Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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FABRIC CARE COMPOSITION AND METHOD
TECHNICAL FIELD
The present invention relates to fabric care compositions, methods, and
articles of
manufacture for treating fabrics in order to improve various properties of
fabrics, in
particular, reduction and/or removal of unwanted wrinkles; fabric wear
reduction; fabric
pill prevention and/or reduction; and/or fabric color maintenance and/or
fading reduction.
BACKGROUND OF THE INVENTION
There is a continuous need for textile technologists to produce compositions
and
products that provide useful benefits to fabrics, especially clothing, such as
maintaining
and/or improving a good appearance, and maintaining fabric condition, e.g.,
strength
and/or size, and reducing fabric wear, through a simple and convenient
application of a
product.
Consumers commonly judge the desirability and wearability of a garment by
many appearance criteria, such as, absence of wrinkles, absence of color
fading, absence
of soiling and staining, absence of damage such as pilling, absence of
malodor, and the
like. Other benefits that consumers value include fabric longevity, e.g.,
fabric wear
prevention or reduction, shrinkage prevention or reduction, and the like.
These benefits
can be more or less provided via textile finishing compositions that are
applied to fabrics
in textile mills and/or garment manufacturing facilities, but 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.
The present invention relates to compositions, methods, and articles of
manufacture that provide some important fabric care benefits, including at
least one of
the following: wrinkle removal and/or reduction, fabric strengthening, fabric
wear
resistance and/or reduction, fabric pilling prevention and/or reduction,
fabric color
maintenance and/or fading reduction, color restoration, fabric soiling
reduction, fabric
shape retention, and/or fabric shrinkage reduction.
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SUMMARY OF THE INVENTION
The present invention relates to fabric care compositions, fabric care
methods,
and articles of manufacture that contain such fabric care composition. The
fabric care
composition comprises:
(A) an effective amount of fabric care polysaccharide with globular structure
having a
backbone comprising at least some 1,3-(3-glycosidic linkages for providing a
fabric
with at least one of the following fabric care benefits: wrinkle removal,
wrinkle reduction, wrinkle resistance, fabric wear reduction, fabric wear
resistance, fabric pilling reduction, fabric color maintenance, fabric color
restoration, fabric color fading reduction, fabric soiling reduction, fabric
soil release, fabric shape retention, and/or fabric shrinkage reduction, said
fabric care polysaccharide comprises polysaccharides with globular
structure and with molecular weight of from about 5,000 to about
500,000; branched versions of said polysaccharides; derivatised versions
of said polysaccharides; substituted versions of said polysaccharides; and
mixtures thereof, the globular structure of said fabric care polysaccharide
has a size of from 2nm to 300nm;
(B) optionally, from about 0.001% to about 20%, by weight of the composition,
of adjunct fabric care oligosaccharide, selected from the group consisting
of oligosaccharides, oligosaccharide mixtures, substituted versions of said
oligosaccharides and/or mixtures, derivatised versions of said
oligosaccharides and/or mixtures, and mixtures thereof;
(C) optionally, to remove and/or reduce wrinkles, an effective amount of
adjunct wrinkle control agent, preferably selected from the group
consisting of fiber lubricant, fabric shape retention polymer, lithium salts,
and mixtures thereof;
(D) optionally, to reduce surface tension, and/or to improve performance and
formulatability, an effective amount of surfactant;
(E) optionally, an effective amount to absorb malodor, of odor control agent;
(F) optionally, an effective amount to provide olfactory effects of perfume;
(G) optionally, an effective amount, to kill, or reduce the growth of
microbes,
of antimicrobial active;
(H) optionally, an effective amount to provide improved antimicrobial action
of aminocarboxylate chelator;
(I) optionally, an effective amount of antimicrobial preservative, in addition
to, or in place of said antimicrobial active; and
(J) optionally, an aqueous carrier;
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said composition optionally being essentially free of any material that would
soil or stain
fabric under usage conditions.
A preferred fabric care composition for treating fabric comprises an effective
amount of said fabric care polysaccharide with a globular structure and is
applied to
fabric and/or an entire fabric garment via, e.g., dipping, soaking, misting
and/or spraying
processes followed by a drying step. The present invention also relates to the
fabric care
compositions incorporated into a spray dispenser and/or mist generator, to
create an
article of manufacture that can facilitate treatment of fabric articles and/or
entire fabric
garments and/or surfaces with said compositions containing fabric care
polysaccharide
with globular structure and other optional ingredients at a level that is
effective, yet is not
discernible when dried on the surfaces.
Also preferred are aqueous or solid, preferably powder, fabric care
compositions
for treating fabric in the rinse step, comprising an effective amount of
fabric care
polysaccharide with globular structure, and optionally, adjunct fabric care
oligosaccharide, fabric softening actives, perfume, and mixtures thereof.
Other preferred aqueous liquid, or solid, preferably powder or granular,
fabric
care compositions to be used in the wash cycle comprises an effective amount
of said
fabric care polysaccharide with globular structure, and optionally, adjunct
fabric care
oligosaccharide, surfactants, builders, perfume, and mixtures thereof.
Also preferred are fabric care compositions for treating fabric in the drying
step,
comprising an effective amount of said fabric care polysaccharide with
globular
structure, and optionally, adjunct fabric care oligosaccharide, fabric
softening actives,
perfume, and mixtures thereof. The dryer-added fabric care composition is
preferably
provided as part of an article of manufacture in combination with a dispensing
means
such as a flexible substrate or a sprayer which effectively releases the
fabric care
composition in an automatic tumble clothes dryer.
The fabric care polysaccharides with globular structure can provide at least
some
fabric care benefits to all types of fabrics, including fabrics made of
natural fibers,
synthetic fibers, and mixtures thereof.
The fabric care polysaccharides with globular structure can reduce the
scratchy feel
of wool fabric articles upon treatment as outlined in the present application.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to solid or stable, preferably translucent, more
preferably clear, aqueous fabric care compositions, fabric care methods, and
articles of
manufacture that use such fabric care composition. It also relates to the use
of fabric care
polysaccharide in a fabric care composition for providing a fabric with at
least one of the
following fabric care benefits: wrinkle removal, wrinkle reduction, wrinkle
resistance,
fabric wear reduction, fabric wear resistance, fabric pilling reduction,
fabric color
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maintenance, fabric color fading reduction, fabric color restoration, fabric
soiling
reduction, fabric soil release, fabric shape retention, and/or fabric
shrinkage reduction,
said fabric care polysaccharide comprising polysaccharides with globular
structure and
with molecular weight of from about 5,000 to about 500,000; branched versions
of said
polysaccharides; derivatised versions of said polysaccharides; substituted
versions of said
polysaccharides; and mixtures thereof.
Said polysaccharides are preferably selected from the group consisting of
arabinogalactan, pachyman, curdlan, callose, paramylon, sceleroglucan,
lentinan,
lichenan, laminarin, szhizophyllan, grifolan, sclerotinia sclerotiorum glucan
(SSG),
Ompharia lapidescence glucan (OL-2), pustulan, dextran, pullulan and mixtures
thereof,
branched versions thereof, substituted versions thereof, derivatised versions
thereof, and
mixtures thereof. One class of preferred fabric care polysaccharides are those
having 1,3-
3-linked backbone, such as, arabinogalactan, pachyman, curdlan, callose,
paramylon,
sceleroglucan, lentinan, lichenan, laminarin, szhizophyllan, grifolan,
sclerotinia
sclerotiorum glucan (SSG), Ompharia lapidescence glucan (OL-2), , and mixtures
thereof, branched versions thereof, substituted versions thereof, derivatised
versions
thereof, and mixtures thereof, more preferably arabinogalactan, its
derivatised versions,
its substituted versions, and mixtures thereof, typically from about 0.001% to
about 20%,
preferably from about 0.01% to about 10%, more preferably from about 0.1% to
about
5%, and even more preferably from about 0.1% to about 2%, by weight of the
composition.
Generally, depending on the method of application, the fabric care
compositions
of the present invention can be in solid (powder, granules, bars, tablets),
dimple tablets,
liquid, paste, gel, spray, stick or foam forms.
A preferred fabric care composition for treating fabric comprises an effective
amount of said fabric care polysaccharides with globular structure, and,
optionally, one,
or more ingredients selected from the group consisting of : adjunct fabric
care
oligosaccharides, perfume, fiber lubricant, fabric shape retention polymer,
lithium salt,
hydrophilic plasticizer, odor control agent including cyclodextrin,
antimicrobial active
and/or preservative, surfactant, fabric softening active, static control
agent, enzymes,
antioxidant, chelating agent, e.g., aminocarboxylate chelating agent, heavy
metal
chelating agent, dye transfer inhibiting agent, dye fixative agent, soil
release agent,
colorant, suds suppressor, insect repelling agent and/or moth repelling agent,
and
mixtures thereof. The composition is typically applied to fabric and/or an
entire fabric
garment via a, e.g., dipping, soaking, misting and/or spraying process,
followed by a
drying step, including the process comprising a step of treating and/or
spraying and/or
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misting the fabric and/or entire fabric garment 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 in a
consumer's home by
the use of commercial product.
The fabric care composition of present invention can also be applied directly
on
an entire garment via an applicator, preferably a spray mechanism and/or mist
mechanism. When applying the fabric care composition of the present invention
to an
entire garment, it is desirable that the spraying and/or misting of the entire
garment
occurs in a manner such that excessive amounts of the fabric/garment care
composition
are prevented from being released to the open environment. For example, the
spraying
and/or misting of the entire garment can occur within a bag or other article
suitable for
containing the garment.
The present invention also relates to concentrated liquid or solid fabric care
compositions, which are diluted to form compositions with the usage
concentrations, as
given hereinabove and/or hereinbelow, for use in the "usage conditions".
Concentrated
compositions for use in the laundry process such as pre-wash treatment
compositions,
wash-added compositions, and rinse-added compositions, comprise a higher level
of
fabric care polysaccharide with globular structure, typically from about I% to
about 99%,
preferably from about 2% to about 65%, more preferably from about 3% to about
25%,
by weight of the concentrated fabric care composition. Concentrated
compositions for
use to apply directly to fabric and/or entire garment, such as in the spraying
process
and/or misting process and/or dipping/soaking process, comprise a lower level;
of fabric
care polysaccharide with globular structure, typically from about 1% to about
40%,
preferably from about 1% to about 25%, more preferably from about 2% to about
15%,
by weight of the concentrated fabric care composition. The concentrated
compositions
optionally comprise at least one ingredient selected from the group consisting
of:
perfume, fiber lubricant, shape retention polymer, lithium salt, odor control
agent
including cyclodextrin, hydrophilic plasticizer, surfactant, antimicrobial
active and/or
antibacterial preservative, aminocarboxylate chelating agent, fabric softening
active,
static control agent, enzyme, antioxidant, suds suppressor, dye transfer
inhibiting agent,
dye fixing agent, insect repelling agent including moth repelling agent,
and/or liquid
carrier, and mixtures thereof. 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 care polysaccharide with globular structure is from about 1% to about
99%, by
weight of the concentrated composition, it is preferable to dilute the
composition before
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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 50% to about 5,000%, by weight of the composition, of
water.
Depending on the target fabric care benefit to be provided, the concentrated
compositions
should also comprise proportionally higher levels of the desired optional
ingredients to
be diluted to be the usage compositions.
The present invention also relates to aqueous fabric care compositions
incorporated into a spray dispenser and/or mist generator to create an article
of
manufacture that can facilitate treatment of fabric articles and/or entire
fabric garments
and/or surfaces with said compositions containing said fabric care
polysaccharide with
globular structure and other optional ingredients at a level that is
effective, yet is not
discernible when dried on the surfaces. The spray dispenser comprises manually
activated and non-manual powered (operated) spray means and a container
containing the
fabric care composition. The articles of manufacture preferably are in
association with
instructions for use to direct the consumer to apply at least an effective
amount of the
fabric care composition and/or fabric care polysaccharide with globular
structure to the
fabric to provide the desired benefit.
The present invention also relates to an article of manufacture comprising the
above aqueous fabric care compositions, to be applied directly via an
applicator,
preferably a spray mechanism and/or mist mechanism, more preferably via
misting
mechanism, on said fabric and/or entire garment in a manner such that
excessive amounts
of the fabric/garment care composition are prevented from being released to
the open
environment, preferably in association with instructions for use which direct
the
consumer to apply at least an effective amount of said fabric care
polysaccharide with
globular structure and/or said composition to said fabric and/or entire
garment is this
manner.
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. The fabric care polysaccharides of the current
invention have a
molecular weight range that is high enough so that they are easily damaged by
the hot
temperature of the ironing process, as is the case of lower molecular weight
oligosaccharides and monosaccharides.
Also preferred is a liquid, preferably aqueous, or solid, preferably powder,
fabric
care composition for treating fabric in the rinse step, comprising an
effective amount of
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said fabric care polysaccharide with globular structure, typically from about
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
fabric care composition. The fabric care composition optionally comprises of:
adjunct
fabric care oligosaccharide, fabric softening active, perfume, electrolyte,
chlorine
scavenging agent, dye transfer inhibiting agent, dye fixing agent, phase
stabilizer,
chemical stabilizer including antioxidant, silicone, antimicrobial actives .
and/or
preservative, chelating agent including aminocarboxylate chelating agent,
colorant,
enzyme, brightener, soil release agent, or mixtures thereof. Said composition
is
preferably packaged into an article of manufacture in association with
instructions for use
to ensure that the consumer knows what benefits can be achieved, and how best
to obtain
these benefits. The present invention also relates to concentrated liquid or
solid
compositions, which are diluted to form rinse-added fabric care compositions
with the
usage concentrations, as given hereinabove, for use in the "usage conditions".
Another preferred aqueous or solid, preferably powder or granular, fabric care
composition of this invention to be used in the wash cycle comprises an
effective amount
of said fabric care polysaccharide with globular structure, and optionally,
adjunct fabric
care oligosaccharide, surfactants, builder, perfume, chlorine scavenging
agent, dye
transfer inhibiting agent, dye fixing agent, dispersant, detergent enzyme,
heavy metal
chelating agent, suds suppressor, fabric softening active, chemical
stabilizers including
antioxidant, silicone, antimicrobial active and/or preservative, soil
suspending agent, soil
release agent, optical brightener, colorant, and the like, or mixtures
thereof. Other wash-
added fabric care compositions can be in the form of tablets, bar, paste, gel,
spray, stick,
foam, and can optionally be contained in a pouch or attached to a releasable
substrate.
These wash-added compositions which can be wash additive compositions or
detergent
compositions are preferably packaged into an article of manufacture in
association with
instructions for use to ensure that the consumer knows what benefits can be
achieved,
and how best to obtain these benefits.
Also preferred are fabric care compositions for treating fabric in the drying
step,
comprising an effective amount of said fabric care polysaccharide with
globular
structure, and optionally, adjunct fabric care oligosaccharides, fabric
softening actives,
distributing agent, perfume, fiber lubricants, fabric shape retention
polymers, lithium
salts, phase stabilizers, chlorine scavenging agents, dye transfer inhibiting
agents, dye
fixing agents, chemical stabilizers including antioxidants, silicones,
antimicrobial actives
and/or preservatives, heavy metal chelating agents, aminocarboxylate chelating
agents,
enzymes, brighteners, soil release agents, and mixtures thereof. The fabric
care
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composition can take a variety of physical forms including liquid, foams, gel
and solid
forms such as solid particulate forms. However, in the preferred substrate
product
embodiment, the dryer-added fabric care composition of the present invention
is
provided as part of an article of manufacture in combination with a dispensing
means
such as a flexible substrate which effectively releases the fabric care
composition in an
automatic tumble clothes dryer. Such dispensing means can be designed for
single usage
or for multiple uses. Preferably the composition is applied onto a sheet
substrate- to form
a dryer sheet product. The substrates in such products are typically non-woven
fabric
substrates, paper, foams, etc. Typical and preferred dispensing means are
described in
U.S. Pat. No. 5,102,564, issued Apr. 7, 1992 to Gardlik et al. Since
the characteristics of the fabric care polysaccharides with globular
structure and other optional ingredients that provide the various fabric care
benefits can
be different and interfering, it can be desirable to provide some of the
fabric care
compositions as one, or more, separate compositions, e.g., as separate areas
on a
substrate, as disclosed hereinafter. Said composition is preferably packaged
with or
without a dispensing means into an article of manufacture in association with
instructions
for use to ensure that the consumer knows what benefits can be achieved.
Another
preferred dispensing means is a sprayer which dispense the liquid fabric care
composition at the beginning and/or during the drying cycle.
The present invention also relates to fabric care compositions for dipping
and/or
soaking pre-wash treatment containing an effective amount of fabric care
polysaccharide
with globular structure, and optionally, adjunct fabric care oligosaccharide,
surfactants,
builders, perfume, chlorine scavenging agents, dye transfer inhibiting agents,
dye fixing
agents, dispersants, detergent enzymes, heavy metal chelating agents, fabric
softening
actives, chemical stabilizers including antioxidants, silicones, antimicrobial
actives
and/or preservatives, soil suspending agents, soil release agents, optical
brighteners,
colorants, and the like, or mixtures thereof. Said composition is preferably
packaged in
association with instructions for use to ensure that the consumer knows what
benefits can
be achieved, and how best to obtain these benefits. The present invention also
relates to
concentrated liquid or solid compositions, which are diluted to form pre-wash
fabric care
compositions with the usage concentrations, for use in the "usage conditions".
The present invention also relates to fabric care methods and articles of
manufacture that use such fabric 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 care polysaccharide with globular structure and other
optional
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ingredients at a level that is effective, yet is not discernible when dried on
the surfaces.
The spray dispenser comprises manually activated and non-manual powered spray
means
and a container containing the fabric care composition. Alternatively, the
article of
manufacture can comprise a fabric care composition and a dispensing means to
distribute
said composition onto the fabrics in a automatic tumble clothes dryer.
Preferably.the
dispensing means is a flexible substrate, e.g., in sheet configuration with
the fabric care
composition releasably affixed onto the substrate. For wash-added and rinse-
added
methods, the article of manufacture can simply comprise a liquid or granular
solid fabric
care composition and a suitable container.
Preferably the articles of manufacture are in association with instructions
for how
to use the composition to treat fabrics correctly, to obtain the desirable
fabric care results,
viz, wrinkle removal and/or reduction, wrinkle resistance, fiber
strengtheninglanti-wear,
fabric wear reduction, fabric shrinkage prevention and/or reduction, fabric
pill prevention
and/or reduction, shrinkage prevention and/or reduction, fabric color
maintenance, fabric
color restoration, fabric color fading reduction, soiling prevention and/or
reduction, soil
release, and/or fabric shape retention, and mixtures thereof, including, e.g.,
the manner
and/or amount of composition to used, and the preferred ways of stretching
and/or
smoothing of the fabrics. It is important that the instructions be as simple
and clear as
possible, so that using pictures and/or icons is desirable.
1. COMPOSITION
Fabric Care Polysaccharides
Suitable fabric care polysaccharides for use in the fabric care composition of
the
present invention are those which have a globular conformation in dilute
aqueous
solution, via a random coiling structure. Said polysaccharides include homo-
and/or
hetero- polysaccharides with simple helical structure with or without
branching, e.g.,
with 1,4-a-linked backbone structure (e.g., 1,4-a-glucan, 1,4-a-xylan) with or
without
branching, 1,3-0-linked backbone with or without branching (e.g., galactan),
and all 1,6-
linked backbones with or without branching (e.g., dextran, pullulan,
pustulan), and with a
weight-average molecular weight of from about 5,000 to about 500,000,
preferably from
about 8,000 to about 250,000, more preferably from about 10,000 to about
150,000,
typically with sizes ranging from about 2 rim to about 300 nm, preferably from
about 3
nm to about 100 rim, more preferably from about 4 rim to about 30 rim. The
size is
defined as the gyration length occupied by the molecule in dilute aqueous
solutions.
Preferably the fabric care polysaccharide is selected from the group
consisting of
arabinogalactan, pachyman, curdlan, callose, paramylon, sceleroglucan,
lentinan,
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lichenan, laminarin, szhizophyllan, grifolan, sclerotinia sclerotiorum glucan
(SSG),
Ompharia lapidescence glucan (OL-2), pustulan, dextran, pullulan, substituted
versions
thereof, derivatised versions thereof, and mixtures thereof. More preferably
the fabric
care polysaccharide is selected from the group consisting of arabinogalactan,
dextran,
curdlan, substituted versions thereof, derivatised versions thereof, and
mixtures thereof,
and even more preferably the fabric care polysaccharide comprises
arabinogalactan,
substituted versions thereof, derivatised versions thereof, and mixtures
thereof.
Substituted and/or derivatised materials of the fabric care polysaccharides
listed
hereinabove are also preferred in the present invention. Nonlimiting examples
of these
materials include: carboxyl and hydroxymethyl substitutions (e.g., some uronic
acid
instead of neutral sugar units); amino polysaccharides (amine substitution);
cationic
quaternized polysaccharides; C,-C18 alkylated polysaccharides; acetylated
polysaccharide
ethers; polysaccharides having amino acid residues attached (small fragments
of
glycoprotein); polysaccharides containing silicone moieties, and the like.
Some
hydrophobic derivatives of the polysaccharides help the polysaccharides
maintaining the
globular conformation.
A preferred class of fabric care polysaccharides suitable for use in the
present
invention include those that have the backbone comprising at least some, but
preferably
almost entirely of 1,3-p-glycosidic linkages, preferably branched, preferably
with either
side chains attached with 1,6-linkages or derivatised for better water
solubility and/or to
maintain the globular structure. The 1,6-linked branched polysaccharides with
1,3-(3-
linked backbone have higher water solubility and/or dispersibility than the
non-branched
polysaccharides, so that branched polysaccharides can be used at higher
molecular
weight ranges. Inserting other types of linkages, such as some 1,4-n linkages
in the1,3-0-
linked backbone also improves the solubility of the polysaccharides.
Nonlimiting
examples of useful fabric care polysaccharides with 1,3-p-linked backbone
include
arabinogalactan, pachyman, curdlan, callose, paramylon, sceleroglucan,
lentinan,
lichenan, laminarin, szhizophyllan, grifolan, sclerotinia sclerotiorum glucan
(SSG),
Ompharia lapidescence glucan (OL-2), and mixtures thereof. Low molecular
weight
materials are preferred for polysaccharides with less or no branching, such as
curdlan,
while higher molecular weight materials for highly branched polysaccharides,
such as
arabinogalactan, can be used. Higher molecular weight polysaccharides with
mixed 1,3-
and 1,4-f linkages, such as lichenan, can also be used.
A preferred fabric care branched polysaccharide with 1,3-0-linked backbone is
arabinogalactan (also named as galactoarabinan or epsilon-galactan).
Arabinogalactans
are long, densely branched high-molecular weight polysaccharides.
Arabinogalactan that
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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 (consisting of (3-galactopyranose, (3-arabinofuranose, and (i-
arabinopyranose). The
major source of arabinogalactan is the larch tree. The genus Larix (larches)
is common
throughout the world. Two main sources of larch trees are western larch (Larix
occidentalis) in Western North America and Mongolian larch (Larix dahurica).
Examples of other larches are eastern larch (Larix laricina) in eastern North
America,
European larch (Larix dicidua), Japanese larch (Larix leptolepis), and
Siberian larch
(Larix siberica). 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. Glycosyl linkage analysis of larch arabinogalactan is consistent with a
highly
branched structure comprising a backbone of 1,3-n-linked galactopyranose
connected by
1,3-0-glycosidic linkages, comprised of 3,4,6-, 3,6-, and 3,4- as well as 3-
linked residues.
The molecular weights of the preferred fractions of larch arabinogalactan
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. The high molecular weight fraction (of
about
100,000 molecular weight), as well as the low molecular weight fraction are
suitable for
use in processes that involve subsequent water treatments, such as, pre-soak,
wash-added
and/or rinse-added laundry processes and products. High grade larch
arabinogalactan is
composed of greater than about 98% arabinogalactan. Larch arabinogalactan and
some
of its derivatives, such as cationic derivatives are commercially available
from Larex,
Inc., St Paul, Minnesota.
Arabinogalactans are also present as minor, water-soluble components of
softwoods such as hemlock, black spruce, parana pine, mugo pine, Douglas fir,
incense
cedar, juniper, and the sapwood of sugar maple. Many edible and inedible
plants are
also rich sources of arabinogalactans, mostly in glycoprotein form, bound to a
protein
spine of either threonine, proline, or serine ("arabinogalactan-protein").
These plants
include leek seeds, carrots, radish, black gram beans, pear, maize, wheat, red
wine,
Italian ryegrass, tomatoes, ragweed, sorghum, bamboo grass, and coconut meat
and milk.
Many herbs with well established immune-enhancing properties, such as
Echinacea
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purpurea, Baptisia tintoria, Thu ja occidentalis, Angelica acutiloba, and
Curcuma longa
contain significant amounts of arabinogalactans. Small quantities of
arabinogalactans
also occur in other plants, such as, green coffee bean (sugar ratio about
2:5), centrosema
seeds (sugar ratio about 1:13), and wheat flour (sugar ratio about 7:3). About
70% of the
water solubles from soybean flour is an arabinogalactan with a sugar ratio of
about 1:2.
Examples of other fabric care polysaccharides that have 1,3-(3-linkage as a
part of
the backbone include: 1,3-p-xylan (from, e.g., Pencillus dunietosus), curdlen,
*a 1,3-P-
glucan (from e.g., Alcaligenes faecalis), paramylon B, a 1,3-p-glucan (from,
e.g.,
Euglena gracilis), lichenin, a (1,3),(1,4)-3-glucan (from various sources
including
Cetraria islandica), sceleroglucan, a (1,3),(1,6)-(3-glucan (from, e.g.,
Sclerotiuni rolfii),
and lentinen, a (1,3),(1,6)-(3-glucan (from, e.g., Lentinus edodes). More
details about
these and other polysaccharides with 1,3-(3-linked backbone are given in
"Chemistry and
Biology of (1-+3)-p-Glucans", B. A. Stone and A. E. Clarke, La Trobe
University Press,
Victoria, Australia, 1992, pp. 68-71, and 82-83,
Substituted and/or derivatised materials of arabinogalactans are also
preferred in
the present invention. Nonlimiting examples of these materials include:
carboxyl and
hydroxymethyl substitutions (e.g., some uronic acid instead of neutral sugar
units);
amino polysaccharides (amine substitution); cationic quaternized
polysaccharides; C,-Cjg
alkylated polysaccharides; acetylated polysaccharide ethers; polysaccharides
having
amino acid residues attached (small fragments of glycoprotein);
polysaccharides
containing silicone moieties. These substituted and/or derivatised
polysaccharides can
provide additional benefits, such as: amine substitution can bind and/or
condense with
oxidatively damaged regions of the fiber to rejuvenate aged fabrics;
acetylated sugar
ethers can serve as bleach activators in subsequent processes where hydrogen
peroxide is
present; polysaccharides having amino acid residues can improve delivery of
fabric care
benefits for fabrics containing proteinaceous fibers, e.g., wool and silk; and
silicone-
derivatised polysaccharides can provide additional fabric softness and
lubricity.
Examples of derivatised arabinogalactan include the 3-chloro-2-
hydroxypropyltrimethyl
ammonium chloride derivative, available from Larex, Inc and the
arabinogalactan-
proteins given hereinabove.
The 1,3-0-linked backbone of the fabric care polysaccharides of the present
invention (as in 1,3-0-galactans, 1,3-0-D-mannans, 1,3-(3-D-xylans and 1,3-(3-
D-glucans)
has a pseudohelical copformation. As such, these polysaccharides have a
backbone chain
that is flexible and in aqueous solution, has a tendency to coil into a
globular structure to
substantially reduce their apparent dimension (gyration volume), as opposed to
the
backbone chain of 1,4-(3-glucan which has an extended dimension. The
polysaccharides
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with 1,3-n-linked backbone and extensive branching via 1,6-linkages, or
polysaccharides
with helical confirmation or polysaccharides with 1,6-linked backbone have
added
flexibility due to the "coiling" nature of the 1,6-linkages. In water these
polysaccharides
with 1,3-0-linked backbone and 1,6-branching, e.g., arabinogalactans, have a
globular
conformation with high flexibility to coil into compact, flexible and
deformable
microscopic particles. For example, an arabinogalactan having a nominal
molecular
weight of about 18,000 has a size (gyration length) of only from 5 rim to
about 10 nm in
dilute aqueous solutions. This structural feature of the globular
polysaccharides with
helical conformation and random coiling nature improves physical properties
such as
water-solubility, low viscosity and emulsification. It is believed that the
globular,
compact and flexible structural property and low viscosity of the fabric care
polysaccharides with 1,3-0-linked backbone of the present invention, such as
arabinogalactans, is important for providing the fabric care benefits, either
via efficient
deposition of the polysaccharide globules on the rough fabric surface or via
appropriate
fitting/filling of these globules in the openings and/or defective spaces on
the fabric fiber
surface, where they can orient itself to conform to the space available.
Furthermore, it is
believed that at low levels, these low molecular weight (about 10,000 to about
150,000)
polysaccharide globules of the present invention can very effectively bond
fibers and/or
microfibrils together by "spot bonding". This way, the fabric care
polysaccharide
globules can provide many desired benefits such as: fabric strengthening,
fabric wear
resistance and/or reduction, wrinkle removal and/or reduction, fabric pilling
prevention
and/or reduction, fabric color maintenance and/or fading reduction, color
restoration,
fabric soiling reduction, fabric shape retention, fabric shrinkage reduction,
and/or
improving fabric feel/smoothness, scratchiness reduction, for different types
of fabrics
such as cellulosic (cotton, rayon, etc.), wool, silk, and the like.
Polysaccharides with helical conformation, but not within the range. of the
molecular weight range specified above have different physical properties such
as low
solubility and gelling characteristics (e.g., starch, a high molecular weight
1,4-ot-D-
glucan).
The fabric care polysaccharides with globular structure of the present
invention
can provide at' least some fabric care benefits to all types of fabrics,
including fabrics
made of natural fibers, synthetic fibers, and mixtures thereof. Nonlimiting
examples of
fabric types that can be treated with the fabric care compositions of the
present invention,
to obtain fabric care benefits include fabrics made of (1) cellulosic fibers
such as cotton,
TM
rayon, linen, Tencel, (2) proteinaceous fibers such as silk, wool and related
mammalian
fibers, (3) synthetic fibers such as polyester, acrylic, nylon, and the like,
(4) long
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vegetable fibers from jute, flax, ramie, coir, kapok, sisal, henequen, abaca,
hemp and
sunn, and (5) mixtures thereof. Other unanimated substrates and/or surfaces
made with
natural fibers and/or synthetic fibers, and/or materials, such as non-woven
fabrics,
paddings, carpets, paper, disposable products, films, foams, can also be
treated with the
fabric care polysaccharides with 1,3-p-linked backbone to improve their
properties.
For specific applications, the composition can contain from about 0.001% to
about 20% of fabric care polysaccharide with globular structure, preferably
from about
0.01% to about 10%, more preferably from about 0.1% to about 5%, by weight of
the
usage composition. The present invention also relates to concentrated liquid
or solid
compositions, which are diluted to form compositions with the usage
concentrations, for
use in the "usage conditions". Concentrated compositions comprise a higher
level of
fabric care polysaccharide, typically from about 1% to about 99%, preferably
from about
2% to about 65%, more preferably from about 3% to about 40%, by weight of the
concentrated fabric care composition. Depending on the target fabric care
benefit to be
provided, the concentrated compositions should also comprise proportionally
higher
levels of the desired optional ingredients.
Typical composition to be dispensed from a sprayer contains a level of fabric
care
polysaccharide with globular structure of from about 0.01% to about 5%,
preferably from
about 0.05% to about 2%, more preferably from about 0.1% to about 1%, by
weight of
the usage composition. Typical usage compositions for a direct dipping and/or
soaking
treatment followed by a drying step, contain a level of fabric care
polysaccharide of from
about 0.001% to about 2%, preferably from about 0.05% to about 1%, more
preferably
from about 0.1 % to about 0.5%, by weight of the usage composition. It is also
common
and practical to provide a more concentrated composition containing typically
from about
0.5% to about 40%, preferably from about 1% to about 25%, more preferably from
about
2% to about 15%, by weight of the concentrated composition, of fabric care
polysaccharide with globular structure, to be diluted down in use to obtain
the desirable
usage dipping or soaking composition. Depending on the target fabric care
benefit to be
provided, the concentrated compositions should also comprise proportionally
higher
levels of the desired optional ingredients. A concentrated composition can
also be used,
and is provided, e.g., as a refill, to prepare usage composition for the spray
product.
Wash-added compositions, including liquid and granular detergent compositions
and wash additive compositions typically contain a level of fabric care
polysaccharide
with globular structure of from about 0.2% to about 30%, preferably from about
1% to
about 20%, more preferably from about 2% to about 10%, by weight of the wash-
added
compositions.
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Typical rinse-added compositions, including liquid fabric conditioner and
other
rinse additive compositions, contain a level of fabric care polysaccharide.
with globular
structure of from about 0.1% to about 50%, preferably from about 0.3% to about
40%,
more preferably from about 1% to about 25%, even more preferably from about 2%
to
about 15%, by weight of the rinse-added compositions.
Typical usage compositions for a dipping and/or soaking pre-wash treatment
and/or for use as a wash-cycle additive contain a level of fabric care
polysaccharide with
globular structure of from about 0.05% to about 40%, preferably from about
0.1% to
about 20%, more preferably from about 0.5% to about 10%, by weight of the
usage
composition. More concentrated compositions comprise a higher level of fabric
care
polysaccharide, typically from about 1% to about 99%, preferably from about 2%
to
about 65%, more preferably from about 3% to about 40%, by weight of the
concentrated
fabric care composition. Depending on the target fabric care benefit to be
provided, the
concentrated compositions should also comprise proportionally higher levels of
the
desired optional ingredients.
Dryer-added compositions typically contain a level of fabric care
polysaccharide
with globular structure of from about 0.01 % to about 40% by weight of the
dryer-added
compositions.
Adjunct Fabric Care Olibosaccharides
An optional but preferred adjunct fabric care agent in the present invention
is
selected from the group consisting of oligosaccharides, especially mixtures of
oligosaccharides, especially, isomaltooligosaccharides (IMO) (including
mixtures), the
individual components of said mixtures, substituted versions thereof,
derivatised versions
thereof, and mixtures thereof. The adjunct fabric fabric care oligosaccharides
help to
provide some fabric benefits, such as wrinkle removal and/or reduction, anti-
pilling, anti-
wear, fabric color maintenance, and overall appearance benefits, especially to
cellulosic
TM
fibers/fabrics, such as cotton, rayon, ramie, jute, flax, linen, polynosic-
fibers, Lyocell
(Tencel ), polyester/cotton blends, other cotton blends, and the like,
especially cotton,
rayon, linen, polyester/cotton blends, and mixtures thereof.
Suitable adjunct fabric care oligosaccharides that are useful in the present
invention include oligosaccharides with a degree of polymerization (DP) of
from about I
to about 15, preferably from about 2 to about 10, and wherein each monomer is
selected
from the group consisting of reducing saccharide containing 5 and/or 6 carbon
atoms,
including isomaltose, isomaltotriose, isomaltotetraose,
isomaltooligosaccharide,
fructooligosaccharide, levooligosaccharides, galactooligosaccharide,
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xylooligosaccharide, gentiooligosaccharides, disaccharides, glucose, fructose,
galactose,
xylose, mannose, arabinose, rhamnose, maltose, 'sucrose, lactose, maltulose,
ribose,
lyxose, allose, altrose, gulose, idose, talose, trehalose, nigerose,
kojibiose, lactulose,
oligosaccharides, maltooligosaccharides, trisaccharides, tetrasaccharides,
pentasaccharides, hexasaccharides, oligosaccharides from partial hydrolysates
of natural
polysaccharide sources, and the like, and mixtures thereof, preferably
mixtures of
isomaltooligosaccharides, especially mixtures including
isomaltooligosaccharides,
comprising from about 3 to about 7 units of glucose, respectively, and which
are linked
by 1,2-a, 1,3-a, 1,4-a- and 1,6-a-linkages, and mixtures of these linkages.
Oligosaccharides containing ¾-linkages are also preferred. Preferred
oligosaccharides are
acyclic and have at least one linkage that is not an a-1,4-glycosidic bond. A
preferred
oligosaccharide is a mixture containing IMO: from 0 to about 20 % by weight of
glucose, from about 10 to about 65 % of isomaltose, from about 1% to about 45%
of
each of isomaltotriose, isomaltetraose and isomaltopentaose, from 0 to about 3
% of each
of isomaltohexaose, isomaltoheptaose, isomaltooctaose and isomaltononaose,
from about
0.2% to about 15% of each of isomaltohexaose and isomaltoheptaose, and from 0
to
about 50 % by weight of said mixture being isomaltooligosaccharides of 2 to 7
glucose
units and from 0 to about 10 % by weight of said mixture being
isomaltooligosaccharides
of about 7 to about 10 glucose units. Other nonlimiting examples of preferred
acyclic
oligosaccharides, with approximate content by weight percent, are:
Isomaltooligosaccharide Mixture I
Trisaccharides (maltotriose, panose, isomaltotriose) 40-65%
Disaccharides (maltose, isomaltose) 5-15%
Monosaccharide (glucose) 0-20%
Higher branched sugars (4 < DP < 10) 10-30%
Isomaltooligosaccharide Mixture II
Trisaccharides (maltotriose, panose, isomaltotriose) 10-25%
Disaccharides (maltose, isomaltose) 10-55%
Monosaccharide (glucose) 10-20%
Higher branched sugars (4 < DP < 10) 5-10%
Isomaltooligosaccharide Mixture III
Tetrasaccharides (stachyose) 10-40%
Trisaccharides (raffinose) 0-10%
Disaccharides (sucrose, trehalose) 10-50%
Monosaccharide (glucose, fructose) 0-10%
Other higher branched sugars (4 < DP <10) 0-5%
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Oligosaccharide mixtures are either prepared by enzymatic reactions or
separated
as natural products from plant materials. The enzymatic synthesis of
oligosaccharides
involves either adding monosaccharides, one at a time, to a di- or higher
saccharide to
produce branched oligosaccharides, or it can involve the degradation of
polysaccharides
followed by transfer of saccharides to branching positions. For instance,
Oligosaccharide
Mixtures I and II are prepared by enzymatic hydrolysis of starch to
maltooligosaccharides, which are then converted to isomaltooligosaccharides by
a
transglucosidase reaction. Oligosaccharide Mixture III, for example, is a
mixture of
oligosaccharides isolated from soybean. Soybean oligosaccharides such as
Mixture III,
are of pure natural origin.
