Note: Descriptions are shown in the official language in which they were submitted.
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~, .
WRINKLE AND MALODOUR REDUCING COMPOSITION
15
Field of the invention
The present invention relates to fabric care compositions and to a method for
treating fabrics in order to improve various properties of fabrics, in
particular,
reduction or removal of unwanted wrinkles and malodour.
Background of the invention
Wrinkles in fabrics are caused by the bending and creasing of the textile
material
which places an external portion of a filament in a yarn under tension while
the
internal portion of that filament in the yam is placed under compression.
Particularly with cotton fabrics, the hydrogen bonding that occurs between the
cellulose molecules contributes to keeping wrinkles in place. The wrinkling of
fabric, in particular clothing, is therefore subject to the inherent tensional
elastic
deformation and recovery properties of the fibers which constitute the yarn
and
fabrics.
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In the modern world, with the increase of hustle and bustle and travel, there
is a
demand for a quick fix which will help to diminish the labor involved in home
laundering and/or the cost and time involved in dry cleaning or commercial
laundering. This has brought additional pressure to bear on textile
technologists
to produce a product that will sufficiently reduce wrinkles in fabrics,
especially
clothing, and to produce a good appearance through a simple, convenient
application of a product.
It has now been found that the use of specific adhesive polymers fulfills such
a
need.
Accordingly, the present invention reduces wrinkles from fabrics, including
clothing, dry cleanables, and draperies, without the need for ironing. The
present
invention can be used on damp or dry clothing to relax wrinkles and give
clothes
a ready to wear look that is demanded by today's fast paced world. The present
invention also essentially eliminates the need for touch up ironing usually
associated with closet, drawer, and suitcase storage of garments.
When ironing is desired however, the present invention can also act as an
excellent ironing aid. The present invention makes the task of ironing easier
and
faste~ by creating less iron drag. When used as an ironing aid, the
composition
of the present invention produces a crisp, smooth appearance.
An additional benefit of the composition of the present invention is an
improved
garment shape, body and crispness.
A further additional benefit to invention composition is the variety of fabric
that
can be treated from the more resistant to the more delicate including fabric
made
of cotton, polycotton, polyester, viscose, rayon, silk, wool, etc...
It is also an object of the invention to provide malodour reducing
compositions.
Accordingly, the formulator of fabric care composition is faced with the
challenge
of formulating a fabric care composition which provides on fabrics both a
reduction of wrinkles and of malodour.
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3
It has now been found that the combination of an adhesive polymei- with an
uncomplexed cyclodextrin fulfills such a need.
Compositions which provide a malodour reducing benefit on fabrics are known in
the
art. Hence, US 5,670,475 describes the use of uncomplexed cyclodextrin for
reducing the malodour on inanimate surfaces such as fabrics.
Summary of the invention
The present invention relates to a wrinkle and malodour reducing composition
for
treating fabrics, comprising:
A. a wrinkle reducing active, comprising a film-forming adhesive polymer
having a weight average molecular weight from 30,000 to 150,000, which has
an organic polymeric backbone, said polymer comprising monomers selected
from the group consisting of A monomers, B monomers and mixtures thereof,
wherein said copolymer is prepared by the polymerisation combination of the
following relative weight percentages of said A monomers, and said B
monomers:
a- from about 0% to about 100%, by weight of said polymer, of a
hydrophobic, A monomer, free radically copolymerizable with said B
monomers;
b- from 0% to about 100%; by weight of said copolymer, of a hydrophilic
reinforcing B monomer, copolymerizable with said A monomer and said A
monomers being selected from the group consisting of acrylic acid esters,
methacrylic acid esters, vinyl compounds, vinylidene compounds, unsaturated
hydrocarbons, CI-C18 alcohol esters of organic acids and organic acid
anhydrides, and mixtures thereof, said B monomers being selected from the
CA 02330604 2006-02-02
3a
group consisting of unsaturated organic mono- and polycarboxylic acids,
unsaturated (meth)acrylates, unsaturated (meth)acrylamides, unsaturated
(meth)acrylate alcohols, unsaturated aminoalkylacrylates, unsaturated organic
acid anhydrides, unsaturated esters of organic acid anhydrides, hydrophilic
unsaturated vinyl compounds, hydrophilic unsaturated allyl compounds,
hydrophilic unsaturated imides, salts of the foregoing compounds, and
mixtures thereof; and
B. an uncomplexed cyclodextrin
In another aspect of the invention, there is provided a method of reducing the
wrinkles and malodours on fabrics which comprises the steps of contacting the
fabrics with a composition of the invention.
25
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Still in a further aspect of the invention, there is provided a packaged
composition
comprising the composition of the invention in a spray dispenser.
Detailed description of the invention
A. Wrinkle reducinci actives: Adhesive polymer comprising monomers selected
from the group consisting of A monomers, B monomers and mixtures thereof
The wrinkle reducing active for use in the present invention is an adhesive
polymer. This adhesive polymer is a polymer comprising monomers selected
from the group consisting of A monomers, B monomers and mixtures thereof,
and mixtures thereof.
