated
sprayers include, but are not limited to, powered sprayers, air aspirated
sprayers, liquid
aspirated sprayers, electrostatic sprayers, and nebulizcr sprayers. The fabric
color care
composition is placed into a spray dispenser in order to be distributed onto
the fabric.
Powered sprayers include self contained powered pumps that pressurize the
aqueous de-wrinkle composition and dispense it through a nozzle to produce a
spray of
liquid droplets. Powered sprayers are attached directly or remotely through
the use of
piping/tubing to a reservoir (such as a bottle) to hold the aqueous fabric
color care
composition. Powered sprayers can include, but are not limited to, centrifugal
or positive
displacement designs. It is preferred that the powered sprayer be powered by a
portable
DC electrical current from either disposable batteries (such as commercially
available
alkaline batteries) or rechargeable battery units (such as commercially
available nickel
cadmium battery units). Powered sprayers can also be powered by standard AC
power
supply available in most buildings. The discharge nozzle design can be varied
to create
specific spray characteristics (such as spray diameter and particle size). It
is also possible
to have multiple spray nozzles for different spray characteristics. The nozzle
may or may
not contain an adjustable nozzle sIu-oud that would allow the spray
characteristics to be
altered.
Nonlirniting examples of commercially available powered sprayers are disclosed
in U.S. Pat. Nos. 4,865,255, Luvisotto, issued Sep. 12, 1989 which is
incorporated herein
by reference. Preferred powered sprayers are readily available from suppliers
such as
Solo, Newport News, Virginia (e.g., Solo SpraystarTM rechargeable sprayer,
listed as
manual part #: US 460 39~) and Multi-sprayer Systems, Minneapolis, Minnesota
(e.g.,
model: Spray 1 ).
Air aspirated sprayers include the classification of sprayers generically
known as
"air brushes". A stream of pressurized air draws up the aqueous fabric color
care
composition and dispenses it through a nozzle to create a spray of liquid. The
fabric
color care composition can be supplied via separate piping/tubing or more
commonly is
contained in a jar to which the aspirating sprayer is attached.
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Nonlimiting examples of commercially available air aspirated sprayers appears
in
U.S. Pat. Nos. 1,536,352, Murray, issued Apr. 22, 1924 and 4,221,339,
Yoshikawa,
issues Sep. 9, 1980; all of said references are; incorporated herein by
reference. Air
aspirated sprayers are readily available from suppliers such as The Badger Air-
Brush Co.,
Franklin Park, Illinois (e.g., model #: 155) and Wilton Air Brush Equipment,
Woodridge,
Illinois (e.g., stock #: 415-4000, 415-4001, 415-4100).
Liquid aspirated sprayers are typical of~ the variety in widespread use to
spray
garden chemicals. The aqueous dewrinkling composition is drawn info a fluid
stream by
means of suction created by a v'enturi effect. The high turbulence serves to
mix the
aqueous fabric color care composition with the fluid stream (typically water)
in order to
provide a uniform mixture/conc~entration. It is possible with this method of
delivery to
dispense the aqueous concentrated fabric color care composition of the present
invention
and then dilute it to a selected ccmcentration wish the delivery stream.
Liquid aspirated sprayers are readily available from suppliers such as Chapin
Manufacturing Works, Batavia, New York (e.g., model #: 6006).
Electrostatic sprayers impart energy to the aqueous dewrinkling composition
via a
high electrical potential. This energy serves to atomize and charge the
aqueous fabric
color care composition, creating a spray of fine, charged particles. As the
charged
particles are carried away from the sprayer, their common charge causes them
to repel
one another. This has two cffecas before the spray reaches the target. First,
it expands
the total spray mist. This is especially important when spraying to fairly
distant, large
areas. The second effect is maintenance of original particle size. Because the
particles
repel one another, they resist collecting together into large, heavier
particles like
uncharged particles do. This lessens gravity's influence, and increases the
charged
particle reaching the target. As the mass of negatively charged particles
approach the
target, they push electrons inside the target inwardly, leaving all the
exposed surfaces of
the target with a temporary positive charge. The resulting attraction between
the particles
and the target overrides the influences of gravity and inertia. As each
particle deposits on
the target, that spot on the target becomes neutralized and no longer
attractive.
Therefore, the next free particle is attracted to the spot immediately
adjacent and the
sequence continues until the entire surface of the target is covered. Hence,
charged
particles improve distribution and reduce drippage.
Nonlimiting examples oi'commercially available electrostatic sprayers appears
in
U.S. Pat. Nos. 5,222,664, Noake;s, issued Jun. 29, 1993; 4,962,885, Coffee,
issued Oct.