Cyclic oligosaccharides can also be useful in the fabric care composition of
the
present invention. Preferred cyclic oligosaccharides include a-cyclodextrin,
(i-
cyclodextrin, y-cyclodextrin, their branched derivatives such as glucosyl-a-
cyclodextrin,
diglucosyl-a-cyclodextrin, maltosyl-a-cyclodextrin, glucosyl-(3-cyclodextrin,
diglucosyl-
(3-cyclodextrin, and mixtures thereof. The cyclodextrins also provide an
optional but
very important benefit of odor control, and are disclosed more fully
hereinbelow.
Substituted and/or derivatised materials of the oligosaccharides listed
hereinabove are also preferred in the present invention. Nonlimiting examples
of these
materials include: carboxyl and hydroxymethyl substitutions (e.g., glucuronic
acid
instead of glucose); amino oligosaccharides (amine substitution, e.g.,
glucosamine
instead of glucose); cationic quaternized oligosaccharides; C1-C6 alkylated
oligosaccharides; acetylated oligosaccharide ethers; oligosaccharides having
amino acid
residues attached (small fragments of glycoprotein); oligosaccharides
containing silicone
moieties. These substituted and/or derivatised oligosaccharides can provide
additional
benefits, such as: carboxyl and hydroxymethyl substitutions can introduce
readily
oxidizable materials on and in the fiber, thus reducing the probability of the
fiber itself
being oxidized by oxidants, such as bleaches; amine substitution can bind
and/or
condense with oxidatively damaged regions of the fiber to rejuvenate aged
fabrics;
acetylated sugar ethers can serve as bleach activators in subsequent processes
where
hydrogen peroxide is present; oligosaccharides having amino acid residues can
improve
delivery of fabric care benefits for fabrics containing proteinaceous fibers,
e.g., wool and
silk; and silicone-derivatised oligosaccharides can provide additional fabric
softness and
lubricity. C6 alkyl oligosaccharide is disclosed (along with other higher,
viz., C6-C30,
alkyl polysaccharides) in U.S. Pat. 4,565,647, issued Jan. 21, 1986 to
Llenado, for use as
foaming agent in foaming compositions such as laundry detergents, personal and
hair
cleaning compositions, and fire fighting compositions. The C6 alkyl
oligosaccharide is a
CA 02346771 2005-11-09
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poor surfactant and not preferred for use as surfactant in the detergent
compositions of
the present invention, but preferably can be used to provide the fabric care
benefits that
are not known, appreciated and/or disclosed in U.S. Pat No. 4,565,647. U.S.
Pat. No.
4,488,981, issued Dec. 18, 1984 discloses the use of some C,-Co alkylated
oligosaccharides (lower alkyl glycosides) in aqueous liquid detergents to
reduce their
viscosity and to prevent phase separation. C,-C6 alkylated oligosaccharides
are not
preferred for use as viscosity and phase modifiers in the liquid detergent
compositions of
the present invention, but can be used to provide the fabric care benefits
that are not
known, appreciated and/or disclosed in U.S. Pat No.4,488,981.
It is believed that the fabric care oligosaccharide is adsorbed and binds with
cellulosic fabrics to improve the properties of the fabrics. It is believed
that the fabric
care oligosaccharide is bound to the cellulosic fibers, diffuses in and fills
the defect sites
(the amorphous region) of the fiber, to provide the above dewrinkling,
increased strength
and improved appearance benefits. The extent of the amorphous, non-crystalline
region
varies with cellulosic fiber types, e.g., the relative crystallinity of cotton
is about 70.%
and for regenerated cellulose, such as, rayon it is about 30.% , as reported
by P. H.
Hermans and A. Weidinger, "X-ray studies on the crystallinity of cellulose" in
the
Journal of Polymer Science, Vol IV, p135-144, 1949. It is believed that the
amorphous
regions are accessible for chemical and physical modifications, and that in
the durable
press treatment, the amorphous regions are filled with molecules that can
crosslink
cellulose polymers by covalent bonds, to deliver wrinkle-free benefits (cf. S.
P. Rawland,
in "Modified Cellulosics," R. M. Rowell and R. A. Young, Eds., Academic Press,
New
York, 1978, pp. 147-167, cited by G. C. Tesoro, in `Crosslinking of
cellulosics',
Handbook of Fiber Science and Technology, Vol. II, p.6, edited by M. Lewin and
S. B.
Sello, published by Marcel Dekker, 1983.
For specific applications, the composition can contain from about 0.001% to
about 20% of the optional, but preferred oligosaccharide, preferably from
about 0.01% to
about 10%, more preferably from about 0.1 % to about 5%, by weight of the
usage
composition. The present invention also relates to concentrated liquid or
solid
compositions, which are diluted to form compositions with the usage
concentrations, for
use in the "usage conditions". Concentrated compositions comprise a higher
level of the
optional fabric care oligosaccharide, typically from about I% to about 50%,
preferably
from about 2% to about 40%, more preferably from about 3% to about 20%, by
weight of
the concentrated fabric care composition.
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Typical composition to be dispensed from a sprayer contains a level of
optional
fabric care oligosaccharide of from about 0.01% to about 3%, preferably from
about
0.05% to about 2%, more preferably from about 0.1% to about 1%, by weight of
the
usage composition. Typical usage compositions for a direct dipping and/or
soaking
treatment followed by a fabric drying step, contain a level of optional fabric
care
oligosaccharide of from about 0.001% to about 2%, preferably from about 0.05%
to
about 1%, more preferably from about 0.1% to about 0.5%, by weight of the
usage
composition. It is also common and more practical to provide a more
concentrated
composition containing typically from about 1 % to about 40%, preferably from
about I%
to about 25%, more preferably from about 2% to about 15%, by weight of the
concentrated composition, of the optional fabric care oligosaccharide, to be
diluted down
in use to obtain the desirable usage dipping or soaking compositions. A
concentrated
composition can also be used, and is provided, e.g., as a refill, to prepare
usage
composition for the spray product.
Wash-added compositions, including liquid and granular detergent compositions
and wash additive compositions typically contain a level of optional fabric
care
oligosaccharide of from about 0.2% to about 30%, preferably from about 1% to
about
20%, more preferably from about 2% to about 12%, by weight of the wash-added
compositions. Typical rinse-added compositions, including liquid fabric
conditioner and
other rinse additive compositions, contain a level of optional fabric care
oligosaccharide
of from about 0.1% to about 50%, preferably from about 1% to about 35%, more
preferably from about 2% to about 18%, and even more preferably from about 2%
to
about 10%, by weight of the rinse-added compositions.
Dryer-added compositions typically contain a level of optional fabric care
oligosaccharide of from about 0.01 % to about 40%, preferably from about 0.1 %
to about
20%, more preferably from about 1% to about 10%, by weight of the dryer-added
compositions. Aqueous dryer-added compositions to be applied directly to the
fabric,
e.g., via a spraying mechanism, contain lower levels of fabric care
polysaccharide,
typically from about 0.01% to about 25%, preferably from about 0.1% to about
10%,
more preferably from about 0.2% to about 5%, even more preferably from about
0.3% to
about 3%, by weight of the compositions.
Both the fabric care polysaccharides and the optional fabric care
oligosaccharides
have a compact structure, but they have different sizes. The smaller
oligosaccharides are
believed to be able to diffuse and penetrate into small defective sites, such
as the
amorphous region of cotton fibers, while the larger polysaccharides can fill
in larger
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openings and/or defective sites on the fabric fiber surface. Therefore
depending on the
fabric care benefit target, the fabric care polysaccharides can be used alone,
or in
mixtures with the optional fabric care oligosaccharides. When the optional
fabric care
oligosaccharides are present, the weight ratio between said oligosaccharides
and the
fabric care polysaccharides is typically from about 1:99 to about 99:1,
preferably from
about 15:85 to about 85:15, and more preferably from about 30:70 to about
70:30.
Nonlimiting examples of other optional ingredients are given hereinbelow.
Other Optional Ingredients
The fabric care compositions of the present invention can contain other
optional
ingredients either to improve the performance of the fabric care
polysaccharide with
globular structure, e.g., in the areas of wrinkle control, anti-wear, soil
release, and the
like, or to provide additional benefits, such as odor control, antimicrobial,
and the like.
Nonlimiting examples of optional ingredients are given hereinbelow.
Fiber Lubricants
The fabric care composition of the present invention can comprise optional
fiber
lubricants to impart a lubricating property, or increased gliding ability, to
fibers in fabric,
particularly clothing. Not to be bound by theory, it is believed that fiber
lubricants
facilitate the movement of fibers with respect to one another (glide) to
release the fibers
from the wrinkle condition in wet or damp fabrics. After the fabric is dried,
the fiber
lubricant, especially silicone, can provide lubricity to reduce the tendency
of fabric to
rewrinkle.
(a). Silicone
The present invention can use silicone, a preferred fiber lubricant, to impart
a
lubricating property, or increased gliding ability, to fibers in fabric,
particularly clothing.
Nonlimiting examples of useful silicones in the composition of the present
invention
include noncurable silicones such as polydimethylsilicone and volatile
silicones, 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. Preferably, the silicones are hydrophobic; are neither
irritating,
toxic, nor otherwise harmful when applied to fabric or when they come in
contact with
human skin; are chemically stable under normal use and storage conditions; and
are
capable of being deposited on fabric.
When the composition of this invention is to be dispensed from a spray
dispenser
in a consumer household setting, the noncurable silicones such as
polydimethylsilicone,
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especially the volatile silicones, are preferred. Curable and/or reactive
silicones such as
amino-functional silicones and silicones with reactive groups such as Si-OH,
Si-H,
silanes, and the like, are less preferred in this situation, because the
portion 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 articles such as a flexible bag, and in other, non-spray
fabric
treatment processes, such as dipping, soaking, in-the-wash, in-the-rinse, and
in-the-dryer
processes. Many types of aminofunctional silicones also cause fabric
yellowing. Thus,
the silicones that cause fabric discoloration are also not preferred.
The preferred silicone is volatile silicone fluid which can be a cyclic
silicone fluid
of the formula [(CH3)2SiO]n where n ranges between about 3 to about 7,
preferably
about 5 (D5), or a linear silicone polymer fluid having the formula
(CH3)3SiO[(CH3)2SiO]mSi(CH3)3 where in can be 0 or greater and has an average
value such that the viscosity at 25 C of the silicone fluid is preferably
about 5 centistokes
or less.
The non-volatile silicones that are useful and preferred in the composition of
the
present invention is polyalkyl and/or phenylsilicones silicone fluids and gums
with the
following structure:
A-Si(R2) -O-[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
viscosity of from about 50 to about 1000,000 centistokes at 25 C. Mixtures of
volatile
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silicones and non-volatile polydimethyl siloxanes are also preferred. 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)2-0]x- {Si(OH)[(CH2)3-NH-(CH2)2-NH2]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". Although silicones with a high
number,
e.g., greater than about 0.5 millimolar equivalent of amine groups can be
used, they are
not preferred because they can cause fabric yellowing.
Similarly, silicone materials which can be used correspond to the formulas:
(R1)aG3-a-Si-(-OSiG2)n-(OSiGb(R1)2-b)m-O-SiG3-a(R1)a
wherein G is selected from the group consisting of hydrogen, phenyl, OH,
and/or C1-C8
alkyl; a denotes 0 or an integer from I to 3; b denotes 0 or 1; the sum of n +
in is a
number from 1 to about 2,000; R1 is a monovalent radical of formula CpH2pL in
which
p is an integer from 2 to 8 and L is selected from the group consisting of:
-N(R2)CH2-CH2-N(R2)2;
-N(R2)2;
-N+(R2)3 A-; and
-N+(R2)CH2-CH2N+H2 A-
wherein each R2 is chosen from the group consisting of hydrogen, phenyl,
benzyl,
saturated hydrocarbon radical, and each A- denotes compatible anion, e.g., a
halide ion;
and
R3-N+(CH3)2-Z-[Si(CH3)20]f Si(CH3)2-Z-N+(CH3)2-R3.2CH3000
wherein
Z = -CH2-CH(OH)--CH2O-CH2)3-
R3 denotes a long chain alkyl group; and
f denotes an integer of at least about 2.
In the formulas herein, each definition is applied individually and averages
are
included.
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
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wherein n and m are the same as before. The preferred silicones of this type
are those
which do not cause fabric discoloration.
Alternatively, the silicone material can be provided as a moiety or a part of
a
oligosaccharide molecule. These materials provide a lubricity benefit in
addition to the
expected fabric care benefits. Other examples of dual function silicone
materials useful
in the present invention are adjunct shape retention copolymers having
siloxane
macromers grafted thereto. The non-silicone backbone of such polymers should
have a
molecular weight of from about 5,000 to about 1,000,000, and the polymer
should have a
glass transition temperature (Tg), i.e., the temperature at which the polymer
changes from
a brittle vitreous state to a plastic state, of greater than about -20 C.
Adjunct fabric shape
retention silicone-containing polymers useful in the present invention are
described in
more detailed herein below along with other adjunct shape retention polymers.
When silicone is present, it is present at least an effective amount to
provide
lubrication of the fibers, typically 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 usage
composition.
Silicone is also a useful optional ingredient in the rinse-added fabric care
compositions of the present invention. The silicone can be either a
polydimethyl
siloxane (polydimethyl silicone or PDMS), or a derivative thereof, e.g., amino
silicones,
ethoxylated silicones, etc. The PDMS, is preferably one with a low molecular
weight,
e.g., one having a viscosity of from about 2 to about 5000 cSt, preferably
from about 5 to
about 500 cSt, more preferably from about 25 to about 200 cSt. Silicone
emulsions can
conveniently be used to prepare the compositions of the present invention.
However, in
compositions containing fabric softening actives, the silicone is preferably
one that is, at
least initially, not emulsified. I.e., the silicone should be emulsified in t
he composition
itself. In the process of preparing the compositions, the silicone is
preferably added to
the "water seat", which comprises the water and, optionally, any other
ingredients that
normally stay in the aqueous phase.
Low molecular weight PDMS is preferred for use in the fabric softener
compositions of this invention. The low molecular weight PDMS is easier to
formulate
without pre-emulsification.
Silicone derivatives such as amino-functional silicones, quatemized silicones,
and silicone derivatives containing Si-OH, Si-H, and/or Si-Cl bonds, can be
used.
However, these silicone derivatives are normally more substantive to fabrics
and can
build up on fabrics after repeated treatments to actually cause a reduction in
fabric
absorbency.
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When added to water, the fabric softener composition deposits the cationic
fabric
softening active on the fabric surface to provide fabric softening effects.
However, in a
typical laundry process, using an automatic washer, cotton fabric water
absorbency can
be appreciably reduced at high softening active levels and/or after multiple
cycles. The
silicone improves the fabric water absorbency, especially for freshly treated
fabrics,
when used with this level of fabric softening active without adversely
affecting the fabric
softening performance. The mechanism by which this improvement in water
absorbency
occurs is not well understood, since the silicones are inherently hydrophobic.
It is very
surprising that there is any improvement in water absorbency, rather than
additional loss
of water absorbency. The PDMS also improves the ease of ironing in addition to
improving the rewettability characteristics of the fabrics.
The amount of PDMS needed to provide a noticeable improvement in water
absorbency is dependent on the initial rewettability performance, which, in
turn, is
dependent on the detergent type used in the wash. Effective amounts range from
about 2
ppm to about 50 ppm in the rinse water, preferably from about 5 to about 20
ppm. The
PDMS to softening active ratio is from about 2:100 to about 50:100, preferably
from
about 3:100 to about 35:100, more preferably from about 4:100 to about 25:100.
This
typically requires from about 0.2% to about 20%, preferably from about 0.5% to
about
10%, more preferably from about 1% to about 5% silicone.
(b). Synthetic solid particles
Solid polymeric particles of average particle size smaller than about 10
microns,
preferably smaller than 5 microns, more preferably smaller than about 1
micron, e.g.,
rm
Velustrol P-40 oxidized polyethylene emulsion available from Clariant, can be
used as a
lubricant, since they can provide a "roller-bearing" action. When solid
polymeric
particles are present, they are present at an effective amount to provide
lubrication of the
fibers, typically from about 0.01% to about 3%, preferably from about 0.05% to
about
1%, more preferably from about 0.1% to about 0.5%, by weight of the usage
composition.
Adjunct Fabric Shape Retention Polymer
These polymers can be natural, or synthetic, 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 impart shape retention to fabric,
particularly
clothing. 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. Other polymers such as starches
can form a
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film and/or bond the fibers together when the treated fabric is pressed by a
hot iron.
Such a film will have adhesive strength, cohesive breaking strength, and
cohesive
breaking strain.
Nonlimiting examples for natural polymers are starches and their derivatives,
and
chitins and their derivatives.
The 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 CI-
C6
unsaturated organic mono-carboxylic and polycarboxylic acids, such as acrylic
acid,
methacrylic acid, crotonic acid, maleic acid and its half esters, itaconic
acid, and mixtures
thereof; esters of said acids with C1-C12 alcohols, such as methanol, ethanol,
1-
propanol, 2-propanol, 1-butanol, 2-methyl-l-propanol, 1-pentanol, 2-pentanol,
3-
pentanol, 2-methyl-l-butanol, 1-methyl-l-butanol, 3-methyl-l-butanol, 1-methyl-
l-
pentanol, 2-methyl-l-pentanol, 3-methyl-l-pentanol, t-butanol, cyclohexanol, 2-
ethyl-l-
butanol, neodecanol, 3-heptanol, benzyl alcohol, 2-octanol, 6-methyl- l -
heptanol, 2-ethyl-
1-hexanol, 3,5-dimethyl-l -hexanol, 3,5,5-trimethyl-l -hexanol, 1-decanol, 1-
dodecanol,
and the like, 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-
butylstyrene,
vinyl toluene, polystyrene macromer, and the like; polar vinyl heterocyclics,
such as vinyl
pyrrolidone, vinyl caprolactam, vinyl pyridine, vinyl imidazole, and mixtures
thereof;
other unsaturated amines and amides, such as vinyl amine, diethylene 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 consisting 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
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acrylamide; vinylpyrrolidone; vinyl pyridine; adipic acid; diethylenetriamine;
salts
thereof and alkyl quaternized derivatives thereof, and mixtures thereof.
Preferably, said monomers form homopolymers and/or copolymers (i.e., the film-
forming and/or adhesive polymer) having a glass transition temperature (Tg) of
from
about -20 C to about 150 C, preferably from about -10 C to about 150 C, more
preferably from about 0 C to about 100 C, most preferably, the adhesive
polymer hereof,
when dried to form a film will have a Tg of at least about 25 C., so that they
are not
unduly sticky, or "tacky" to the touch. Preferably said polymer is soluble
and/or
dispersible in water and/or alcohol. Said polymer typically has a molecular
weight of at
least about 500, preferably from about 1,000 to about 2,000,000, more
preferably from
about 5,000 to about 1,000,000, and even more preferably from about 30,000 to
about
300,000 for some polymers.
Some non-limiting examples of homopolymers and copolymers which can be
used as film-forming and/or adhesive polymers of the present invention are:
adipic
acid/dimethylaminohydroxypropyl diethylenetriamine copolymer; adipic
acid/epoxypropyl diethylenetriamine copolymer; poly(vinylpyrrolidone/
dimethylaminoethyl methacrylate); polyvinyl alcohol; polyvinylpyridine n-
oxide;
methacryloyl ethyl betaine/methacrylates copolymer; ethyl acrylate/methyl
methacrylate/methacrylic acid/acrylic acid copolymer; polyamine resins; and
polyquatemary amine resins; poly(ethenylformamide); poly(vinylamine)
hydrochloride;
poly(vinyl alcohol-co-6% vinylamine); poly(vinyl alcohol-co-12% vinylamine);
poly(vinyl alcohol-co-6% vinylamine hydrochloride); and poly(vinyl alcohol-co-
12%
vinylamine hydrochloride). Preferably, said copolymer and/or homopolymers are
selected from the group consisting of adipic acid/dimethylaminohydroxypropyl
diethylenetriamine copolymer; poly(vinylpyrrolidone/dimethylaminoethyl
methacrylate);
polyvinyl alcohol; ethyl acrylate/methyl methacrylate/methacrylic acid/acrylic
acid
copolymer; methacryloyl ethyl betaine/methacrylates copolymer; polyquaternary
amine
resins; poly(ethenylformamide); poly(vinylamine) hydrochloride; poly(vinyl
alcohol-co-
6% vinylamine); poly(vinyl alcohol-co-12% vinylamine); poly(vinyl alcohol-co-
6%
vinylamine hydrochloride); and poly(vinyl 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
weight of about 1,000,000, available from GAF Chemicals Corporation; adipic
acid/dimethylaminohydroxypropyl diethylenetriamine copolymer, such as
Cartareti F-
4 and F-23, available from Sandoz Chemicals Corporation; methacryloyl ethyl
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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 101 ,
available from
Hercules Incorporated; polyamine resins, such as Cypro 515 , available from
Cytec
Industries; polyquaternary amine resins, such as Kymene 557H , available from
Hercules Incorporated; and polyvinylpyrrolidone/acrylic acid, such as Sokalan
EG 310 ,
available from BASF.
Preferred polymers useful in the present invention are selected from the group
consisting of copolymers of hydrophilic monomers and hydrophobic monomers. The
polymer can be linear random or block copolymers, and mixtures thereof. Such
hydrophobic/hydrophilic copolymers typically have a hydrophobic
monomer/hydrophilic
monomer ratio of from about 95:5 to about 20:80, preferably from about 90:10
to about
40:60, more preferably from about 80:20 to about 50:50 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 form a homogeneous solution, as is well understood to those
skilled in the art.
Nonlimiting examples of useful hydrophobic monomers are acrylic acid C1-C18
alkyl esters, such as methyl acrylate, ethyl acrylate, t-butyl acrylate;
methacrylic C1-C18
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
toluene; vinyl ethers, such as methyl vinyl ether; vinyl chloride; vinylidene
chloride;
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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.
Nonlimiting examples of useful hydrophilic monomers are unsaturated organic
mono-carboxylic and polycarboxylic acids, such as acrylic acid, methacrylic
acid,
crotonic acid, maleic 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 sulfonate;
unsaturated
amides, such as acrylamides, e.g., N,N-dimethylacrylamide, N-t-butyl
acrylamide;
hydroxyethyl methacrylate; dimethylaminoethyl 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 acrylamide, N,N-dimethyl
methacrylamide, N-t-butyl acrylamide, dimethylamino ethyl methacrylate, vinyl
pyrrolidone, salts thereof and alkyl quatemized derivatives thereof, and
mixtures thereof.
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 marks 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-25 by Union Carbide (ethyl acrylate/methacrylic
acid/methyl methacrylate/acrylic acid copolymer), and Poligen A by BASF
(polyacrylate dispersion).
Preferably, the adjunct shape retention polymers contain an effective amount
of
monomers having carboxylic groups. Highly preferred adjunct shape retention
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, maleic acid and its half esters,
itaconic acid, and
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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, maleic 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 hereinabove with C 1-C 12 alcohols, such as methanol, ethanol, 1-
propanol, 2-
propanol, 1-butanol, 2-methyl-l-propanol, 1-pentanol, 2-pentanol, 3-pentanol,
2-methyl-
1-butanol, 1-methyl-I -butanol, 3-methyl-l -butanol, 1-methyl-I -pentanol, 2-
methyl-l -
pentanol, 3-methyl-l-pentanol, t-butanol, cyclohexanol, 2-ethyl-l-butanol, and
mixtures
thereof, preferably methanol, ethanol, I-propanol, 2-propanol, 1-butanol, 2-
methyl-l-
propanol, t-butanol, and mixtures thereof. One highly 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
15:85, 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 about 30,000 to
about
300,000, and with an approximate acrylic acid/tert-butyl acrylate weight ratio
of about
25:75 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
35:65 and an
average molecular weight of from about 60,000 to about 90,000.
The film-forming and/or adhesive polymer of the present invention is present
at
least an effective amount to provide shape retention, 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 1.5%, by weight of the usage
composition.
The adhesive polymer is present in the composition in a sufficient amount to
result in an amount of from about 0.001% to about 1%, preferably from about
0.01% to
about 0.5%, more preferably from about 0.02% to about 0.4% by weight of
polymer per
weight of dry fabrics.
It is not intended to exclude the use of higher or lower levels of the
polymers, as
long as an effective amount is used to provide adhesive and film-forming
properties to
the composition and the composition can be formulated and effectively applied
for its
intended purpose.
Silicones and film-forming polymers can be combined to produce preferred
wrinkle reducing actives. Typically the weight ratio of silicone to film-
forming polymer
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is from about 10:1 to about 1:10, preferably from about 5: 1 to about 1:5, and
more
preferably from about 2:1 to about 1:2. Typically, the preferred wrinkle
reducing active
of silicone plus polymer is present at a level of from about 0.1 % to about
8%, preferably
from about 0.3% to about 5%, more preferably from about 0.5% to about 3%, by
weight
of the composition.
Optional but preferred adhesive and/or film forming polymers that are useful
in
the composition of the present invention actually contain silicone moieties in
the
polymers themselves. These preferred polymers include 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 shape retention, body, and/or good, soft fabric
feel. Highly
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,
maleic acid and its half esters, itaconic acid, and salts thereof, and
mixtures thereof; and
optionally other hydrophilic monomers.
Both silicone-containing graft and block copolymers useful in the present
invention have the following properties:
(1) the silicone portion is covalently attached to the non-silicone portion;
(2) the molecular weight of the silicone portion is from about 1,000 to about
50,000; and
(3) the non-silicone portion must render the entire copolymer soluble or
dispersible in the wrinkle control composition vehicle and permit the
copolymer to deposit on/adhere to the treated fabrics.
Suitable silicone copolymers include the following:
(a) Silicone Graft Copolymers
Preferred silicone-containing polymers are the silicone graft copolymers
comprising acrylate groups described, along with methods of making them, in
U.S.
Patent No. 5,658,557, Bolich et al., issued Aug. 19, 1997, U.S. Patent No.
4,693,935,
Mazurek, issued Sept. 15, 1987, and U.S. Patent No. 4,728,571, Clemens et al.,
issued
Mar. 1, 1988. Additional silicone-containing polymers are disclosed in U.S.
Pat. Nos.
5,480,634, Hayama et al, issued Oct. 2, 1996, 5,166,276, Hayama et al., issued
Nov. 24,
1992, 5,061,481, issued Oct. 29, 1991, Suzuki et al., 5,106,609, Bolich et
al., issued Apr.
21, 1992, 5,100,658, Bolich et al., issued Mar. 31, 1992, 5,100,657, Ansher-
Jackson, et
al., issued Mar. 31, 1992, 5,104,646, Bolich et al., issued Apr. 14, 1992.
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These polymers preferably include copolymers having a vinyl polymeric
backbone having grafted onto it monovalent' siloxane polymeric moieties, and
components consisting of non-silicone hydrophilic and hydrophobic monomers.
The silicone-containing monomers are exemplified by the general formula:
X(Y)n Si(R)3-m Zm
wherein X is a polymerizable group, such as a vinyl group, which is part of
the backbone
of the polymer; Y is a divalent linking group; R is a hydrogen, hydroxyl,
lower alkyl (e.g.
C1-C4), aryl, alkaryl, alkoxy, or alkylamino; Z is a monovalent polymeric
siloxane
moiety having an average molecular weight of at least about 500, is
essentially unreactive
under copolymerization conditions, and is pendant from the vinyl polymeric
backbone
described above; n is 0 or 1; and in is an integer from I to 3.
The preferred silicone-containing monomer has a weight average molecular
weight of from about 1,000 to about 50,000, preferably from about 3,000 to
about
40,000, most preferably from about 5,000 to about 20,000.
Nonlimiting examples of preferred silicone-containing monomers have the
following formulas:
0
11
X-C-O--(CH2)q-(O)p--S~(R')3-m m
X--Si(R') 3-m Zm
X (CH2)q-(O)P Si(R')3-m Zm
0 H O R"
II 1 II I
X-C-O-(CH2)2-N-C-N Si(R1)3-m 7m
O OH R"
11 1 X-C-O-CH2-CH-CH2-N-(CH2)q-Si(R1) 3-m Zm
0 H O R"
11 1 11 X-C-O-(CH2)2-N-C-N-(CH2)q---Si(R') 3-m Zm
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In these structures m is an integer from 1 to 3, preferably 1; p is 0 or 1; q
is an
integer from 2 to 6; n is an integer from 0 to 4, preferably 0 or 1, more
preferably 0; R1 is
hydrogen, lower alkyl, alkoxy, hydroxyl, aryl, alkylamino, preferably R1 is
alkyl; R" is
alkyl or hydrogen; X is
CH(R3)==C(R4)-
R3 is hydrogen or -COOH, preferably hydrogen; R4 is hydrogen, methyl or -
CH2COOH,
preferably methyl; Z is
RS-[Si(R6)(R7) 0 ]r
wherein R5, R6, and R7, independently are lower alkyl, alkoxy, alkylamino,
hydrogen or
hydroxyl, preferably alkyl; and r is an integer of from about 10 to about 700,
preferably
from about 40 to about 600, more preferably from about 70 to about 300. Most
preferably, R5, R6, and R7 are methyl, p = 0, and q = 3.
Silicone-containing adhesive and/or film-forming copolymers useful in the
present invention comprise from 0% to about 90%, preferably from about 10% to
about
80%, more preferably from about 40% to about 75% of hydrophobic monomer, from
about 0% to about 90%, preferably from about 5% to about 80% of hydrophilic
monomer, and from about 5% to about 50%, preferably from about 10% to about
40%,
more preferably from about 15% to about 25% of silicone-containing monomer.
The composition of any particular copolymer will help determine its
formulation
properties. In fact, by appropriate selection and combination of particular
hydrophobic,
hydrophilic and silicone-containing components, the copolymer can be optimized
for
inclusion in specific vehicles. For example, polymers which are soluble in an
aqueous
formulation preferably contain from 0% to about 70%, preferably from about 5%
to
about 70% of hydrophobic monomer, and from about 30% to about 98%, preferably
from
about 30% to about 80%, of hydrophilic monomer, and from about I% to about
'40% of
silicone-containing monomer. Polymers which are dispersible preferably contain
from
0% to about 70%, more preferably from about 5% to about 70%, of hydrophobic
monomer, and from about 20% to about 80%, more preferably from about 20% to
about
60%, of hydrophilic monomer, and from about 1% to about 40% of silicone-
containing
monomer.
The silicone-containing copolymers preferably have a weight average molecular
weight of from about 10,000 to about 1,000,000, preferably from about 30,000
to about
300,000.
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The preferred polymers comprise a vinyl polymeric backbone, preferably having
a
Tg or a Tm as defined above of about -201C. and, grafted to the backbone, a
polydimethylsiloxane macromer having a weight average molecular weight of from
about
1,000 to about 50,000, preferably from about 5,000 to about 40,000, most
preferably
from about 7,000 to about 20,000. The polymer is such that when it is
formulated into
the finished composition, and then dried, the polymer phase separates into a
discontinuous phase which includes the polydimethylsiloxane macromer and a
continuous phase which includes the backbone. Exemplary silicone grafted
polymers for
use in the present invention include the following, where the composition of
the
copolymer is given with the approximate weight percentage of each monomer used
in the
polymerization reaction to prepare the copolymer: N,N-
dimethylacrylamide/isobutyl
methacrylate/(PDMS macromer - 20,000 approximate molecular weight)(PDMS is
polydimethylsiloxane) (20/60/20 w/w/w), copolymer of average molecular weight
of
about 400,000; N,N-dimethylacrylamide/(PDMS macromer -20,000 approximate
molecular weight) (80/20 w/w), copolymer of average molecular weight of about
300,000; t-butylacrylate/N,N-dimethylacrylamide/(PDMS macromer - 10,000
approximate molecular weight) (70/10/20), copolymer of average molecular
weight of
about 400,000; and (N,N,N-trimethylammonioethylmethacrylate chloride)/ N,N-
dimethylacrylamide/(PDMS macromer - 15,000 approximate molecular weight)
(40/40/20), copolymer of average molecular weight of about 150,000.
Highly preferred adjunct shape retention copolymers of this type contain
hydrophobic monomers, silicone-containing monomers and hydrophilic monomers
which
comprise unsaturated organic mono- and polycarboxylic acid monomers, such as
acrylic
acid, methacrylic acid, crotonic acid, maleic acid and its half esters,
itaconic acid, and
salts thereof, and mixtures thereof. A highly preferred copolymer is composed
of acrylic
acid, t-butyl acrylate and silicone-containing monomeric units, preferably
with from
about 20% to about 90%, preferably from about 30% to about 80%, more
preferably from
about 50% to about 75% t-butyl acrylate; from about 5% to about 60%,
preferably from
about 8% to about 45%, more preferably from about 10% to about 30% of acrylic
acid;
and from about 5% to about 50%, preferably from about 7% to about 40%, more
preferably from about 10% to about 30% of polydimethylsiloxane of an average
molecular weight of from about 1,000 to about 50,000, preferably from about
5,000 to
about 40,000, most preferably from about 7,000 to about 20,000. Nonlimiting
examples
of acrylic acid/tert-butyl acrylate/polydimethyl siloxane macromer copolymers
useful in
the present invention, with approximate monomer weight ratio, are: t-
butylacrylate/acrylic acid/(polydimethylsiloxane macromer, 10,000 approximate
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molecular weight) (70/10/20 w/w/w), copolymer of average molecular weight of
about
300,000; t-butylacrylate/acrylic acid/(polydimethylsiloxane macromer, 10,000
approximate molecular weight) (65/25/10 w/w/w), copolymer of average molecular
weight of about 200,000; t-butyl acrylate/acrylic acid/(polydimethylsiloxane
macromer,
10,000 approximate molecular weight) (63/20/17), copolymer of average
molecular
weight of from about 120,000 to about 150,000; and n-butylmethacrylate/acrylic
acid/
(polydimethylsiloxane macromer - 20,000 approximate molecular weight)
(70/10/20
w/w/w), copolymer of average molecular weight of about 100,000. A useful
copolymer
of this type is Diahold ME from Mitsubishi Chemical Corp., which is a t-butyl
acrylate/acrylic acid/ (polydimethylsiloxane macromer, 12,000 approximate
molecular
weight) (60/20/20), copolymer of average molecular weight of about 128,000.
(b) Silicone Block Copolymers
Also useful herein are silicone block copolymers comprising repeating block
units of polysiloxanes.
Examples of silicone-containing block copolymers are found in U.S. Patent No.
5,523,365, to Geck et at., issued June 4, 1996; U.S. Patent No. 4,689,289, to
Crivello,
issued Aug. 25, 1987; U.S. Patent No. 4,584,356, to Crivello, issued April 22,
1986;
Macromolecular Design, Concept & Practice, Ed: M. K. Mishra, Polymer Frontiers
International, Inc., Hopewell Jct., NY (1994), and Block Copolymers, A. Noshay
and J.
E. McGrath, Academic Press, NY (1977). Other silicone block copolymers
suitable for
use herein are those described, along with methods of making them, in the
above noted
U.S. Patent No. 5,658,577.
The silicone-containing block copolymers useful in the present invention can
be
described by the formulas A-B, A-B-A, and -(A-B)n- wherein n is an integer of
2 or
greater. A-B represents a diblock structure, A-B-A represents a triblock
structure, and -
(A-B)n- represents a multiblock structure. The block copolymers can comprise
mixtures
of diblocks, triblocks, and higher multiblock combinations as well as small
amounts of
homopolymers.
The silicone block portion, B, can be represented by the following polymeric
structure
--(SiR2O)m--,
wherein each R is independently selected from the group consisting of
hydrogen,
hydroxyl, CI-C6 alkyl, CI-C6 alkoxy, C2-C6 alkylamino, styryl, phenyl, CI-C6
alkyl or
alkoxy-substituted phenyl, preferably methyl; and in is an integer of about 10
or greater,
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preferablyof about 40 or greater, more preferably of about 60 or greater, and
most
preferably of about 100 or greater.
The non-silicone block, A, comprises monomers selected from the monomers as
described hereinabove in reference to the non-silicone hydrophilic and
hydrophobic
monomers for the silicone grafted copolymers. Vinyl blocks are preferred co-
monomers.
The block copolymers preferably contain one or more non-silicone blocks, and
up to
about 50%, preferably from about 10% to about 20%, by weight of one or more
polydimethyl siloxane blocks.
(c) Sulfur-Linked Silicone-Containing Copolymers
Also useful herein are sulfur-linked silicone containing copolymers,
including block copolymers. As used herein in reference to silicone containing
copolymers, the term "sulfur-linked" means that the copolymer contains a
sulfur linkage
(i.e., -S-), a disulfide linkage (i.e., -S-S-), or a sulfhydryl group (i.e.,-
SH).