By "adhesive" it is meant that when applied as a solution to a surface and
dried,
the polymer forms a film which attaches to the surface.
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 0.2% by weight, and preferably not
soluble at
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 0.2% by weight, and
are preferably soluble at 1.0% 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.
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The polymers must comprises at least one polymerisable hydrophobic monomer.
The polymer can be homopolymers or copolymers of hydrophobic monomers,
e.g. linear random or block polymers. Such polymers are derived from a variety
of monomer units. Alternatively, the present polymers may be a copolymer of a
5 hydrophilic monomer and a hydrophobic monomer, or mixtures thereof. Hence,
the present polymers comprise from 0 to 100%, preferably from 50% to 100%,
more preferably from 70% to about 100% of a polymerizable hydrophobic
monomer (A, as defined herein after), or mixtures thereof, and from 0 to 100%,
preferably from 0% to 50%, more preferably from 0% to about 30% of a
polymerizable hydrophilic monomer B, as defined herein after) or mixtures
thereof. Of course, if the polymer comprises both A monomer and B monomer,
then the monomers must be copolymerizable with each other.
The term "copolymerizable" is used herein to describe a material which can be
reacted with another material (e.g. the A monomers, and B monomers) in a
polymerization reaction using one or more conventional synthetic techniques,
such as ionic, emulsion, dispersion, Ziegler-Natta, free radical, group
transfer or
step growth polymerization. The preferred copolymerization synthetic technique
is free radical polymerization.
The hydrophobic A monomer, which is free radically copolymerizable with B
monomers, is selected from the group consisting of acrylic acid esters,
methacrylic acid esters, vinyl compounds, vinylidene compounds, unsaturated
hydrocarbons, C, -C18 alcohol esters of organic acids and organic acid
anhydrides, and mixtures thereof. Representative examples of hydrophobic A
monomers are acrylic or methacrylic acid esters of C, -C,8 alcohols, such as
methanol, ethanol, methoxy ethanol, 1-propanol, 2-propanol, 1-butanol, 2-
methyl-
I-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-l-butanol, 1-methyl-1-
butanol, 3-methyl-1-butanol, 1-methyl-1-pentanol, 2-methyl-1-pentanol, 3-
methyl-
1-pentanol, t-butanol(2-methyl-2-propanol), cyclohexanol, neodecanol, 2-ethyl-
1-
butanol, 3-heptanol, benzyl alcohol, 2-octanol, 6-methyl-1-heptanol, 2-ethyl-1-
hexanol, 3,5-dimethyl-l-hexanol, 3,5,5-tri methyl-1-hexanol, 1-decanol, 1-
dodecanol, 1-hexadecanol, 1-octa decanol, and the like, the alcohols having
from
about 1-18 carbon atoms with the number of carbon atoms preferably being from
about 1-12; styrene; polystyrene monomer; vinyl acetate; vinyl chloride;
vinylidene chloride; vinyl propionate; alpha-methylstyrene; t-butylstyrene;
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butadiene; cyclohexadiene; ethylene; propylene; vinyl toluene; t-butyl
acrylate, t-
butyl methacrylate, n-butyl methacrylate, n-butyl acrylate, isobutyl
methacrylate,
2-ethylhexyl methacrylate, methyl methacrylate, and mixtures thereof.
Other hydrophobic organic A monomer include the condensation polymer such
as the polyamides, polyesters, polyurethanes, and mixtures thereof.
Preferred A monomers are vinyl monomers, more preferably selected from t-butyl
acrylate, t-butyl methacrylate, t-butyl styrene, n-butyl methacrylate, n-butyl
acrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, methyl
methacrylate,
and mixtures thereof.
tn these polymers, it is more preferred that A be selected from t-butyl
acrylate, t-
butyl methacrylate, n-butyl methacrylate, n-butyl acrylate, and mixtures
thereof,
since such polymers can be dissolved directly in cyclomethicone solvents
without
requiring co-solvents.
The hydrophilic, reinforcing B monomer, which is copolymerizable with the A
monomers, is selected from the group consisting of unsaturated organic mono-
and polycarboxylic acids, unsaturated (meth)acrylates, unsaturated
(meth)acrylamides, unsaturated (meth)acrylate alcohols, unsaturated
aminoalkylacrylates, unsaturated organic acid anhydrides, unsaturated esters
of
organic acid anhydrides, hydrophilic unsaturated vinyl compounds, hydrophilic
unsaturated allyl compounds, hydrophilic unsaturated imides, salts of the
foregoing compounds, and mixtures thereof.