16, 1990; 2,695,002, Miller, issuc;d Nov. 1954; 5,405,090, Greene, issued Apr.
1 l, 1995;
4,752,034, Kuhn, issued Jun. 2l, lt)88; 2,989,241, Badger, issued Jun. 1961;
all of said
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54
patents are incorporated herein by reference. Electrostatic sprayers are
readily available
from suppliers such as Tae In Tech Co, South Korea and Spectrum, Houston,
Texas.
Nebulizer sprayers impart energy to the aqueous dewrinkling composition via
ultrasonic energy supplied via a transducer. This energy results in the
aqueous fabric
color care composition to be atomized. Various types of nebulizers include,
but are not
limited to, heated, ultrasonic, gas, venturi, and refillable nebulizers.
Nonlimiting examples of commercially available nebulizer sprayers appears in
U.S. Pat. Nos. 3,901,443, Mitsui, issued Aug. 26, 1975; 2,847,248, Schmitt,
issued Aug.
1958; 5,511,726, Greenspan, issued Apr. 30, 1996; all of said patents are
incorporated
herein by reference. Nebulizer sprayers are readily available from suppliers
such as A&D
Engineering, Inc., Milpitas, California (e.g., model A&D Un-231 ultrasonic
handy
nebulizer) and Amici, Inc., Spring City, Pennsylvania (model: swirler
nebulizer).
The preferred article of manufacture herein comprises a non-manually operated
sprayer, such as a battery-powered sprayer, containing the aqueous fabric
color care
composition. More preferably the article of manufacture comprises a
combination of a
non-manually operated sprayer and a separate container of the aqueous fabric
color care
composition, to be added to the sprayer before use and/or to be separated for
filling/refilling. The separate container can contain an usage composition, or
a
concentrated composition to be diluted before use, and/or to be used with a
diluting
sprayer, such as with a liquid aspirated sprayer, as described herein above.
Also, as described hercinbefore, the separate container should have structure
that
mates with the rest of the sprayer to ensure a solid fit without leakage, even
after motion,
impact, etc. and when handled by inexperienced consumers. The sprayer
desirably can
also have an attachment system that is safe and preferably designed to allow
for the
liquid container to be replaced by another container that is filled. E.g., the
fluid reservoir
can be replaced by a filled container. This can minimize problems with
filling, including
minimizing leakage, if the proper mating and sealing means are present on both
the
sprayer and the container. Desirably, the sprayer can contain a shroud to
ensure proper
alignment and/or to permit the use of thinner walls on the replacement
container. This
minimizes the amount of material to be recycled and/or discarded. The package
sealing
or mating system can be a threaded closure (sprayer) which replaces the
existing closure
on the filled and threaded container. A gasket is desirably added to provide
additional
seal security and minimize leakage. The gasket can be broken by action of the
sprayer
closure. These threaded sealing systems can be based on industry standards.
However, it
is highly desirable to use a threaded sealing system that has non-standard
dimensions to
ensure that the proper sprayer/bottlc combination is always used. This helps
prevent the
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WO 00/24858 PCT/1LJS99/24925
use of fluids that are toxic, which could then be dispensed when the sprayer
is used for its
intended purpose.
An alternative sealing system can be based on one or more interlocking lugs
and
channels. Such systems are commonly referred to as "bayonet" systems. Such
systems
can be made in a variety of configurations, thus better ensuring that the
proper
replacement fluid is used. For convenience, the locking system can also be one
that
enables the provision of a "child-proof' cap on the refill bottle. This "lock-
and-key" type
of system thus provides highly desirable safety features. There are a variety
of ways to
design such lock and key sealing systems.
Care must be taken, however, to prevent the system from making the filling and
sealing operation too difficult. If desired, the lock and key can be integral
to the sealing
mechanism. However, for the purpose of ensuring that the correct recharge or
refill is
used, the interlocking pieces c<~n be separate from the sealing system. E.g.,
the shroud
and the container could be designed for compatibility. In this way, the unique
design of
the container alone could provide the requisite assurance that the proper
recharge/refill is
used.
Examples of threaded closures and bayonet systems can be found in U.S. Pat.
4,781,31 l, Nov. 1, 1988 (Angular Positioned Trigger Sprayer with Selective
Snap-Screw
Container Connection, Clorox).. LLS. Pat. 5,560,505, Oct. 1, 1996 (Container
and Stopper
Assembly Locked Together lay Relative Rotation and Use Thereof, Cebal SA), and
U.S.
Pat. 5,725,132, Mar. 10, 1998 (Dispenser with Snap-Fit Container Connection,
Centico
International). All of said patents are incorporated herein by reference.