These sulfur-linked silicone-containing copolymers are represented by the
following general formula:
(R1)3-x G5 (R3)3-q
Si (Oii)y OSi
(G2SR2)( G6 (R4SG4)q
wherein
each G5 and G6 is independently selected from the group consisting of alkyl,
aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen, and -ZSA, wherein A
represents a vinyl polymeric segment consisting essentially of polymerized
free radically
polymerizable monomer, and Z is a divalent linking group (Useful divalent
linking
groups Z include but are not limited to the following: C l to C 10 alkylene,
alkarylene,
arylene, and alkoxyalkylene. Preferably, Z is selected from the group
consisting of
methylene and propylene for reasons of commercial availability.);
each G2 comprises A;
each G4 comprises A;
each R1 is a monovalent moiety selected from the group consisting of alkyl,
aryl,
alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen, and hydroxyl (Preferably,
R1
represents monovalent moieties which can independently be the same or
different
selected from the group consisting of C 1-4 alkyl and hydroxyl for reasons of
commercial
availability. Most preferably, R1 is methyl.);
each R2 is a divalent linking group (Suitable divalent linking groups include
but
are not limited to the following: C l to CIO alkylene, arylene, alkarylene,
and
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alkoxyalkylene. Preferably, R2 is selected from the group consisting of C1-3
alkylene
and C7-C 10 alkarylene due to ease of synthesis of the compound. Most
preferably, R2 is
selected from the group consisting of-CH2-, 1,3-propylene, and
_ CH2 O CH2CH2-
each R3 represents monovalent moieties which can independently be the.same or
different and are selected from the group consisting of alkyl, aryl, alkaryl,
alkoxy,
alkylamino, fluoroalkyl, hydrogen, and hydroxyl (Preferably, R3 represents
monovalent
moieties which can independently be the same or different selected from the
group
consisting of C1-4 alkyl and hydroxyl for reasons of commercial availability.
Most
preferably, R3 is methyl.);
each R4 is a divalent linking group(Suitable divalent linking groups include
but
are not limited to the following: Cl to C10 alkylene, arylene, alkarylene, and
alkoxyalkylene. Preferably, R4 is selected from the group consisting of C1_3
alkylene
and C7-C10 alkarylene for ease of synthesis. Most preferably, R4 is selected
from the
group consisting of --CH2-, 1,3-propylene, and
-CH2 O CH2CH2_
x is an integer of 0-3;
y is an integer of 5 or greater(preferably y is an integer ranging from about
14 to
about 700, preferably from about 20 to about 200); and
q is an integer of 0-3;
wherein at least one of the following is true:
q is an integer of at least 1;
x is an integer of at least 1;
G5 comprises at least one -ZSA moiety; or
G6 comprises at least one -ZSA moiety.
As noted above, A is a vinyl polymeric segment formed from polymerized free
radically polymerizable monomers. The selection of A is typically based upon
the
intended uses of the composition, and the properties the copolymer must
possess in order
to accomplish its intended purpose. If A comprises a block in the case of
block
copolymers, a polymer having AB and/or ABA architecture will be obtained
depending
upon whether a mercapto functional group -SH is attached to one or both
terminal
silicon atoms of the mercapto functional silicone compounds, respectively. The
weight
ratio of vinyl polymer block or segment, to silicone segment of the copolymer
can vary.
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The preferred copolymers are those wherein the weight ratio of vinyl polymer
segment to
silicone segment ranges from about 98:2 to 50:50, in order that the copolymer
possesses
properties inherent to each of the different polymeric segments while
retaining the overall
polymer's solubility.
Sulfur linked silicone copolymers are described in more detail in U.S. Patent
No.
5,468,477, to Kumar et al., issued November 21, 1995, and PCT Application No.
WO
95/03776, assigned to 3M, published February 9, 1995.
Other useful silicone-containing polymers are those containing hydrophilic
portions, such as polyvinylpyrrolidone/quatemaries, polyacrylates,
polyacrylamides,
polysulfonates, and mixtures thereof, and are disclosed, e.g., in U.S. Pat.
No. 5,120,812,
The film-forming and/or adhesive silicone-containing copolymer of the present
invention is present at least an effective amount to provide shape retention,
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
1.5%, by weight of the usage composition.
The silicone-containing copolymer is present in the composition in a
sufficient
amount to result in an amount of from about 0.001% to about 1%, preferably
from about
0.01% to about 0.5%, more preferably from about 0.02% to about 0.4% by weight
of
polymer per weight of dry fabrics.
When the optional cyclodextrin is present in the composition, the polymer
useful
in providing shape retention in the composition of the present invention
should be
cyclodextrin-compatible, that is it should not substantially form 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 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 C7-C18 alcohols, such as neodecanol, 3-heptanol,
benzyl
alcohol, 2-octanol, 6-methyl-l-heptanol, 2-ethyl-l-hexanol, 3,5-dimethyl-l-
hexanol,
3,5,5-trimethyl-l-hexanol, and 1-decanol; aromatic vinyls, such as styrene; t-
butylstyrene; vinyl toluene; and the like.
Starch
Starch is not normally preferred, since it makes the fabric resistant to
deformation. However, it does provide increased "body" which is often desired.
Starch
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is particularly preferred in compositions of this invention to be used with
ironing. When
used, starch is solubilized or dispersed in the composition. Any type of
starch, e.g. those
derived from corn, wheat, rice, grain sorghum, waxy grain sorghum, waxy maize
or
tapioca, or mixtures thereof and water soluble or dispersible modifications or
derivatives
thereof, can be used in the composition of the present invention. Low
viscosity
commercially available propoxylated and/or ethoxylated starches are useable in
the
present composition and are preferred since their low viscosity at relatively
high solids
concentrations make them very adaptable to spraying processes. Suitable
alkoxylated,
low viscosity starches are submicron sized particles of hydrophobic starch
that are readily
dispersed in water and are prepared by alkoxylation of granular starch with a
monofunctional alkoxylating agent which provides the starch with ether linked
hydrophilic groups. A suitable method for their preparation is taught in U.S.
Pat. No.
3,462,283. In accordance with the invention, the propoxylated or ethoxylated
starch
derivatives are dispersed in the aqueous medium in an amount of from about
0.1% to
about 10%, preferably from about 0.5% to about 6%, more preferably from about
1% to
about 4% by weight of the usage composition.
Lithium Salts.
Optional lithium salts are useful in the fabric care compositions of the
present
invention for providing improved fabric wrinkle control. Nonlimiting examples
of
lithium salts that are useful in the present invention are lithium bromide,
lithium
chloride, lithium lactate, lithium benzoate, lithium acetate, lithium sulfate,
lithium
tartrate, and/or lithium bitartrate, preferably lithium bromide and/or lithium
lactate.
Some water soluble salts such as , lithium benzoate are not preferred when the
optional
cyclodextrin is present because they can form complexes with cyclodextrin.
Useful
levels of lithium salts are from about 0.1% to about 10%, preferably from
about 0.5% to
about 7%, more preferably from about 1% to about 5%, by weight of the usage
composition.
Hydrophilic Plasticizer
Optionally, the composition can contain a hydrophilic plasticizer to soften
both
the fabric fibers, especially cotton fibers, and the adjunct adhesive and/or
film-forming
shape retention polymers. Examples of the preferred hydrophilic plasticizers
are short
chain low molecular weight polyhydric alcohols, such as is glycerol, ethylene
glycol,
propylene glycol, diethylene glycol, dipropylene glycol, sorbitol, erythritol
or mixtures
thereof, more preferably diethylene glycol, dipropylene glycol, ethylene
glycol, propylene
glycol and mixtures thereof. When a hydrophilic plasticizer is used, it is
present in the at
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a level of from 0.01% to 5%, preferably from 0.05% to 2%, more preferably from
0. 1%
to I% by weight of the usage composition.
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 wrinkle control agents such as silicones and/or certain
relatively water
insoluble adjunct shape retention polymers. The surfactant can provide some
plasticizing
effect to the adjunct shape retention polymers resulting in a more flexible
polymer
network. 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 care polysaccharide with globular structure,
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:
R8-Z-(CH2CH2O)5B
wherein R8 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
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
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carboxylate group, or a sulfate group; and linking group Z is -0-, -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-
lipophilic 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 C8-C18 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 C8-C18 alkyl
and/or
alkenyl, e.g., 3-hexadecyl, 2-octadecyl, 4-eicosanyl, 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 C8-
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 C8-C 15 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 11, 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-C 10, s =
2.7, HLB =
8.5), Neodol 23-3 (C12-C13, s = 2.9, 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 adjunct shape
retention
polymers such as copolymers containing acrylic acid and tert-butyl acrylate
and silicone-
containing 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 (C12-18) esters of ethoxylated (E05-100) 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
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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 12 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-15 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, 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 1.3 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
RZO(CnH2nO)t(glycosyl)x
wherein R2 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.
Another class of preferred surfactants that are useful in the formulation of
the
compositions of the present invention, to solubilize and/or disperse silicone
lubricants
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and/or silicone-containing adjunct shape retention copolymers, are silicone
surfactants.
They can be used alone and/or preferably in combination with the preferred
alkyl
ethoxylate surfactants described herein above. Nonlimiting examples of
silicone
surfactants are the polyalkylene oxide polysiloxanes having a dimethyl
polysiloxane
hydrophobic moiety and one or more hydrophilic polyalkylene side chains, and
having the
general formula:
R 1--(CH3)2SiO-[(CH3)2SiO]x--[(CH3)(R 1)SiO]b--Si(CH3)2---R 1
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(ethyleneoxy/propyleneoxy) copolymer group,
and
wherein n is 3 or 4, preferably 3; total c (for all polyalkyleneoxy side
groups) has a value
of from I to about 100, preferably from about 6 to about 100; 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 5 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 I to 4
carbon atoms, and an acetyl group, preferably hydrogen and methyl group. Each
polyalkylene oxide polysiloxane has at least one R1 group being a
poly(ethyleneoxide/propyleneoxide) copolymer group.
Nonlimiting examples of this type of surfactants are the Silwet surfactants
which
are available OSi Specialties, Inc., Danbury, Connecticut. Representative
Silwet
surfactants which contain only ethyleneoxy (C2H40) groups are as follows.
Name Average MW Average a+b Average total c
L-7608 600 1 9
L-7607 1,000 2 17
L-77 600 1 9
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 10,000 88 75
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Nonlimiting examples of surfactants which contain both ethyleneoxy (C2 H4 0)
and propyleneoxy (C3 H6 0) groups are as follows.
Name TM Average MW EO/PO ratio
Silwet L-720 12,000 50/50
Silwet L-7001 20,000 40/60
Silwet L-7002 8,000 50/50
Silwet L-721 0 13,000 20/80
Silwet L-7200 19,000 75/25
Silwet L-7220 17,000 20/80
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 (RI)
must be sufficient to render the polyalkylene oxide polysiloxane water
dispersible or water
soluble. If propyleneoxy groups are 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 not preferred. Preferred
Silwet
surfactants are L-7600, L-7602, L-7604, L-7605, L-7657, and mixtures thereof.
The most
preferred Silwet surfactant for solubilizing and/or dispersing the adjunct
silicone-
containing shape retention polymers and/or the volatile silicone is the low
molecular
weight L-77. Besides surface activity, polyalkylene oxide polysiloxane
surfactants can
also provide other benefits, such as antistatic benefits, lubricity and
softness to fabrics.
Other useful silicone surfactants 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, 5,073,619, and 5,237,035.
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Fabric care composition of the present invention to be used in the wash cycle
can
be either used along with a general laundry detergent or actually a detergent
composition
comprising a fabric care polysaccharide with globular structure. The detergent
compositions according to the present invention comprise a surfactant or
surfactant
system wherein the surfactant can be selected from nonionic and/or anionic
and/or
cationic and/or ampholytic and/or zwitterionic and/or semi-polar nonionic
surfactants.
The surfactant is typically present at a level of from 0.1 % to 60% by.
weight.
More preferred levels of incorporation are 1% to 35% by weight, most
preferably from
I% to 30% by weight of detergent compositions in accord with the invention.
The surfactant is preferably formulated to be compatible with the fabric care
polysaccharide with globular structure present in the composition.
Examples of suitable nonionic, anionic, cationic, ampholytic, zwitterionic and
semi-polar nonionic surfactants are disclosed in U.S. Patent Nos. 5,707,950
and
5,576,282.
Highly preferred nonionic surfactants are polyhydroxy fatty acid amide
surfactants of the formula:
R2-C(O)-N(R1)-Z,
wherein R1 is H, or R1 is C1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl
or a
mixture thereof, R2 is C5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl
having a
linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the
chain, or an
alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight C11-
15 alkyl or
C16-18 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z
is derived
from a reducing sugar such as glucose, fructose, maltose, lactose, in a
reductive
arnination reaction.
Highly preferred anionic surfactants include alkyl alkoxylated sulfate
surfactants
hereof are water soluble salts or acids of the formula RO(A)mSO3M wherein R is
an
unsubstituted C 10-C24 alkyl or hydroxyalkyl group having a C 10-CZ4 alkyl
component,
preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl or
hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero,
typically between
about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is
H or a
cation which can be, for example, a metal cation (e.g., sodium, potassium,
lithium,
calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl
ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated
herein.
When included therein, the laundry detergent compositions of the present
invention typically comprise from about 1% to about 40%, preferably from about
3% to
about 20% by weight of such anionic surfactants.
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Highly preferred cationic surfactants are the water-soluble quaternary
ammonium
compounds useful in the present composition having the formula :
R1R2R3R4N+X-
wherein RI is C8-C16 alkyl, each of R2, R3 and R4 is independently CI-C4
alkyl, C l -
C4 hydroxy alkyl, benzyl, and -(C2H40)XH where x has a value from 2 to 5, and
X is an
anion. Not more than one of R2, R3 or R4 should be benzyl.
When included therein, the detergent compositions of the present invention
typically comprise from 0.2% to about 25%, preferably from about 1% to about
8% by
weight of such cationic surfactants.
When included therein, the detergent compositions of the present invention
typically comprise from 0.2% to about 15%, preferably from about I% to about
10% by
weight of such ampholytic surfactants.
When included therein, the detergent compositions of the present invention
typically comprise from 0.2% to about 15%, preferably from about 1% to about
10% by
weight of such zwitterionic surfactants.
When included therein, the detergent compositions of the present invention
typically comprise from 0.2% to about 15%, preferably from about 1% to about
10% by
weight of such semi-polar nonionic surfactants.
The detergent composition of the present invention can further comprise a
cosurfactant selected from the group of primary or tertiary amines.
Suitable primary amines for use herein include amines according to the formula
R1NH2 wherein RI is a C6-C12, preferably C6-C10 alkyl chain or R4X(CH2)n, X is
-0-, -C(O)NH- or -NH- R4 is a C6-C 12 alkyl chain n is between 1 to 5,
preferably 3. RI
alkyl chains can be straight or branched and can be interrupted with up to 12,
preferably
less than 5 ethylene oxide moieties.
Preferred amines according to the formula herein above are n-alkyl amines.
Suitable amines for use herein can be selected from 1-hexylamine, I -
octylamine, 1-
decylamine and laurylamine. Other preferred primary amines include C8-CIO
oxypropylamine, octyloxypropylamine, 2-ethyihexyl-oxypropylamine, lauryl amido
propylamine and amido propylamine.
Suitable tertiary amines for use herein include tertiary amines having the
formula
R 1 R2R3N wherein R I and R2 are C 1-C8 alkyl chains or
R5
-C CH2-CH-O)H
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R3 is either a C6-C12, preferably C6-C10 alkyl chain, or R3 is R4X(CH2)n,
whereby X
is -0-, -C(O)NH- or -NH-,R4 is a C4-C12, n is between I to 5, preferably 2-3,
R5 is H
or C 1-C2 alkyl and x is between I to 6.
R3 and R4 can be linear or branched ; R3 alkyl chains can be interrupted with
up
to 12, preferably less than 5, ethylene oxide moieties.
Preferred tertiary amines are R 1 R2R3N where RI is a C6-C12 alkyl chain, R2
and R3 are C 1-C3 alkyl or
R5
-~ CH2-CH-O)H
where R5 is H or CH3 and x = 1-2.
Also preferred are the amidoamines of the formula:
0
11
R1-C-NH-(CH2 n N-(R2 2
wherein R1 is C6-C12 alkyl; n is 2-4,
preferably n is 3; R2 and R3 is C1-C4
Most preferred amines of the present invention include 1-octylamine, 1-
hexylamine, 1-decylamine, 1-dodecylamine,C8-10oxypropylamine, N coco 1-
3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl
bis(hydroxyethyl)amine, coco bis(hydroxyethyl)amine, lauryl amine 2 moles
propoxylated, octyl amine 2 moles propoxylated, lauryl
amidopropyldimethylamine, C8-
amidopropyldimethylamine and C10 amidopropyldimethylamine.
The most preferred amines for use in the compositions herein are 1-hexylamine,
1-octylamine, 1-decylamine, 1-dodecylamine. Especially desirable are n-
dodecyldimethylamine and bishydroxyethylcoconutalkylamine and oleylamine 7
times
ethoxylated, lauryl amido propylamine and cocoamido propylamine.
Odor Control Agent
The compositions for odor control are of the type disclosed in U.S. Pats.
5,534,165; 5,578,563; 5,663,134; 5,668,097; 5,670,475; and 5,714,137, Trinh et
al.
issued Jul. 9, 1_996; Nov. 26, 1996; Sep. 2, 1997; Sep. 16, 1997; Sep. 23,
1997; and Feb.
3, 1998 respectively. 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
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As used herein, the term "cyclodextrin" includes any of the known
cyclodextrins
such as unsubstituted cyclodextrins containing from six to twelve glucose
units,
especially, alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and/or
their
derivatives and/or mixtures thereof. The alpha-cyclodextrin consists of six
glucose units,
the beta-cyclodextrin consists of seven glucose units, and the gamma-
cyclodextrin
consists of eight glucose units arranged in 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, which 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
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.
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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 -CH2CH2-OH group; branched cyclodextrins such as maltose-
bonded cyclodextrins; cationic cyclodextrins such as those containing 2-
hydroxy-3-
(dimethylamino)propyl ether, wherein R is CH2-CH(OH)-CH2-N(CH3)2 which is
cationic at low pH; quaternary ammonium, e.g., 2-hydroxy-3-
(trimethylammonio)propyl
ether chloride groups, wherein R is CH2-CH(OH)-CH2-N+(CH3)3Cl-; anionic
cyclodextrins such as carboxymethyl cyclodextrins, cyclodextrin sulfates, and
cyclodextrin succinylates; amphoteric cyclodextrins such as
carboxymethyl/quaternary
ammonium cyclodextrins; cyclodextrins wherein at least one glucopyranose unit
has a 3-
6-anhydro-cyclomalto structure, e.g., the mono-3-6-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; and mixtures
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 1, 1969; 3,459,731,
Gramera et al.,
issued Aug. 5, 1969; 3,553,191, Parmerter et al., issued Jan. 5, 1971;
3,565,887,
Parmerter et al., issued Feb. 23, 1971; 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..
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
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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 typically have a degree of substitution of from about
1 to about
18, preferably from about 3 to about 16. A known methylated 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 12.6. 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
Wacker
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
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-
cyclodextrin, 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.
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. It is preferable that the
treated fabric
contains 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.
Low Molecular Weight Polyols
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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
the present invention enhances the formation of the cyclodextrin inclusion
complexes as
the fabric dries.
It is believed that the polyols' 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 cyclodextrin cavity that is unable to be filled by
some malodor
molecules of relatively smaller sizes. 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 metallic salts are selected from the group
consisting of
copper salts, zinc salts, and mixtures thereof.
Copper salts have some antimicrobial 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,
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comprising at least slightly water-soluble salts of acylacetone, including
copper salts and
zinc salts.
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. Highly-
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 ZnC12. 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
are
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
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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, etc. which form water-insoluble
salts.
(d). Zeolites
When the clarity of the solution is not needed, and the solution is not
sprayed on
fabrics, other optional odor absorbing materials, e.g., zeolites and/or
activated carbon,
can also be used. A preferred class of zeolites is characterized as
"intermediate"
silicate/aluminate zeolites. The intermediate zeolites are characterized by
Si02/A102
molar ratios of less than about 10. Preferably the molar ratio of Si02/A1O2
ranges from
about 2 to about 10. The intermediate zeolites have an advantage over the
"high"
zeolites. The intermediate zeolites have a higher affinity for amine-type
odors, they are
more weight efficient for odor absorption because they have a larger surface
area, and
they are more moisture tolerant and retain more of their odor absorbing
capacity in water
than the high zeolites. A wide variety of intermediate zeolites suitable for
use herein are
commercially available as Valfor CP301-68, Valfor 300-63, Valfor CP300-35,
and
Valfor CP300-56, available from PQ Corporation, and the CBV 100 series of
zeolites
from Conteka.
Zeolite materials marketed under the trade name Abscents and Smellrite ,
available from The Union Carbide Corporation and UOP are also preferred. These
materials are typically available as a white powder in the 3-5 micron particle
size range.
Such materials are preferred over the intermediate zeolites for control of
sulfur-
containing odors, e.g., thiols, mercaptans.
(e). Activated Carbon
The carbon material suitable for use in the present invention is the material
well
known in commercial practice as an absorbent for organic molecules and/or for
air
purification purposes. Often, such carbon material is referred to as
"activated" carbon or
"activated" charcoal. Such carbon is available from commercial sources under
such trade
names as; Calgon-Type CPG ; Type PCB ; Type SGL ; Type CAL ; and Type OL .
(f). Mixtures Thereof
Mixtures of the above materials are desirable, especially when the mixture
provides control over a broader range of odors.
Perfume
The fabric care 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 scent signal 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
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about 0.001% to about 0.5%, 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.
When long lasting fragrance odor on fabrics is desired, it is preferred to use
at
least an effective amount of substantive perfume ingredients. Nonlimiting
examples of
such preferred ingredients are given in U.S. Pat. Nos. 5,500,138 and
5,652,206, issued
Mar. 19, 1996 and July 29, 1997, respectively, to Bacon et al. It is
also preferred to use materials that can slowly
release perfume ingredients after the fabric is treated by the fabric care
composition of
this invention. Examples of materials of this type are given in U.S. Pat.
5,531,910,
Severns et al., issued July 2, 1996.
As used herein, perfume includes fragrant substance or mixture of substances
including natural (i.e., obtained by extraction of flowers, herbs, leaves,
roots, barks,
wood, blossoms or plants), artificial (i.e., a mixture of different nature
oils or oil
constituents) and synthetic (i.e., synthetically produced) odoriferous
substances. Such
materials are often accompanied by auxiliary materials, such as fixatives,
extenders,
stabilizers and solvents. These auxiliaries are also included within the
meaning of
"perfume", as used herein. Typically, perfumes are complex mixtures of a
plurality of
organic compounds.
Examples of perfume ingredients useful in the perfumes of the present
invention
compositions include, but are not limited to, those materials disclosed in
said patents.
The perfumes useful in the present invention compositions are preferably
substantially free of halogenated materials and nitromusks.
Suitable solvents, diluents or carriers for perfumes ingredients mentioned
above
are for examples, ethanol, isopropanol, diethylene glycol, monoethyl ether,
dipropylene
glycol, diethyl phthalate, triethyl citrate, etc. The amount of such solvents,
diluents or
carriers incorporated in the perfumes is preferably kept to the minimum needed
to
provide a homogeneous perfume solution.
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Perfume can be present at a level of from 0% to about 15%, preferably from
about 0.1% to about 8%, and more preferably from about 0.2% to about 5%, by
weight of
the finished fabric care composition.
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.
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 100:1, 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
octanol/water partition
coefficient P. The octanol/water 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
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high values, they are more conveniently given in the form of their logarithm
to the base
10, logP. Thus the preferred perfume hydrophilic perfume ingredients of this
invention
have logP of about 3.5 or smaller, preferably of about 3.0 or smaller.
The logP of many perfume ingredients have been reported; for example, the
TM
Pomona92 database, available from Daylight Chemical Information Systems, Inc.
(Daylight CIS), Irvine, California, contains many, along with citations to the
original
literature. However, the logP values are most conveniently calculated by the
"CLOGP"
program, also available from Daylight CIS. This program also lists
experimental logP
values when they are available in the Pomona92 database. The "calculated logP"
(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). 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
estimates for this physicochemical property, are used instead of the
experimental logP
values in the selection of perfume ingredients which are useful in the present
invention.
Non-limiting examples of the more preferred hydrophilic perfume ingredients
are
allyl amyl glycolate, ally] caproate, amyl acetate, amyl propionate, anisic
aldehyde, anisyl
acetate, anisole, benzaldehyde, benzyl acetate, benzyl acetone, benzyl
alcohol, benzyl
formate, benzyl iso valerate, benzyl propionate, beta gamma hexenol, calone,
camphor
gum, laevo-carveol, d-carvone, laevo-carvone, cinnamic alcohol, cinnamyl
acetate,
cinnamic alcohol, cinnamyl formate, cinnamyl propionate, cis-jasmone, cis-3-
hexenyl
acetate, coumarin, cuminic alcohol, cuminic aldehyde, Cyclal C,
cyclogalbanate,
dihydroeuginol, dihydro isojasmonate, dimethyl benzyl carbinol, dimethyl
benzyl
carbinyl acetate, ethyl acetate, ethyl aceto acetate, ethyl amyl ketone, ethyl
anthranilate,
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, for acetate (tricyclo decenyl acetate), fructone, frutene
(tricyclo 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 cyclo
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
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acetate, methyl cinnamate, methyl dihydrojasmonate, methyl eugenol, methyl
heptenone,
methyl heptine carbonate, methyl heptyl ketone, methyl hexyl ketone, methyl
isobutenyl
tetrahydropyran, methyl-N-methyl anthranilate, methyl beta naphthyl ketone,
methyl
phenyl carbinyl acetate, methyl salicylate, nerol, nonalactone, octalactone,
octyl alcohol
(octanol-2), para-anisic aldehyde, pars-cresol, para-cresyl methyl ether, para
hydroxy
phenyl butanone, para-methoxy acetophenone, 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 mixtures thereof.
Nonlimiting examples of other preferred hydrophilic perfume ingredients which
can be used in perfume compositions of this invention are ally] 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
nitrile, 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,
The use of small amounts of
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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, lilial, 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.
Examples of these ingredients are 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, for acetate, florhydral, fructone, frutene,
heliotropin, keone,
indole, iso cyclo citral, isoeugenol, lyral, methyl heptine carbonate,
linalool, 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 ingredients minimizes the level of organic
material that is
released into the atmosphere.
Antimicrobial Active
Optionally, the fabric care 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 2%, more preferably from about 0.002% to
about
1%, even more preferably from about 0.003% to about 0.3%, by weight of the
usage
composition. The effective antimicrobial active can function as
disinfectants/sanitizers,
and is useful in providing protection against organisms that become attached
to the
fabrics.
Given below are nonlimiting examples of antimicrobial actives which are useful
in the present invention:
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Pyrithiones, especially the zinc complex (ZPT); Octopirox; Parabens, including
Methylparaben, Propylparaben, Butylparaben, Ethylparaben, Isopropylparaben,
Isobutylparaben, Benzylparaben, Sodium Methylparaben, and Sodium
Propylparaben;
DMDM Hydantoin (Glydant); Methylchloroisothiazolinone/methylisothiazolinone
TM
(Kathon CG); Sodium Sulfite; Sodium Bisulfite; Imidazolidinyl Urea;
Diazolidinyl Urea
(GermailTM 2); Sorbic Acid/Potassium Sorbate; Dehydroacetic Acid/Sodium
Dehydroacetate; Benzyl Alcohol; Sodium Borate; 2-Bromo-2-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 Hydroxymethylglycinate; Polymethoxy Bicyclic Oxazolidine;
Dimethoxane; Thimersol; Dichlorobenzyl alcohol; Captan; Chlorphenenesin;
Dichlorophene; Chlorbutanol; Phenoxyethanol; Phenoxyisopropanol; Halogenated
Diphenyl Ethers; 2,4,4'-trichloro-2'-hydroxy-diphenyl ether (Triclosan); 2,2'-
dihydroxy-5,5'-dibromo-diphenyl ether;
Phenolic Compounds - (including phenol and its homologs, mono- and poly-alkyl
and
aromatic halophenols, resorcinol and its derivatives, bisphenolic compounds
and
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-Hexyl o-Chlorophenol, n-Heptyl o-Chlorophenol, o-Benzyl p-
Chlorophenol, o-benzyl-m-methyl p-Chlorophenol, o-Benzyl-m, m-dimethyl p-
Chlorophenol, o-Phenylethyl p-Chlorophenol, o-Phenylethyl-m-methyl p-
Chlorophenol,
3-Methyl p-Chlorophenol, 3,5-Dimethyl 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-
Chiorophenol, 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-
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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, tert-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, 5-methyl-2-pentylphenol, 4-
isopropyl-3-methylphenol, para-chloro-meta-xylenol (PCMX), 5-Chloro-2-
hydroxydiphenylmethane; 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 his (4-chiorophenol), 2,2'-methylene 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 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 actives 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, Hydastis carradensis,
Berberidaceae. daceae, Ratanhiae and Curcuma longa. 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, camphene, 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 are antibacterial metal salts. This class generally
includes
salts of metals in groups 3b-7b, 8 and 3a-5a. Specifically are the salts of
aluminum,
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zirconium, zinc, silver, gold, copper, lanthanum, tin, mercury, bismuth,
selenium,
strontium, scandium, yttrium, cerium, praseodymiun, 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
TM
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 Witco/Sherex), and Hyamine
(available from Lonza); (2) di(C6-C 14)alkyl di-short chain (CI-4 alkyl and/or
hydroxyalkyl) quaternary such as Bardac products of Lonza. These quaternary
compounds contain two relatively short chains, e.g., C14 alkyl and/or hydroxy
alkyl
groups and two C6_12, preferably C6-10, and more preferably C8, alkyl
groups,(3) N-(3-
chloroallyl) hexaminium chlorides such as Dowicide and Dowicil available
from
Dow; (4) benzethonium chloride such as Hyamine 1622 from Rohm & Haas; (5)
methylbenzethonium chloride represented by Hyamine I OX supplied by Rohm &
Haas,
(6) cetylpyridinium chloride such as Cepacol chloride available from of
Merrell Labs.
Tm
Examples of the preferred dialkyl quaternary compounds are di(C8-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 preferably 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%, preferably from
about
0.006% to about 1.2%, and more preferably from about 0.1 % 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
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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.
Bi uanides. 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.
Other useful biguanide compounds include Cosmoci CQ , Vantocil IB,
including poly (hexamethylene biguanide) hydrochloride. Other useful cationic
antimicrobial agents include the bis-biguanide alkanes. Usable water soluble
salts of the
above are chlorides, bromides, sulfates, alkyl sulfonates such as methyl
sulfonate and
ethyl sulfonate, phenylsulfonates such as p-methylphenyl sulfonates, nitrates,
acetates,
gluconates, and the like.
Examples of suitable bis biguanide compounds are chlorhexidine; 1,6-bis-(2-
ethylhexylbiguanidohexane)dihydrochloride; I ,6-di-(N 1,N 1'-phenyldiguanido-
N5,N5')-
hexane tetrahydrochloride; 1 ,6-di-(N 1,N 1'-phenyl-N 1,N 1'-methyldiguanido-
N5,N5')-
hexane dihydrochloride; 1,6-di(N1,N1'-o-chlorophenyldiguanido-N5,N5')-hexane
dihydrochloride; 1,6-di(N1,N1'-2,6-dichlorophenyldiguanido-N5,N5')hexane
dihydrochloride; 1,6-di[N1,N1'-.beta.-(p-methoxyphenyl) diguanido-N5,N5']-
hexane
dihydrochloride; 1,6-di(N1,N1'-.alpha. -methyl-.beta.-phenyldiguanido-N5,N5')-
hexane
dihydrochloride; 1,6-di(N1,N1'-p-nitrophenyldiguanido-N5,N5')hexane
dihydrochloride;.omega.:.omega.'-di-(N 1,N 1'-phenyldiguanido-N5,N5')-di-n-
propylether
dihydrochloride;.omega:omega'-di(N 1,N 1'-p-chlorophenyldiguanido-N5,N5')-di-n-
propylether tetrahydrochloride; 1,6-di(N1,N1'-2,4-dichlorophenyldiguanido-
N5,N5')hexane tetrahydrochloride; 1 ,6-di (N 1,N 1'-p-methylphenyldiguanido-
N5,N5')hexane dihydrochloride; 1,6-di(N1,N1'-2,4,5-trichlorophenyldiguanido-
N5,N5')hexane tetrahydrochloride; 1 ,6-di[N 1,N 1'-.alpha.-(p-chlorophenyl)
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ethyldiguanido-N5,N5'] hexane dihydrochloride;.omega.:.omega.'di(Nl, Nl'-p-
chlorophenyldiguanido-N5,N5')m-xylene dihydrochloride; 1,1 2-di(N 1,N l'-p-
chlorophenyldiguanido-N5,N5') dodecane dihydrochloride; 1,10-di(N1,Nl'-
phenyldiguanido-N5,N5')-decane tetrahydrochloride; 1,12-di(N1,Nl'-
phenyldiguanido-
N5,N5') dodecane tetrahydrochloride; 1,6-di(NI,NI'-o-chlorophenyldiguanido-
N5,N5')
hexane dihydrochloride; 1,6-di(N1,N1'-p-chlorophenyldiguanido-N5,N5')-hexane
tetrahydrochloride; ethylene bis (1-tolyl biguanide); ethylene bis (p-tolyl
biguanide);
ethylene bis(3,5-dimethylphenyl biguanide); ethylene bis(p-tert-amylphenyl
biguanide);
ethylene bis(nonylphenyl biguanide); ethylene bis (phenyl biguanide); ethylene
bis (N-
butylphenyl biguanide); ethylene bis (2,5-diethoxyphenyl biguanide); ethylene
bis(2,4-
dimethylphenyl biguanide); ethylene bis(o-diphenylbiguanide); ethylene
bis(mixed amyl
naphthyl biguanide); N-butyl ethylene bis(phenylbiguanide); trimethylene bis(o-
tolyl
biguanide); N-butyl trimethylene bis(phenyl biguanide); and the corresponding
pharmaceutically acceptable salts of all of the above such as the acetates;
gluconates;
hydrochlorides; hydrobromides; citrates; bisulfites; fluorides; polymaleates;
N-
coconutalkylsarcosinates; phosphites; hypophosphites; perfluorooctanoates;
silicates;
sorbates; salicylates; maleates; tartrates; fumarates;
ethylenediaminetetraacetates;
iminodiacetates; cinnamates; thiocyanates; arginates; pyromellitates;
tetracarboxybutyrates; benzoates; glutarates; monofluorophosphates; and
perfluoropropionates, and mixtures thereof. Preferred antimicrobials from this
group are
1,6-di-(N1,Nl'-phenyldiguanido-N5,N5')-hexane tetrahydrochloride; 1,6-
di(N1,N1'-o-
chlorophenyldiguanido-N5,N5')-hexane dihydrochloride; 1,6-di(Nl,N1'-2,6-
dichlorophenyldiguanido-N5,N5')hexane dihydrochloride; 1,6-di(N1,NI'-2,4-
dichlorophenyldiguanido-N5,N5')hexane tetrahydrochloride; 1,6-di[N1,N1'-
.alpha.-(p-
chlorophenyl) ethyldiguanido-N5,N5'] hexane
dihydrochloride;.omega.:.omega.'di(N1,
N1'-p-chlorophenyldiguanido-N5,N5')m-xylene dihydrochloride; 1,12-di(N1,N1'-p-
chlorophenyldiguanido-N5,N5') dodecane dihydrochloride; 1,6-di(Nj,N1'-o
chlorophenyldiguanido-N5,N5') hexane dihydrochloride; 1,6-di(N1,N1'-p-
chlorophenyldiguanido-N5,N5')-hexane tetrahydrochloride; and mixtures thereof;
more
preferably, I ,6-di(N 1,N 1'-o-chlorophenyldiguanido-N5,N5')-hexane
dihydrochloride;
1,6-di(N1,Nl'-2,6-dichlorophenyldiguanido-N5,N5')hexane dihydrochloride; 1,6-
di(NI,NI'-2,4-dichlorophenyldiguanido-N5,N5')hexane tetrahydrochloride; 1,6-
di[N1,N1'-.alpha.-(p-chlorophenyl) ethyldiguanido-N5,N5'1 hexane
dihydrochloride;.omega.:.omega.'di(NI, N1'-p-chlorophenyldiguanido-N5,N5')m-
xylene
dihydrochloride; 1,12-di(N 1,N 1'-p-chlorophenyldiguanido-N5,N5') dodecane
dihydrochloride; 1,6-di(N1,N1'-o-chlorophenyldiguanido-N5,N5') hexane
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dihydrochloride; 1,6-di(N1,N1'-p-chlorophenyldiguanido-N5,N5')-hexane
tetrahydrochloride; and mixtures thereof. As stated hereinbefore, the bis
biguanide of
choice is chlorhexidine its salts, e.g., digluconate, dihydrochloride,
diacetate, and
mixtures thereof.
The surfactants, when added to the antimicrobials tend to provide improved
antimicrobial action. This is especially true for the siloxane surfactants,
and especially
when the siloxane surfactants are combined with the chlorhexidine
antimicrobial actives.
Aminocarboxylate Chelators
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/preservatives in the compositions of the present invention.
Aminocarboxylate chelators can potentiate the performance of many of the
cationic,
anionic, and nonionic antimicrobials/preservatives, phenolic compounds, and
isothiazolinones, that are used as antimicrobials/preservatives 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
DowicilT 200, Dowicide MQ, PreventolMDI, benzalkonium chloride, cetrimonium,
T myristalkonium chloride, cetylpyridinium chloride, lauryl pyridinium
chloride, and the
like. Nonlimiting examples of useful anionic antimicrobials/preservatives
which are
enhanced by aminocarboxylate chelators are sorbic acid and potassium sorbate.