Representative examples of hydrophilic reinforcing B monomers include acrylic
acid, methacrylic acid, N,N-dimethyiacrylamide, dimethyl aminoethyl
methacrylate, quaternized dimethylaminoethyl methacrylate, methacrylamide, N-
t-butyl acrylamide, t-butyl acrylamide, maleic acid, maleic anhydride and its
half
esters, crotonic acid, itaconic acid, acrylamide, acrylate alcohols,
hydroxyethyl
methacrylate, diallyldimethyl ammonium chloride, vinyl pyrrolidone, vinyl
ethers
(such as methyl vinyl ether), maleimides, vinyl pyridine, vinyl imidazole,
other
polar vinyl heterocyclics, styrene sulfonate, allyl alcohol, vinyl alcohol
(such as
that produced by the hydrolysis of vinyl acetate after polymerization), salts
of any
acids and amines listed above, and mixtures thereof.
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Other hydrophilic, reinforcing B monomer include the condensation polymers
such as the polyisocyanates, polyalcohols, polyamines, polyethylenimines,
polyethylene glycol and mixtures thereof. When a polyethylene imine is used, a
dual benefit may be obtained: that of dewrinkling from the polymer and that of
color care by the polyethyleneimine unit.
Preferred B monomers include monomers selected from the group consisting of
acrylic acid, methacrylic acid, N,N-dimethyl acrylamide, methacrylamide, N t-
butyl
arylamide, dimethylamino ethyl methacrylate, t-butyl acrylamide, vinyl
pyrrolidone, salts thereof and alkyl quaternized derivatives thereof, and
mixtures
thereof.
The steps and process for making said polymer are those conventionally known
to the skilled person. Disclosure of these polymers and preparation thereof
are
disclosed in US 5,120,532.
The polymer has a weight average molecular weight from 5000 to 1,000,000,
which has an organic polymeric backbone, said copolymer comprising monomers
selected from the group consisting of A monomers, B monomers and mixtures
thereof, wherein said copolymer is prepared by the polymerisation combination
of
the following relative weight percentages of said A monomers, and said B
monomers:
a- from 0% to about 100%, by weight of said copolymer, of a
hydrophobic, A monomer, free radically copolymerizable with said B
monomers;
b-from 0% to about 100%, by weight of said copolymer, of a hydrophilic
reinforcing B monomer, copolymerizable with said A monomer, said B
monomer being selected from the group consisting of polar monomers
and macromers and mixtures thereof.
The polymers are prepared by the polymerization combination of A monomer,
and, if used, B monomer. The copolymer composition is characterized by the
amount of each monomer charged to the polymerization reaction vessel. In
general, the adhesive polymer will comprise from about 0% to about 100%,
preferably from about 50% to about 100%, more preferably from about 60% to
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8
about 90%, most preferably from about 70% to about 80%, of the hydrophobic, A
monomer;. and from 0% to about 100%, preferably from 0% to about 50.0%,
preferably from 10% to about 40%, more preferably from about 20% to about
30% of the hydrophilic, reinforcing B monomer.
Preferably, the polymer of use herein has a molecular weight between about
30,000 and about 150,000.
Exemplary polymers for use in the present invention include the following,
where
the composition of the copolymer is given as weight percentage of each
monomer used in the polymerization reaction used to prepare the polymer: vinyl
pyn-olidone/vinyl acetate copolymers (at ratios of up to about 30%, by weight,
vinyl pyrrolidone); vinyl acetate homopolymer; t-butyl acrylate homopolymer; t-
butyl styrene/ ethyl hexyl methacrylate copolymer (50/50, by weight); dimethyl
acrylamide/ t-butyl acrylate/ethyl hexyl methacrylate copolymer (10/45/45);
ethylene/vinyl acetate copolymer (12.5/87.5); allyl alcohol/styrene copolymer
(19/81);- vinyl chloride/vinyl acetate copolymer (83/17 and lower); vinyl
pyrrolidone/vinyl acetate/butyl acrylate copolymer (10/78/12 and 10/70/20);
vinyl
pyrrolidone/ vinyl acetate/butyl acrylate/styrene sulfonate copolymer
(10/70/15/5);
vinyl pyrrolidone/vinyl propionate copolymer (5/95); vinyi 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); and Resyn 28-2930® by National Starch (vinyl acetate/vinyl
neodecanoate%rotonic acid copolymer), and Amerhold DR-25 by Union Carbide
(ethyl acrylate/metacrylic acid/methyl methacrylate/acrylic acid copolymer),
Poligen A by BASF (polyacrylate dispersion), APPRETAN from Clariant (polyvinyl
acetate), MOWEOL from Clariant (polyvinyl alcohol), and SOKALAN EG 310
from BASF (PVP/AA: polyvinylpyrrolidone/acrylic acid).
The most preferred polymers among the one above disclosed are the polymer
made of acrylic acid and t-butyl acrylate monomeric units, more preferably
with
acrylic acid from about 20% to 30% by weight, and t-butyl acrylate from about
70
% to about 80%.
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Of course, the term "adhesive polymer" can also encompass mixed adhesive
polymers.
The adhesive polymer is present in the composition in a sufficient amount to
result in an amount of from 0.01 % to 1%, preferably from 0.01 % to 0.5 %,
more
preferably from 0.01 % to 0.1 % by weight of polymer per weight of dry
fabrics.