III. METHOD OF USE
The fabric color care composition, which contains a fabric color care active,
and
optionally, e.g., perfume, odor control agent including cyclodextrin,
antimicrobial actives
and/or preservative, surfactant, antioxidant, metal chelating agent including
aminocarboxylate chelating agent, antistatic agent, insect and moth repelling
agent, fabric
softener active, dye transfer inhibiting agent, brightener, soil release
agent, dispersant,
suds suppressor, and mixtures thereof, can be used by distributing, e.g., by
placing, an
effective amount of the aqueous solution onto tile fabric surface or fabric
article to be
treated. Distribution can be achieved by using a spray device, a roller, a
pad, etc.,
preferably a spray dispenser. For wrinkle control, for wrinkle removal, an
effective
amount means an amount sufficient to remove or noticeably reduce the
appearance of
wrinkles on fabric. Preferably, the amount of fabric care solution is not so
much as to
saturate or create a pool of liquid on said article or surface and so that
when dry there is
no visual deposit readily discernible.
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An effective amount of the liquid composition of the present invention is
preferably sprayed onto fabric and/or fabric articles. When the composition is
sprayed
onto fabric, an effective amount should be deposited onto the fabric, with the
fabric
becoming damp or totally saturated with the composition, typically from about
5% to
about 150%, preferably from about 10% to about 100%, more preferably from
about 20%
to about 75%, by weight of the fabric. The treated fabric typically has from
about 0.005%
to about 4%, preferably from about 0.01 % to about 2%, more preferably from
about
0.05% to about 1 %, by weight of the fabric of said fabric color care active.
Once the
fabric has been sprayed, it is hung until dry. It is preferable that the
treatment is
performed in accordance with the instructions for use, to ensure that the
consumer knows
what benefits can be achieved, and how best to obtain these benefits.
Since the treatment of the worn, faded fabric necessarily changes the
intensity of
the fabric color, it is essential that the treatment needs to be uniform,
either by fully
treated the fabric surface with the fabric color care composition, or by
uniforn~ly spraying
the fabric surface with small droplets of the composition, so that visually
the color
improvement appears uniform. In other words, preferably, the fabric color care
composition is applied uniformly to the entire visible surface of the fabric.
Thus, it is
preferable that the treatment is performed in accordance with an instruction
for use, to
ensure that the fabric needs to be applied uniformly to achieve the optimal
color
restoration and/or rejuvenation benefit.
The spraying means should be capable of providing droplets with a weight
average diameter of from about 5 prn to about 250 Vim, preferably from about 8
~m to
about 120 pm, more preferably from about 10 ym to about 80 Vim. When the
compositions are applied in the form of the very small particles (droplets),
the
distribution is further improved and overall performance is also improved. The
presence
of the optional surfactant promotes spreading of the solution and helps a
uniform
distribution of the fabric color care active on the fabric surface.
The fabric color care composition can also be applied to fabric via a dipping
and/or soaking process followed by a drying step. The application can be done
in
consumer's home by the use of commercial product.
The present invention also comprises a method of using concentrated liquid or
solid fabric color care compositions, which are diluted to form compositions
with the
usage concentrations, as given hercinabove, for use in the "usage conditions".
Concentrated compositions comprise a higher level of fabric color care active,
typically
from about 1 % to about 99%, preferably from about 2% to about 65%, more
preferably
from about 3% to about 25%, by weight of the concentrated fabric color care
CA 02346805 2001-04-09
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57
composition. Concentrated compositions are used in order to provide a less
expensive
product per use. The concentrated product is preferably diluted with about
50°,% to about
10,000%, more preferably from about 50% to about 8,000%, and even more
preferably
from about SO% to about 5,000°,'°, by weight of the composition,
of water.
The compositions of the present invention can also be used as ironing aids. An
effective amount of the composition can be sprayed onto fabric and the fabric
is ironed at
the normal temperature at which it should be ironed. The fabric can either be
sprayed
with an effective amount of the composition, allowed to dry and then ironed,
or sprayed
and ironed immediately.
In a still further aspect of the invention, the composition can be sprayed
onto
fabrics in an enclosed chamber containing the fabric to be de-wrinkled and/or
treated for
the color restoration/rejuvenation benefit, thereby providing ease of
operation. Examples
of an enclosed chamber include a closed flexible bag, such as a plastic bag,
which is
similar.to a garment bag, preferably with a flexible opening which can be
zipped up, or a
cabinet or similar apparatus, with a door hingedly attached. Any spraying
mechanism
can be used to apply the fabric color care composition to fabrics. A preferred
distribution
of the garment care composition is achieved by using a fog form. The mean
particulate
diameter size of the fabric color care composition fog is preferably from
about 3 microns
to about 50 microns, more preferably from about 5 microns to about 30 microns,
and
most preferably from about 10 microns to about 20 microns.