Nonlimiting examples of useful nonionic antimicrobials/preservatives which are
potentiated by aminocarboxylate chelators are DMDM hydantoin, phenethyl
alcohol,
TM
monolaurin, imidazolidinyl urea, andBromopol(2-bromo-2-nitropropane-l,3-diol).
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Examples of useful phenolic antimicrobials/preservatives potentiated by these
chelators are chloroxylenol, phenol, tert-butyl hydioxyanisole, salicylic
acid, resorcinol,
and sodium o-phenyl phenate. Nonlimiting examples of isothiazolinone
antimicrobials/preservatives which are enhanced by aminocarboxylate chelators
are
Kathon, Proxe 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.
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 solubilized, water-soluble,
antimicrobial
preservative, to protect the fabric care polysaccharide with globular
structure and/or other
easily degradable organic ingredients such as cyclodextrin, 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 care polysaccharide with
globular structure.
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
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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
Pseudomonas species.
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 U.S. Pats. 5,534,165; 5,578,563; 5,663,134;
5,668,097;
5,670,475; and 5,714,137, Trinh et al. issued Jul. 9, 1996; Nov. 26, 1996;
Sep. 2, 1997;
Sep. 16, 1997; Sep. 23, 1997; and Feb. 3, 1998.
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
antimicrobial
preservatives are those that are water-soluble and are effective at low
levels. Water-
soluble 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 the composition is deposited in order
to
eliminate odors produced by microorganisms. Instead, it is preferably being
used to
prevent spoilage of the fabric care polysaccharide with globular structure
solution in
order to increase the shelf-life of the composition. Preferred levels of
preservative are
from 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.
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The preservative can be any organic preservative material which will not cause
damage to fabric appearance, e.g., 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 microorganisms.
Bacteriostatic effects can sometimes be obtained for aqueous compositions by
adjusting the composition pH to an acid pH, e.g., less than about pH 4,
preferably less
than about pH 3, or a basic pH, e.g., greater than about 10, preferably
greater than about
11.
Fabric Softening Active
The fabric care composition herein can optionally contain fabric softening
active.
A liquid rinse-added composition typically contains from about 1% to about
75%,
preferably from about 2% to about 65%, more preferably from about 3% to about
45%,
and even more preferably from about 4% to about 35% by weight of the
composition, of
a fabric softener active. For a dryer-added composition, the levels are from
about I% to
about 99%, preferably from about 10% to about 80%, more preferably from about
20% to
about 70%, and even more preferably from about 25% to about 60% of fabric
softening
active. For a spray-on composition the levels are from about 0.05% to about
10%,
preferably from about 0.1% to about 7%, more preferably from about 0.5% to
about 5%.
The rinse-added fabric care compositions containing fabric softening actives
herein
can comprise liquid compositions that can be either dispersions or clear.
Dispersion Compositions
Stable "dispersion" compositions can be prepared like those disclosed in U.S.
Pat.
No. 4,661,269, issued April 28, 1987, to T. Trinh et al., and in U.S. Pat. No.
5,545,340,
issued Aug. 13, 1996, to Wahl et al.
Suitable optional components in addition to the softening active are disclosed
hereinafter.
The dispersion liquid compositions herein can be both dilute and concentrated,
but are
preferably concentrated.
Clear Compositions
Preferred compositions are concentrate and clear, comprising:
I. from about 2% to about 80%, preferably from about 13% to about 75%, more
preferably from about 17% to about 70%, and even more preferably from about
19% to
about 65%, by weight of the composition, of fabric softening active, having a
phase
transition temperature of less than. about 50 C, preferably less than about 35
C, more
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preferably less than about 20 C, and even more preferably less than about 0 C,
preferably
being biodegradable fabric softening active containing unsaturated alkyl
groups and/or
branched fatty alkyl groups, said unsaturated alkyl groups having an average
Iodine
Value (IV) of at least about 40, a level of polyunsaturation preferably being
at least about
5%, and with the level of C18:3 acyl groups in the starting fatty acyl source
feedstock for
making the said softening active preferably being less than about I % by
weight.
H. less than about 40%, preferably from about 10% to about 35%, more
preferably
from about 12% to about 25%, and even more preferably from about 14% to about
20 /a,
by weight of the composition of principal solvent having a ClogP of from about
-2.0 to
about 2.6, preferably from about -1.7 to about 1.7, and more preferably from
about -1.0
to about 1.0, and preferably having some degree of asymmetry; optionally, but
preferably,
an effective amount, sufficient to improve clarity, of low molecular weight
water soluble
solvents like ethanol, isopropanol, propylene glycol, 1,3-propanediol,
propylene
carbonate, etc.; and optionally, but preferably, an effective amount to
improve clarity, of
water soluble calcium and/or magnesium salt, preferably chloride;
H. optionally, but highly preferred for clear/translucent compositions, at
least an
effective level of principal solvent preferably having a ClogP of from about -
2.0 to about
2.6, more preferably from about -1.7 to about 1.6, and even more preferably
from about -
1.0 to about 1.0, as defined hereinafter, typically at a level that is less
than about 40%,
preferably from about I% to about 25%, more preferably from about 3% to about
8% by
weight of the composition;
III. optionally, but preferably, from about 0.1 % to about 10% by weight,
preferably
from about 0.75 % to about 2.5 % by weight of the composition, and more
preferably
from about 1 % to about 2 % by weight of the composition of electrolyte as
defined
hereinafter;
IV. optionally, but preferably, from 0% to about 15%, preferably from about
0.1 % to
about 7%, and more preferably from about 1% to about 6%, by weight ' of the
composition of phase stabilizer, preferably surfactant containing
alkoxylation, and also
preferably having an HLB of from about 8 to about 20, more preferably from
about 10 to
about 18, and even more preferably from about I 1 to about 15; and
V. the balance water, minor ingredients and/or water soluble solvents.
The preferred principal solvent and/or electrolyte levels, as well as the
identity of
the principal solvent, are selected normally according to the level and
identity of the
softener.
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C1ogP of a solvent is the calculated logarithm to the base 10 of the
octanol/water
partition coefficient (P) of said solvent. ClogP values are conveniently
calculated by the
"CLOGP" program, available from Daylight Chemical Information Systems, Inc.
(Daylight CIS), Irvine, California. 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). The fragment approach is
based on the chemical structure of each ingredient, and takes into account the
numbers
and types of atoms, the atom connectivity, and chemical bonding. Other methods
that
can be used to compute ClogP include, e.g., Crippen's fragmentation method as
disclosed
in J. Chem. Inf. Comput. Sci., 27, 21 (1987); Viswanadhan's fragmentation
method as
disclose in J. Chem. Inf. Comput. Sci., 29, 163 (1989); and Broto's method as
disclosed
in Eur. J. Med. Chem. - Chim. Theor., 19, 71 (1984).
Fabric Softening Actives
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. 5, 1978; 4,161,604,
Elster et al.,
issued July 17, 1979; 4,189,593, Wechsler et al., issued Feb. 19, 1980;
4,339,391,
Hoffman 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 Rieke; 4,237,016, Rudkin, Clint, and Young; 4,885,102, Yamamura et at.,
issued
Dec. 5, 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 published
applications
336,267, Rutzen et a.l. and 423,894, Contor et al. and International Patent WO
91/01295, Trius et at., published Feb. 7, 1991.
Other preferred fabric softening actives for liquid rinse-added compositions
are
disclosed in U.S. Pat. No. 4,661,269, 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. 5,545,340, issued Aug.
13, 1996, to
Wahl et at. Biodegradable unsaturated ester and/or amide linked fabric
softening actives
in concentrated clear compositions are disclosed in U. S. Pat. No. 5,759,990,
issued Jun.
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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 names of Wahl, Trinh, Gosselink, Letton,
and
Sivik. Examples of suitable amine
softening actives that can be used in the present invention are disclosed in
PCT
application WO 99/06509, K. A. Grimm, D. R. Bacon, T. Trinh, E. H. Wahl, and
H. B.
Tordil, published on Feb. 11, 1999.
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 groups, can be use in the
rinse-added
fabric care composition of the present invention. Biodegradable fabric
softening actives
are preferred.
A preferred fabric 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.
These highly unsaturated and/or branched fabric softening actives have the
required
properties for permitting high usage levels to provide additional fabric
appearance
benefits, including recovery of fabric color appearance, improved color
integrity, and
anti-wrinkling benefits. Fabric softening actives with saturated and/or low
degree of
unsaturation, e.g., Iodine Value of less than about 10, and fabric softening
actives with
unsaturated chains having the trans configuration, can normally provide a
better softening
performance per unit weight, but are more difficult to concentrate, thus can
be used in
compositions with lower levels of fabric softening active, typically below
about 30%,
preferably below 25%, more preferably below 20%, by weight of the composition.
Preferred fabric softening actives of the invention comprise a majority of
compounds as follows:
Diester Quaternary Ammonium Fabric Softening Active Compound (DEOA)
(1) The first type of DEQA preferably comprises, as the principal active,
compounds of the formula
{R4-m - N+ - [(CH2)n - Y - R1]m) A-
wherein each R substituent is either hydrogen, a short chain C1-C6, preferably
C1-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 in is 2 or 3; each n is from I to about 4; each Y is -O-(O)C-, -C(O)-O-, -
NR-C(O)-
, or -C(O)-NR-; the sum of carbons in each R1, plus one when Y is -O-(O)C- or -
NR-
C(O) -, is C12-C22, preferably C14-C20, with each R1 being a hydrocarbyl, or
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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 RI groups present.)
(2) A second type of DEQA 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(CH2O(O)CRl)O(O)CR1] C1(-)
where each R is a methyl or ethyl group 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. 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 acy) is the same as that of FA1
mixture
disclosed hereinafter.
These biodegradable quaternary ammonium fabric softening compounds preferably
contain the group C(O)R' which is derived, primarily from saturated fatty
acids, such as
stearic acid, but more preferably derived from partially saturated fatty acids
and/or
partially hydrogenated fatty acids from natural sources, e.g., derived from
animal fat,
such as tallow fatty acids. Also preferred are unsaturated fatty acids, e.g.,
oleic acid, and
polyunsaturated fatty acids, such as those derived from vegetable 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 concentrated, clear fabric softening
compositions of
the present invention.
Mixtures of fatty acids can be used, and are preferred. Nonlimiting examples
of
fatty acids that can be blended, to form fatty acid mixtures (FA's) of this
invention are as
follows:
Fatty Acyl Group FA1 FA2 FA3
C14 0 0 1
C16 3 11 25
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C18 3 4 20
C14:1 0 0 0
C16:1 1 1 0
C18:1 79 27 45
C18:2 13 50 6
C18:3 1 7 0
Unknowns 0 0 3
Total 100 100 100
N 99 125-138 56
cis/trans (C18:1) 5-6 Not Available 7
TPU 14 57 6
FA1 is a partially hydrogenated fatty acid prepared from canola oil, FA2 is a
fatty
acid prepared from soy bean oil, and FA3 is a slightly hydrogenated tallow
fatty acid.
Iodine Value (referred to as "N" 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 the R1 group is derived from, is also used to
define the
level of unsaturation of a fabric softening active. The N 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
about 140, more preferably from about 80 to about 130, and even more
preferably from
about 90 to about 115, 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%. The cis/trans ratio for the unsaturated fatty
acyl groups
is important, with a preferred cis/trans ratio of from 1:1 to about 50:1, the
minimum
being 1:1, preferably at least 3:1, and more preferably from about 4:1 to
about 20:1.
The long chain hydrocabon groups can also comprise branched chains, e.g., from
isostearic acid, for at least part of the groups. The total of active
represented by the
branched chain groups, when they are present, is typically from about I% to
about 100%,
preferably from about 10% to about 70%, more preferably from about 20% to
about 50%.
The unsaturated, including the polyunsaturated, fatty acyl groups not only
provide
surprisingly effective softening, but also provide better absorbency
characteristics, good
antistatic characteristics, and superior recovery after freezing and thawing.
These highly
unsaturated/branched materials provide excellent softening while minimizing
loss of
water absorbency and "greasy" fabric feel. These two characteristics allow one
to use
higher levels of softening active than would be ordinarily desirable, which
provides
several additional benefits, including noticeable color maintenance,
protection, and/or
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recovery for colored fabrics, especially colored cotton and cotton blend
fabrics, improved
anti-wrinkling benefit, improved fiber integrity, i.e., less damage to
fabrics, improved
antistatic benefits, and a high level of softness.
The highly unsaturated materials are also easier to formulate into
concentrated
premixes that maintain their low viscosity and are therefore easier to
process, e.g., pump,
mixing, etc. These highly unsaturated materials with only a low amount of
solvent that
normally is associated with such materials, i.e., from about 5% to about 20%,
preferably
from about 8% to about 25%, more preferably from about 10% to about 20%,
weight of
the total softening active/solvent mixture, are also easier to formulate into
concentrated,
stable dispersion compositions of the present invention, even at ambient
temperatures.
It will be understood that substituents R and R1 can optionally be substituted
with
various groups such as alkoxyl or hydroxyl groups, so long as the R1 groups
maintain
their basically hydrophobic character. The preferred compounds can be
considered to be
biodegradable diester variations of ditallow dimethyl ammonium chloride
(hereinafter
referred to as "DTDMAC"), which is a widely used fabric softening active. A
preferred
long chain DEQA is the DEQA prepared from sources containing high levels of
polyunsaturation, i.e., N,N-di(acyl-oxyethyl)-N,N-dimethyl ammonium chloride,
where
the acyl is derived from fatty acids containing sufficient polyunsaturation.
As used herein, when the diester (m=2) is specified, it can include the
monoester
(m=1) and/or triester (m=3) that is present. Preferably, at least about 70% of
the DEQA
is in the diester form, and from 0% to about 30% can be DEQA monoester. For
softening, under no/low detergent carry-over laundry conditions the percentage
of
monoester should be as low as possible, preferably no more than about 15%.
However,
under high, anionic detergent surfactant or detergent builder carry-over
conditions, some
monoester or monoamide can be preferred. The overall ratios of diester to
monoester, or
diamide to monoamide, are from about 100:1 to about 2:1, preferably from about
50:1 to
about 5:1, more preferably from about 13:1 to about 8:1. Under high detergent
carry-
over conditions, the di/monoester ratio is preferably about 11:1. The level of
monoester,
or monoamide, present can be controlled in manufacturing the DEQA.
The above compounds, used as the biodegradable quatemized ester-amine or
amido-amine, softening material in the practice of this invention, can be
prepared using
standard reaction chemistry. In one synthesis of a diester variation of
DTDMAC, an
amine of the formula RN(CH2CH2OH)2 is esterified at both hydroxyl groups with
an
acid chloride of the formula R1C(O)C1, then quaternized with an alkyl halide,
RX, to
yield the desired reaction product (wherein R and Rl are as defined
hereinbefore).
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However, it will be appreciated by those skilled in the chemical arts that
this reaction
sequence allows a broad selection of agents to be prepared.
Yet another DEQA softening active that is suitable for the formulation of the
concentrated, liquid fabric care compositions of the present invention, has
the above
formula (1) wherein one R group is a C l-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. Such DEQA is a quaternized product of condensation between: (a)-a
fraction of
saturated or unsaturated, linear or branched fatty acids, or of derivatives of
said acids,
said fatty acids or derivatives each possessing a hydrocarbon chain in which
the number
of atoms is between 5 and 21, and (b) triethanolamine, characterized in that
said
condensation product has an acid value, measured by titration of the
condensation
product with a standard KOH solution against a phenolphthalein indicator, of
less than
about 6.5. The acid value is preferably less than or equal to about 5, more
preferably less
than about 3. Indeed, the lower the AV, the better softness performance is
obtained.
The acid value is determined by titration of the condensation product with a
standard KOH solution against a phenolphthalein indicator according to
ISO#53402. The
AV is expressed as mg KOH/g of the condensation product.
For optimum softness benefit, it is preferred that the reactants are present
in a
molar ratio of fatty acid fraction to triethanolamine of from about 1:1 to
about 2.5:1.
It has also been found that the optimum softness performance is also affected
by
the detergent carry-over laundry conditions, and more especially by the
presence of the
anionic surfactant in the solution in which the softening composition is used.
Indeed, the
presence of anionic surfactant that is usually carried over from the wash will
interact with
the softener compound, thereby reducing its performance. Thus, depending on
usage
conditions, the mole ratio of fatty acid/ triethanolamine can be critical.
Accordingly,
where no rinse occurs between the wash cycle and the rinse cycle containing
the
softening compound, a high amount of anionic surfactant will be carried over
in the rinse
cycle containing the softening compound. In this instance, it has been found
that a fatty
acid fraction/triethanolamine mole ratio of about 1.4:1 to about 1.8:1 is
preferred. By
high amount of anionic surfactant, it is meant that the presence of anionic in
the rinse
cycle at a level such that the molar ratio anionic surfactant/cationic
softener compound of
the invention is at least about 1/10.
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The compositions can also contain medium-chain cationic ammonium fabric
softening compound, including DEQAs having the above formula (1) and/or
formula (2),
below, wherein:
each Y is -O-(O)C-, -(R)N-(O)C-, -C(O)-N(R)-, or -C(O)-O-, preferably -O-(O)C-
m is 2 or 3, preferably 2;
each n is 1 to 4, preferably 2;
each R is as defined hereinbefore;
each RI, or YR1 hydrophobic group is a saturated, C8-C14, preferably a C12-14
hydrocarbyl, or substituted hydrocarbyl substituent (the IV is preferably
about 10
or less, more preferably less than about 5), [The sum of the carbons in the
hydrophobic group is the number of carbon atoms in the R1 group, or in the YRI
group when Y is -O-(O)C- or -(R)N-(O)C-.] and the counterion, A-, is the same
as above. Preferably A- does not include phosphate salts.
The saturated C8-C14 fatty acyl groups can be pure derivatives or can be mixed
chainlengths.
Suitable fatty acid sources for said fatty acyl groups are coco, lauric,
caprylic, and
capric acids.
For C12-C14 (or C1 1-C 13) hydrocarbyl groups, the groups are preferably
saturated, e.g., the IV is preferably less than about 10, preferably less than
about 5.
It will be understood that substituents R and RI can optionally be substituted
with
various groups such as alkoxyl or hydroxyl groups, and can be straight, or
branched so
long as the RI groups maintain their basically hydrophobic character.
The DEQA actives described hereinabove can contain a low level of the fatty
acids
which can be unreacted starting material and/or by-product of any partial
degradation,
e.g., hydrolysis, of the softening actives in the finished compositions. It is
preferred that
the level of free fatty acid be low, preferably below about 10%, more
preferably below
about 5%, by weight of the softening active.
Other types of fabric softening actives can be used in the rinse-added fabric
care
compositions of the present invention:
(3) The DEQA actives described hereinabove also include the neutralized amine
softening actives wherein at least one R group is a hydrogen atom. A non-
limiting
example of actives of this type is the chloride salt of (unsaturated
alkoyloxyethyl)(unsaturated alkylamidotrimethylene)methylamine. Other examples
of
suitable amine softening actives are disclosed in PCT application WO 99/06509,
K. A.
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Grimm, D. R. Bacon, T. Trinh, E. H. Wahl, and H. B. Tordil, published on Feb.
11,
1999,
(4) Polyquatemary Ammonium Softening Actives. Fabric softening actives
carrying more than one positive quaternary ammonium charge are also useful in
the
rinse-added compositions of the present invention. An example of this type of
softening
active is that having the formula:
R R 20
N
-R2-N
r1
N N 2AO
R'
wherein each R is H or a short chain C1-C6, preferably C1-C3 alkyl or
hydroxyalkyl
group, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, and the
like, benzyl, or
(R2 O)2-4H; each RI is a C6-C22, 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 C12-C18 alkyl or alkenyl; each R2 is a C1-6 alkylene group,
preferably an
ethylene group; and A- are defined as below. Fabric softening actives having
the
following formula:
CH3 CH3\
N-CH2CH2-N 2CH3SO4e
N ~N
R1 R'
wherein R1 is derived from oleic acid is available from Witco Company.
The following polyquaternary ammonium compounds are disclosed by reference
herein as also suitable for use in this invention: European Patent Application
EP
0,803,498, Al, Robert O. Keys and Floyd E. Friedli, filed April 25, 1997;
British Pat.
808,265, issued Jan. 28, 1956 to Arnold Hoffman & Co., Incorporated; British
Pat.
1,161,552, Koebner and Potts, issued Aug. 13, 1969; DE 4,203,489 Al, Henkel,
published Aug. 12, 1993; EP 0,221,855, Topfl, Heinz, and Jorg, issued Nov. 3,
1986; EP
0,503,155, Rewo, issued Dec. 20, 1991; EP 0,507,003, Rewo, issued Dec. 20,
1991; EPA
0,803,498, published October 29, 1997; French Pat. 2,523,606, Marie-Helene
Fraikin,
Alan Dillarstone, and Marc Couterau, filed Mar. 22, 1983; Japanese Pat. 84-
273918,
Terumi Kawai and Hiroshi Kitamura, 1986; Japanese Pat. 2-011,545, issued to
Kao
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Corp., Jan. 16, 1990; U.S. Pat. 3,079,436, Hwa, issued Feb. 26, 1963; U.S.
Pat.
4,418,054, Green et al., issued Nov. 29, 1983; U.S. Pat. 4,721,512, Topfl,
Abel, and
Binz, issued Jan. 26, 1988; U.S. Pat. 4,728,337, Abel, Topfl, and Riehen,
issued Mar. 1,
1988; U.S. Pat. 4,906,413, Topfl and Binz, issued Mar. 6, 1990; U.S. Pat.
5,194,667,
Oxenrider et al., issued Mar. 16, 1993; U.S. Pat. 5,235,082, Hill and Snow,
issued Aug.
10, 1993; U.S. Pat. 5,670,472, Keys, issued Sep. 23, 1997; Weirong Miao, Wei
Hou, Lie
Chen, and Zongshi Li, Studies on Multifunctional Finishing Agents, Riyong
Huaxue
Gonye, No. 2, pp. 8-10, 1992; Yokagaku, Vol 41, No. 4 (1992); and
Disinfection,
Sterilization, and Preservation, 4th Edition, published 1991 by Lea & Febiger,
Chapter
13, pp. 226-30. The products formed by quaternization of
reaction products of fatty acid with
N,N,N',N', tetraakis(hydroxyethyl)-1,6-diaminohexane are also suitable for
this
invention.
(5) Softening active having the formula:
R4-m - N(+) - Rlm A-
wherein each m is 2 or 3, each R1 is a C6-C22, preferably C14-C20, but no more
than
one being less than about C12 and then the other is at least about 16,
hydrocarbyl, or
substituted hydrocarbyl substituent, preferably C10-C20 alkyl or alkenyl, most
preferably
C12-C18 alkyl or alkenyl, and where the Iodine Value of a fatty acid
containing this R1
group is from 0 to about 140, more preferably from about 40 to about 130; with
a
cis/trans ratio of from about 1:1 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 RI can also be a branched chain
C14-C22
alkyl group, preferably a branched chain C16-C18 group; each R is H or a short
chain
C1-C6, preferably C1-C3 alkyl or hydroxyalkyl group, e.g., methyl (most
preferred),
ethyl, propyl, hydroxyethyl, and the like, benzyl, or (R2 0)2-4H; and A- is a
softening
active compatible anion, preferably, chloride, bromide, methylsulfate,
ethylsulfate,
sulfate, and nitrate, more preferably chloride and methyl sulfate;
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(6) Softening active having the formula:
1N CH2
O Rl C I A
II N CH2
Rl C G R2,,-
R
wherein each R, R 1, and A- have the definitions given above; each R2 is a C 1-
6 alkylene
group, preferably an ethylene group; and G is an oxygen atom or an -NR- group;
(7) Softening active having the formula:
N-CH2
RI-<
N-CH2
RI-C-G_R~
wherein R1, R2 and G are defined as above;
(8) Reaction products of substantially unsaturated and/or branched chain
higher
fatty acids with dialkylenetriamines in, e.g., a molecular ratio of about 2:1,
said reaction
products containing compounds of the formula:
R 1-C(O)-NH-R2-NH-R3-NH-C(O) -R 1
wherein R1, R2 are defined as above, and each R3 is a C1-6 alkylene group,
preferably
an ethylene group;
(9) Softening active having the formula:
[RI-C(O)-NR-R2-N(R)2-R3 NR-C(O)-R1]+ A-
wherein R, R1, R2, R3 and A- are defined as above;
(10) The reaction product of substantially unsaturated and/or branched chain
higher fatty acid with hydroxyalkylalkylenediamines in a molecular ratio of
about 2:1,
said reaction products containing compounds of the formula:
R 1-C(O)-NH-R2-N(R3OH)-C(O)-R1
wherein R1, R2 and R3 are defined as above; and
(11) Mixtures thereof.
Examples of Compound (5) are dialkylenedimethylammonium salts such as
dicanoladimethylammonium chloride, dicanoladimethylammonium methylsulfate,
.........................
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di(partially hydrogenated soybean, cis/trans ratio of about
4:1)dimethylammonium
chloride, dioleyldimethylammonium chloride. Dioleyldimethylammonium chloride
and
di(canola)dimethylammonium chloride are preferred. An example of commercially
available dialkylenedimethylammonium salts usable in the present invention is
dioleyldimethylammonium chloride available from Witco Corporation under the
trade
mark Adogen 472.
An example of Compound (6) is 1-methyl-l-oleylamidoethyl-2-
oleylimidazolinium methylsulfate wherein R1 is an acyclic aliphatic C15-C17
hydrocarbon group, R2 is an ethylene group, G is a NH group, R5 is a methyl
group and
A- is a methyl sulfate anion, available commercially from the Witco
Corporation under
the trade :mark! Varisoft 3690.
An example of Compound (7) is I-oleylamidoethyl-2-oleylimidazoline wherein R1
is an acyclic aliphatic C15-C17 hydrocarbon group, R2 is an ethylene group,
and G is a
NH group.
An example of Compound (8) is reaction products of oleic acids with
diethylenetriamine in a molecular ratio of about 2:1, said reaction product
mixture
containing N,N"-dioleoyldiethylenetriamine with the formula:
R1-C(O)-NH-CH2CH2-NH-CH2CH2-NH-C(O)-RI
wherein RI-C(O) is oleoyl group of a commercially available oleic acid derived
from a
vegetable or animal source, such as Emersol 223LL or Emersol 7021, available
from
Henkel Corporation, and R2 and R3 are divalent ethylene groups.
An example of Compound (9) is a difatty amidoamine based softening active
having the formula:
[RI-C(O)-NH-CH2CH2-N(CH3)(CH2CH20H)-CH2CH2-NH-C(O)-Rl]+ CH3SO4-
wherein R1-C(O) is oleoyl group, available commercially from the Witco
Corporation
under the trademark Varisoft 222LT.
An example of Compound (10) is reaction products of oleic acids with N-2-
hydroxyethylethylenediamine in a molecular ratio of about 2:1, said reaction
product
mixture containing a compound of the formula:
R1 -C(O)-NH-CH2CH2-N(CH2CH2OH)-C(O)-R 1
wherein R1-C(O) is oleoyl group of a commercially available oleic acid derived
from a
vegetable or animal source, such as Emersol 223LL or Emersol 7021, available
from
Henkel Corporation.
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The above individual Compounds (actives) can be used individually or as
mixtures.
One type of optional but highly desirable cationic compound which can be used
in combination with the above softening actives are compounds containing one
long
chain acyclic C8-C22 hydrocarbon group, selected from the group consisting of
wherein R7 is hydrogen or a C1-C4 saturated alkyl or hydroxyalkyl group, and
R1 and A-
are defined as herein above;
(12) Acyclic quaternary ammonium salts having the formula:
[R1-N(R5)2-R6] A-
wherein R5 and R6 are C 1-C4 alkyl or hydroxyalkyl groups, and R1 and A- are
defined
as herein above;
(13) Substituted imidazolinium salts having the formula:
O
~N-CH2
Rl- A
N- H2
R7/ 'H
wherein R7 is hydrogen or a C1-C4 saturated alkyl or hydroxyalkyl group, and
R1 and A
are defined as hereinabove;
(14) Substituted imidazolinium salts having the formula:
-CH2
RAC AO
-
HO-R2/ N \RS H2
wherein R5 is a C 1-C4 alkyl or hydroxyalkyl group, and R 1, R2, and A- are as
defined
above;
(15) Alkylpyridinium salts having the formula:
[R4_N] 00 AAO
wherein R4 is an acyclic aliphatic C8-C22 hydrocarbon group and A- is an
anion;
(16) Alkanamide alkylene pyridinium salts having the formula:
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O
RI-8-NH-R2-N 00 AO
wherein R1, R2 and A- are defined as herein above; and
(17) Monoalkyl diquatemary salts, e.g., that having the formula:
A- [R 1- N(+)(R)2-R2 N(+)(R)3] A
wherein R, R1, R2 and A- are defined as herein above; and
(18) Mixtures thereof.
Examples of Compound (12) are the monoalkenyltrimethylammonium salts such
as monooleyltrimethylammonium chloride, monocanolatrimethylammonium chloride,
and soyatrimethylammonium chloride. Monooleyltrimethylammonium chloride and
monocanolatrimethylammonium chloride are preferred. Other examples of Compound
(12) are soyatrimethylammonium chloride available from Witco Corporation under
the
trade mark Adogen 415, erucyltrimethylammonium chloride wherein RI is a C22
hydrocarbon group derived from a natural source; soyadimethylethylammonium
ethylsulfate wherein R1 is a C16-C18 hydrocarbon group, R5 is a methyl group,
R6 is an
ethyl group, and A- is an ethylsulfate anion; and methyl bis(2-
hydroxyethyl)oleylammonium chloride wherein R1 is a C18 hydrocarbon group, R5
is a
2-hydroxyethyl group and R6 is a methyl group.
An example of Compound (14) is 1-ethyl-l -(2-hydroxyethyl)-2-
isoheptadecylimidazolinium ethylsulfate wherein R1 is a C17 hydrocarbon group,
R2 is
an ethylene group, R5 is an ethyl group, and A- is an ethylsulfate anion.
An example of Compound (17) is N-tallow pentamethyl propane diammonium
dichloride, with the formula:
Cl- [(tallowalkyl)- N(+)(CH3)2- CH2 - CH2 - N(+)(CH3)3] Cl-
available from Witco Corporation under the trade mark Adogen 477.
Anion A
In the cationic nitrogenous salts herein, the anion A- , which is any
softening active
compatible anion, provides electrical neutrality. Most often, the anion used
to provide
electrical neutrality in these salts is from a strong acid, especially a
halide, such as
chloride, methylsulfate, bromide, or iodide. However, other anions can be
used, such as
ethylsulfate, acetate, formate, sulfate, carbonate, and the like. Chloride and
methylsulfate
are preferred herein as anion A.
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Dryer-Added Compositions. The fabric softening compound, or compounds,
which are useful in the dryer-added fabric care composition can be selected
from
cationic, nonionic, amphoteric and/or anionic fabric softening compound.
The typical cationic fabric softening compounds include the water-insoluble
quaternary-ammonium fabric softening actives, the most commonly used having
been
di(long alkylchain)dimethylammonium (CI-C4 alkyl)sulfate or chloride,
preferably the
methyl sulfate, compounds including the following:
1) di(tallowalkyl)dimethylammonium methyl sulfate (DTDMAMS);
2) di(hydrogenated tallowalkyl)dimethylammonium methyl sulfate;
3) di(hydrogenated tallowalkyl)dimethylammonium chloride (DTDMAC);
4) distearyldimethylammonium methyl sulfate;
5) dioleyldimethylammonium methyl sulfate;
6) dipalmitylhydroxyethylmethylammonium methyl sulfate;
7) stearylbenzyldimethylammonium methyl sulfate;
8) tallowalkyltrimethylammonium methyl sulfate;
9) (hydrogenated tallowalkyl)trimethylammonium methyl sulfate;
10) (C 12-14 alkyl)hydroxyethyldimethylammonium methyl sulfate;
11) (C12-18 alkyl)di(hydroxyethyl)methylammonium methyl sulfate;
12) di(stearoyloxyethyl)dimethylammonium chloride;
13) di(tallowoyloxyethyl)dimethylammonium methyl sulfate;
14) ditallowalkylimidazolinium methyl sulfate;
15) 1-(2-tallowylamidoethyl)-2-tallowylimidazolinium methyl sulfate; and
16) mixtures thereof.
The currently preferred compounds, like 12) and 13) are more environmentally-
friendly materials, being rapidly biodegradable quaternary ammonium compounds
that
are alternatives to the traditionally used di(long alkyl
chain)dimethylammonium methyl
sulfate. Such quaternary ammonium compounds can contain long chain alk(en)yl
groups
interrupted by functional groups such as carboxy groups. Said materials and
fabric
softening compositions containing them are disclosed in numerous publications
such as
EP-A-0,040,562, and EP-A-0,239,910. Similar quaternary ammonium compounds
useful in the dryer-added compositions are those given hereinabove for rinse-
added
compositions.
Nonionic softening actives can also be used in dryer-added compositions of the
present invention. Typically, such nonionic fabric softening materials have an
HLB of
from about 2 to about 9, more typically from about 3 to about 7. In general,
the materials
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selected should be relatively crystalline, higher melting, (e.g., >25 C,
preferably >40 C)
and relatively water-insoluble.
The level of nonionic softener in the solid composition, when present, is
typically
from about 0.1 % to about 50%, preferably from about 5% to about 30%.
Highly preferred optional nonionic softening agents for use in the present
invention
are C10-C26 acyl sorbitan esters and polyglycerol monostearate. Sorbitan
esters are
esterified dehydration products of sorbitol. Sorbitol, which is typically
prepared by the
catalytic hydrogenation of glucose, can be dehydrated in well known fashion to
form
mixtures of 1,4- and 1,5-sorbitol anhydrides and small amounts of isosorbides.
(See U.S.
Pat. No. 2,322,821, Brown, issued June 29, 1943). The
foregoing types of complex mixtures of anhydrides of sorbitol are collectively
referred to
herein as "sorbitan." It will be recognized that this "sorbitan" mixture will
also contain
some free, uncyclized sorbitol.
The preferred sorbitan ester comprises a member selected from the group
consisting of C10-C26 acyl sorbitan monoesters and C10-C26 acyl sorbitan
diesters. It is
also preferred that a significant amount of trisorbitan esters are present in
the ester
mixture. Ester mixtures having from 20-50% mono-ester, 25-50% di-ester and 10-
35%
of tri- and tetra-esters are preferred. For the purpose of the present
invention, sorbitan
esters containing unsaturation (e.g., sorbitan monooleate) can be utilized.
Details, including formula, of the preferred sorbitan esters can be found in
U.S.
Pat. No. 4,128,484,
Certain derivatives of the preferred sorbitan esters herein, especially the
"lower"
ethoxylates thereof, i.e., mono-, di-, and tri-esters wherein one or more of
the unesterified
-OH groups contain one to about twenty ethylene oxide units (e.g., Tweens )
are also
useful in the composition of the present invention. Therefore, for purposes of
the present
invention, the term "sorbitan ester" includes such derivatives.
Other preferred nonionic softeners are fatty acid partial esters of polyhydric
alcohols, or anhydrides thereof, wherein the alcohol, or anhydride, contains
from about 2
to about 18, preferably from about 2 to about 8, carbon atoms, and each fatty
acid moiety
contains from about 8 to about 30, preferably from about 12 to about 20,
carbon atoms.
Typically, such softeners contain from about one to about 3, preferably about
2 fatty acid
groups per molecule. The polyhydric alcohol portion of the ester can be
ethylene glycol,
glycerol, poly (e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol,
xylitol, sucrose,
erythritol, and/or pentaerythritol.
Dryer-added fabric care compositions employed herein can cpntain as a softener
component, at a level of from about 1% to about 60%, preferably from about 5%
to about
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50%, more preferably from about 10% to about 40%, by weight of the composition
of a
carboxylic acid salt of a tertiary amine and/or ester amine which has the
formula:
rR6 -O
RS N H O-C-R7
R4
wherein R5 is a long chain aliphatic group containing from about 8 to about 30
carbon
atoms; R6 and R4 are the same or different from each other and are selected
from the
group consisting of aliphatic groups containing from about I to about 30,
preferably 1,
carbon atoms, hydroxyalkyl groups of the Formula -R8OH wherein R8 is an
alkylene
group of from about 2 to about 30 carbon atoms, and alkyl ether groups of the
formula
R9(OCnH2n)m- wherein R9 is alkyl or alkenyl of from about I to about 30,
preferably 2
or 3, carbon atoms or hydrogen, n is 2 or 3, and m is from about 1 to about
30, preferably
from I to about 5; wherein R4, R5, R6, R8, and R9 chains can be ester
interrupted
groups; and wherein R7 is selected from the group consisting of unsubstituted
alkyl,
alkenyl, aryl, alkaryl and aralkyl of about 8 to about 30 carbon atoms, and
substituted
alkyl, alkenyl, aryl, alkaryl, and aralkyl of from about 1 to about 30 carbon
atoms
wherein the substituents are selected from the group consisting of halogen,
carboxyl, and
hydroxyl.
This component provides the following benefits: superior odor, and/or improved
fabric softening performance, compared to similar composition which utilize
primary
amine or ammonium compounds as the sole fabric conditioning agent. Either R4,
R5,
R6, R7, R8, and/or R9 chains can contain unsaturation.