Typically, the adhesive polymer is present in the composition of the present
invention in an amount of from 0.05 % to about 5.0%, preferably from about 0.1
% to about 2.0%, more preferably from about 0.2 % to about 1.0 % by weight of
the composition.
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.
B-Uncomplexed cyciodextrin
In a preferred aspect of the invention, the composition of the invention
comprises
an cyclodextrin. This will impart the composition with odour absorbing
properties,
which is especially useful for application on inanimate surfaces to control
the
malodour, whilst not being detrimental to the dewrinkling performance of the
composition.
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
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WO 99/55951 PCT/US98/17577
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
5 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
10 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 derivatized cyclodextrins.
Preferably, the 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 for use herein 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
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11
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 hydroxyethytl 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)propyi 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)3CI"; 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 at., issued Feb. 4, 1969; 3,453,257;
3,453,258;
3,453,259; and 3,453,260, all in the names of Parmerter et at., 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
more efficient odor control performance than non-water-soluble cyclodextrin
when
deposited onto surfaces, especially fabric.
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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-0-methyl-R-
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
odots 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. It
is preferable that the usage compositions of the present invention contain low
levels of cyclodextrin so that a visible stain does not appear on the fabric
at
normal usage levels. Preferably, the solution used to treat the surface under
usage conditions is virtually not discernible when dry. Typical levels of
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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
0.2% to about 2% by weight of the composition. Compositions with higher
concentrations can leave unacceptable visible stains on fabrics as the
solution
evaporates off of the fabric. This is especially a problem on thin, colored,
synthetic fabrics. In order to avoid or minimize the occurrence of fabric
staining,
it is preferable that the fabric be treated at a level of less than about 5 mg
of
cyclodextrin per gram of fabric, more preferably less than about 2 mg of
cyclodextrin per gram of fabric. The presence of the surfactant can improve
appearance by minimizing localized spotting.
Concentrated compositions can also be used in order to deliver a less
expensive
product. When a concentrated product is used, i.e., when the level of
cyclodextrin used is from about 3% to about 20%, more preferably from about
5% to about 10%, by weight of the concentrated composition, it is preferable
to
dilute the concentrated composition before treating fabrics in order to avoid
staining. Preferably the concentrated cyclodextrin composition is diluted with
about 50% to about 6000%, more preferably with about 75% to about 2000%,
most preferably with about 100% to about 1000% by weight of the concentrated
composition of water. The resulting diluted compositions have usage
concentrations of cyclodextrin as discussed hereinbefore, e.g., of from about
0.1 % to about 5%, by weight of the diluted composition.
C. Optional Ingredients
1-Carrier
Any type of carrier is suitable for use in the present invention. However, a
preferred carrier for the purpose of the invention is a liquid carrier.
Preferably, the
liquid carrier is an aqueous system comprising water. Optionally, but not
preferably, in addition to the water, the carrier can contain a low molecular
weight
organic solvent that is highly soluble in water, e.g., C1-C4 monohydric
alcohols,
alkylene carbonates, and mixtures thereof. Examples of these water-soluble
solvents include ethanol, propanol, isopropanol, etc. Water is the main liquid
carrier due to its low cost, availability, safety, and environmental
compatibility.
Water can be distilled, deionized, or tap water.
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The level of liquid carrier in the compositions of the present invention is
typically
greater than 80%, preferably greater than 90%, more preferably greater than
95%, by weight of the composition. When a concentrated composition is used,
the level of liquid carrier is typically from 50% to 95%, by weight of the
composition, preferably from 60% to 97%, more preferably from 70% to 99%, by
weight of the composition.
2-Wetting agent
A wetting agent is another preferred optional ingredient for use in the
present
invention. When employed, it will provide the further solubilisation of the
polymer
but also further ensures an effective plasticizing of the polymer resulting in
a
flexible polymer network. The wetting agent for use herein are water-soluble
surfactants, preferably selected from a cationic surfactant, a nonionic
surfactant
and an anionic surfactant. Further suitable wetting agents are the
zwiterrionic
surfactants such as the betaine or sulphobetaine surfactants commercially
available from Seppic and Albright & Wilson respectively, under the trade
marks
of Amonyl 265 and Empigen BB/L. These wetting agent facilitates the action
of water. Indeed, the water penetrates into the fabric where it breaks
hydrogen
bonds between fibers resulting in fiber relaxation. By use of the wetting
agent,
the water action is further facilitated via the wetting properties of the
water
soluble surfactant.
By "water-soluble wetting agent", it is meant that the wetting agent forms
substantially clear, isotropic solutions when dissolved in water at 0.2 weight
percent at 25 C.