Another aspect of the present invention is the method of using an aqueous or
solid, preferably powder, fabri~~ color care composition for treating fabric
in the rinse
step, comprising an effective amount of said fabric color care active, and
optionally,
perfume, fabric softener active, chlorine scavenging agent, dye transfer
inhibiting agent,
chemical stabilizer including antioxidant, antimicrobial actives and/or
preservative,
chelating agent, aminocarboxylate chelating agent, brighteners, soil release
agents or
mixtures thereof. The rinse water should contain typically from about
0.0005°.'° to about
1 %, preferably from about 0.0008% to about 0.1 %, more preferably from about
0.001
to about 0.02% of the fabric color care active.
The present invention also relates to a method for treating fabric in the
drying
step, comprising an effective amount of said fabric color care active, and
optionally,
perfume, fabric softener active, dye transfer inhibiting agents, dye fixing
agent, chemical
stabilizer including antioxidant, antimicrobial active and/or preservative,
aminocarboxylate chelating agent, brightener, soil release agent, and mixtures
thereof. A
preferred method comprises the treatment of worn, faded fabrics with a fabric
color care
composition dispensed from a sprayer at the beginning and/or during the drying
cycle. It
i
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is preferable that the treatment is performed in accordance with the
instructions for use,
to ensure that the consumer knows what benefits can be achieved, and how best
to obtain
these benefits.
All percentages, ratios, and parts herein, in the Specification, Examples, and
Claims are by weight and are the normal approximations unless otherwise
stated.
The following are examples of the instant composition. The following
compositions are prepared by mixing and dissolving the ingredients into clear
or
translucent solutions.
Example I
Ia Ib lc ld le If
Ingredients Wt.°,« Wt.% Wt.°/~ Wt.% Wt.% Wt.%
Arabinogalactan A~~~ I __ __ __ __ __
Arabinogalactan B~~~ __ 0_7 __ -- O.S --
Arabinogalactan C~3~ __ -- 0.5 -- -- 0.5
Curdlan~'~~ __ __ __ 1 __ __
Dextran~s~
Carrageenan -- -- -- -- -- I
Perfume 0.1 0.05 0.07 0.1 0.05 0.05
Polysorbate 60~6~ 0.2 0.1 0.1 S 0.2 0.1 0. I
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
(1) Arabinogalaetan fraction that has the average molecular weight of from
about 16,000
to about 20,000.
(2) Arabinogalactan fraction that has the average molecular weight of about
100,000.
(3) Arabinogalactan fraction that has the average molecular weight of from
about I 0,000
to about 150,000.
(4) Average molecular weight of about 72,000.
(5) Average molecular weight of about 40,000.
(6) A mixture of stearate esters of sorbitol and sorbitol anhydride,
consisting
predominantly of the monoester, condensed with about 20 moles of ethylene
oxide.
Example II
IIa lIb lIc IId IIe Ilf
Ingredients Wt.'% Wt. ~o Wt.% Wt.% Wt.% Wt.%
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59
Arabinogalactan 5 -- -- 5 -- --
A~l~
Arabinogalactan __ 15 -- -- 15 --
B~z~
Arabinogalactan __ -- 25 -- -- 25
C~~~
Perfume -- -- -- 0.3 1 1.5
Polysorbate 60 -- -- -- 0.5 1.5 3
Kathon CG 5 ppm 5 ppm 10 ppm 5 ppm 5 ppm 10 ppm
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
Concentrated compositions water obtain
of Irxamples to usage
II are diluted
with
compositions for,
e.g., spraying,
soaking, dipping,
cellulosic fabrics.
Example III
IIIa IIIb
Ingredients VVt.% Wt.%
Silwet L-7001 1 --
Silwet L-7200 --- 0.8
Perfume C 0.05 0.1
Polysorbate 60 0.1 0.2
Kathon CG 3 hpm 3 ppm
Deionizcd Water Bal. Bal.
Example IV
I'r'a IVb IVc
Ingredients Wt.'ioWt.% Wt.%
Copolymer A(~~ 0.'7 -_ __
Copolymer B(8~ w- 0.8 --
Silicone Emulsion -- --- 3
A~~~
Perfume 0..06 0.05 0.05
Polysorbate 60 0.1 0.1 0.1
Silwet L-7602 0.5 ~-- --
Kathon CG 3 ppm 3 ppm 3 ppm
Deionized Water B.al. Bal. Bal.