Examples of preferred tertiary amines as starting material for the reaction
between
the amine and carboxylic acid to form the tertiary amine salts are:
lauryldimethylamine,
myristyldimethylamine, stearyldimethylamine, tallowdimethylamine,
coconutdimethylamine, dilaurylmethylamine, distearylmethylamine,
ditallowmethylamine, oleyldimethylamine, dioleylmethylamine, lauryldi(3-
hydroxypropyl)amine, stearyldi(2-hydroxyethyl)amine, trilaurylamine,
laurylethylmethylamine, and
C 18H37N(C2H4O)10H-
Preferred carboxylic acids are stearic, oleic, lauric, myristic, palmitic, and
mixtures
thereof.
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The amine salt can be formed by a simple addition reaction, well known in the
art,
disclosed in U.S. Pat. No. 4,237,155, Kardouche, issued Dec. 2, 1980.
Excessive
levels of free amines can result in odor
problems, and generally fee amines provide poorer softening performance than
the
amine salts.
Additional fabric softening materials can be used in addition
or alternatively to the above fabric
softeners. These can be selected from other nonionic, amphoteric and/or
anionic fabric
softening materials. Disclosure of such materials can be found in US
4,327,133; US
4,421,792; US 4,426,299; US 4,460,485; US 3,644,203; US 4,661,269; U.S
4,439,335;
U.S 3,861,870; US 4,308,151; US 3,886,075; US 4,233,164; US 4,401,578; US
3,974,076; US 4,237,016 and EP 472,178.,
Principal Solvent System
The principal solvent, when present, is typically used at an effective level
up to
about 40% by weight, preferably from about 1 % to about 25%, more preferably
from
about 3 % to about 8 %, by weight of the composition. The principal solvent
can be used
most effectively when in combination with high electrolyte level and/or the
phase
stabilizers. E.g., without the high level of electrolyte, the ClogP
of the principal solvent system disclosed therein
would typically be limited to a range of from about 0.15 to about 0.64 as
disclosed in
U.S. Pat. No. 5,747,443.
With the electrolyte present, levels of principal solvent that are
substantially less
than about 15% by weight of the composition can be used, which is preferred
for odor,
safety and economy reasons. The phase stabilizer as defined hereinafter, in
combination
with a very low level of principal solvent is sufficient to provide good
clarity and/or
stability of the composition when the electrolyte is present. Said electrolyte
and/or said
phase stabilizer can be used to either make a composition translucent or
clear, or can be
used to increase the temperature range at which the composition is translucent
or clear.
Principal solvents are efficient in that they provide the maximum advantage
for a
given weight of solvent. It is understood that "solvent", as used herein,
refers to the
effect of the principal solvent and not to its physical form at a given
temperature, since
some of the principal solvents are solids at ambient temperature.
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Principal solvents that can be present are selected to minimize solvent odor
impact in the composition and to provide a low viscosity to the final
composition.
The principal solvents are typically selected from those having a ClogP of
from -
2.0 to 2.6, preferably from -1.7 to 1.6, and more preferably from -1.0 to 1Ø
= The most preferred solvents can be identified by the appearance of the
dilute
treatment compositions used to treat fabrics. These dilute compositions have
dispersions
of fabric softener that exhibit a more uni-lamellar appearance than
conventional fabric
softener compositions. The closer to uni-lamellar the appearance, the better
the
compositions seem to perform. These compositions provide surprisingly good
fabric
softening as compared to similar compositions prepared in the conventional way
with the
same fabric softener active.
Operable solvents have been disclosed, listed under various listings, e.g.,
aliphatic
and/or alicyclic diols with a given number of carbon atoms; monols;
derivatives of
glycerine; alkoxylates of diols; and mixtures of all of the above can be found
in said U.S.
Pats. Nos. 5,759,990 and 5,747,443 and PCT application WO 97/03169 published
on 30
January 1997, the most pertinent disclosure appearing
at pages 24-82 and 94-108 (methods of preparation)
of the said WO 97/03169 specification and in columns 11-54 and 66-78 (methods
of
preparation) of the `443 patent. Some inoperable solvents listed in the `443
disclosure
can be used in mixtures with operable solvents and/or with the high
electrolyte levels
and/or phase stabilizers, to make concentrated fabric softener compositions
that meet the
stability/clarity requirements set forth herein.
There is a clear similarity between the acceptability (formulatability) of a
saturated diol and its unsaturated homologs, or analogs, having higher
molecular weights.
The unsaturated homologs/analogs have the same formulatability as the parent
saturated
solvent with the condition that the unsaturated solvents have one additional
methylene
(viz., CH2) group for each double bond in the chemical formula. In other
words, there is
an apparent "addition rule" in that for each good saturated solvent of this
invention,
which is suitable for the formulation of clear, concentrated fabric softener
compositions,
there are suitable unsaturated solvents where one, or more, CH2 groups are
added while,
for each CH2 group added, two hydrogen atoms are removed from adjacent carbon
atoms
in the molecule to form one carbon-carbon double bond, thus holding the number
of
hydrogen atoms in the molecule constant with respect to the chemical formula
of the
"parent" saturated solvent. This is due to a surprising fact that adding a -
CH2- group to a
solvent chemical formula has an effect of increasing its ClogP value by about
0.53, while
removing two adjacent hydrogen atoms to form a double bond has an effect of
decreasing
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its ClogP value by about a similar amount, viz., about 0.48, thus about
compensating for
the -CH2- addition. Therefore one goes from a preferred saturated solvent to
the
preferred higher molecular weight unsaturated analogs/homologs containing at
least one
more carbon atom by inserting one double bond for each additional CH2 group,
and thus
the total number of hydrogen atoms is kept the same as in the parent saturated
solvent, as
long as the ClogP value of the new solvent remains within the effective range.
The
following are some illustrative examples:
It is possible to substitute for part of the principal solvent mixture a
secondary
solvent, or a mixture of secondary solvents, which by themselves are not
operable as a
principal solvent of this invention, as long as an effective amount of the
operable
principal solvents of this invention is still present in the liquid
concentrated, clear fabric
softener composition. An effective amount of the principal solvents of this
invention is
at least greater than about 1%, preferably more than about 3%, more preferably
more
than about 5% of the composition, when at least about 15% of the softener
active is also
present.
Principal solvents preferred for improved clarity at 50 F are 1,2-hexanediol;
1,2-
pentanediol; hexylene glycol; 1,2-butanediol; 1,4-cyclohexanediol; pinacol;
1,5-
hexanediol; 1,6-hexanediol; and/or 2,4-dimethyl-2,4-pentanediol.
Electrolyte
The clear rinse-added fabric care compositions containing a high level of
fabric
softening agent of this invention can optionally, but preferably, contain an
effective
amount of electrolyte, e.g., from about 0.5% to about 10%, preferably from
about 0.75%
to about 3%, and more preferably from about 1% to about 2%, by weight of the
composition. U.S. Pat. No. 5,759,990, discloses that
the principal solvent in clear formulations should have a ClogP of from about
0.15 to
about 0.64. An effective amount of electrolyte allows the use of principal
solvents with a
ClogP of from about -2.0 to about 2.6, preferably from about -1.7 to about
1.6, and more
preferably from about -1.0 to about 1Ø The principal solvents are also more
effective
with the high electrolyte level, thus allowing one to use less of such
principal solvents.
Electrolyte also helps to alleviate a thickening phenomenon some concentrate,
clear
fabric softener compositions are diluted.
Suitable inorganic salts for use as electrolyte include MgI2, MgBr2, MgCl2,
Mg(N03)2, Mg3(PO4)2, Mg2P2O7, MgSO4, magnesium silicate, NaI, NaBr, NaCl, NaF,
Na3(P04), NaSO3, Na2SO4, Na2SO3, NaNO3i Na103, Na3(PO4), Na4P207, sodium
silicate,
sodium metasilicate, sodium tetrachloroaluminate, sodium tripolyphosphate
(STPP),
Na2Si3O7, sodium zirconate, CaF2, CaC12, CaBr2, Ca12, CaSO4, Ca(N03)2, Ca, KI,
KBr,
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KCI, KF, KNO3, K103, K2S04, K2S03, K3(PO4), K4(P20A), potassium pyrosulfate,
potassium pyrosulfite, LiI, LiBr, LiCI, LiF, LiN03i A1F3, A1C13, A1Br3, A1I3i
A12(SO4)3,
Al(PO4), Al(NO3)3i aluminum silicate; including hydrates of these salts and
including
combinations of these salts or salts with mixed cations e.g. potassium alum
A1K(SO4)2
and salts with mixed anions, e.g. potassium tetrachloroaluminate and sodium
tetrafluoroaluminate. Salts incorporating cations from groups lira, Na, Va,
VIa, Vila,
VIII, Ib, and IIb on the periodic chart with atomic numbers > 13 are also
useful in
reducing dilution viscosity but less preferred due to their tendency to change
oxidation
states and thus they can adversely affect the odor or color of the formulation
or lower
weight efficiency. Salts with cations from group Ia or Ila with atomic numbers
> 20 as
well as salts with cations from the lactinide or actinide series are useful in
reducing
dilution viscosity, but less preferred due to lower weight efficiency or
toxicity. Mixtures
of above salts are also useful.
Organic salts useful in this invention include, magnesium, sodium, lithium,
potassium, zinc, and aluminum salts of the carboxylic acids including formate,
acetate,
proprionate, pelargonate, citrate, gluconate, lactate aromatic acids e.g.
benzoates,
phenolate and substituted benzoates or phenolates, such as phenolate,
salicylate,
polyaromatic acids terephthalates, and polyacids e.g. oxylate, adipate,
succinate,
benzenedicarboxylate, benzenetricarboxylate. Other useful organic salts
include
carbonate and/or hydrogencarbonate (HC03-1) when the pH is suitable, alkyl and
aromatic sulfates and sulfonates e.g. sodium methyl sulfate, benzene
sulfonates and
derivatives such as xylene sulfonate, and amino acids when the pH is suitable.
Electrolytes can comprise mixed salts of the above, salts neutralized with
mixed cations
such as potassium/sodium tartrate, partially neutralized salts such as sodium
hydrogen
tartrate or potassium hydrogen phthalate, and salts comprising one cation with
mixed
anions.
Generally, inorganic electrolytes are preferred over organic electrolytes for
better
weight efficiency and lower costs. Mixtures of inorganic and organic salts can
be used.
Typical levels of electrolyte in the compositions are less than about 10%.
Preferably
from about 0.5 % to about 5% by weight, more preferably from about 0.75 % to
about
2.5 %, and most preferably from about 1 % to about 2 % by weight of the fabric
softener
composition.
Phase Stabilizer
Phase stabilizers are highly desirable to formulating a clear or translucent
fabric softener composition with high electrolyte levels of the present
invention. The
phase stabilizers provide an improved range of temperatures at which the
compositions
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are clear and stable. They allow more electrolyte to be used without
instability. They
can also reduce the amount of principal solvent needed to achieve clarity
and/or stability.
Typical levels of the optional phase stabilizer in the softening compositions
are from
about 0.1 % to about 15%, preferably from about 0.3% to about 7%, more
preferably from
about I% to about 5% by weight of the composition.
The phase stabilizers useful in the compositions of the present invention are
selected surface actives materials commonly comprise of hydrophobic and
hydrophilic
moieties. A preferred hydrophilic moiety is polyalkoxylated group, preferably
polyethoxylated group.
Preferred phase stabilizers are nonionic surfactants derived from saturated
and/or
unsaturated primary, secondary, and/or branched, amine, amide, amine-oxide
fatty
alcohol, fatty acid, alkyl phenol, and/or alkyl aryl carboxylic acid
compounds, each
preferably having from about 6 to about 22, more preferably from about 8 to
about 18,
carbon atoms in a hydrophobic chain, more preferably an alkyl or alkylene
chain, wherein
at least one active hydrogen of said compounds is ethoxylated with _5 50,
preferably <_ 30,
more preferably from about 5 to about 15, and even more preferably from about
8 to
about 12, ethylene oxide moieties to provide an HLB of from about 8 to about
20,
preferably from about 10 to about 18, and more preferably from about 11 to
about 15. he
various stabilizers have different advantages. For example, alkoxylated
cationic
materials or cationic surfactant complexes improve softness and provide
enhanced
wrinkle release benefits. In order to reduce the amount of principal solvent
used, the
preferred phase stabilizers are alkoxylated alkyls, alkoxylated acyl amides,
alkoxylated
alkyl amines or alkoxylated quaternary alkyl ammonium salts, surfactant
complexes, and
mixtures thereof.
Suitable phase stabilizers also include nonionic surfactants with bulky head
groups selected from:
a. surfactants having the formula
R'-C(O)-Y'-[C(R5)]m CH2O(R2O)zH
wherein RI is selected from the group consisting of saturated or unsaturated,
primary,
secondary or branched chain alkyl or alkyl-aryl hydrocarbons; said hydrocarbon
chain
having a length of from about 6 to about 22; Y' is selected from the following
groups: -
0-; -N(A)-; and mixtures thereof; and A is selected from the following groups:
H; R1; -
(R2-O)z-H; -(CH2).CH3i phenyl, or substituted aryl, wherein 0 _< x<_ about 3
and z is from
about 5 to about 30; each R2 is selected from the following groups or
combinations of the
following groups: -(CH2),,- and/or -[CH(CH3)CH2]-; and each R5 is selected
from the
following groups: -OH; and -O(R2O)z-H ; and m is from about 2 to about 4;
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b. surfactants having the formulas:
R5 R5 ::::
R5 R5
R5
wherein Y" = N or 0; and each R5 is selected independently from the following:
-H, -OH, -(CH2)xCH3, -O(OR2)Z H, -OR', - OC(O)R', and -CH(CH2-(OR2),.-H)-CH2-
(OR2)Z.-C(O) R', x and R are as defined above and 5 5 z, z', and z" <_ 20,
more
preferably 5 5 z + z' + z" <_ 20, and most preferably, the heterocyclic ring
is a five
member ring with Y" = 0, one R5 is -H, two R5 are -O-(R2O)z-H, and at least
one R5 is
the following structure -CH(CH2-(OR2)z -H)-CH2-(OR2)z.-C(O) R' with 8:5 z + z'
+ z"
20 and R1 is a hydrocarbon with from 8 to 20 carbon atoms and no aryl group;
c. polyhydroxy fatty acid amide surfactants of the formula:
R2-C(O)-N(Ri)-Z
wherein: each R 1 is H, C 1-C4 hydrocarbyl, C I -C4 alkoxyalkyl, or
hydroxyalkyl; and R2
is a C5-C31 hydrocarbyl moiety; and each Z is a polyhydroxyhydrocarbyl moiety
having
a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the
chain, or an
ethoxylated derivative thereof; and each R' is H or a cyclic mono- or poly-
saccharide, or
alkoxylated derivative thereof; and
d. mixtures thereof.
Suitable phase stabilizers also include surfactant complexes formed by one
surfactant ion being neutralized with surfactant ion of opposite charge or an
electrolyte
ion that is suitable for reducing dilution viscosity and block copolymer
surfactants
comprising polyethylene oxide moieties and propylene oxide moieties
Examples of representative phase stabilizers include:
(1)- Alkyl or alkyl-aryl alkoxylated nonionic surfactants
Suitable alkyl alkoxylated nonionic surfactants are generally derived from
saturated or unsaturated primary, secondary, and branched fatty alcohols,
fatty acids,
alkyl phenols, or alkyl aryl (e.g., benzoic) carboxylic acid, where the active
hydrogen(s)
is alkoxylated with <_ about 30 alkylene, preferably ethylene, oxide moieties
(e.g.
ethylene oxide and/or propylene oxide). These nonionic surfactants for use
herein
preferably have from about 6 to about 22 carbon atoms on the alkyl or alkenyl
chain, and
are in either straight chain or branched chain configuration, preferably
straight chain
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configurations having from about 8 to about 18 carbon atoms, with the alkylene
oxide
being present, preferably at the primary position, in average amounts of <_
about 30 moles
of alkylene oxide per alkyl chain, more preferably from about 5 to about 15
moles of
alkylene oxide, and most preferably from about 8 to about 12 moles of alkylene
oxide.
Preferred materials of this class also have pour points of about 70 F and/or
do. not
solidify in these clear formulations. Examples of alkyl alkoxylated
surfactants with
straight chains include Neodol 91-8, 25-9, 1-9, 25-12, 1-9, and 45-13 from
Shell,
Plurafac B-26 and C-17 from BASF, and Brij 76 and 35 from ICI Surfactants.
Examples of branched alkyl alkoxylated surfactants include Tergitol 15-S-12,
15-S-15,
and 15-S-20 from Union Carbide and Emulphogene BC-720 and BC-840 from GAF.
Examples of alkyl-aryl alkoxylated surfactants include Igepal CO-620 and CO-
710,
from Rhone Poulenc, Triton N-111 and N-150 from Union Carbide, Dowfax 9N5
from
Dow and Lutensol AP9 and AP14, from BASF.
(2)- Alkyl or alkyl-aryl amine or amine oxide nonionic alkoxylated surfactants
Suitable alkyl alkoxylated nonionic surfactants with amine functionality are
generally derived from saturated or unsaturated, primary, secondary, and
branched fatty
alcohols, fatty acids, fatty methyl esters, alkyl phenol, alkyl benzoates, and
alkyl benzoic
acids that are converted to amines, amine-oxides, and optionally substituted
with a
second alkyl or alkyl-aryl hydrocarbon with one or two alkylene oxide chains
attached at
the amine functionality each having <_ about 50 moles alkylene oxide moieties
(e.g.
ethylene oxide and/or propylene oxide) per mole of amine. The amine, amide or
amine-
oxide surfactants for use herein have from about 6 to about 22 carbon atoms,
and are in
either straight chain or branched chain configuration, preferably there is one
hydrocarbon
in a straight chain configuration having about 8 to about 18 carbon atoms with
one or two
alkylene oxide chains attached to the amine moiety, in average amounts of <_
50 about
moles of alkylene oxide per amine moiety, more preferably from about 5 to
about 15
moles of alkylene oxide, and most preferably a single alkylene oxide chain on
the amine
moiety containing from about 8 to about 12 moles of alkylene oxide per amine
moiety.
Preferred materials of this class also have pour points about 70 F and/or do
not solidify
in these clear formulations. Examples of ethoxylated amine surfactants include
Berol
397 and 303 from Rhone Poulenc and Ethomeens C/20, C25, T/25, S/20, S/25 and
Ethodumeens T/20 and T25 from Akzo.
Preferably, the compounds of the alkyl or alkyl-aryl alkoxylated surfactants
and
alkyl or alkyl-aryl amine, amide, and amine-oxide alkoxylated have the
following general
formula:
RIm-Y-[(RZ-O)z-H]p
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wherein each RI is selected from the group consisting of saturated or
unsaturated,
primary, secondary or branched chain alkyl or alkyl-aryl hydrocarbons; said
hydrocarbon
chain preferably having a length of from about 6 to about 22, more preferably
from about
8 to about 18 carbon atoms, and even more preferably from about 8 to about 15
carbon
atoms, preferably, linear and with no aryl moiety; wherein each R2 is selected
from the
following groups or combinations of the following groups: -(CH2)õ- and/or -
[CH(CH3)CH2]-; wherein about 1 < n:5 about 3; Y is selected from the following
groups:
-0-; -N(A)q-; -C(O)O-; - (O+-)N(A)q-; -B-R3-O-; -B-R3-N(A)q-; -B-R3-C(O)O-; -B-
R3-
N(- .O)(A)-; and mixtures thereof; wherein A is selected from the following
groups: H;
R1; -(R2-O)Z-H; -(CH2)xCH3i phenyl, or substituted aryl, wherein 0:5 x <_
about 3 and B is
selected from the following groups: -0-; -N(A)-; -C(0)0-;and mixtures thereof
in
which A is as defined above; and wherein each R3 is selected from the
following groups:
R2; phenyl; or substituted aryl. The terminal hydrogen in each alkoxy chain
can be
replaced by a short chain C14 alkyl or acyl group to "cap" the alkoxy chain. z
is from
about 5 to about 30. p is the number of ethoxylate chains, typically one or
two,
preferably one and m is the number of hydrophobic chains, typically one or
two,
preferably one and q is a number that completes the structure, usually one.
Preferred structures are those in which m = 1, p = 1 or 2, and 5 5 z <_ 30,
and q
can be 1 or 0, but when p = 2, q must be 0; more preferred are structures in
which m = 1,
p = 1 or 2, and 7:5 z <_ 20; and even more preferred are structures in which m
= 1, p = 1
or 2, and 9:5 z <_ 12. The preferred y is 0.
(3)- Alkoxylated and non-alkoxylated nonionic surfactants with bulky head
groups
Suitable alkoxylated and non-alkoxylated phase stabilizers with bulky head
groups are generally derived from saturated or unsaturated, primary,
secondary, and
branched fatty alcohols, fatty acids, alkyl phenol, and alkyl benzoic acids
that are
derivatized with a carbohydrate group or heterocyclic head group. This
structure can
then be optionally substituted with more alkyl or alkyl-aryl alkoxylated or
non-
alkoxylated hydrocarbons. The heterocyclic or carbohydrate is alkoxylated with
one or
more alkylene oxide chains (e.g. ethylene oxide and/or propylene oxide) each
having <_
about 50, preferably _< about 30, moles per mole of heterocyclic or
carbohydrate. The
hydrocarbon groups on the carbohydrate or heterocyclic surfactant for use
herein have
from about 6 to about 22 carbon atoms, and are in either straight chain or
branched chain
configuration, preferably there is one hydrocarbon having from about 8 to
about 18
carbon atoms with one or two alkylene oxide chains carbohydrate or
heterocyclic moiety
with each alkylene oxide chain present in average amounts of S about 50,
preferably <_
about 30, moles of carbohydrate or heterocyclic moiety, more preferably from
about 5 to
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about 15 moles of alkylene oxide per alkylene oxide chain, and most preferably
between
about 8 and about 12 moles of alkylene oxide total per surfactant molecule
including
alkylene oxide on both the hydrocarbon chain and on the heterocyclic or
carbohydrate
moiety. Examples of phase stabilizers in this class are Tween 40, 60, and 80
available
from ICI Surfactants.
Preferably the compounds of the alkoxylated and non-alkoxylated nonionic
surfactants with bulky head groups have the following general formulas:
R'-C(O)-Y'-[C(R5)]n; CH2O(R20)ZH
wherein RI is selected from the group consisting of saturated or unsaturated,
primary,
secondary or branched chain alkyl or alkyl-aryl hydrocarbons; said hydrocarbon
chain
having a length of from about 6 to about 22; Y' is selected from the following
groups: -
0-; -N(A)-; and mixtures thereof; and A is selected from the following groups:
H; R'; -
(R2-O)Z H; -(CH2)XCH3i phenyl, or substituted aryl, wherein 0 _< x _< about 3
and z is from
about 5 to about 30; each R2 is selected from the following groups or
combinations of the
following groups: -(CH2)n- and/or -[CH(CH3)CH2]-; and each R5 is selected from
the
following groups: -OH; and -O(R2O)Z H ; and m is from about 2 to about 4;
Another useful general formula for this class of surfactants is
RS Y" RS ::'::
R5 R5
R5
wherein Y" = N or 0; and each R5 is selected independently from the following:
-H, -OH, -(CH2)xCH3, -(OR2)z-H, -OR', - OC(O)R', and -CH2(CH2-(OR 2)i =-H)-CH2-
(OR2)Z'-C(O) R'. With x R', and R2as defined above in section D above and z,
z', and
z" are all from about 5 _< to _< about 20, more preferably the total number of
z + z' + z"
is from about 5 5 to 5 about 20. In a particularly preferred form of this
structure the
heterocyclic ring is a five member ring with Y" = 0, one R5 is -H, two R5 are -
0-
(R2O)Z H, and at least one R5 has the following structure -CH(CH2-(OR2)Z>.-H)-
CH2-
(OR2)Z'-OC(O) R' with the total z + z' + z" = to from about 8:5 to :5 about 20
and R' is
a hydrocarbon with from about 8 to about 20 carbon atoms and no aryl group.
Another group of surfactants that can be used are polyhydroxy fatty acid amide
surfactants of the formula:
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R6 - C(O) - N(R7) - W
wherein: each R7 is H, C 1-C4 hydrocarbyl, C 1-C4 alkoxyalkyl, or
hydroxyalkyl, e.g., 2-
hydroxyethyl, 2-hydroxypropyl, etc., preferably CI-C4 alkyl, more preferably C
l or C2
alkyl, most preferably Cl alkyl (i.e., methyl) or methoxyalkyl; and R6 is a C5-
C31
hydrocarbyl moiety, preferably straight chain C7-C19 alkyl or alkenyl, more
preferably
straight chain C9-C 17 alkyl or alkenyl, most preferably straight chain C 11-C
17 alkyl or
alkenyl, or mixture thereof; and W is a polyhydroxyhydrocarbyl moiety having a
linear
hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain,
or an
alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. W
preferably
will be derived from a reducing sugar in a reductive amination reaction; more
preferably
W is a glycityl moiety. W preferably will be selected from the group
consisting of -CH2-
(CHOH)n-CH2OH, -CH(CH2OH)-(CHOH)n-CH2OH, -CH2-
(CHOH)2(CHOR')(CHOH)-CH2OH, where n is an integer from 3 to 5, inclusive, and
R'
is H or a cyclic mono- or poly- saccharide, and alkoxylated derivatives
thereof. Most
preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2O.
Mixtures of
the above W moieties are desirable.
R6 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-
isobutyl, N-2-hydroxyethyl, N-1-methoxypropyl, or N-2-hydroxypropyl.
R6-CO-N< can be, for example, cocamide, stearamide, oleamide, lauramide,
myristamide, capricamide, palmitamide, tallowamide, etc.
W can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityI, l -deoxylactityl,
1-
deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
(4)- Alkoxylated cationic quaternary ammonium surfactants
Alkoxylated cationic quaternary ammonium surfactants suitable for this
invention
are generally derived from fatty alcohols, fatty acids, fatty methyl esters,
alkyl
substituted phenols, alkyl substituted benzoic acids, and/or alkyl substituted
benzoate
esters, and/or fatty acids that are converted to amines which can optionally
be further
reacted with another long chain alkyl or alkyl-aryl group; this amine compound
is then
alkoxylated with one or two alkylene oxide chains each having _< about 50
moles
alkylene oxide moieties (e.g. ethylene oxide and/or propylene oxide) per mole
of amine.
Typical of this class are products obtained from the quaternization of
aliphatic saturated
or unsaturated, primary, secondary, or branched amines having one or two
hydrocarbon
chains from about 6 to about 22 carbon atoms alkoxylated with one or two
alkylene
oxide chains on the amine atom each having less than <_ about 50 alkylene
oxide
moieties. The amine hydrocarbons for use herein have from about 6 to about 22
carbon
atoms, and are in either straight chain or branched chain configuration,
preferably there is
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one alkyl hydrocarbon group in a straight chain configuration having about 8
to about 18
carbon atoms. Suitable quaternary ammonium surfactants are made with one or
two
alkylene oxide chains attached to the amine moiety, in average amounts of <
about 50
moles of alkylene oxide per alkyl chain, more preferably from about 3 to about
20 moles
of alkylene oxide, and most preferably from about 5 to about 12 moles of
alkylene oxide
per hydrophobic, e.g., alkyl group. Preferred materials of this class also
have a pour
points below about 70 F and/or do not solidify in these clear formulations.
Examples of
suitable phase stabilizers of this type include Ethoquad 18/25, C/25, and
0/25 from
Akzo and Variquat -66 (soft tallow alkyl bis(polyoxyethyl) ammonium ethyl
sulfate with
a total of about 16 ethoxy units) from Witco.
Preferably, the compounds of the ammonium alkoxylated cationic surfactants
have
the following general formula:
{R'm - Y - [(R2-0)Z - H]p}+ X_
wherein RI and R2 are as defined previously in section D above;
Y is selected from the following groups: = N+-(A)q; -(CH2)n N+-(A)q; -B-(CH2)õ-
N+-(A)2; -(phenyl)-N+-(A)q; -(B-phenyl)-N+-(A)q; with n being from about I to
about 4.
Each A is independently selected from the following groups: H; R'; -(R20)Z H; -
(CH2)XCH3; phenyl, and substituted aryl; where 0:5 x 5 about 3; and B is
selected from
the following groups: -0-; -NA-; -NA2; -C(O)O-; and -C(O)N(A)-; wherein R2 is
defined as hereinbefore; q = I or 2; and
X- is an anion which is compatible with fabric softener actives and adjunct
ingredients.
Preferred structures are those in which in = 1, p = 1 or 2, and about 5 5 z 5
about
50, more preferred are structures in which in = 1, p = I or 2, and about 7 <_
z <_ about 20,
and most preferred are structures in which in = 1, p = I or 2, and about 9<_
z:5 about 12.
(5)- Surfactant complexes
Surfactant complexes are considered to be surfactant ions neutralized with a
surfactant ion of opposite charge or a surfactant neutralized with an
electrolyte that is
suitable for reducing dilution viscosity, an ammonium salt, or a polycationic
ammonium
salt. For the purpose of this invention, if a surfactant complex is formed by
surfactants of
opposite charge, it is preferable that the surfactants have distinctly
different chain lengths
e.g. a long-chain surfactant complexed with a short-chain surfactant to
enhance the
solubility of the complex and it is more preferable that the that the long
chain surfactant
be the amine or ammonium containing surfactant. Long chain surfactants are
defined as
containing alkyl chains with from about 6 to about 22 carbon atoms. These
alkyl chains
can optionally contain a phenyl or substituted phenyl group or alkylene oxide
moieties
between the chain and the head group. Short chain surfactants are defined as
containing
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alkyl chains with less than 6 carbons and optionally these alkyl chains could
contain a
phenyl or substituted phenyl group or alkylene oxide moieties between the
alkyl chain
and the head group. Examples of suitable surfactant complexes include mixtures
of
Armeen APA-10 and calcium xylene sulfonate, Armeen APA-10 and magnesium
chloride, lauryl carboxylate and triethanol amine, linear alkyl benzene
sulfonate and C5-
dimethyl amine, or alkyl ethoxylated sulfate and tetrakis N,N,N'N' (2-
hydroxylpropyl)
ethylenediamine.
Preferably, long-chain surfactants for making complexes have the following
general formula:
R'-Y2
wherein R1 is as hereinbefore from section D above and Y2 can be chosen from
the following structures: -N(A)2; -C(O)N(A)2; -(O+-)N(A)2; -B-R3-N(A)2i -B-R3-
C(O)N(A)2; -B-R3-N(-*O)(A)2; -C02_; -S03-2; -OS03-2; -O(R20).C02-; -
O(R20).S03"2;
and -O(R20)XOSO3-2; with B and R3 as is hereinbefore section D above and 0 <
x<_ 4 .
Preferably, short-chain surfactants for making complexes have the following
general formula:
R4-Y2
wherein R', R3, B, and Y2are as hereinbefore and R4 can be chosen from the
following: -(CH2)yCH3i -(CH2)y-phenyl or -(CH2)y substituted phenyl with 0:5
y5 6.
(6)- Block copolymers obtained by copolymerization of ethylene oxide and
propylene
oxide
Suitable polymers include a copolymer having blocks of terephthalate and
polyethylene oxide. More specifically, these polymers are comprised of
repeating units
of ethylene and/or propylene terephthalate and polyethylene oxide
terephthalate at a
preferred molar ratio of ethylene terephthalate units to polyethylene oxide
terephthalate
units of from about 25:75 to about 35:65, said polyethylene oxide
terephthalate
containing polyethylene oxide blocks having molecular weights of from about
300 to
about 2000. The molecular weight of this polymer is in the range of from about
5,000 to
about 55,000.
Another preferred polymer is a crystallizable polyester with repeat units of
ethylene terephthalate units containing from about 10% to about 15% by weight
of
ethylene terephthalate units together with from about 10% to about 50% by
weight of
polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of
average
molecular weight of from about 300 to about 6,000, and the molar ratio of
ethylene
terephthalate units to polyoxyethylene terephthalate units in the
crystallizable polymeric
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compound is between 2:1 and 6:1. Examples of this polymer include the
commercially
available materials Zelcon 4780 (from DuPont) and Milease T (from ICI).
Highly preferred polymers have the generic formula:
X-(OCH2CH2)n-[O-C(O)-RI-C(O)-O-R2)u-[O-C(O)-RI-C(O)-O)-(CH2CH2O)n-X (1)
in which X can be any suitable capping group, with each X being selected from
the
group consisting of H, and alkyl or acyl groups containing from about 1 to
about 4
carbon atoms, preferably methyl, n is selected for water solubility and
generally is from
about 6 to about 113, preferably from about 20 to about 50, and u is critical
to
formulation in a liquid composition having a relatively high ionic strength.
There should
be very little material in which u is greater than 10. Furthermore, there
should be at least
20%, preferably at least 40%, of material in which u ranges from about 3 to
about 5.
The RI moieties are essentially 1,4-phenylene moieties. As used herein, the
term
"the RI moieties are essentially 1,4-phenylene moieties" refers to compounds
where the
RI moieties consist entirely of 1,4-phenylene moieties, or are partially
substituted with
other arylene or alkarylene moieties, alkylene moieties, alkenylene moieties,
or mixtures
thereof. Arylene and alkarylene moieties which can be partially substituted
for
1,4-phenylene include 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-
naphthylene,
2,2-biphenylene, 4,4-biphenylene and mixtures thereof. Alkylene and alkenylene
moieties which can be partially substituted include ethylene, 1,2-propylene,
1,4-butylene,
1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8-octamethylene,
1,4-cyclohexylene, and mixtures thereof.
For the RI moieties, the degree of partial substitution with moieties other
than
I,4-phenylene should be such that the desired properties of the compound are
not
adversely affected to any great extent. Generally, the degree of partial
substitution
which can be tolerated will depend upon the backbone length of the compound,
i.e.,
longer backbones can have greater partial substitution for 1,4-phenylene
moieties.
Usually, compounds where the RI comprise from about 50% to about 100%
1,4-phenylene moieties (from 0 to about 50% moieties other than 1,4-phenylene)
are
adequate. Preferably, the RI moieties consist entirely of (i.e., comprise
100%)
1,4-phenylene moieties, i.e., each RI moiety is 1,4-phenylene.
For the R2 moieties, suitable ethylene or substituted ethylene moieties
include
ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene, 3-methoxy-1,2-propylene
and
mixtures thereof. Preferably, the R2 moieties are essentially ethylene
moieties,
1,2-propylene moieties or mixture thereof. Surprisingly, inclusion of a
greater percentage
of 1,2-propylene moieties tends to improve the water solubility of the
compounds.
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Therefore, the use of 1,2-propylene moieties or a similar branched equivalent
is
desirable for incorporation of any substantial pari of the polymer in the
liquid fabric
softener compositions. Preferably, from about 75% to about 100%, more
preferably
from about 90% to about 100%, of the R2 moieties are 1,2-propylene moieties.
The value for each n is at least about 6, and preferably is at least about 10.
The
value for each n usually ranges from about 12 to about 113. Typically, the
value for
each n is in the range of from about 12 to about 43.
A more complete disclosure of these polymers is contained in European Patent
Application 185,427, Gosselink, published June 25, 1986.
Other preferred copolymers include surfactants, such as the
polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block
polymers.
The copolymer can optionally contain propylene oxide in an amount up to about
15% by weight. Other preferred copolymer surfactants can be prepared by the
processes
described in U.S. Patent 4,223,163, issued September 16, 1980, Builloty.
Suitable block polyoxyethylene-polyoxypropylene polymeric compounds that meet
the requirements described hereinbefore include those based on ethylene
glycol,
propylene glycol, glycerol, trimethylolpropane and ethylenediamine as
initiator reactive
hydrogen compound. Certain of the block polymer surfactant compounds
designated
PLURONIC and TETRONIC by the BASF-Wyandotte Corp., Wyandotte, Michigan,
are suitable in compositions of the invention.
A particularly preferred copolymer contains from about 40% to about 70% of a
polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend
comprising
about 75%, by weight of the blend, of a reverse block copolymer of
polyoxyethylene and
polyoxypropylene containing 17 moles of ethylene oxide and 44 moles of
propylene
oxide; and about 25%, by weight of the blend, of a block copolymer of
polyoxyethylene
and polyoxypropylene initiated with trimethylolpropane and containing 99 moles
of
propylene oxide and 24 moles of ethylene oxide per mole of trimethylolpropane.
Suitable for use as copolymer are those having relatively high hydrophilic-
lipophilic balance (HLB).
Other polymers useful herein include the polyethylene glycols having a
molecular
weight of from about 950 to about 30,000 which can be obtained from the Dow
Chemical Company of Midland, Michigan. Such compounds for example, have a
melting point within the range of from about 30 C to about 100 C, can be
obtained at
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molecular weights of 1,450, 3,400, 4,500, 6,000, 7,400, 9,500, and 20,000.
Such
compounds are formed by the polymerization of ethylene glycol with the
requisite
number of moles of ethylene oxide to provide the desired molecular weight and
melting
point of the respective polyethylene glycol.
(7)- Alkyl amide alkoxylated nonionic surfactants
Suitable surfactants have the formula:
R - C(O) - N(R4)n - [(R1 O)x(R20)yR3]m
wherein R is C7_21 linear alkyl, C7_21 branched alkyl, C7_21 linear alkenyl,
C7_21
branched alkenyl, and mixtures thereof. Preferably R is C8_18 linear alkyl or
alkenyl.
R' is -CH2-CH2- , R2 is C3-C4 linear alkyl, C3-C4 branched alkyl, and mixtures
thereof; preferably R2 is -CH(CH3)-CH2-. Surfactants which comprise a mixture
of RI
and R2 units preferably comprise from about 4 to about 12 -CH2-CH2- units in
combination with from about I to about 4 -CH(CH3)-CH2- units. The units may be
alternating or grouped together in any combination suitable to the formulator.