Water-soluble catlonic surfactant
Any type -of water-soluble cationic surfactant can be used to impart the
wetting
property. However, some water-soluble cationic surfactants and mixtures
thereof
are more preferred. Hence, it is preferred that the cationic surfactant is a
surface-
active molecule with a linear or branched hydrophobic tail and a positively
charged hydrophilic head group, more preferably, the cationic surfactant for
use
in the present invention is quatemary ammonium salt of formula:
[R~N+R3]X'
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wherein the R' group is C,o-C22hydrocarbon group, preferably C12-C1e alkyl
group
or the corresponding ester linkage interrupted group with a short alkylene (C,-
C4)
group between the ester linkage and the N, and having a similar hydrocarbon
group, e.g., a fatty acid ester of choline, preferably C,Z-C14 (coco) choline
ester
5 and/or C1B-C18 tallow choline ester. The hydrocarbon group may be
interrupted by
further groups like COO, OCO, 0, CO, OCOO, CONH, NHCO, OCONH and
NHCOO. Each R is a C1-C4 alkyl or substituted (e.g., hydroxy) alkyl, or
hydrogen, preferably methyl, and the counterion X' is a softener compatible
anion, for example, chloride, bromide, methyl surface, etc.
The long chain group R1, of the single-long-chain-alkyl surfactant, typically
contains an alkylene group having from 10 to 22 carbon atoms, preferably from
12 to about 16 carbon atoms, more preferably from 12 to 18 carbon atoms. This
R' group can be attached to the cationic nitrogen atom through a group
containing one, or more, ester, amide, ether, amine, etc., preferably ester,
linking
..groups which can be desirable for increased hydrophilicity,
biodegradability, etc.
- Such linking groups are preferably within about three carbon atoms of the
nitrogen atom. A preferred cationic surfactant of this type is N,N dimethyl-N-
(2-
hydroxyethyl)-N-dodecyVtetradecyi ammonium bromide.
If the corresponding, non-quatemary amines are used, any acid (preferably a
mineral or polycarboxylic acid) which is added to keep the ester groups stable
will also keep the amine protonated in the compositions.
Typical disclosure of these cationic surfactants suitable for use in the
present
invention are the choline ester surfactants of formula:
R2
5 I +
R - ~ O (~ - ( C H ) -(Y) (CH ) -N-R M
1 (~n b a 2 m v 2 t 3
a I
R4
wherein R1 is a C10-C22 linear or branched alkyl, alkenyl or alkaryl chain or
M-.
N+(R6R7R8)(CH2)s; X and Y, independently, are selected from the group
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16
consisting of COO, OCO, 0, CO, OCOO, CONH, NHCO, OCONH and NHCOO
wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO
group; R2, R3, R4, R6, R7, and R8 are independently selected from the group
consisting of alkyl, alkenyl, hydroxyalkyl and hydroxy-alkenyl groups having
from
1 to 4 carbon atoms and alkaryl groups; and R5 is independently H or a C1-C3
alkyl group; wherein the values of m, n, s and t independently lie in the
range of
from 0 to 8, the value of b lies in the range from 0 to 20, and the values of
a, u
and v independently are either 0 or 1 with the proviso that at least one of u
or v
must be 1; and wherein M is a counter anion.
Preferably M is selected from the group consisting of halide, methyl sulfate,
sulfate, and nitrate, more preferably methyl sulfate, chloride, bromide or
iodide.
A preferred choline ester surfactant is selected from those having the
formula:
R2
R5
+
R1 _ O ~CH~nO (X) - (CH26 _ N - R3 M-
b
a
R4
wherein R1 is a Ct0-C22, preferably a C12-C14 linear or branched alkyl,
alkenyl
or alkaryl chain; X is selected from the group consisting of COO, OCO, OCOO,
OCONH and NHCOO; R2, R3, and R4 are independently selected from the
group consisting of alkyl and hydroxyalkyl groups having from I to 4 carbon
atoms; and R5 is independently H or a C1-C3 alkyl group; wherein the value of
n
lies in the range of from 0 to 8, the value of b lies in the range from 0 to
20, the
value of a is either 0 or 1, and the value of m is from 3 to 8.
More preferably R2, R3 and R4 are independently selected from a C1-C4 alkyl
group and a C1-C4 hydroxyalkyl group. In one preferred aspect at least one,
preferably only one of R2, R3 and R4 is a hydroxyalkyl group. The hydroxyalkyl
preferably has from 1 to 4 carbon atoms, more preferably 2 or 3 carbon atoms,
most preferably 2 carbon atoms. In another preferred aspect at least one of
R2,
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R3 and R4 is a C2-C3 alkyl group, more preferably two C2-C3 alkyl groups are
present.
Highly preferred water soluble choline ester surfactants are the esters having
the
formula:
0
11 IH3
R1- C- O-(CH2)m - N+ - CH3 M-
.
CH3
where m is from 1 to 4, preferably 2 or 3 and wherein R1 is a C1 1 -C19 linear
or
branched alkyl chain.