(7) Acrylic acid/tert-butylacryiatecopolymer,with an approximate acrylic
acid/tert-
butyl acrylate weight nd an average molecular
ratio of about weight of from
25/75 a
about 70,000 to 00,000-
about 1
CA 02346805 2001-04-09
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(8) Acrylic acid/tert-butyl acrylate copolymer, with an approximate acrylic
acid/tert-
butyl acrylate weight ratio of about 35/65 and an average molecular weight of
from
about 60,000 to about 90,000.
(9) DC-2-5932 silicone microemulsion (25% active) from Dow Corning, with a
particle
size of about 24 nm, a cationic surfactant system, and a silicone with an
internal phase
viscosity of about 1,200 cps.
Example V
Va Vb Vc Vd Ve
Ingredients Wt./~ Wt.% Wt.% Wt.%
Wt.%
Arabinogalactan 1.2 -- -- -- 5
A~ ~ ~
Copolymer E(10) -- 0.5 -- -- --
Copolymer F(11 0.2 -- 0.5 -- --
)
Copolymer G( 12) -- -- -- 0.5 --
PDMS 10,000 cst -- -- -- 0.3 --
Silicone Emulsion -- -- 1 -- 2
B(13)
Perfume -- -- 0.04 -- 0.5
Polysorbate 60 0.1 0.1 -- 0.1 0.5
Neodo123-3 -- 0.25 -- 0.2 --
Neodol25-3 0.2 -- 0.6 -- 0.3
Silwet L-77 0.6 0.7 -- 1 --
Silwet L-7604 -- -- 0.5 -- --
Kathon CG 3 ppm 3 3 ppm 3 ppm 3 ppm
ppm
Deionized Water Bal. Bal. Bal. Bal. Bal.
(10) Silicone-containingcopolymerhaving butyl acrylate/acrylic
t- acid/
(polydimethylsiloxane 10,000approximate
macromer, molecular
weight)
monomer
at an approximate ht , and an ge molecular weight
63/20/17 weig ratioof avera of
about 130,000.
(11) Silicone-containing copolymer having t-butylacrylate/acrylic acid/
(polydimethylsiloxane macromer, 10,000 approximate molecular weight) monomer
at an approximate 65/25/10 weight ratio, and of average molecular weight of
about
200,000.
(12) Silicone-containing copolymer having (N,N,N-trimethylammonioethyl
methacrylate chloride)/N,N-dimethylacrylamide/(PDMS macromer - 15,000
approximate molecular weight) at an approximate 40/40/20 weight ratio, and of
average molecular weight of about 150,000.
(13) DC-1550 silicone microemulsion (25% active) from Dow Corning, with a
particle
size of about 50 nm, an anionic/nonionic surfactant system, and a silicone
with an
internal phase viscosity of about 100,000 cps.
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The composition of Example Ve is a concentrated composition, to be diluted for
use.
_VI
Ingredients Wt%
GE 176-12669 Silicone Emulsion1.43
(1)
GE SM 2658 Silicone Emulsion1.43
(2}
Polyvinyl alcohol (~>) 0.065
Glycerin 0.01
Kathon CG 3 ppm
Perfume 0.1
Distilled water Bal.
(1) Cationic emulsion ofhydroxy silicone, about 35°/~ active.
(2) Cationic emulsion of amino-functional silicone, about 35% active.
(3) Weight average molecular weight range from about 18,000 to about 27,000.
The compositions of Examples I to VI (diluted when appropriate) are sprayed
onto worn, faded color clothing using, e.g., the TS-800 sprayer from Calmar,
and allowed
to evaporate off of the clothing.
The compositions of Examples I to V1 (diluted when appropriate} are sprayed
onto worn, faded color clothing, using a blue inserted Guala~ trigger sprayer,
available
from Berry Plastics Corp. and a ;,ylindrical Euromist II~ pump sprayer
available from
Seaquest Dispensing, respectively, and allowed to evaporate off of the
clothing.
The compositions of Examples I to VI (diluted when appropriate) contained in
rechargeable battery-operated Solo Spraystar sprayers are sprayed onto large
wom, faded
color fabric surfaces of fabric, i.e., several pieces of clothing, and allowed
to evaporate off of
these surfaces. The level of coverage is uniform and the ease and conveuence
of application
is superior to conventional manually operated trigger sprayers.
The compositions of Examples I to VI (diluted when appropriate) are used for
soaking or dipping of worn, faded color fabrics which are then optionally
wrung or
squeezed to remove excess liquid and subsequently dried.