Preferably
the ratio of R1 units to R2 units is from about 4 : 1 to about 8 : 1.
Preferably an R2 unit
(i.e. -C(CH3)H-CH2-) is attached to the nitrogen atom followed by the balance
of the
chain comprising from about 4 to 8 -CH2-CH2- units.
R3 is hydrogen, C1-C4 linear alkyl, C3-C4 branched alkyl, and mixtures
thereof;
preferably hydrogen or methyl, more preferably hydrogen.
R4 is hydrogen, C1-C4 linear alkyl, C3-C4 branched alkyl, and mixtures
thereof;
preferably hydrogen. When the index m is equal to 2 the index n must be equal
to 0 and
the R4 unit is absent.
The index m is 1 or 2, the index n is 0 or 1, provided that m + n equals 2;
preferably m is equal to I and n is equal to 1, resulting in one -
[(R'O)x(R2O)yR3] unit
and R4 being present on the nitrogen. The index x is from 0 to about 50,
preferably from
about 3 to about 25, more preferably from about 3 to about 10. The index y is
from 0 to
about 10, preferably 0, however when the index y is not equal to 0, y is from
I to about 4.
Preferably all the alkyleneoxy units are ethyleneoxy units.
Examples of suitable ethoxylated alkyl amide surfactants are Rewopal C6 from
Witco, Amidox C5 from Stepan, and Ethomid 0 / 17 and Ethomid HT / 60 from
Akzo.; and
(8).- Mixtures thereof.
Auxiliary Whiteness Preservatives
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Auxiliary whiteness preservatives are optionally, but preferably incorporated
in
order to improve fabric whiteness. Auxiliary whiteness preservatives can be
used
together with the metal chelant to give an extra boost to whiteness
maintenance.
1. Brighteners
Optical brighteners also known as fluorescent whitening agents (FWAs) or
fluorescent brighteners preserve whiteness by compensating for the yellow
appearance by
adding a complementary color to the fabric and thus the undesired yellowing is
rendered
invisible. When a white fabric is stored for a length of time, it can appear
to be yellow.
Not to be bound by theory, but it is believed that auto-oxidation of
polyunsaturated
materials such as body fatty acids or fabric softener actives generate
compounds that
appear yellow on white fabrics, because these compounds absorb short-
wavelength light,
light in the range of violet to blue or wavelengths between about 370 nm to
550 nm.
Optical brighteners absorb light in the range of ultraviolet light and emit
light via
fluorescence in the blue to blue violet range of the spectrum. Thus optical
brighteners
replace this missing part of the spectrum on yellowing fabric and so a white
appearance
is retained.
The product contains from about 0.005% to about 5%, preferably from about
0.05% to about 3%, more preferably from about 0.1 % to about 2%, even more
preferably
from about 0.15% to about I %, by weight of the composition, optical
brightener. Lower
levels of brightener are used in the presence of the metal chelating compound.
In the
absence of the metal chelating compound, higher levels of brightener are
preferred.
Preferred optical brighteners are colorless on the substrate and do not absorb
in
the visible part of the spectrum. Preferred optical brighteners are also
lightfast, meaning
that these do not degrade substantially in sunlight. Optical brighteners
suitable for use in
this invention absorb light in the ultraviolet portion of the spectrum between
275 nm and
about 400 nm and emit light in the violet to violet-blue range of the spectrum
from about
400 nm to about 550 nm. Preferably, the optical brightener will contain an
uninterrupted
chain of conjugated double bounds. Optical brighteners are typically, but not
limited to,
derivatives of stilbene or 4,4'-diaminostilbene, biphenyl, five-membered
heterocycles
such as triazoles, oxazoles, imidiazoles, etc., or six-membered heterocycles
(coumarins,
naphthalamide, s-triazine, etc.). Many specific brightener structures are
described in The
Kirk-Othmer Encyclopedia of Chemistry 3id Ed., pp 214-226 and in references
therein U.
= S. Pat. No. 5,759,990 at column 21, lines 15-60; as suitable
for use in this invention. Ionic brighteners with a positive
or negative charge are preferred as this improves solubility in the
compositions disclosed
herein and thus are easier to formulate and are more stable. Cationic
brighteners are also
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preferred since these can compete effectively with cationic fabric softeners
to partition to
the surface of the fabric.
Some preferred, but nonlimiting brighteners are Optiblanc GL and Optiblanc
LSN from 3V Inc., Weehawken, New Jersey, Tinopals CBS SP Slurry 33, PLC, UNPA-
GX, 4BM, 4BMS, 5BM, 5BMS, 5BM-GX, AMS-GX, DMS-X, DCS Liquid, K, ERN,
LCS, LFW, and TAS, Univex , SK, ERN, and AT, from Ciba, High Point, North
Carolina, Blankophor FBW, FB, LPG , and HRS, from Mobay. In addition to
preventing auto-oxidation, some brighteners also prevent dye transfer.
2. Bluing Agents
Bluing agents also act to preserve whiteness by compensating for the yellow
appearance by again adding a complementary color to the fabric and thus the
undesired
yellowing is no longer noticeable. Like optical brighteners, bluing agents
replace this
missing part of the spectrum and so a white appearance is retained.
3. UV Absorbers
Not to be bound by theory, but UV absorbers can operate by protecting the
fabric
and any fabric softener compound deposited on the fabric from UV exposure. UV
light
is know to initiate auto-oxidation processes and UV absorbers can be deposited
on fabric
in such a way that UV light is blocked from the fabric and unsaturated fatty
materials,
thus preventing the initiation of auto-oxidation.
5. Oxidative Stabilizers
Oxidative stabilizers can be present in the compositions of the present
invention
and these prevent yellowing by acting as a scavenger for the oxidative
processes, thus
preventing and/or terminating auto-oxidation, or by reversing oxidation and
thus
reversing yellowing. The term "oxidative stabilizer," as used herein, includes
antioxidants and reductive agents. These agents are present at a level of from
0% to
about 2%, preferably from about 0.01% to about 0.2%, more preferably from
about
0.035% to about 0.1% for antioxidants, and, preferably, from about 0.01% to
about 0.2%
for reductive agents.
Examples of antioxidants that can be added to the compositions and in the
processing of this invention include a mixture of ascorbic acid, ascorbic
palmitate, propyl
gallate, available from Eastman Chemical Products, Inc., under the trade
marks. Tenox
PG and Tenox S-1; a mixture of BHT (butylated hydroxytoluene), BHA (butylated
hydroxyanisole), propyl gallate, and citric acid, available from Eastman
Chemical
Products, Inc., under the trade mark Tenox -6; butylated hydroxytoluene,
available from
UOP Process Division under the trade mark Sustane BHT; tertiary
butylhydroquinone,
Eastman Chemical Products, Inc., as Tenox TBHQ; natural tocopherols, Eastman
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Chemical Products, Inc., as Tenox GT-1/GT-2; and butylated hydroxyanisole,
Eastman
Chemical Products, Inc., as BHA; long chain esters'(C8-C22) of gallic acid,
e.g., dodecyl
gallate; Irganox 1010; Irganox 1035; Irganox B 1171; Irganox 1425; Irganox
3114;
Irganox 3125; and mixtures thereof; preferably Irganox 3125, Irganox 1425,
Irganox
3114, and mixtures thereof; more preferably Irganox 3125 alone or mixed with
citric
acid and/or other chelators such as isopropyl citrate, Dequest 2010,
available from
Monsanto with a chemical name of 1-hydroxyethylidene-1, 1-diphosphonic acid
(etidronic acid), and Tiron , available from Kodak with a chemical name of 4,5-
di-
hydroxy-m-benzene-sulfonic acid/sodium salt, and DTPA , available from Aldrich
with
a chemical name of diethylenetriaminepentaacetic acid.
Oxidative stabilizers can also be added at any point during the process of
making
fabric softener raw materials where polyunsaturated compounds would be
present. E.g.,
these could be added into oils used to make fatty acids, during fatty acid
making and/or
storage during fabric softener making and/or storage. These assure good odor
stability
under long term storage conditions.
Other Optional Ingredients
The fabric care composition of the present invention can optionally contain
adjunct odor-controlling materials, chelating agents, antistatic agents,
insect and moth
repelling agents, colorants, especially bluing agents, antioxidants, and
mixtures thereof in
addition to the cyclic silicone molecules. 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.
Incorporating adjunct odor-controlling materials can enhance the capacity of
the
cyclodextrin to control odors as well as broaden the range of odor types and
molecule
sizes which can be controlled. Such materials include, for example, metallic
salts, water-
soluble cationic and anionic polymers, zeolites, water-soluble bicarbonate
salts, and
mixtures thereof.
Water-Soluble Polyionic Polymers
Some water-soluble polyionic polymers, e.g., water-soluble cationic polymer
and
water-soluble anionic polymers can be used in the composition of the present
invention
to provide additional odor control benefits.
Cationic polymers, e.g., polvamines
Water-soluble cationic polymers, e.g., those containing amino functionalities,
amido functionalities, and mixtures thereof, are useful in the present
invention to control
certain acid-type odors.
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Anionic polymers, e.g., polyacrylic acid
Water-soluble anionic polymers, e.g., polyacrylic acids and their water-
soluble
salts are useful in the present invention to control certain amine-type odors.
Preferred
polyacrylic acids and their alkali metal salts have an average molecular
weight of less
than about 20,000, more preferably less than 5,000000, preferably less than
10,000, more
preferably from about 500 to about 5,000. Polymers containing sulfonic acid
groups,
phosphoric acid groups, phosphonic acid groups, and their water-soluble salts,
and
mixtures thereof, and mixtures with carboxylic acid and carboxylate groups,
are also
suitable.
Water-soluble polymers containing both cationic and anionic functionalities
are
also suitable. Examples of these polymers are given in U.S. Pat. 4,909,986,
issued
March 20, 1990 to N. Kobayashi and A. Kawazoe.
Another example of water-soluble polymers containing both cationic and anionic
functionalities is a copolymer of dimethyldiallyl ammonium chloride and
acrylic acid,
commercially available under the trade name Merquat 280 from Calgon.
When a water-soluble polymer is used it is typically present at a level of
from
about 0.001% to about 3%, preferably from about 0.005% to about 2%, more
preferably
from about 0.01% to about 1%, and even more preferably from about 0.05% to
about
0.5%, by weight of the usage composition.
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 mark
Dehyquart E from Henkel, and ethyl bis(polyethoxy ethanol) alkylammonium
ethylsulfate, available under the trade mark 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)2+-CH2CH2OCH2CH2]-x 2+ 2x[Cl-]
available under the trade mark Mirapol A-15 from Rhone-Poulenc, and
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-[N(CH3)2-(CH2)3-NH-CO-(CH2)4-CO-NH-(CH2)3-N(CH3)2-(CH2CH2OCH2CH2]-
x+ x[Cl-],
available under the trade name Mirapol AD-1 from Rhone-Poulenc, quaternized
polyethyleneimines, vinylpyrrolidone/methacrylamidopropyltrimethylammonium
chloride copolymer, available under the trade mark Gafquat HS-100 from GAF;
triethonium hydrolyzed collagen ethosulfate, available under the trade mark
Quat-Pro E
from Maybrook; neutralized sulfonated polystyrene, available, e.g., under the
trade
mark Versa TL-130 from Alco Chemical, neutralized sulfonated styrene/maleic
anhydride copolymers, available, e.g., under the trade mark Versa TL-4 from
Alco
Chemical; 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.
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, I -
dodeeene, etc.
Other examples of insect and/or moth repellents useful in the composition of
the present
invention are disclosed in U.S. Pat. Nos. 4,449,987, 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. When an insect and/or moth repellent is used it
is typically
present at a level of from about 0.005% to about 3%, by weight of the usage
composition.
Colorant
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Colorants and dyes, especially bluing agents, can be optionally added to the
fabric
care compositions for visual appeal and performance impression. When colorants
are
used, they are used at extremely low levels to avoid fabric staining.
Preferred colorants
for use in the present compositions are highly water-soluble dyes, e.g.,
Liquitint dyes
available from Milliken Chemical Co. Non-limiting examples of suitable dyes
are,
Liquitint Blue HP , Liquitint Blue 65 , Liquitint Patent Blue , Liquitint
Royal Blue
,
Liquitint Experimental Yellow 8949-43 , Liquitint Green HMC , Liquitint Yellow
II
,
and mixtures thereof, preferably Liquitint Blue HP , Liquitint Blue 65 ,
Liquitint
Patent Blue , Liquitint Royal Blue , Liquitint Experimental Yellow 8949-43 ,
and
mixtures thereof.
Optional Anti-Clogging AEent
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 2 carbon
atoms. The anti-clogging agent inhibits the formation of "plugs" in the spray
nozzle. An
example of the preferred anti-clogging 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% to about 0.5%, more preferably,
from
about 0.1 % to about 0.3% by weight of the usage composition.
Builders
The compositions according to the present invention can further comprise a
builder or builder system, especially for detergent compositions. Any
conventional
builder system is suitable for use herein including aluminosilicate materials,
silicates,
polycarboxylates, alkyl- or alkenyl-succinic acid and fatty acids, materials
such as
ethylenediamine tetraacetate, diethylene triamine pentamethyleneacetate, metal
ion
sequestrants such as aminopolyphosphonates, particularly ethylenediamine
tetramethylene phosphonic acid and diethylene triamine
pentamethylenephosphonic acid.
Phosphate builders can also be used herein.
The present invention can include a suitable builder or detergency salt. The
level
of detergent salt/builder can vary widely depending upon the end use of the
composition
and its desired physical form. When present, the compositions will typically
comprise at
least about 1% builder and more typically from about 10% to about 80%, even
more
typically from about 15% to about 50% by weight, of the builder. Lower or
higher
levels, however, are not meant to be excluded.
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Inorganic or P-containing detergent salts include, but are not limited to, the
alkali
metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by
the
tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates),
phosphonates, phytic acid, silicates, carbonates (including bicarbonates and
sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate
salts are
required in some locales. Importantly, the compositions herein function
surprisingly well
even in the presence of the so-called "weak" builders (as compared with
phosphates)
such as citrate, or in the so-called "underbuilt" situation that may occur
with zeolite or
layered silicate builders.
Organic detergent builders suitable for the purposes of the present invention
include, but are not restricted to, a wide variety of polycarboxylate
compounds. As used
herein, "polycarboxylate" refers to compounds having a plurality of
carboxylate groups,
preferably at least 3 carboxylates. Polycarboxylate builder can generally be
added to the
composition in acid form, but can also be added in the form of a neutralized
salt. When
utilized in salt form, alkali metals, such as sodium, potassium, and lithium,
or
alkanolammonium salts are preferred.
Examples of suitable silicate builders, carbonate salts, aluminosilicate
builders,
polycarboxylate builders, citrate builders, 3,3-dicarboxy-4-oxa-1,6-
hexanedioate builders
and related compounds disclosed in U.S. Patent No. 4,566,984, to Bush,
succinic acid
builders, phosphorous-based builders and fatty acids, are disclosed in U.S.
Patent Nos.
5,576,282, 5,728,671 and 5,707,950.
Additional suitable builders can be an inorganic ion exchange material,
commonly an inorganic hydrated aluminosilicate material, more particularly a
hydrated
synthetic zeolite such as hydrated zeolite A, X, B, HS or MAP.
Specific polycarboxylates suitable for the present invention are
polycarboxylates
containing one carboxy group include lactic acid, glycolic acid and ether
derivatives
thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370.
Polycarboxylates containing two carboxy groups include the water-soluble salts
of
succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid,
diglycollic acid,
tartaric acid, tartronic acid and fumaric acid, as well as the ether
carboxylates described
in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No.
3,935,257
and the sulfinyl carboxylates described in Belgian Patent No. 840,623.
Polycarboxylates
containing three carboxy groups include, in particular, water-soluble
citrates, aconitrates
and citraconates as well as succinate derivatives such as the
carboxymethyloxysuccinates
described in British Patent No. 1,379,241, lactoxysuccinates described in
Canadian
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Patent No. 973771, and the oxypolycarboxylate materials such as 2-oxa- 1, 1,3-
propane
tricarboxylates described in British Patent No. 1,381,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates,
1,1,3,3-
propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
Polycarboxylates
containing sulfo substituents include the sulfosuccinate derivatives disclosed
in British
Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the
sulfonated pyrolysed citrates described in British Patent No. 1,082,179, while
polycarboxylates containing phosphone substituents are disclosed in British
Patent No.
1,439,000.
Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-
tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydro-
furan - cis, cis,
cis-tetracarboxylates, 2,5-tetrahydro-furan -cis - dicarboxylates, 2,2,5,5-
tetrahydrofuran -
tetracarboxylates, 1,2,3,4,5,6-hexane -hexacarboxylates and carboxymethyl
derivatives of
polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic poly-
carboxylates
include mellitic acid, pyromellitic acid and the phthalic acid derivatives
disclosed in
British Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates
containing
up to three carboxy groups per molecule, more particularly citrates.
Preferred builder systems for use in the present compositions include a
mixture of
a water-insoluble aluminosilicate builder such as zeolite A or of a layered
silicate (SKS-
6), and a water-soluble carboxylate chelating agent such as citric acid.
Preferred builder systems include a mixture of a water-insoluble
aluminosilicate
builder such as zeolite A, and a water soluble carboxylate chelating agent
such as citric
acid. Preferred builder systems for use in liquid detergent compositions of
the present
invention are soaps and polycarboxylates.
Other suitable water-soluble organic salts are the homo- or copolymeric acids
or
their salts, in which the polycarboxylic acid comprises at least two carboxyl
radicals
separated from each other by not more than two carbon atoms. Polymers of this
type are
disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MW
2000-
5000 and their copolymers with maleic anhydride, such copolymers having a
molecular
weight of from 20,000 to 70,000, especially about 40,000.
Detergency builder salts are normally included in amounts of from 5% to 80% by
weight of the composition preferably from 10% to 70% and most usually from 30%
to
60% by weight.
Bleaching Agent
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Additional optional detergent ingredients that can be included in the
detergent
compositions of the present invention include bleaching agents such as
hydrogen
peroxide, PB1, PB4 and percarbonate with a particle size of 400-800 microns.
These
bleaching agent components can include one or more oxygen bleaching agents
and,
depending upon the bleaching agent chosen, one or more bleach activators. When
present oxygen bleaching compounds will typically be present at levels of from
about I%
to about 25%.
The bleaching agent component for use herein can be any of the bleaching
agents
useful for detergent compositions including oxygen bleaches as well as others
known in
the art. The bleaching agent suitable for the present invention can be an
activated or non-
activated bleaching agent.
Examples of suitable bleaching agents are disclosed in U.S. Patent Nos.
5,707,950 and 5,576,282.
The hydrogen peroxide releasing agents can be used in combination with, for
example, the bleach activators disclosed in U.S. Patent No. 5,707,950 or
Phenolsulfonate
ester of N-nonanoyl-6-aminocaproic acid (NACA-OBS), described in W094/28106),
which are perhydrolyzed to form a peracid as the active bleaching species,
leading to
improved bleaching effect. Also suitable activators are acylated citrate
esters.
Useful bleaching agents, including peroxyacids and bleaching systems
comprising
bleach activators and peroxygen bleaching compounds for use in detergent
compositions
according to the invention are described in W095/27772, W095/27773,
W095127774,
W095/27775 and U.S. Patent No. 5,707,950.
Metal-containing catalysts for use in bleach compositions, include cobalt-
containing catalysts such as pentamine acetate cobalt(III) salts and manganese-
containing
catalysts such as those described in EPA 549 271; EPA 549 272; EPA 458 397; US
5,246,621; EPA 458 398; US 5,194,416 and US 5,114,611. Bleaching composition
comprising a peroxy compound, a manganese-containing bleach catalyst and a
chelating
agent is described in EP 718398.
Dve Transfer Inhibiting Agents
The fabric care compositions of the present invention can also include
compounds for inhibiting dye transfer from one fabric to another of
solubilized and
suspended dyes encountered during fabric laundering and conditioning
operations
involving colored fabrics.
Polymeric dye transfer inhibiting agents
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The fabric care compositions according to the present invention can also
comprise
from 0.001% to 10 %, preferably from 0.01% to 2%, more preferably from 0.05%
to 1%
by weight of polymeric dye transfer inhibiting agents. Said polymeric dye
transfer
inhibiting agents are normally incorporated into fabric care compositions in
order to
inhibit the transfer of dyes from colored fabrics onto fabrics washed
therewith. 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.
Especially suitable polymeric dye transfer inhibiting agents 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 are disclosed in U.S. Pat. No. 5,804,219,
issued Sept. 8,
1998 to T. Trinh, S. L.-L. Sung, H. B. Tordil, and P. A. Wendland, and in U.S.
Patent
Nos. 5,707,950 and 5,707,951_
Additional suitable dye transfer inhibiting agents include, but are not
limited to,
cross-linked polymers. Cross-linked polymers are polymers whose backbone are
interconnected to a certain degree; these links can be of chemical or physical
nature,
possibly with active groups n the backbone or on branches; cross-linked
polymers have
been described in the Journal of Polymer Science, volume 22, pages 1035-1039.
In one embodiment, the cross-linked polymers are made in such a way that they
form a three-dimensional rigid structure, which can entrap dyes in the pores
formed by
the three-dimensional structure. In another embodiment, the cross-linked
polymers entrap
the dyes by swelling.
Such cross-linked polymers are described in European patent 719856.
Chlorine Scavenging Agents
Chlorine scavenging agents are actives that react with chlorine, or with
chlorine-
generating materials, such as hypochlorite, to eliminate or reduce the
bleaching activity
of the chlorine materials. Chlorine is used in many parts of the world to
sanitize water.
To make sure that the water is safe, a small amount, typically about 1 to 2
ppm of
chlorine is left in the water. It has been found that this small amount of
chlorine in the
tap water can cause fading of some fabric dyes. For rinse-added compositions,
it is
suitable to incorporate enough chlorine scavenging agent to neutralize about I
ppm,
preferably 2 ppm, more preferably 3 ppm, and even more preferably 10 ppm of
chlorine
in rinse water.
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Suitable levels of the optional chlorine scavengers in the rinse-added
composition
of the present invention range from about 0.01% to about 10%, preferably from
about
0.02% to about 5%, more preferably from about 0.05% to about 4%.
The fabric softener compositions, and especially the preferred compositions
herein, can contain an effective amount of chlorine scavenger, preferably
selected from
the group consisting of:
a. amines and their salts;
b. ammonium salts;
c. amino acids and their salts;
d. polyamino acids and their salts;
e. polyethyleneimines and their salts;
f. polyamines and their salts;
g. polyamineamides and their salts;
h. polyacrylamides; and
i. mixtures thereof.
Non-limiting examples of chlorine scavengers include amines, preferably
primary
and secondary amines, including primary and secondary fatty amines, and
alkanolamines;
and their salts; ammonium salts, e.g., chloride, bromide, citrate, sulfate;
amine-functional
polymers and their salts; amino acid homopolymers with amino groups and their
salts,
such as polyarginine, polylysine, polyhistidine; amino acid copolymers with
amino
groups and their salts, including 1,5-di-ammonium-2-methyl-panthene dichloride
and
lysine monohydrochloride; amino acids and their salts, preferably those having
more
than one amino group per molecule, such as arginine, histidine, and lysine,
reducing
anions such as sulfite, bisulfite, thiosulfate, and nitrite. antioxidants such
as ascorbate,
carbamate, phenols; and mixtures thereof.
Preferred chlorine scavengers are water soluble, especially, low molecular
weight
primary and secondary amines of low volatility, e.g., monoethanolamine,
diethanolamine, tris(hydroxymethyl)aminomethane, hexamethylenetetramine, and
their
salts, and mixtures thereof. Suitable chlorine scavenger polymers include:
water soluble
amine-functional polymers, e.g., polyethyleneimines, polyamines,
polyamineamides,
polyacrylamides, and their salts, and mixtures thereof. The preferred polymers
are
polyethyleneimines; the polyamines, including, e.g., di(higher alkyl)cyclic
amines and
their condensation products, and polymers containing amino groups;
polyamineamides,
and their salts; and mixtures thereof. Preferred polymers for use in the
fabric softening
compositions of the present invention are polyethyleneimines and their salts.
Preferred
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polyethyleneimines have a molecular weight of less than about 2000, more
preferably
from about 200 to about 1500. The water solubility is preferably at least
about l g/l00 g
water, more preferably at least about 3 g/l00 g water, even more preferably at
least about
g/100 g water.
Some polyamines with the general formula (RI)2N(CX2)nN(R2)2 can serve both
as a chlorine scavenging agent and a "chelant" color care agent. Non-limiting
examples
of such preferred polyamines are N,N,N',N'-tetrakis(2-hydroxypropyl)
ethylenediamine
and N,N,N',N",N"-penta(2-hydroxypropyl)diethylenetriamine.
Preferred polymeric chlorine scavengers have an average molecular weight of
less
than about 5,000, more preferably from about 200 to about 2,000, even more
preferably
from about 200 to about 1,000. Low molecular weight polymers are easier to
remove
from fabrics than higher molecular weight polymers, resulting in less buildup
of the
chlorine scavenger and therefore less discoloration of the fabrics. Liquid
chlorine
scavengers can be used in liquid softener compositions, but amine-functional
chlorine
scavengers are preferably neutralized by an acid, before they are added into
the
compositions.
Polymeric Soil Release Aeents
Soil release agents, usually polymers, are especially desirable additives at
levels of
from about 0.05% to about 5%, preferably from about 0.1% to about 4%, more
preferably
from about 0.2% to about 3%. Suitable soil release agents are disclosed in
U.S. Pat.
Nos.: 4,702,857, Gosselink, issued Oct. 27, 1987; 4,711,730, Gosselink and
Diehl, issued
Dec. 8, 1987; 4,713,194, Gosselink issued Dec. 15, 1987; 4,877,896, Maldonado,
Trinh,
and Gosselink, issued Oct. 31, 1989; 4,956,447, Gosselink, Hardy, and Trinh,
issued Sep_
11, 1990; and 4,749,596, Evans, Huntington, Stewart, Wolf, and Zimmerer,
issued
June 7, 1988.,
Especially desirable optional ingredients are polymeric soil release agents
comprising block copolymers of polyalkylene terephthalate and polyoxyethylene
tere-
phthalate, and block copolymers of polyalkylene terephthalate and polyethylene
glycol.
The polyalkylene terephthalate blocks preferably comprise ethylene and/or
propylene
groups. Many such soil release polymers are nonionic.
A preferred nonionic soil release polymer has the following average structure:
CH3O(CH2CH2O)40 -[C(O)-C6H4-C(O)-OCH2CH(CH3)O -]5
-C(O)-C6H4 C(O)-(OCH2CH2 )4000H3 .
Such soil release polymers are described in U.S. Pat. No. 4,849,257, Borcher,
Trinh and Bolich, issued July 18, 1989,
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Another highly preferred nonionic soil release polymer is described in New
Zealand Pat. No. 242,150, issued Aug. 7, 1995 to Pan, Gosselink, and Honsa.
The polymeric soil release agents useful in the present invention can include
anionic and cationic polymeric soil release agents. Suitable anionic polymeric
or
oligomeric soil release agents are disclosed in U.S. Pat. No. 4,018,569,
Trinh, Gosselink
and Rattinger, issued April 4, 1989.
Other suitable polymers are disclosed in U.S. Pat. No. 4,808,086, Evans,
Huntington,
Stewart, Wolf, and Zimmerer, issued Feb. 24, 1989.
Suitable cationic soil release polymers are described in U.S. Pat. No.
4,956,447, Gosselink, Hardy, and Trinh, issued Sept. 11, 1990,
Dve Fixing Agents
The optional dye fixing agents, or "fixatives", are materials which are useful
to
improve the appearance of dyed fabrics by minimizing the loss of dye from
fabrics due to
washing.
Many dye fixing agents are cationic, and 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. Cationic fixatives are available under
various trade
names from several suppliers. Representative examples include: CROSCOLOR PMF
and CROSCOLOR NOFF available from Crosfield; INDOSOL E-50
(polyethyleneamine-based) and SANDOFIX TPS from Sandoz; and CARTAFIX CB
from Clariant.. Additional non-limiting examples include SANDOFIX SWE (a
cationic
resinous compound) from Sandoz; REWIN SRF, REWIN SRF-O and REWIN DWR
from CHT-Beitlich GMBH; Tinofix ECO, Tinofix FRD and Solfin from Ciba-
Geigy. Preferred optional dye fixing agents for use in the compositions of
the. present
invention are SANDOFIX TPS and CARTAFIX CB.
Other cationic dye fixing agents are described in "Aftertreatments for
Improving
the Fastness of Dyes on Textile Fibres", Christopher C. Cook, Rev. Prog.
Coloration,
Vol. XII, (1982). Optional dye fixing agents suitable for use in the present
invention are
ammonium compounds such as fatty acid-diamine condensates inter alia the
hydrochloride, acetate, metosulphate and benzy] hydrochloride salts of diamine
esters.
Non-limiting examples include oleyldiethyl aminoethylamide, oleylmethyl
diethylenediamine methosulphate, monostearylethylene diaminotrimethylammonium
methosulphate. In addition, the N-oxides of tertiary amines; derivatives of
polymeric
alkyldiamines, polyamine-cyanuric chloride condensates, and aminated glycerol
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dichlorohydrins are suitable for use as dye fixatives in the compositions of
the present
invention.
Another class of optional dye fixing agents suitable for use in the present
invention are cellulose reactive dye fixing agents. The cellulose reactive dye
fixatives
may be suitably combined with one or more dye fixatives described herein above
in order
to comprise a "dye fixative system".
The term "cellulose reactive dye fixing agent" is defined herein as "a dye-
fixative
agent which reacts with the cellulose fibers upon application of heat or upon
a heat
treatment either in situ or by the formulator".
Typically cellulose reactive dye fixing agents are compounds which contain a
cellulose reactive moiety. Non limiting examples of these compounds include
halogeno-
triazines, vinyl sulphones, epichlorhydrine derivatives, hydroxyethylene urea
derivatives,
formaldehyde condensation products, polycarboxylates, glyoxal and
glutaraldehyde
derivatives, and mixtures thereof. Further examples can be found in "Textile
Processing
and Properties", Tyrone L. Vigo, at page 120 to 121, Elsevier (1997), which
discloses
specific electrophilic groups and their corresponding cellulose affinity.
Preferred hydroxyethylene urea derivatives include dimethyloldihydroxy
ethylene, urea, and dimethyl urea glyoxal. Preferred formaldehyde condensation
products include the condensation products derived from formaldehyde and a
group
selected from an amino-group, an imino-group, a phenol group, an urea group, a
cyanamide group and an aromatic group. Commercially available compounds among
TM TM TM
this class are Sandofix WE 56 from Clariant, Zetex E from Zeneca and Levogen
BF from
Bayer. Preferred polycarboxylates derivatives include butane tetracarboxilic
acid
derivatives, citric acid derivatives, polyacrvrvlates and derivatives thereof.
A referred
cellulosic reactive dye fixing agent is Indosol CR (hydroxyethylene urea
derivative) from
Clariant. Other preferred cellulosic reactive dye fixing agents are Rewin DWR
and
Tm
Rewin WBS from CHT R. Beitlich.
The compositions of the present invention optionally comprise from about
0.001% to about 40%, preferably from about 0.5% to more preferably to about
10%,
more preferably from about I% to about 5%, by weight of the fabric care
composition, of
one or more dye fixing agents.
Dispersants
The detergent composition of the present invention can also contain
dispersants.
Suitable water-soluble organic salts are the homo- or co-polymeric acids or
their salts, in
which the polycarboxylic acid comprises at least two carboxyl radicals
separated from
each other by not more than two carbon atoms.
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Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts
are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride,
such
copolymers having a molecular weight of from 1,000 to 100,000.
Especially, copolymer of acrylate and methylacrylate such as the 480N having a
molecular weight of 4000, at a level from 0.5-20% by weight of composition can
be
added in the detergent compositions of the present invention.
The compositions of the invention can contain a lime soap peptiser compound,
which has a lime soap dispersing power (LSDP), as defined hereinafter of no
more than
8, preferably no more than 7, most preferably no more than 6. The lime soap
peptiser
compound is preferably present at a level from 0% to 20% by weight.
A numerical measure of the effectiveness of a lime soap peptiser is given by
the
lime soap dispersant power (LSDP) which is determined using the lime soap
dispersant
test as described in an article by H.C. Borghetty and C.A. Bergman, J. Am.
Oil. Chem.
Soc., volume 27, pages 88-90, (1950). This lime soap dispersion test method is
widely
used by practitioners in this art field being referred to, for example, in the
following
review articles; W.N. Linfield, Surfactant science Series, Volume 7, page 3;
W.N.
Linfield, Tenside surf. det., volume 27, pages 159-163, (1990); and M.K.
Nagarajan,
W.F. Masler, Cosmetics and Toiletries, volume 104, pages 71-73, (1989). The
LSDP is
the % weight ratio of dispersing agent to sodium oleate required to disperse
the lime soap
deposits formed by 0.025g of sodium oleate in 30 ml of water of 333ppm CaCO3
(Ca:Mg=3:2) equivalent hardness.
Surfactants having good lime soap peptizer capability will include certain
amine
oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated
alcohols.
Exemplary surfactants having a LSDP of no more.than 8 for use in accord with
the present invention include C16-C18 dimethyl amine oxide, C1 2-C 18 alkyl
ethoxysulfates with an average degree of ethoxylation of from 1-5,
particularly C 12-C 15
alkyl ethoxysulfate surfactant with a degree of ethoxylation of amount 3
(LSDP=4), and
the C14-C15 ethoxylated alcohols with an average degree of ethoxylation of
either 12
(LSDP=6) or 30, sold under the trademarks Lutensol A012 and Lutensol A030
respectively, by BASF GmbH.
Polymeric lime soap peptizers suitable for use herein are described in the
article
by M.K. Nagarajan, W.F. Masler, to be found in Cosmetics and Toiletries,
volume 104,
pages 71-73, (1989).
Hydrophobic bleaches such as 4-[N-octanoyl-6-aminohexanoyl]benzene
sulfonate, 4-[N-nonanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-decanoyl-6-
aminohexanoyl]benzene sulfonate and mixtures thereof; and nonanoyloxy benzene
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sulfonate together with hydrophilic / hydrophobic bleach formulations can also
be used
as lime soap peptizers compounds.
Examples of other suitable dispersing agents are disclosed in U.S. Patent Nos.
5,576,282 and 5,728,671.
Enzymes
Optional enzymes are useful in the compositions , especially wash-added and
rinse-added compositions, of the present invention to improve cleaning, odor.
control
and/or fabric appearance benefits. Preferred enzymes include laundry detergent
and/or
fabric care applicable enzymes like protease, amylase, lipase, cutinase and/or
cellulase.
Examples of suitable enzymes are disclosed in U.S. Patent Nos. 5,576,282,
5,728,671 and 5,707,950
Particularly useful proteases are described in PCT publications: WO 95/30010
published November 9, 1995 by The Procter & Gamble Company; WO 95/30011
published November 9, 1995 by The Procter & Gamble Company; and WO 95/29979
published November 9, 1995 by The Procter & Gamble Company.
In addition to the peroxidase enzymes disclosed in U.S. Patent Nos. 5,576,282,
5,728,671 and 5,707,950, other suitable peroxidase enzymes are disclosed in
European
Patent publication 927242. Also suitable is the laccase enzyme.
Preferred enhancers are substituted phenthiazine and phenoxasine 10-
Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid
(EPC), 10-
phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO
94/12621) and substituted syringates (C3-C5 substituted alkyl syringates) and
phenols.
Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
Said peroxidases are normally incorporated in the detergent composition at
levels
from 0.0001 % to 2% of active enzyme by weight of the detergent composition.
Other preferred enzymes that can be included in the fabric care or detergent
compositions of the present invention include lipases. Suitable lipase enzymes
for
detergent usage include those produced by microorganisms of the Pseudomonas
group,
such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent
1,372,034.
Suitable lipases include those which show a positive immunological cross-
reaction with
the antibody of the lipase, produced by the microorganism Pseudomonas
fluorescent
IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya,
Japan,
under the trade marks Lipase P "Amano," hereinafter referred to as "Amano-P".
Other
suitable commercial lipases include Amano-CES, lipases ex Chromobacter
viscosum,
e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co.,
Tagata,
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Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and
Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. Especially
suitable
lipases are lipases such as M1 LipaseR and LipomaxR (Gist-Brocades) and
LipolaseR
and Lipolase UltraR(Novo) which have found to be very effective when used in
combination with the compositions of the present invention.
Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special
kind of lipase, namely lipases which do not require interfacial activation.
Addition of
cutinases to detergent compositions have been described in e.g. WO 88/09367
(Genencor).
The lipases and/or cutinases are normally incorporated in the detergent
composition at levels from 0.0001% to 2% of active enzyme by weight of the
detergent
composition.
Known amylases ((x and/or 13) can be included for removal of carbohydrate-
based
stains. WO 94/02597, Novo Nordisk A/S published February 03, 1994, describes
cleaning compositions which incorporate mutant amylases. See also W094/18314,
Genencor, published August 18, 1994 and W095/10603, Novo Nordisk A/S,
published
April 20, 1995. Other amylases known for use in detergent compositions include
both a-
and 0-amylases. a-Amylases are known in the art and include those disclosed in
US Pat.
5,003,257; EP 252,666; WO 91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP
368,341; and British Patent Specification No. 1,296,839 (Novo). Other suitable
amylase
are stability-enhanced amylases including Purafact Ox AmR described in WO
94/18314,
published August 18, 1994 and W096/05295, Genencor, published February 22,
1996
and amylase variants from Novo Nordisk A/S, disclosed in WO 95/10603,
published
April 95.