Particularly preferred choline esters of this type include the stearoyl
choline ester
quatemary methylammonium halides (R1=C17 alkyl), palmitoyl choline ester
quaternary methylammonium halides (R1=C15 alkyl), myristoyl choline ester
quatemary methylammonium halides (RI=C13 alkyl), lauroyl choline ester
methylammonium halides (R1=C1j alkyl), cocoyl choline ester quaternary
methylammonium halides (RI=Cj1-C13 alkyl), tallowyl choline ester quatemary
methylammonium halides (R1=C I 5-C 17 alkyl), and any mixtures thereof.
Most particularly preferred choline esters of this type are selected from
myristoyl
choline ester quatemary methylammonium halides, lauroyl choline ester
methylammonium halides, cocoyl choline ester quaternary methylammonium
halides, and any mixtures thereof.
Other suitable choline ester surfactants have the structural formulas below,
wherein d may be from 0 to 20.
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O CH3
R1-O-C-( CH2 )a C-O-CH2CHz-N CH3 M
I
CH3
3 H 0 0 CH3
M CH3-N-+ -CH2-CH2-O-C-( CH2 ) a 1+
CH3M
CH3 CH3
The particularly preferred choline esters, given above, may be prepared by the
direct esterification of a fatty acid of the desired chain length with
dimethylaminoethanol, in the presence of an acid catalyst. The reaction
product
is then quaternized with a methyl halide, preferably in the presence of a
solvent
such as ethanol, water, propylene glycol or preferably a fatty alcohol
ethoxylate
such as C10-C18 fatty alcohol ethoxylate having a degree of ethoxylation of
from
3 to 50 ethoxy groups per mole forming the desired cationic material. They may
also be prepared by the direct esterification of a long chain fatty acid of
the
desired chain length together with 2-haloethanol, in the presence of an acid
catalyst material. The reaction product is then quaternized with
trimethylamine,
forming the desired cationic material.
Still other suitable water-soluble cationic surfactants for use in the present
invention are the cationic materials with ring structures such as alkyl
imidazoline,
imdazolinium, pyridine, and pyridinium salts having a single C,Z-C30 alkyl
chain
can also be used.
Some alkyl imidazolinium salts useful in the present invention have the
general
formula:
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CH2 CH2
I
N N' - C, Ha 1'Z R7 X.
\ / \
C R6
I
R8
wherein Y2 is -C(O)-O-, -O-(O)-C-, -C(O)-N(R5), or -N(R5)-C(O)- in which R5 is
hydrogen or a C1-C. alkyl radical; Re is a C1-C4 alkyl radical; R' and R8 are
each
independently selected from R and R2 as defined hereinbefore for the single-
long-chain cationic surfactant with only one being R2.
Some alkyl pyridinium salts useful in the present invention have the general
formula:
R2 +N I
wherein R 2 and X are as defined above. A typical material of this type is
cetyl
pyridinium chloride.
Water-soluble nonionic surfactant
Suitable nonionic surfactants are the alkoxylated surfactants. It provides a
low
surface tension that permits the composition to spread readily and more
uniformly on hydrophobic surfaces like polyester and nylon. Said 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
to distribute more evenly, and to prevent clogging of the spray apparatus. The
spreading of the composition also allows it to dry faster, so that the treated
material is ready to use sooner. For concentrated compositions, the surfactant
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facilitates the dispersion of many actives such as antimicrobial actives and
perfumes in the concentrated aqueous compositions.
Still further nonionic surfactants which may be of use herein are the
5 polyhydroxyfatty acid surfactants as described in EP-A-659870.
Nonlimiting examples of nonionic alkoxylated surfactants include addition
products of ethylene oxide with fatty alcohols, fatty acids, fatty amines,
etc.
Optionally, addition products of propylene oxide with fatty alcohols, fatty
acids,
10 fatty amines may be used.
Suitable compounds are surfactants of the general formula:
R2 - Y - (C2H40)z - C2H4OH
wherein R2 is selected from the group consisting of primary, secondary and
15 branched chain alkyl and/or acyl hydrocarbyl groups; primary, secondary and
branched chain alkenyl hydrocarbyl groups; and primary, secondary and
branched chain alkyl- and alkenyl-substituted phenolic hydrocarbyl groups;
said
hydrocarbyl groups preferably having a hydrocarbyl chain length of from 6 to
20,
preferably from 8 to 18 carbon atoms. More preferably the hydrocarbyl chain
20 length is from 10 to 18 carbon atoms. In the general formula for the
ethoxylated
nonionic surfactants herein, Y is -0-, -C(O)O-, -C(O)N(R)-, or -C(O)N(R)R-, in
which R, when present, is R2 or hydrogen, and z is at least 2, preferably at
least
4, more preferably from 5 to 11.
The nonionic surfactants herein are characterised by an HLB (hydrophilic-
lipophilic balance) of from 7 to 20, preferably from 8 to 15. Of course, by
defining
R2 and the number of ethoxylate groups, the HLB of the surfactant is, in
general,
determined. However, it is to be noted that the nonionic ethoxylated
surfactants
useful herein contain relatively long chain R2 groups and are relatively
highly
ethoxylated. While shorter alkyl chain surfactants having short ethoxylated
groups may possess the requisite HLB, they are not as effective herein.