Examples of commercial a-amylases products are TERMAMYL , BAN ,
FUNGAMYL and DURAMYL , all available from Novo Nordisk A/S Denmark.
W095/26397 describes other suitable amylases : a-amylases characterised by
having a
specific activity at least 25% higher than the specific activity of TERMAMYL
at a
temperature range of 25 C to 55 C and at a pH value in the range of 8 to 10,
measured by
the PHADEBAS a-amylase activity assay. Other amylolytic enzymes with improved
properties with respect to the activity level and the combination of
thermostability and a
higher activity level are described in W095/35382.
The cellulases usable in the present invention include both bacterial or
fungal
cellulases. Preferably, they will have a pH optimum of between 5 and 12 and an
activity
above 50 CEVU (Cellulose Viscosity Unit). Suitable cellulases are disclosed in
U.S.
Patent 4,435,307, Barbesgoard et al, J61078384 and W096/02653 which discloses
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fungal cellulase produced respectively from Humicola insolens, Trichoderma,
Thielavia
and Sporotrichurn. EP 739 982 describes cellulases isolated from novel
Bacillus species.
Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-
OS-
2.247.832 and W095/26398.
Examples of such cellulases are cellulases produced by a strain of Humicola
insolens (Humicola grisea var. thermoidea), particularly the Humicola strain
DSM 1800.
Other suitable cellulases are cellulases originated from Humicola insolens
having a
molecular weight of about 50KDa, an isoelectric point of 5.5 and containing
415 amino
acids; and a "43kD endoglucanase derived from Humicola insolens, DSM 1800,
exhibiting cellulase activity; a preferred endoglucanase component has the
amino acid
sequence disclosed in PCT Patent Application No. WO 91/17243. Also suitable
cellulases are the EGIII cellulases from Trichoderma longibrachiatum described
in
W094/21801, Genencor, published September 29, 1994. Especially suitable
cellulases
are the cellulases having color care benefits. Examples of such cellulases are
cellulases
described in European published Patent Application 495257
(Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See
also
W091/17244 and W091/21901. Other suitable cellulases for fabric care and/or
cleaning
properties are described in W096/34092, W096/17994 and W095/24471. Suitable
cellulases and their appropriate levels useful in rinse-added compositions of
the present
invention are described in U.S. Pat. No. 5,445,747, issued Aug. 29, 1995 to L.
L.
Kvietok, T. Trinh and J. A. Hollingshead.
Said cellulases are normally incorporated in the detergent composition at
levels
from 0.0001 % to 2% of active enzyme by weight of the detergent composition.
The above-mentioned enzymes can be of any suitable origin, such as vegetable,
animal, bacterial, fungal and yeast origin. Purified or non-purified forms of
these
enzymes can be used. Also included by definition, are mutants of native
enzymes.
Mutants can be obtained e.g. by protein and/or genetic engineering, chemical
and/or
physical modifications of native enzymes. Common practice as well is the
expression of
the enzyme via host organisms in which the genetic material responsible for
the
production of the enzyme has been cloned.
Enzymes are normally incorporated in the detergent composition at levels from
0.0001 % to 2% of active enzyme by weight of the detergent composition. The
enzymes
can be added as separate single ingredients (prills, granulates, stabilized
liquids, etc.
containing one enzyme) or as mixtures of two or more enzymes ( e.g.
cogranulates).
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Other suitable detergent ingredients that can be added are enzyme oxidation
scavengers. Examples of such enzyme oxidation scavengers are ethoxylated
tetraethylene
polyamines.
A range of enzyme materials and means for their incorporation into synthetic
detergent compositions is also disclosed in WO 9307263 and WO 9307260 to
Genencor
International, WO 8908694 to Novo, and U.S. 3,553,139, January 5, 1971 to
McCarty et
al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18,
1978, and in
U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid
detergent
formulations, and their incorporation into such formulations, are disclosed in
U.S.
4,261,868, Hora et al, April 14, 1981. Enzymes for use in detergents can be
stabilized by
various techniques. Enzyme stabilization techniques are disclosed and
exemplified in
U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586,
October 29,
1986, Venegas. Enzyme stabilization systems are also described, for example,
in U.S.
3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases and
cellulases, is
described in WO 9401532 to Novo.
Enzymes can also be used to control certain types of malodor, especially
malodor
from urine and other types of excretions, including regurgitated materials.
Proteases are
especially desirable. The activity of commercial enzymes depends very much on
the type
and purity of the enzyme being considered. Enzymes that are water soluble
proteases
like pepsin, tripsin, ficin, bromelin, papain, rennin, and mixtures thereof
are particularly
useful.
For odor control purpose, enzymes are normally incorporated at levels
sufficient
to provide up to about 5 mg by weight, preferably from about 0.001 mg to about
3 mg,
more preferably from about 0.002 mg to about 1 mg, of active enzyme per gram
of the
aqueous compositions. Stated otherwise, the aqueous compositions herein can
comprise
from about 0.0001% to about 0.5%, preferably from about 0.001% to about 0.3%,
more
preferably from about 0.005% to about 0.2% by weight of a commercial enzyme
preparation. Protease enzymes are usually present in such commercial
preparations at
levels sufficient to provide from 0.0005 to 0.1 Anson units (AU) of activity
per gram of
aqueous composition.
Nonlimiting examples of suitable, commercially available, water soluble
proteases are pepsin, tripsin, ficin, bromelin, papain, rennin, and mixtures
thereof.
Papain can be isolated, e.g., from papaya latex, and is available commercially
in the
purified form of up to, e.g., about 80% protein, or cruder, technical grade of
much lower
activity. Other suitable examples of proteases are the subtilisins which are
obtained from
particular strains of B. subtilis and B. licheniforms. Another suitable
protease is obtained
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from a strain of Bacillus, having maximum activity throughout the pH range of
8-12,
developed and sold by Novo Industries A/S under the registered trade mark
ESPERASE . The preparation of this enzyme and analogous enzymes is described
in
British Patent Specification No. 1,243,784 of Novo. Proteolytic enzymes
suitable for
removing protein-based stains that are commercially available include those
sold under
the trade marks ALCALASE and SAVINASE by Novo Industries A/S (Denmark)
and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands). Other
proteases include Protease A (see European Patent Application 130,756,
published
January 9, 1985); Protease B (see European Patent Application 251,446,
and European Patent Application 130,756, Bott et al., published
January 9, 1985); and proteases made by Genencor International, Inc.,
according to one
or more of the following patents: Caldwell et al, U.S. Patent Nos. 5,185,258,
5,204,015
and 5,244,791.
A wide range of enzyme materials and means for their incorporation into liquid
compositions are also disclosed in U.S. Patent 3,553,139, issued January 5,
1971 to
McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101,457, Place
et al,
issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26,
1985.
Other enzyme materials useful for liquid formulations, and their incorporation
into such
formulations, are disclosed in U.S. Patent 4,261,868, Hora et al, issued April
14, 1981.
Enzymes can be stabilized by various techniques, e.g., those disclosed and
exemplified in
U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al., European
Patent
Application Publication No. 0 199 405, published October
29, 1986, Venegas, and in U.S. Patent 3,519,570.
Enzyme-polyethylene glycol conjugates are also preferred. Such polyethylene
glycol (PEG) derivatives of enzymes, wherein the PEG or alkoxy-PEG moieties
are
coupled to the protein molecule through, e.g., secondary amine linkages.
Suitable
derivatization decreases immunogenicity, thus minimizes allergic reactions,
while still
maintaining some enzymatic activity. An example of protease-PEG's is PEG-
subtilisin
Carlsberg from B. lichenniformis coupled to methoxy-PEGs through secondary
amine
linkage, and is available from Sigma-Aldrich Corp., St. Louis, Missouri.
Heavy Metal Chelating Agents
The wash-added fabric care compositions herein can also optionally contain one
or more iron and/or manganese chelating agents. Suitable chelating agents is
selected
from the group consisting of amino carboxylates, amino phosphonates,
polyfunctionally-
substituted aromatic chelating agents and mixtures thereof. The chelating
agents
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disclosed in said U. S. Pat. No. 5,759,990 at column 26, line 29 through
column 27, line
38 are suitable. Other examples of suitable chelating agents are disclosed in
U.S. Patent
No. 5,728,671.
A suitable amine-based metal chelator that can be used herein is
ethylenediamine-
N,N'-disuccinate (EDDS). EDDS is described in U.S. Patent No. 4,704,233, and
has the
formula (shown in free acid form):
HN(L)C2H4N(L)H
wherein L is a CH2(COOH)CH2(COOH) group.
The compositions herein can also contain water-soluble methyl glycine diacetic
acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for
example,
insoluble builders such as zeolites, layered silicates and the like.
If utilized, these chelating agents will generally comprise from about 0.1% to
about 15% by weight of the detergent compositions herein. More preferably, if
utilized,
the chelating agents will comprise from about 0.1% to about 3.0% by weight of
such
compositions.
For rinse-added compositions, preferred metal chelating agents contain amine
and
especially tertiary amine moieties since these tend to be fabric substantive
and very
effectively chelate copper and iron as well as other metals. A preferred amine-
based
metal chelating compound for use in compositions of the present invention has
the
following general structure:
(R 1)(R2)N(CX2)nN(R3)(R4)
wherein X is selected from the group consisting of hydrogen, linear or
branched,
substituted or unsubstituted alkyl having from 1 to 10 carbons atoms and
substituted or
unsubstituted aryl having at least 6 carbon atoms; n is an integer from 0 to
6; R1, R2, R3,
and R4 are independently selected from the group consisting of alkyl; aryl;
alkaryl;
arylalkyl; hydroxyalkyl; polyhydroxyalkyl; polyalkylether having the formula -
((CH2)yO)zR7 where R7 is hydrogen or a linear, branched, substituted or
unsubstituted
alkyl chain having from 1 to 10 carbon atoms and where y is an integer from 2
to 10 and
z is an integer from I to 30; alkoxy; polyalkoxy having the formula: -
(O(CH2)y)zR7; the
group -C(O)R8 where R8 is alkyl; alkaryl; arylalkyl; hydroxyalkyl;
polyhydroxyalkyl and
polyalkyether as defined in R1, R2, R3, and R4; (CX2),,N(R5)(R6) with no more
than
one of R1, R2, R3, and R4 being (CX2)õN(R5)(R6) and wherein R5 and R6 are
alkyl;
alkaryl; arylalkyl; hydroxyalkyl; polyhydroxyalkyl; polyalkylether; alkoxy and
polyalkoxy as defined in R1, R2, R3, and R4; and either of R1 + R3 or R4 or R2
+ R3 or
R4 can combine to form a cyclic substituent.
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Preferred chelating agents include those where R1, R2, R3, and R4 are
independently selected from the group consisting of alkyl groups having from 1
to 10
carbon atoms and hydroxyalkyl groups having from 1 to 5 carbon atoms,
preferably ethyl,
methyl, hydroxyethyl, hydroxypropyl and isohydroxypropyl. The preferred
chelating
agent has more than about 1% nitrogen by weight of the compound, and
preferably more
than 7%. A preferred chelating agent is tetrakis-(2-hydroxylpropyl)
ethylenediamine
(TPED).
The rinse-added composition contains at least about 0.01%, preferably at least
about 0.05%, more preferably at least about 0.10% and less than about 10%,
preferably
less than about 5% and more preferably less than about 1% of chelating agent,
by weight
of the composition.
Suds Suppressor
Another optional ingredient is a suds suppressor, exemplified by silicones,
and
silica-silicone mixtures. Examples of suitable suds suppressors are disclosed
in U.S.
Patent Nos. 5,707,950 and 5,728,671. These suds suppressors are normally
employed at
levels of from 0.001% to 2% by weight of the composition, preferably from
0.01% to 1%
by weight.
Aqueous Carrier
The preferred carrier of the present invention is water. The water which is
used
can be distilled, deionized, or tap water. Water is the main liquid carrier
due to its low
cost, availability, safety, and environmental compatibility. Aqueous solutions
are
preferred for wrinkle control and odor control.
Water is very useful for fabric wrinkle removal or reduction. Not to be bound
by
theory, it is believed that water breaks many intrafiber and interfiber
hydrogen bonds that
keep the fabric in a wrinkle state. It also swells, lubricates and relaxes the
fibers to help
the wrinkle removal process.
Water serves as the liquid carrier for the fabric care branched polysaccharide
and
other soluble and/or dispersible optional ingredients.
Water also serves as the liquid carrier for the cyclodextrins, and facilitates
the
complexation reaction between the cyclodextrin molecules and any malodorous
molecules that are on the fabric when it is treated. The dilute aqueous
solution also
provides the maximum separation of cyclodextrin molecules on the fabric and
thereby
maximizes the chance that an odor molecule will interact with a cyclodextrin
molecule.
It has recently also been discovered that water has an unexpected odor
controlling effect
of its own. It has been discovered that the intensity of the odor generated by
some polar,
low molecular weight organic amines, acids, and mercaptans is reduced when the
odor-
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contaminated fabrics are treated with an aqueous solution. Not to be bound by
theory, it
is believed that water solubilizes and depresses the vapor pressure of these
polar, low
molecular weight organic molecules, thus reducing their odor intensity.
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
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 alcohols can help the
treated fabric
to dry faster. The optional solvent is also useful in the solubilization of
some adjunct
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 also relates to an article of manufacture comprising the
fabric care composition in a package, in association with instructions for how
to use the
composition to treat fabrics correctly, in order to obtain the desirable
fabric care results,
viz, wrinkle removal and/or reduction, wrinkle resistance, fiber
strengthening/anti-wear,
fabric wear reduction, fabric shrinkage prevention and/or reduction, fabric
pill prevention
and/or reduction, shrinkage prevention and/or reduction, fabric color
maintenance, fabric
color fading reduction, soiling prevention and/or reduction, and/or fabric
shape retention,
and mixtures thereof. A preferred article of manufacture comprises said
composition in a
spray dispenser, in association with instructions for how to use the
composition to treat
fabrics correctly, including, e.g., the manner and/or amount of composition to
spray, and
the preferred ways of stretching and/or smoothing of the fabrics to remove
wrinkles, as
will be described with more detailed herein below. It is important that the
instructions be
as simple and clear as possible, so that using pictures and/or icons is
desirable.
The instructions for use direct the consumer to apply an amount of composition
to provide
from about 0.005% to about 4%, preferably from about 0.01% to about 2%, more
preferably from
about 0.05% to about 1% of fabric care polysaccharide, by weight of the
fabric.
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SPRAY DISPENSER
An article of manufacture herein comprises a spray dispenser. The fabric 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, e.g. trigger-type, pump-type, non-
aerosol self-
pressurized, and aerosol-type spray means, for treating the fabric care
composition to
small fabric surface areas and/or a small number of garments, as well as non-
manually
operated, powered sprayers for conveniently treating the wrinkle control
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 care
composition. It has been found that the performance is increased by providing
smaller
particle droplets. Desirably, the Sauter mean particle diameter is from about
10 gm to
about 120 m, more preferably, from about 20 m to about 100 m. Dewrinkling
benefits for example are improved by providing small particles (droplets),
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 fabric care 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 fabric
care
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 et al., issued August 17, 1971,
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Preferably the spray dispenser can be a self-pressurized non-aerosol container
having a convoluted liner and an elastomeric sleeve. Said self-pressurized
dispenser
comprises a liner/sleeve assembly containing a thin, 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 care composition and of causing said
composition 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.
Another type of aerosol spray dispenser is one wherein a barrier separates the
fabric care
composition from the propellant (preferably compressed air or nitrogen), as
disclosed in
U.S. Pat. No. 4,260,110, issued April 7, 1981.
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 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,
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
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polyethylene, vinyl acetate, and rubber elastomer. 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 care
composition. The trigger-spray dispenser herein is typically one which acts
upon a
discrete amount of the fabric 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
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 through 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; 4,161, 288,
McKinney, issued Jul. 17, 1985; 4,434,917, Saito et al., issued Mar. 6, 1984;
and
4,819,835, Tasaki, issued Apr. 11, 1989; 5,303,867, Peterson, issued Apr. 19,
1994,
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, Inc.),
St. Peters,
Missouri; Berry Plastics Corp., Evansville, Indiana, a distributor of Guala
sprayers; or
Seaquest Dispensing, Cary, Illinois.
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The preferred trigger sprayers are the blue inserted Guala sprayer, available
from Berry Plastics Corp., or the Calmar TS800-1A , TS1300 , and TS-800-2 ,
available from Calmar Inc., because of the fine 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 500 ml) of good ergonomics similar in shape to
the Cinch
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.
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 II from Seaquest Dispensing. More preferred are those
with
precompression features.
The article of manufacture herein 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 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 nebulizer sprayers. The fabric 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 fabric care 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
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 shroud that would allow the spray
characteristics to be
altered.
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Nonlimiting examples of commercially available powered sprayers are disclosed
in U.S. Pat. Nos. 4,865,255, Luvisotto, issued Sep. 12, 1989.
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 460 395) 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 care
composition
and dispenses it through a nozzle to create a spray of liquid. The fabric care
composition
can be supplied via separate piping/tubing or more commonly is contained in a
jar to
which the aspirating sprayer is attached.
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. 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 into a fluid
stream by
means of suction created by a Venturi effect. The high turbulence serves to
mix the
aqueous fabric care composition with the fluid stream (typically water) in
order to
provide a uniform mixture/concentration. It is possible with this method of
delivery to
dispense the aqueous concentrated fabric care composition of the present
invention and
then dilute it to a selected concentration with 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 fabric care composition
via a
high electrical potential. This energy serves to atomize and charge the
aqueous fabric
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 effects 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
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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 of commercially available electrostatic sprayers appears
in
U.S. Pat. Nos. 5,222,664, Noakes, issued Jun. 29, 1993; 4,962,885, Coffee,
issued Oct.
16, 1990; 2,695,002, Miller, issued Nov. 1954; 5,405,090, Greene, issued Apr.
11, 1995;
4,752,034, Kuhn, issued Jun. 21, 1988; 2,989,241, Badger, issued Jun. 1961. =
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
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.
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 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
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 hereinbefore, 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
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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/bottle combination is always used. This helps
prevent the
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 can 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.
4,781,311, Nov. 1, 1988 (Angular Positioned Trigger Sprayer with Selective
Snap-Screw
Container Connection, Clorox), U.S. Pat. 5,560,505, Oct. 1, 1996 (Container
and Stopper
Assembly Locked Together by 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).
The present invention also relates to an article of manufacture comprising a
fabric
care composition for use in spraying and/or misting an entire garment in a
manner such
that excessive amounts of the fabric/garment care composition are prevented
from being
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released to the open environment, provided in association with instructions
for use to
ensure that the consumer applies at least an 'effective amount of fabric care
polysaccharied with globular structure and/or fabric care composition, to
provide the
desired garment care benefit, typically from about 0.001% to about 0.5%,
preferably from
about 0.01% to about 0.2%, more preferably from about 0.02% to about 0.05%, by
weight of the garment.
Other fabric care compositions of the present invention for use to treat
fabrics in
different steps of the laundry process, e.g., pre-wash, wash cycle, rinse
cycle, and drying
cycle, can be packaged in association with instructions for how to use the
composition to
treat fabrics correctly, in order to obtain the desirable fabric care results,
viz, wrinkle
removal and/or reduction, wrinkle resistance, fiber strengthening/anti-wear,
fabric wear
reduction, fabric shrinkage prevention and/or reduction, fabric pill
prevention and/or
reduction, shrinkage prevention and/or reduction, fabric color maintenance,
fabric color
fading reduction, soiling prevention and/or reduction, and/or fabric shape
retention, and
mixtures thereof.
III. METHOD OF USE
The fabric care composition, which contains a fabric care polysaccharide with
globular structure, and optionally, e.g., adjunct fabric care
oligosaccharides, perfume,
fiber lubricant, adjunct fabric shape retention polymer, lithium salt,
hydrophilic
plasticizer, odor control agent including cyclodextrin, antimicrobial actives
and/or
preservative, surfactant, enzyme, antioxidant, metal chelating agent including
aminocarboxylate chelating agent, antistatic agent, insect and moth repelling
agent, fabric
softener active, electrolyte, chlorine scavenging agent, dye transfer
inhibiting agent, dye
fixing agent, phase stabilizer, colorant, brightener, soil release agent,
builder, dispersant,
suds suppressor, etc., and mixtures thereof, can be used by distributing,
e.g., by placing,
an effective amount of the aqueous solution onto the 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.
The compositions and articles of the present invention which contain a fabric
care
polysaccharide with globular structure can be used to treat fabrics, garments,
and the like,
to provide at least one of the following fabric care benefits: wrinkle
removal, wrinkle
reduction, wrinkle resistance, fabric wear reduction, fabric wear resistance,
fabric pilling
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reduction, fabric color maintenance, fabric color fading reduction, fabric
color
restoration, fabric soiling reduction, fabric shape retention, and/or fabric
shrinkage
reduction.
An effective amount of the liquid composition of the present invention is
preferably sprayed onto fabric and/or fabric articles include, but are not
limited to,
clothes, curtains, drapes, upholstered furniture, carpeting, bed linens, bath
linens,
tablecloths, sleeping bags, tents, car interiors, etc. 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 care polysaccharide with
globular
structure. For wrinkle removal, once an effective amount of the composition is
sprayed
onto the fabric, the fabric is optionally, but preferably stretched. The
fabric is typically
stretched perpendicular to the wrinkle. The fabric can also be smoothed by
hand after it
has been sprayed. The smoothing movement works particularly well on areas of
clothing
that have an interface sewn into them, or on the hems of clothing. Once the
fabric has
been sprayed and optionally, but preferably, stretched, 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.
The spraying means should be capable of providing droplets with a weight
average diameter of from about 5 m to about 250 m, preferably from about 8
p.m to
about 120 m, more preferably from about 10 ltm to about 80 m. 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 the optional
antimicrobial active provides improved odor control as well as antimicrobial
action, by
minimizing the formation of odors.
The fabric care composition can also be applied to fabric via a dipping and/or
soaking process followed by a squeezing step and/or a drying step. The
application can be
done industrially by large scale processes on textiles and/or finished
garments and
clothings, or in consumer's home by the use of commercial product.
The present invention also comprises a method of using concentrated liquid or
solid fabric care compositions, which are diluted to form compositions with
the usage
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concentrations, as given hereinabove, for use in the "usage conditions".
Concentrated
compositions comprise a higher level of fabric care polysaccharide with
globular
structure, 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
care composition. Concentrated compositions are used in order to provide a
less
expensive product. 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 50% 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
and/or
misted onto fabrics and/or entire garments in need of de-wrinkling and/or
other fabric
care benefits in a manner such that excessive amounts of the fabric/garment
care
composition are prevented from being released to the open environment,
provided in
association with instructions for use to ensure that the consumer applies at
least an
effective amount of fabric care polysaccharide with globular structure and/or
fabric care
composition, to provide the desired garment care benefit. Any spraying
mechanism
and/or misting mechanism can be used to apply the fabric care composition to
fabrics
and/or garments. A preferred distribution of the garment care composition is
achieved by
using a fog form. The mean particulate diameter size of the fabric 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, fabric care composition for treating fabric in the
rinse step,
comprising an effective amount of said fabric care polysaccharide with
globular
structure, and optionally, adjunct fabric care oligosaccharides, fabric
softener actives,
perfume, electrolytes, chlorine scavenging agents, dye transfer inhibiting
agents, dye
fixing agents, phase stabilizers, chemical stabilizers including antioxidants,
silicones,
antimicrobial actives and/or preservatives, chelating agents, aminocarboxylate
chelating
agents, colorants, enzymes, brighteners, soil release agents, or mixtures
thereof. The
rinse water should contain typically from about 0.0005% to about 1%,
preferably from
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about 0.0008% to about 0.1 %, more preferably from about 0.001 % to about
0.02% of the
fabric care polysaccharides.
The present invention also relates to a method of using an aqueous or solid,
preferably powder or granular, fabric care composition to treat the fabrics in
the wash
cycle, said compositions comprise fabric care polysaccharide with globular
structure, and
optionally, adjunct fabric care oligosaccharides, surfactants, builders,
perfume, chlorine
scavenging agents, dye transfer inhibiting agents, dye fixing agents,
dispersants,
detergent enzymes, heavy metal chelating agents, suds suppressors, fabric
softener
actives, chemical stabilizers including antioxidants, silicones, antimicrobial
actives
and/or preservatives, soil suspending agents, soil release agents, optical
brighteners,
colorants, and the like, or mixtures thereof. Depending on the selection of
optional
ingredients, such as the level and type of surfactants, the wash-added fabric
care
composition can be used as a wash additive composition (when the surfactant
level is
low) or as a laundry detergent which also has additional fabric care benefits.
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.
The present invention also relates to a method for treating fabric in the
drying
step, comprising an effective amount of said fabric care polysaccharide with
globular
structure, and optionally, adjunct fabric care oligosaccharides, fabric
softener actives,
distributing agent, perfume, fiber lubricants, fabric shape retention
polymers, lithium
salts, phase stabilizers, chlorine scavenging agents, dye transfer inhibiting
agents, dye
fixing agents, chemical stabilizers including antioxidants, silicones,
antimicrobial actives
and/or preservatives, heavy metal chelating agents, aminocarboxylate chelating
agents,
enzymes, brighteners, soil release agents, and mixtures thereof. The fabric
care
composition can take a variety of physical forms including liquid, foams, gel
and solid
forms such as solid particulate forms. A preferred method comprises the
treatment of
fabric with a dryer-added fabric care composition in combination with a
dispensing
means such as a flexible substrate which effectively releases the fabric care
composition
in an automatic tumble clothes dryer. Such dispensing means can be designed
for single
usage or for multiple uses. Preferably the composition is applied onto a sheet
substrate to
form a dryer sheet product. Another preferred method comprises the treatment
of fabrics
with a fabric care composition dispensed from a a sprayer at the beginning
and/or during
the drying cycle. 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.
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The present invention also relates to a fabric care method of dipping and/or
soaking fabrics before the fabrics is laundered, with a pre-wash fabric care
composition
containing an effective amount of fabric care polysaccharide with globular
structure, and
optionally, adjunct fabric care oligosaccharides, surfactants, builders,
perfume, chlorine
scavenging agents, dye transfer inhibiting agents, dye fixing agents,
dispersants,
detergent enzymes, heavy metal chelating agents, fabric softener actives,
chemical
stabilizers including antioxidants, silicones, antimicrobial actives and/or
preservatives,
soil suspending agents, soil release agents, optical brighteners, colorants,
and the like, or
mixtures thereof. 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.
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 non-limiting examples of the instant composition.
Illustrative examples of fabric care polysaccharides with globular structure
and
with 1,3-a-linked backbone to be used in the following Examples are as
follows:
Arabinogalactan A: arabinogalactan fraction that has the average molecular
weight of
from about 16,000 to about 20,000.
Arabinogalactan B: arabinogalactan fraction that has the average molecular
weight of
about 100,000.
Arabinogalactan C: arabinogalactan fraction that has the average molecular
weight of
from about 10,000 to about 150,000.
Illustrative examples of adjunct fabric care oligosaccharide mixtures to be
used in
the following Examples are as follows:
Isomaltooligosaccharide (IMO Mixture A
Trisaccharides (maltotriose, panose, isomaltotriose) 40%
Disaccharides (maltose, isomaltose) 25%
Monosaccharide (glucose) 20%
Higher branched sugars (4 < DP <10) 15%
Isomaltooli og saccharide (IMO) Mixture B
Trisaccharides (maltotriose, panose, isomaltotriose) 25%
Disaccharides (maltose, isomaltose) 56%
Monosaccharide (glucose) 16%
Higher branched sugars (DP >4 <10) 4%
Branched Oligosaccharide Mixture C
Tetrasaccharides (stachyose) 32%
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Trisaccharides (raffinose) 6%
Disaccharides (sucrose, trehalose) 39%
Monosaccharide (glucose, fructose) 1%
Higher branched sugars (4 < DP <10) 0-5%
Isomaltooligosaccharide (IMO) Mixture D
Trisaccharides (maltotriose, panose, isomaltotriose) 62%
Disaccharides (maltose, isomaltose) 13%
Monosaccharide (glucose) 1%
Higher branched sugars (4 < DP <10) 24%
Illustrative examples of perfume compositions to be used in the following
Examples are as follows:
Volatile Perfume A
Perfume Ingredients wt. %
alpha-Pinene 5.0
Dihydro Myrcenol 10.0
Eucalyptol 10.0
Eugenol 5.0
Flor Acetate 10.0
Lemon Oil 10.0
Linalool 10.0
Linalyl Acetate 5.0
Orange Terpenes 15.0
Phenyl Ethyl Alcohol 20.0
Total 100.0
Substantive Perfume B
Perfume Ingredients Wt. %
Benzyl Salicylate 10.0
Coumarin 5.0
Ethyl Vanillin 2.0
Ethylene Brassylate 10.0
Galaxolide 15.0
Hexyl Cinnamic Aldehyde 20.0
Gamma Methyl Ionone 10.0
Lilial 15.0
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Methyl Dihydrojasmonate 5.0
Patchouli 5.0
Tonalid 3.0
Total 100.0
Hydrophilic Perfume C
Perfume In edients Wt.%
Benzophenone 0.3
Benzyl acetate 4.0
Benzyl propionate 1.0
beta gamma Hexenol 0.3
Cetalox TM 0.1
cis 3 Hexenyl acetate 0.5
cis Jasmone 0.3
cis-3-Hexenyl salicylate 0.5
Citral 0.5
Citronellal nitrite 0.7
Citronellol 1.5
Coumarin 3.0
Cyclal C 0.3
Cyclo galbanate 0.4
beta Damascone 0.1
Dihydro myrcenol 2.0
Ebanol 0.5
Flor acetate 4.5
Florhydral 1.0
Fructone 4.0
Frutene 5.0
Geranyl nitrite 0.4
Heliotropin 1.5
Hydroxycitronellal 3.0
Linalool 2.5
Linalyl acetate 0.5
Methyl dihydro jasmonate 5.0
Methyl heptine carbonate 0.3
Methyl iso butenyl tetrahydro pyran 0.2
Methyl phenyl carbinyl acetate 0.5
Nonalactone 1.5
P. T. BucinalTm 2.0
para Hydroxy phenyl butanone 1.3
Phenoxy ethanol 30.0
Phenyl ethyl acetate 0.8
Phenyl ethyl alcohol 15.0
Prenyl acetate 1.5
Terpineol 2.0
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Verdox 1.0
Vanillin 0.5 -
Total 100.0
The following non-limiting fabric care compositions are prepared by mixing and
dissolving the ingredients into clear or translucent solutions,. in accord
with the present
invention:
Example IA
la Ib Ic Id le if
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.% Wt.%
Arabinogalactan A 0.5 -- -- l -- --
Arabinogalactan B -- 0.3 -- -- 0.5 --
Arabinogalactan C -- -- 0.5 -- -- 0.5
Volatile Perfume A -- -- -- 0.1 --
Substantive Perfume B -- -- -- -- 0.03 --
Hydrophilic Perfume C -- -- -- -- -- 0.05
Polysorbate 60WlW -- -- -- 0.2 0.1 --
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
(1) A mixture of stearate esters of sorbitol and sorbitol anhydride,
consisting
predominantly of the monoester, condensed with about 20 moles of ethylene
oxide.
Example lB
Ig Ih Ii Ij Ik II
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.% wt .%
Quatemized 0.5 -- -- 1 -- --
Arabinogalactan A(2)
Curdlan(3) -- 0.3 -- -- 0.3 --
Dextran( ) -- -- 0.6 -- -- 0.5
Volatile Perfume A -- -- -- 0.1 -- --
Substantive Perfume B -- -- -- -- 0.03 --
Hydrophilic Perfume C -- -- -- -- -- 0.05
Polysorbate 60 -- -- -- 0.2 0.1 --
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
(2) Quaternized arabinogalactan containing about 1.5% by weight of 3-chloro-2-
hydroxypropyltrimethyl ammonium chloride.
(3) Average molecular weight of about 72,000.(4) Average molecular weight of
about
40,000.
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Example II
IIa lib IIc IN lie III
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.% Wt.%
Arabinogalactan A 2 0.3 0.5 0.5 1 --
Arabinogalactan B
Oligosaccharide Mixture A -- 0.3 -- -- -- --
Oligosaccharide Mixture B -- -- 0.5 -- -- --
Oligosaccharide Mixture C -- -- -- 0.3 -- --
Oligosaccharide Mixture D -- -- -- -- 0.5 0.5
Volatile Perfume A 0.1 -- -- 0.1 -- --
Substantive Perfume B 0.2 -- -- -- 0.03 --
Hydrophilic Perfume C -- -- 0.05 -- -- 0.05
Polysorbate 60 0.3 -- -- 0.2 0.1 --
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
Fabric care compositions of Examples I and II are usage compositions for,
e.g., spraying,
soaking, dipping of fabrics, and/or pre-wash treatments.
Example III
Ilia IIIb IIIc IIld Ille IIIf
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.% Wt.%
Arabinogalactan A 15 -- -- 5 -- --
Arabinogalactan B -- 25 -- -- 15 --
Arabinogalactan C -- -- 5 -- -- 25
Perfume A -- -- -- -- I --
Perfume B -- -- -- 0.3 -- --
Perfume C -- -- -- -- -- 1.5
Polysorbate 60 -- -- -- 0.5 1.5 1
Kathon CG 5 ppm 10 5 ppm 5 ppm 5 ppm 5 ppm
ppm
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
Example IV
IVa IVb IVc IVd IVe IVf
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.% Wt.%
Arabinogalactan A 1.5 -- 20 3 10 --
Arabinogalactan B -- --2 -- -- -- 2
Oligosaccharide Mixture A -- -- -- 2 --
Oligosaccharide Mixture B -- -- -- -- 5 --
Oligosaccharide Mixture C -- -- 5 -- -- --
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Oligosaccharide Mixture D 3.5 8 -- --- -- 20
Perfume A -- -- -- , -- 1 --
Perfume B -- -- -- 0.3 -- --
Perfume C -- -- -- -- -- 1.5
Polysorbate 60 -- -- -- 0.5 1.5 1
Kathon CG 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
Concentrated compositions of Examples Ill and N are diluted with water to
obtain usage
compositions for, e.g., spraying, soaking and/or dipping fabric articles. They
can also be
used undiluted to treat fabric as wash additive and/or rinse additive
compositions.
Example V
Va Vb Vc Vd Ve
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.%
Arabinogalactan A I -- -- -- 1.5
Arabinogalactan B -- 0.5 -- 1 --
Arabinogalactan C -- -- 0.5 -- --
LiBr 3 -- -- 2 2
Silicone Emulsion A(5) -- 1.5 -- -- 2.0
D5 Volatile Silicone -- -- 0.5 0.5 --
Perfume A -- -- -- -- 0.03
Perfume B -- -- -- 0.05 --
Perfume C 0.03 -- -- -- --
Polysorbate 60 -- -- -- 0.1 0.05
Silwet L-7602 -- -- -- 0.5 --
Silwet L-7622 -- -- -- -- 0.3
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Deionized Water Bal. Bal. Bal. Bal. Bal.
(5) 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 VIA
VIa VIb VIc VId Vle
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.%
Arabinogalactan A 0.45 0.5 0.7 0.8 --
Arabinogalactan B -- -- -- -- 0.2
Oligosaccharide Mixture A 0.05 -- -- -- --
Oligosaccharide Mixture B -- 1 -- -- --
Oligosaccharide Mixture C -- -- 0.3 -- --
Oligosaccharide Mixture D -- -- -- 1.2 0.8
LiBr 3 -- -- 2 2
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Silicone Emulsion A(5) -- 1.5 -- -- 2.0
D5 Volatile Silicone -- -- 0.5 0.5 --
Perfume A -- -- -- -- 0.03
Perfume B -- -- -- 0.05 --
Perfume C 0.03 -- -- -- --
Polysorbate 60 -- -- -- 0.1 0.05
Silwet L-7602 -- -- -- 0.5 --
Silwet L-7622 -- -- -- -- 0.3
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Deionized Water Bal. Bal. Bal. Bal. Bal.
(5) 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 VIB
VIf VIg VIh vii VIj
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.%
Quaternized
Arabinogalactan A 0.75 -- -- -- 0.2
Curdlan -- 0.3 -- -- --
Dextran -- -- 0.7 0.8 --
Oligosaccharide Mixture A 0.05 -- -- -- --
Oligosaccharide Mixture B -- 1 -- -- --
Oligosaccharide Mixture C -- -- 0.3 -- --
Oligosaccharide Mixture D -- -- -- 1.2 0.8
LiBr 3 -- -- 2 2
Silicone Emulsion A(5) -- 1.5 -- -- 2.0
D5 Volatile Silicone -- -- 0.5 0.5 --
Perfume A -- -- -- -- 0.03
Perfume B -- -- -- 0.05 --
Perfume C 0.03 -- -- -- --
Polysorbate 60 -- -- -- 0.1 0.05
Silwet L-7602 -- -- -- 0.5 --
Silwet L-7622 -- -- -- -- 0.3
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Deionized Water Bal. Bal. Bal. Bal. Bal.
Example VII
VIIa VIIb VIIc VIN VIIe VIIf
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.% Wt.%
Arabinogalactan A 0.7 -- -- 1 0.5
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Arabinogalactan B -- 0.5 -- -- -- 0.5
Arabinogalactan C -- -- 0.5 -- -- --
Copolymer A(6) 0.4 -- -- -- -- 0.5
Copolymer B(7) -- 0.5 -- 0.3 -- --
Copolymer C(8) -- -- 0.6 -- 0.5 --
LiBr -- -- -- 3 -- 2
Silicone Emulsion A(S) -- -- -- -- 1.5 --
D5 Volatile Silicone -- -- 0.5
Perfume A 0.06 -- -- -- -- 0.07
Perfume B -- 0.03 -- 0.03 -- --
Perfume C -- -- 0.04 -- 0.03 --
Polysorbate 60 0.1 0.1 0.03 0.1 0.1 0.1
Silwet L-7600 -- -- -- 0.5 -- --
Silwet L-7602 -- -- -- -- -- 0.7
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
(5) DC-2-5932 silicone microemulsion (25% active) from Dow Coming, 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.
(6) Acrylic acid/tert-butyl acrylate copolymer, with an approximate acrylic
acid/tert-
butyl acrylate weight ratio of about 25/75 and an average molecular weight of
from
about 70,000 to about 100,000.
(7) 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.
(8) Acrylic acid/tert-butyl acrylate copolymer, with an approximate acrylic
acid/tert-
butyl acrylate weight ratio of about 20/80 and an average molecular weight of
from
about 80,000 to about 110,000.
Example VIII
VIIIa VIIIb VIIIc VIIId VIIIVe VIIIf
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.% Wt.%
Arabinogalactan A 0.9 -- -- 0.5 0.75 0.7
Arabinogalactan B -- 0.5 -- -- -- --
Arabinogalactan C -- -- 0.5 -- -- --
Oligosaccharide Mixture A 0.3 -- -- -- 0.25 --
Oligosaccharide Mixture B -- 1 -- -- -- --
Oligosaccharide Mixture C -- -- 0.5 -- -- --
Oligosaccharide Mixture D -- -- -- 1.5 -- 1
Copolymer A(6) 0.4 -- -- -- -- 0.5
Copolymer B(7) -- 0.5 -- 0.3 -- --
Copolymer C(8) -- -- 0.6 -- 0.5 --
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LiBr -- -- -- 3 -- 2
Silicone Emulsion A(5) -- -- --. -- 1.5 --
D5 Volatile Silicone -- -- -- -- -- 0.5
Perfume A 0.06 -- -- -- -- 0.07
Perfume B -- 0.03 -- 0.03 -- --
Perfume C -- -- 0.04 -- 0.03 --
Polysorbate 60 0.1 0.1 0.03 0.1 0.1 0.1
Silwet L-7600 -- -- -- 0.5 -- --
Silwet L-7602 0.7.
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
Example IX
IXa IXb IXc IXd IXe IXf
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.% Wt.%
Arabinogalactan A 0.7 7 1
Arabinogalactan B -- 0.5 -- 0.5 -- --
Arabinogalactan C -- -- 0.5 -- -- --
Copolymer D(9) 0.4 -- -- -- 2 0.25
Copolymer E(10) -- 0.5 -- -- -- 0.25
Copolymer F(11) -- -- 0.4 -- -- --
Copolymer G(12) -- -- -- 0.5 -- --
D5 Volatile Silicone -- 0.25 -- -- -- --
PDMS 10,000 cst -- -- -- 0.3 -- --
Silicone Emulsion B(13) -- -- 1 -- 2 --
Perfume A 0.06 -- -- -- -- 0.07
Perfume B -- 0.03 -- 0.03 -- --
Perfume C, -- -- 0.04 -- 0.5 --
Polysorbate 60 0.1 0.1 -- 0.1 0.5 0.1
Neodol 23-3 -- 0.25 -- 0.2 -- --
Neodol25-3 -- -- 0.3 -- 0.3 0.25-
Silwet L-77 -- 0.7 -- 1 -- --
Silwet L-7604 -- -- 0.5 -- -- 0.7
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 5 ppm 3 ppm
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
(9) Acrylic acid/tert-butyl acrylate copolymer, with an approximate acrylic
acid/tert-
butyl acrylate weight ratio of about 23/77 and an average molecular weight of
about
82,000.
(10) Silicone-containing copolymer having t-butyl acrylate/acrylic acid/
(polydimethylsiloxane macromer, 10,000 approximate molecular weight) monomer
at an approximate 63/20/17 weight ratio, and of an average molecular weight of
about 130,000.
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(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.
The composition of Example IXe is a concentrated composition, to be diluted
for use.
Example X
Xa Xb Xc Xd Xe Xf
Ingredients Wt.% Wt.% Wt.% Wt.% Wt.% Wt.%
Arabinogalactan A -- 0.5 0.8 -- 6 2
Arabinogalactan B 0.7 -- -- -- -- --
Arabinogalactan C -- -- -- 0.35 -- --
Oligosaccharide Mixture A 0.7 -- -- -- -- --
Oligosaccharide Mixture B -- 1 -- 0.85 -- --
Oligosaccharide Mixture C -- -- 0.2 -- -- --
Oligosaccharide Mixture D -- -- -- -- 5 0.5
Copolymer D(9) 0.4 -- -- -- 2 0.25
Copolymer E(10) -- 0.5 -- -- -- 0.25
Copolymer F(11) -- -- 0.4 -- -- --
Copolymer G(12) -- -- -- 0.5 -- --
D5 Volatile Silicone -- 0.25 -- -- -- --
PDMS 10,000 cst -- -- -- 0.3
Silicone Emulsion B(13) -- -- 1 -- 2 --
Perfume A 0.06 -- -- -- -- 0.07
Perfume B -- 0.03 -- 0.03 -- --
Perfume C -- -- 0.04 -- 0.5 --
Polysorbate 60 0.1 0.1 -- 0.1 0.5 0.1
Neodol 23-3 -- 0.25 -- 0.2 -- --
Neodol25-3 -- -- 0.3 -- 0.3 0.25
Silwet L-77 -- 0.7 -- 1 -- --
Silwet L-7604 -- -- 0.5 -- -- 0.7
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 10 3 ppm
ppm
Deionized Water Bal. Bal. Bal. Bal. Bal. Bal.
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The composition of Example Xe is a concentrated composition, to be diluted for
use.
Example XI
XIa XIb XIc XId XIe XIf
Ingredients Wt% Wt% Wt% Wt% Wt% Wt%
Arabinogalactan A 0.8 -- -- 1 -- 1.5
Arabinogalactan B -- 0.5 -- -- 0.7 --
Arabino alactan C -- -- 0.5 --
HPBCD(14) 1 -- 0.5 -- 0.5
RAMEB(15) -- 1 -- -- -- --
HPACD(16) -- -- 0.5 -- -- --
a-Cyclodextrin -- -- -- -- Ø5 0.5
(3-Cyclodextrin -- -- -- 0.5 -- 0.5
ZnC12 -- 1.0 -- 1.0 -- I
Silwet L-7657 -- -- -- -- 0.05 --
Perfume C 0.1 0.07 0.05 -- 0.1 0.05
Propylene glycol 0.06 -- 0.05 -- 0.03 --
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
HC1 -- to pH 4.5 -- to pH 5 -- to pH 4.5
Distilled water Bal. Bal. Bal. Bal. Bal. Bal.
(14) Hydroxypropyl beta-cyclodextrin.
(15) Randomly methylated beta-cyclodextrin.
(16) Hydroxypropyl alpha-cyclodextrin.
Example XII
XIIa XIIb XIIc Xlld XIIe XIIf
Ingredients Wt% Wt% Wt% Wt% Wt% Wt%
Arabinogalactan A 0.6 0.6 1 0.1 -- --
Arabinogalactan B -- -- -- -- 0.5 --
Arabinogalactan C -- -- -- -- -- 0.3
Oligosaccharide Mixture A 0.9 -- -- -- -- --
Oligosaccharide Mixture B -- 0.4 -- -- 0.7 0.7
Oligosaccharide Mixture C -- -- 0.5 -- -- --
Oligosaccharide Mixture D 0.9
HPBCD(14) 1 -- 0.5 -- 0.5 --
RAMEB(15) -- 1 -- -- -- --
HPACD(16) -- -- 0.5 -- -- --
a-Cyclodextrin -- -- -- -- 0.5 0.5
.3-Cyclodextrin -- -- -- 0.5 -- 0.5
ZnC12 -- 1.0 -- 1.0 -- 1
Silwet L-7657 -- -- -- -- 0.05 --
Perfume C 0.1 0.07 0.05 -- 0.1 0.05
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Propylene glycol 0.06 -- 0.05 -- 0.03 --
Kathon CG 3 ppm 3 ppm 3=ppm 3 ppm 3 ppm 3 ppm
HC1 -- to pH 4.5 -- to pH 5 -- to pH 4.5
Distilled water Bal. Bal. Bal. Bal. Bal. Bal.
Example XIII
XIIIa XIIIb XIIIc XIIId XIIIe XIIIf
Ingredients Wt% Wt% Wt% Wt% Wt% Wt%
Arabinogalactan A 0.7 -- -- 0.5 1 1
Arabinogalactan B -- 0.5 -- -- -- --
Arabinogalactan C -- -- 1 -- -- --
HPBCD 1.0 -- -- -- -- --
RAMEB -- 1.0 -- -- -- --
Silwet L-7604 0.3 0.2 0.2 -- -- 0.1
Chlorhexidine 0.01 -- -- -- -- 0.005
Barquat 4250(17) -- -- 0.03 -- -- --
Bardac 2050(18) -- -- -- 0.03 0.03 --
Perfume C 0.08 0.08 0.05 0.05 -- --
HC1 to pH 4 -- -- -- -- --
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Distilled water Bal. Bal. Bal. Bal. Bal. Bal.
(17) Benzalkonium chloride, 50% solution.
(18) Dioctyl dimethyl ammonium chloride, 50% solution.
Example XIVA
XIVa XIVb XIVc XIVd XIVe XIVf
Ingredients Wt% Wt% Wt% Wt% Wt% Wt%
Arabinogalactan A 1 1 0.3 0.9 -- --
Arabinogalactan B -- -- -- -- 0.5 --
Arabinogalactan C -- -- -- -- -- 0.2
Oligosaccharide Mixture A 0.7 -- -- -- -- --
Oligosaccharide Mixture B -- 0.5 -- -- 0.5 --
Oligosaccharide Mixture C -- -- 1.2 -- -- --
Oligosaccharide Mixture D -- -- -- 0.6 -- 1.8
HPBCD 1.0 -- -- -- -- --
RAMEB -- 1.0 -- -- -- --
Silwet L-7604 0.3 0.2 0.2 -- -- 0.1
Chlorhexidine 0.01 -- -- -- -- 0.005
Barquat 4250(17) -- -- 0.03 -- -- --
Bardac 2050(18) -- -- -- 0.03 0.03 --
Perfume C 0.08 0.08 0.05 0.05 -- --
HCI to pH-4 -- -- -- -- --
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Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Distilled water Bal. Bal. Bal. Bal. Bal. Bal.
Example X1VB
XIVg XIVh XIVi XIVi XIVk XIVI
Ingredients Wt% Wt% Wt% Wt% Wt% Wt%
Quaternized 0.5 -- - 0.6 -- --
Arabinogalactan A
Curdlan -- 0.3 -- - 0.2 --
Dextran -- -- 0.3 -- -- 0.2
Oligosaccharide Mixture A 0.5 -- -- -- -- --
Oligosaccharide Mixture B -- 0.5 -- -- 0.7 --
Oligosaccharide Mixture C -- -- 1.2 -- -- --
Oligosaccharide Mixture D -- -- -- 0.6 -- 1.8
HPBCD 1.0 -- -- -- -- --
RAMEB -- 1.0 -- -- -- --
Silwet L-7604 0.3 0.2 0.2 -- -- 0.1
Chlorhexidine 0.01 -- -- -- -- 0.005
Barquat 4250 - -- 0.03 -- -- --
Bardac 2050 -- -- -- 0.03 0.03 --
Perfume C 0.08 0.08 0.05 0.05 -- --
HCl to pH 4 -- -- -- -- --
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Distilled water Bal. Bal. Bal. Bal. Bal. Bal.
The compositions of Examples 1 to XIV (diluted when appropriate) are sprayed
TM
onto clothing using, e.g., the TS-800 sprayer from Calmar, and allowed to
evaporate off
of the clothing.
The compositions of Examples I to X1V (diluted when appropriate) are sprayed
onto clothing, using a blue inserted Guala trigger sprayer, available from
Berry Plastics
Corp. and a cylindrical Euromist II pump sprayer available from Seaquest
Dispensing,
respectively, and allowed to evaporate off of the clothing.
The compositions of Examples I to XIV (diluted when appropriate) contained in
TM
rechargeable battery-operated Solo Spraystar sprayers are sprayed onto large
surfaces of
fabric, such as several pieces of clothing, and allowed to evaporate off of
these surfaces.
The compositions of Examples I to XIV (diluted when appropriate) are used for
soaking or dipping of fabrics which are then optionally wrung or squeezed to
remove
excess liquid and subsequently dried.
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Following are Examples for rinse-added fabric care compositions in accordance
with
the present invention:
Example XV
XVa XVb XVc XVd We
Ingredients Wt% Wt% Wt% Wt.% Wt%
Arabinogalactan A 8 -- -- 20 --
Arabinogalactan B -- 3 -- -- 15
Arabinogalactan C -- -- 5 -- --
Fabric softener A"9) 4.5 -- -- -- --
Fabric softener B(20) -- 24 -- -- --
Fabric softener C(21) -- -- 26 -- --
Fabric softener D(22) -- -- -- 28 28
Fabric softener E(23) 3.4 -- -- -- --
1,2-Hexanediol -- -- 18 -- --
2-Ethyl.--1,3-hexanediol -- -- -- 6 --
Neodol91-8 -- -- - 5 3
Pluronicc'L-35 -- - -- I
Hexylene glycol -- -- -- -- 3
Hexylene glycol (from
softener active) -- -- -- 2.5 2.5
Ethanol (from softener
active) - 4.2 4.6 2.3 2.3
Perfume B 0.3 1.3 1.3 2 1.2
Tenon 6 antioxidant 0.02 0.04 0.04 0.04 0.04
CaC12 0.05 0.4 0.5 -- 2
MgC12 - -- -- 1.6 --
HC1 to pH 6 to pH 3.5 to pH 3.5 to pH 3 to pH 3
Kathon CG 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm
Deionized water and other
minor ingredients Bal. Bal. Bal. Bal. Bal.
(19) Di(hydrogenated tallowyl) dimethyl ammonium chloride/hydrogenated
tallowy]
trimethyl ammonium chloride blend of about 83:17 weight ratio.
(20) Di(acyloxyethyl) dimethyl ammonium chloride wherein the acyl group is
derived
from soft tallow fatty acids and with a diester-to-monoester weight ratio of
about
11:1.
(21) Di(acyloxyethyl) dimethyl ammonium chloride wherein the acyl group is
derived
from partially hydrogenated canola fatty acids and with a diester-to-monoester
weight ratio of about 11:1.
(22) Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate wherein
the
acyl group is derived from partially hydrogenated canola fatty acids.
(23) l -Tallow(amidoethyl)-2-tallowimidazoline.
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Example XVI
XVIa XVIb XVIc XVId XVIe XVIf
In edients Wt% Wt% Wt% Wt.% Wt% Wt%
Arabinogalactan A 5 -- -- 5 9 15
Arabinogalactan B -- 3 -- -- -- --
Arabinogalactan C -- -- 2 -- -- --
Oligosaccharide Mixture A -- 3 -- -- -- --
Oligosaccharide Mixture B 5 -- -- -- -- --
Oligosaccharide Mixture C -- -- -- -- 3 --
Oligosaccharide Mixture D -- -- 8 2 --
Fabric softener A(19) 4.5 -- -- -- -- --
Fabric softener B(20) -- 24 -- -- -- --
Fabric softener C(21) -- -- 26 -- --
Fabric softener D(22) -- -- -- 28 28 --
Fabric softener E(23) 3.4 -- -- -- -- --
1,2-Hexanediol -- -- 18 --
2-Ethyl- 1,3-hexanediol -- -- -- 6 -- --
Neodol 91-8 -- -- - 5 3 --
Pluronic L-35 -- -- -- 1 --
Hexylene glycol -- -- -- -- 3 --
Hexylene glycol (from
softener active) -- -- -- 2.5 2.5 --
Ethanol (from softener
active) -- 4.2 4.6 2.3 2.3 --
Perfume B 0.3 1.3 1.3 2 1.2 1.2
Tenox 6 antioxidant 0.02 0.04 0.04 0.04 0.04
CaC12 0.05 0.4 0.5 -- 2 --
MgC12 -- -- -- 1.6 -- --
HCl to pH 6 to pH to pH to pH to pH --
3.5 3.5 3 3
Polysorbate 60 -- -- -- -- -- 1
Deionized water and other
minor ingredients Bal. Bal. Bal. Bal. Bal. Bal.
Example XVII
XVIIa XVIIb XVIIc XVIId XVIIe XVIIf
Ingredients Wt% Wt% Wt% Wt.% Wt% Wt%
Arabinogalactan A 6 -- -- 15 -- 30
Arabinogalactan B -- 20 -- -- 10 --
Arabinogalactan C -- -- 16 -- --
Fabric softener A(' 9) 4.5 -- -- -- -- --
Fabric softener B(20) -- 22 25 25 -- --
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Fabric softener E(23) 3.4 -- -- -- -- --
PVP K-15(24 1 3 -- -- 5 --
PVNO(25) -- -- 1 -- -- --
Cellulase(26) -- -- -- 1 -- 2--
Perfume B 0.4 1.3 1.3 1.3 2 --
Perfume C -- -- -- -- -- 1.5
Polysorbate 60 -- -- -- -- 5 1
HCl to pH 5 to pH to pH to pH -- --
3.5 3.5 3.5
Kathon CG 5 ppm 5 ppm 5 ppm 5 ppm 5 ppm 10 ppm
Deionized water and
minor ingredients Bal. Bal. Bal. Bal. Bal. Bal.
(19) Di(hydrogenated tallowyl) dimethyl ammonium chloride/hydrogenated
tallowy]
trimethyl ammonium chloride blend of about 83:17 weight ratio. .
(20) Di(acyloxyethyl) dimethyl ammonium chloride wherein the acyl group is
derived
from soft tallow fatty acids and with a diester-to-monoester weight ratio of
about
11:1.
(23) 1 -Tallow(amidoethyl)-2-tallowimidazoline.
(24) Polyvinylpyrrolidone with an average molecular weight of about 10,000.
(25) Poly(4-vinylpyridine-N-oxide) with an average molecular weight of about
25,000.
(26) The cellulase consists essentially of a homogeneous endoglucanase
component,
which is immunoreactive with an antibody raised against a hightly purified 43
1cD
cellulase derived from Humicola insolens, DMS 1800, or which is homologous to
said 43 kD endoglucanase; the cellulase solution used provides about 5,000
CEVU's
per gram.
Example XVHI
XVIIIa XVIIIb XVIIIc XVIIId XVIIIe XVIIIf
Ingredients Wt% Wt% Wt% Wt.% Wt% Wt%
Arabinogalactan A 4 5 -- 15 -- 16
Arabinogalactan B -- -- 5-- -- -- --
Arabinogalactan C -- -- -- -- 6 --
Oligosaccharide Mixture A 6 -- -- 10 -- --
Oligosaccharide Mixture B -- 10 -- -- 6 --
Oligosaccharide Mixture C 5
Oligosaccharide Mixture D -- -- -- 5 -- 4
Fabric softener A 4.5 -- -- -- -- --
Fabric softener B -- 22 25 25 -- --
Fabric softener E 3.4 -- -- -- -- --
PVP K-15 1 3 -- -- 5 --
PVNO -- -- 1 -- -- --
Cellulase(26) -- -- -- I -- 2
Perfume B 0.4 1.3 1.3 1.3 2 --
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Perfume C -- -- -- -- -- 1.5
Polysorbate 60 -- -- . -- -- 5 1
HCl to pH 5 to pH to pH to pH -- --
3.5 3.5 3.5
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Deionized water and minor
ingredients Bal. Bal. Bal. Bal. Bal. Bal.
Example XIX
XIXa XIXb XIXc XIXd XIXe XIXf
Ingredients Wt% Wt% Wt% Wt% Wt% Wt%
Arabinogalactan A 10 -- -- -- -- --
Arabinogalactan B -- 16 -- -- -- --
Arabinogalactan C -- -- 12 -- -- --
Quaternized
Arabinogalactan A(2) -- -- -- 12 -- --
Curdlan(3) -- -- -- -- 8 --
Dextran(4) -- -- -- -- -- 12
Fabric softener D(22) 35 35 35 35 35 35
TMPD(27) 5 5 5 5 5 5
Neodol 91-8 6 6.5 6.5 6 6.5 6.5
Pluronic L-35 1 1 1.5 1 1 1.5
Hexylene glycol (from
softener active) 3.1 3.1 3.1 3.1 3.1 3.1
Ethanol (from softener
active) 2.9 2.9 2.9 2.9 2.9 2.9
TPED(28) 0.75 0.75 0.75 0.75 0.75 0.75
DTPA(29) 0.01 0.1 0.01 0.01 0.1 0.01
Perfume 2.5 3 1.8 2.5 3 1.8
MgC12 1.75 1 1 1.75 1 1
Blue dye 6 ppm 6 ppm 6 ppm 6 ppm 6 ppm 6 ppm
HCl to pH to pH to pH to pH to pH to pH
6 3.5 3.5 6 3.5 3.5
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Deionized water and
other minor ingredients Bal. Bal. Bal. Bal. Bal. Bal.
(22) Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate wherein
the
acyl'group is derived from partially hydrogenated canola fatty acids.
(27) 2,2,4-Trimethyl-1,3-pentanediol.
(28) Tetrakis-(2-hydroxypropyl) ethylenediamine.
(29) Sodium diethylenetriaminepentaacetate.
Example XX
XXa XXb XXc XXd XXe XXf
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Ingredients Wt% Wt% Wt% Wt% Wt% Wt%
Arabinogalactan A 6 -- --
Arabinogalactan B -- 10 -- -- -- --
Arabinogalactan C -- -- 4 -- -- --
Quaternized
Arabinogalactan A(2) -- -- -- 10 --
Curdlan(3) -- -- -- -- 3 --
Dextran(4) -- -- -- -- -- 8
Oligosaccharide Mixture A -- -- -- 2 - --
Oligosaccharide Mixture B -- -- 8 -- 5 --
Oligosaccharide Mixture C -- 6 -- -- -- --
Oligosaccharide Mixture D 6 -- -- -- -- 4
Fabric softener D(22) 35 35 35 35 35 35
TMPD(27) 5 5 5 5 5 5
Neodol 91-8 6 6.5 6.5 6 6.5 6.5
Pluronic L-35 1 1 1.5 1 1 1.5
Hexylene glycol (from
softener active) 3.1 3.1 3.1 3.1 3.1 3.1
Ethanol (from softener
active) 2.9 2.9 2.9 2.9 2.9 2.9
TPEDI28) 0.75 0.75 0.75 0.75 0.75 0.75
DTPA(29) 0.01 0.1 0.01 0.01 0.1 0.01
Perfume 2.5 3 1.8 2.5 3 1.8
MgCl2 1.75 1 1 1.75 1 1
Blue dye 6 ppm 6 ppm 6 ppm 6 ppm 6 ppm 6 ppm
HCl to pH to pH to pH to pH to pH to pH
6 3.5 3.5 6 3.5 3.5
Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Deionized water and other
minor ingredients Bal. Bal. Bal. Bal. Bal. Bal.
Following are Examples for laundry detergent fabric care compositions in
accordance with
the present invention:
Example XXI
XXIa XXIb XXIc XXId XXIe
Ingredients Wt% Wt.% Wt% Wt.% Wt.%
LAS(a) 8 8 8 7 7
C25E3(b) 3.4 3.4 3.4 3.4 3.4
QAS(C) -- 0.8 -- 0.8 0.8
Zeolite A 17 17 17 16 16
Carbonate 13 24 13 22 22
Silicate 1.4 3 1.4 3 3
Sulfate 25 16 24 12 12
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PB4(d) 9 8 9 8 7
TAED(e) 1.5 1.5 . 1.5 1.5 1.5
DETPMP(0 0.25 0.25 0.25 0.25 0.25
HEDP(9) 0.3 0.3 0.3 0.3 0.3
Arabinogalactan A 18 -- -- 15 14
Arabinogalactan B -- 15 -- -- --
Arabinogalactan C -- -- 20 -- --
Oligosaccharide Mixture A -- -- -- 8 --
Oligosaccharide Mixture D -- -- -- -- 10
Protease 26 ppm 26 ppm 26 ppm 26 ppm 26 ppm
MA/AA(h) 0.3 0.3 0.3 0.3 0.3
CMCO) 0.2 0.2 0.2 0.2 0.2
Photoactivated Bleach -- 10 ppm -- 10 ppm 10 ppm
Brightener 0.09 0.09 0.09 0.09 0.09
Perfume 0.3 0.3 0.3 0.3 0.3
Silicone antifoam 0.5 0.5 0.5 0.5 0.5
Moisture and Miscellaneous Balance Balance Balance Balance Balance
La)-Sodium linear C 12 alkyl benzene sulphonate.
(hhA C12-C15 predominantly linear primary alcohol condensed with an average of
3
moles of ethylene oxide.
)JC 12-C 14) N+(CH3)2(C2H4OH)
fAhSodium perborate.4H20.
LTetraacetyl ethylene diamine.
ffLDiethylene triamine penta(methylene phosphonic acid), marketed by Monsanto
under
the Trade name Dequest 2060.
(gL1,1-Hydroxyethane diphosphonic acid.
(h) Copolymer of 1:4 maleic/acrylic acid, average molecular weight about
70,000-
80,000.
Sodium carboxymethyl cellulose.
Example XXII
Nil bleach-containing laundry detergent fabric care compositions of particular
use in the
washing of colored clothing:
XXIIa XXIIb XXIIc XXIId XXIIe
Ingredients Wt% Wt.% Wt% Wt.% Wt.%
Blown Powder
Zeolite A 13 14 13 13 13
Sodium sulfate -- 14 -- 13 12
LAS 2.8 3 2.8 3 2.8
DETPMP 0.4 0.5 0.4 0.5 0.5
CMC 0.4 0.4 0.4 0.4 0.4
MA/AA 3.8 4 3.8 3.5 3.8
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Agglomerates
LAS 5.5 5 . 5.5 5 5
TAS0) 3 2 3 2 2
Silicate 4 4 4 4 4
Zeolite A 8 13 9 12 12
Carbonate 8 7 9 6 7
Spray On
Perfume 0.3 0.3 0.3 0.3 0.3
C45E7(k) 4 4 4 4 4
C25E3 1.8 1.8 1.8 1.8 1.8
Dry additives
Na Citrate 9.5 -- 10 -- --
Na Bicarbonate 6.5 3 6.5 3 3
Na Carbonate 7.5 5 7.5 4.5 4.5
PVPVI/PVNO(') 0.5 0.5 0.5 0.5 0.5
Arabinogalactan A 15 -- -- 15 --
Arabinogalactan B -- 12 -- -- 9
Arabinogalactan C -- -- 12 -- --
Oligosaccharide Mixture C -- -- -- 5 --
Oligosaccharide Mixture D -- -- -- -- 9
Protease 0.026 0.016 0.026 0.016 0.016
Lipase 0.009 0.009 0.009 0.009 0.009
Amylase 0.005 -- 0.005 -- --
Cellulase 0.006 0.006 0.006 0.006 0.006
Silicone antifoam 4 3 4 3.5 3
Moisture and Miscellaneous Balance Balance Balance Balance Balance
(j) Sodium tallow alkyl sulphate.
(k) A C 14-C 15 predominantly linear primary alcohol condensed with an average
of 7
moles of ethylene oxide
(1) Copolymer of vinyl-imidazole and vinyl-pyrrolidone/poly (4-vinylpyridine)-
N-oxide.
Example XXIII
Examples of liquid detergent fabric care compositions according to the present
invention:
XXIIIa XXIIIb XXIIIc XXIIId XXIIIe
Ingredients Wt% Wt.% Wt% Wt% Wt%
LAS 9 8 -- 22 --
C25AS(m) 4 2 9 -- 12
C25E3S(") 1 -- 3 -- 3.5
C25E7 6 12 2.5 -- 3.5
TFAA( ) -- -- 4.5 -- 7.5
QAS -- -- -- 3 --
TPKFA(P) 2 12 2 -- 5.5
Canola fatty acids -- -- 5 -- 4
Citric 2 1 1.5 1 1
Dodecenyl/ tetradecenyl 10 -- -- 14 --
succinic acid
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Oleic acid 4 1 -- 1 --
Ethanol 4 6 2 6 2
1,2 Propanediol 4 2 6 6 10
Mono Ethanol Amine -- -- 5 -- 8
Tri Ethanol Amine -- 7 -- -- --
NaOH (pH) 8 7.5 7.5 8 8
Ethoxylated tetraethylene 0.5 0.5 0.2 -- 0.3
pentamine
DETPMP 1 0.5 1 2 --
Soil Release Polymer 0.3 0.3 0.1 -- 0.1
PVNO(q) -- -- -- -- 0.1
Arabinogalactan A 15 -- -- -- --
Arabinogalactan B -- 12 -- -- --
Arabinogalactan C -- -- 15 -- --
Curdlan -- -- -- 12 --
Dextran -- -- -- -- 10
Protease 50 ppm 40 ppm 30 ppm 0.08 60 ppm
Lipase -- -- 2 ppm -- 30 ppm
Amylase 20 ppm 50 ppm 40 ppm 20 ppm 50 ppm
Cellulase -- -- 1 ppm -- 4 ppm
Boric acid 0.1 -- 2 1 2.5
Na formate -- 1 -- -- --
Ca chloride -- -- 0.01 -- --
Bentonite clay -- -- -- 3.5 --
Suspending clay -- -- -- 0.6 --
Water and Miscellaneous Bal. Bal. Bal. Bal. Bal.
(m) Sodium C12-C15 alkyl sulfate.
(n) C12-C15 sodium alkyl sulfate condensed with an average of 3 moles of
ethylene
oxide per mole.
(o) C 16-C 18 alkyl N-methyl glucose amide.
(p) C12-C14 topped whole cut fatty acids.
(q) Poly(4-vinylpyridine-N-oxide) dye transfer inhibiting agent.
Example XXIV
Examples of liquid detergent fabric care compositions according to the present
invention:
XXIVa XXIVb XXIVc XXIVd XXIVe
Ingredients Wt% Wt.% Wt% Wt% Wt%
LAS 8 8 -- 19 --
C25AS 4 2 8 -- 11
C25E3S 1 -- 3 3.5
C25E7 5.5 11 2.5 -- 3.5
TFAA -- -- 4.5 -- 7.5
QAS -- -- -- 3 --
TPKFA 2 11 2 -- 5
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Canola fatty acids -- -- 4.5 -- 4
Citric 2 1 1.5 1 1
Dodecenyl/ tetradecenyl 9.5 -- -- 13 --
succinic acid
Oleic acid 4 1 -- 1 --
Ethanol 4 6 2 6 2
1,2 Propanediol 4 2 5.5 6 8
Mono Ethanol Amine -- -- 5 -- 7
Tri Ethanol Amine -- 6 -- --
NaOH (pH) 8 7.5 7.5 8 8
Ethoxylated tetraethylene 0.5 0.5 0.2 -- 0.3
pentamine
DETPMP 1 0.5 1 2 --
Soil Release Polymer 0.3 0.3 0.1 -- 0.1
PVNO -- -- -- -- 0.1
Arabinogalactan A 12 15
Arabinogalactan B 12 10
Arabinogalactan C 5
Oligosaccharide Mixture A 5 -- -- -- --
Oligosaccharide Mixture C -- 3 -- -- 5
Oligosaccharide Mixture D -- -- 12 5 --
Protease 50 ppm 40 ppm 30 ppm 0.08 60 ppm
Lipase -- -- 2 ppm -- 30 ppm
Amylase 20 ppm 50 ppm 40 ppm 20 ppm 50 ppm
Cellulase -- -- 1 ppm -- 4 ppm
Boric acid 0.1 -- 2 1 2.5
Na formate -- 1 -- -- --
Ca chloride -- -- 0.01 -- --
Bentonite clay -- -- -- 2.5 --
Suspending clay SD3 -- -- -- 0.5 --
Water and Miscellaneous Bal. Bal. Bal. Bal. Bal.
Example XXV
Examples of liquid detergent fabric care compositions for fine fabrics
according to the
present invention:
XXVa XXVb XXVc XXVd
Ingredients Wt.% Wt% Wt.% Wt.%
Arabinogalactan A 12 -- 2 9
Arabinogalactan B -- 9 -- --
Oligosaccharide Mixture C -- -- 7 --
Oligosaccharide Mixture D -- -- -- 3
C12-15AE1.8S 10.3 9.7 9.7 10.3
Neodol 23-9 -- 0.3 0.3 --
Neodol 45-7 2.9 -- -- 2.9
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C8-10 Amidopropyl -- 0.25 0.25 --
dimethylamine
CFAA(T) -- 1 1 --
C12 trimethylammonium 3.8 -- -- 3.8
chloride
Citric Acid 0.75 1.7 1.7 0.75
C12-16 Fatty Acid -- 1.2 1.2 --
Ethanol 1.5 1.6 1.6 1.5
1,2-Propanediol 2.6 4 4 2.6
Mono Ethanol Amine 0.55 0.45 0.45 0.55
Na Formate 0.07 0.45 0.45 0.07
Na Toluene Sulfonate 0.25 0.2 0.2 0.25
Borax 0.1 0.5 0.5 0.1
NaOH -- 1.7 1.7 --
Ethoxylated 0.65 0.55 0.55 0.65
Tetraethylenepentamine
Ethoxylated -- 1.1 1.1 --
polyethyleneimine
Protease 0.07 0.03 0.03 0.07
Amylase 0.15 0.06 0.06 0.15
Mannanase 0.15 -- -- 0.15
Silwet L77 3.6 0.3 0.3 3.6
PVNO 0.25 -- -- 0.25
Suds Suppressor -- 0.05 0.05 --
Perfume 0.5 0.35 0.35 0.5
Dye 7 ppm -- -- 7 ppm
Water and Miscellaneous Bal. Bal. Bal. Bal.
(r) C12-C14 alkyl N-methyl glucose amide.
Example XXVI
Examples of syndet bar fabric detergent fabric care compositions in accord
with the
present invention:
XXVIa XXVIb XXVIc
Ingredients Wt% Wt.% Wt.%
C26 AS 18 18 18
CFAA 5 5 5
LAS (C11-13) 10 10 10
Sodium carbonate 22 25 20
Sodium pyrophosphate 6 6 6
STPP(S) 6 6 6
Zeolite A 5 5 5
CMC 0.2 0.2 0.2
Polyacrylate (MW 1400) 0.2 0.2 0.2
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Coconut monethanolamide 5 5 5
Arabinogalactan A 12 -- 12
Arabinogalactan B -- 10 --
Oligosaccharide Mixture D -- -- 5
Amylase -- 0.02 0.02
Protease -- 0.3 0.3
Perfume 0.2 0.2 0.2
Brightener 0.1 0.1 0.1
CaSO4 1 1 l
MgSO4 I I I
Perfume 0.2 0.3 0.2
Water 4 4 4
Filler`) Balance Balance Balance
(s) Anhydrous sodium tripolyphosphate.
(t) Can be selected from convenient materials such as CaCO3, talc, clay
(Kaolinite,
Smectite), silicates, and the like.
Following are Examples for fabric care pre-wash and wash additive
'compositions in
accordance with the present invention:
Example XXVII
XXVIIa XXVIIb XXVIIc XXV11d
Ingredients Wt.% Wt.% Wt.% Wt.%
Arabinogalactan A 15 -- -- --
Arabinogalactan B -- 10 -- --
Arabinogalactan C -- -- 7 --
Curdlan -- -- -- 8
Dye Fixative Agene ) 2 - -- --
Dye transfer Inhibitor") -- -- -- --
Polysorbate 60 0.8 0.8 1 0.8
Perfume 0.5 0.5 0.8 0.5
Kathon CG 5 ppm 5 ppm 5 ppm 5 ppm
Deionized Water Bal. Bal. Bal. Bal.
TM
(u) Cartafix CB from Clariant
(v) Polyvinylpyrrolidone 85K
Example XXVIII
XXVIIIa XXVIIIb XXVIIIc XXVIIId
In ear dients Wt.% Wt.% Wt.% Wt.%
Arabinogalactan A 3 10 10 5
Oligosaccharide Mixture A 5 -- 5 --
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Oligosaccharide Mixture D -- 10 -- 10
Dye Fixative Agent(') 2.5 -- -- --
Dye transfer Inhibitor(v) 5 7 -- --
Polysorbate 60 0.5 1 1 0.5
Perfume 0.3 1 0.8 0.5
Kathon CG 5 ppm 5 ppm 5 ppm 5 ppm
Deionized Water Bal. Bal. Bal. Bal.
Example XXIX
XXIXa XXIXb XXIXc XXIXd
Ingredients Wt.% Wt.% Wt.% Wt.%
Arabinogalactan A 10 7 -- --
Arabinogalactan B -- -- 5 --
Arabinogalactan C -- -- -- 5
Oligosaccharide Mixture A -- -- 4 --
Oligosaccharide Mixture B -- -- -- 5
Oligosaccharide Mixture C 3 -- -- --
Oligosaccharide Mixture D -- 7 -- --
Dye Fixative Agent(u) 2.5 -- 2 --
Dye transfer Inhibitor(") 5 5 3.5 3.5
Polysorbate 60 0.8 0.7 0.7 1
Perfume 0.5 0.4 0.5 1
Kathon CG 5 ppm 5 ppm 5 ppm
Deionized Water Bal. Bal. Bal.
The compositions of Examples XXVII - XXIX can be diluted with from about 3
times to
about 30 times to make pre-wash soaking solutions to provide fabric care
benefits. The
compositions of Examples XXVII - XXIX can also be added to wash and/or rinse
water
to provide fabric care benefits.