Examples of nonionic surfactants follow. The nonionic surfactants of this
invention are not limited to these examples. In the examples, the integer
defines
the number of ethoxyl (EO) groups in the rnolecuie.
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a. Straight-Chain. Primary Alcohol Alkoxylates
The tri-, penta-, hepta-ethoxylates of dodecanol, and tetradecanol are useful
surfactants in the context of this invention. The ethoxylates of mixed natural
or
synthetic alcohols in the "coco" chain length range are also useful herein.
Commercially available straight-chain, primary alcohol alkoxylates for use
herein
are available under the trade marks Marlipal 24/70, Marlipal 24/100, Marlipal
24/150 from Huls, and Genapol C-050 from Hoechst.
b. Straight-Chain. Secondary Alcohol Alkoxylates
The tri-, penta-, hepta-ethoxylates of 3-hexadecanol, 2-octadecanol, 4-
eicosanol,
and 5-eicosanol are useful surfactants in the context of this invention.
A commercially availabie straight-chain secondary alcohol ethoxylate for use
herein is the material marketed under the trade mark Tergitol 15-S-7 from
Union
Carbide, which comprises a mixture of secondary alcohols having an average
hydrocarbyl chain length of 11 to 15 carbon atoms condensed with an average 7
moles of ethylene oxide per mole equivalent of alcohol. Still another suitable
commercially available straight-chain secondary alcohol ethoxylate for use
herein
is the material marketed under the trade mark Softanol obtainable from BP
Chemicals Ltd. or Nippon Catalytic of Japan. Particularly useful herein are
Softanol 50, Softanol 90, which comprises a mixture of linear secondary
alcohol
having an average hydrocarbyl chain length of 11 to 16 carbon atoms condensed
with an average of 5 to 10 moles of ethylene oxide per mole equivalent of
alcohol.
c. Alkyl Phenol Alkoxylates
Suitable alkyl phenol alkoxylates are the polyethylene oxide condensates of
alkyl
phenols, e.g., the condensation products of alkyl phenois having an alkyl or
alkenyl group containing from 6 to 20 carbon atoms in a primary, secondary or
branched chain configuration, preferably from 8 to 12 carbon atoms, with
ethylene oxide, the said ethylene oxide being preferably present in amounts
equal to 3 to 11 moles of ethylene oxide per mole of alkyl phenol. The alkyl
substituent in.such compounds may be derived from polymerized propylene,
diisobutylene, octane, and nonane.
Examples of this type of nonionic surfactants include Triton N-57 a nonyl
phenol ethoxylate (5E0) from Rohm & Haas, Dowfax 9N5 from Dow and
Lutensol AP6 from BASF.
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d. Olefinic Alkoxylates
The alkenyl alcohols, both primary and secondary, and alkenyl phenois
corresponding to those disclosed immediately hereinabove can be ethoxylated
and used as surfactants.
Commercially available olefinic alkoxylates for use herein are available under
the
trade mark Genapol 0-050 from Hoechst.
e. Branched Chain Alkoxylates
Branched chain primary and secondary alcohols ( or Guerbet alcohols) which
may be available from the well-known "OXO" process or modification thereof can
be ethoxylated.
Particularly preferred among these ethoxylates of the primary OXO alcohols are
the surfactants marketed under the trade mark Lutensol by BASF or pobanolTM by
the
Shell Chemicals, U.K., LTD. The preferred Dobanols are primary alcohols with
hydrocarbyl groups of 9 to 15 carbon atoms, with the majority having a
hydrocarbyl group of 13 carbon atoms. Particularly preferred are Dobanols with
an average degree of ethoxylation of 3 to 11, and preferably 7 on the average.
An example of this type of material is an aliphatic alcohol ethylene oxide
condensate having from 3 to less than 9 moles of ethylene oxide per mole of
aliphatic alcohol, the aliphatic alcohol fraction having from 9 to 14 carbon
atoms.
Other examples of this type of nonionic surfactants include certain of the
commercially available Dobanot , Neodol marketed by Shell, Lutensol from
BASF, or Lial from Enichem. For example Dobanol 23.5 (C12-C13 E05),
Dobanol 91.5 (C9-C1 i EO 5), Neodol 45 E5, and Lial-145.7 EO (oxo C 14 15
alcohol + 7.0 mol of EO), Lial 111 EO 6 and lsaichemTM 123 series from
Enichem.
Further nonlimiting examples of nonionic alkoxylated surfactants include the
surfactant which are cyciodextrin-compatible, that is it should not
substantially
form a complex with the cyclodextrin so as to diminish performance of the
cyclodextrin and/or the surfactant. Complex formation diminishes both the
ability
of the cyclodextrin to absorb odors and the ability of the surfactant to lower
the
surface tension of the aqueous composition. This include block copolymers of
ethylene oxide and propylene oxide. Suitable block polyoxyethylene-
polyoxypropylene polymeric surfactants, that are compatible with most
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cyclodextrins, include those based on ethylene glycol, propylene glycol,
glycerol,
trimethylolpropane and ethylenediamine as the initial reactive hydrogen
compound. Polymeric compounds made from a sequential ethoxylation and
propoxylation of initial compounds with a single reactive hydrogen atom, such
as
C12-18 aliphatic alcohols, are not generally compatible with the cyclodextrin.
Certain of the block polymer surfactant compounds designated Pluronic and
Tetronic by the BASF-Wyandotte Corp., Wyandotte, Michigan, are readily
available.
Non limiting examples of surfactants of this type include:
Pluronic Surfactants with the general formula H(EO)n(PO)m(EO)nH,
wherein EO is an ethylene oxide group, PO is a propylene oxide group, and n
and m are numbers that indicate the average number of the groups in the
surfactants. Typical examples of cyclodextrin-compatible Pluronic surfactants
are:
Name Average MW Average n Average m
L-44 2,200 10 23
L-43 1,850 6 22
F-38 4,700 43 16
P-84 4,200 19 43,
and mixtures thereof.
Tetronic Surfactants with the general formula:
H(EO)n(PO) ; /PO)m(EO)nH
NCH2CH2N
H(EO)n(PO)m \((PO)m(EO)nH
wherein EO, PO, n, and m have the same meanings as above. Typical
examples of cyclodextrin-compatible Tetronic surfactants are:
Name Average MW Average n Average m
901 4,700 3 18
908 25,000 114 22,
and mixtures thereof.
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"Reverse" Pluronic and Tetronic surfactants have the following general
formulas:
Reverse Pluronic Surfactants H(PO)m(EO)n(PO)mH
Reverse Tetronic Surfactants
H(PO)n(EO)rr\ /(EO)m(PO)~
/NCH2CH2N
H(PO)n(EO)m ~ (EO)m(PO)nH
wherein EO, PO, n, and m have the same meanings as above. Typical
examples of Reverse Pluronic and Reverse Tetronic surfactants are:
Reverse Pluronic surfactants:
Name Average MW Average n Average m
10 R5 1,950 8 22
25 R1 2,700 21 6
Reverse Tetronic surfactants
Name Average MW Average n Average m
130 R2 7,740 9 26
70 R2 3,870 4 13
and mixtures thereof.
The silicone surfactants
A preferred class of nonionic alkoxylated surfactants are the
polyalkyleneoxide
polysiloxanes having a dimethyl polysiloxane hydrophobic moiety and one or
more
hydrophilic polyalkylene side chains. Examples of this type of surfactants are
the
Silwet surfactants which are available OSi Specialties, Inc., Danbury,
Connecticut, and have the general formula:
CH3 CH3
(CH3)3SiO-'-(SiO)a (SiO)b--Si(CH3)3
CH3 R~
wherein a + b are from about 1 to about 50, preferably from about 3 to about
30 ,
more preferably from about 10 to about 25, and R1 is mainly one or more random
poly(ethyleneoxide/propyleneoxide) copolymer groups having the general
formula:
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-(CH2)n O(C2 H4 O)c (C3 H6 0)d R2
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
5 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 1 to 4 carbon atoms, and an acetyl group, preferably
hydrogen and methyl group.
Representative Silwet surfactants are as follows.
10 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
15 L-7604 4,000 21 53
L-7600 4,000 11 68
L-7657 5,000 20 76
L-7602 3,000 20 29
20 The molecular weight of the polyatkyteneoxy 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
25 (-C2H40) in the polyether chain (R1) must be sufficient to render the
polyalkyleneoxide polysiloxane water dispersible or water soluble. 'If
propyleneoxy
groups are present in the polyatkylenoxy chain, they can be distributed
randomly
in the chain or exist as blocks. Preferred Silwet surfactants are L-7600, L-
7602,
L-7604, L-7605, L-7657, and mixtures thereof. Besides surface activity,
polyatkyleneoxide polysiloxane surfactants can also provide other benefits,
such
as antistatic benefits, lubricity and softness to fabrics.
The preparation of polyalkyleneoxide polysiloxanes is well known in the art.
Polyalkyleneoxide polysiloxanes of the present invention can be prepared
according to the procedure set forth in U.S. Pat. No. 3,299,112.
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Typically, polyalkyleneoxide polysiloxanes of the surfactant blend
of the present invention are readily prepared by an addition reaction
between a hydrosiloxane (i.e., a siloxane containing silicon-bonded hydrogen)
and an alkenyl ether (e.g., a vinyl, allyl, or methallyl ether) of an alkoxy
or
hydroxy end-biocked polyalkylene oxide). The reaction conditions employed in
addition reactions of this type are well known in the art and in general
involve
heating the reactants (e.g., at a temperature of from about 85 C. to 110 C.)
in
the presence of a platinum catalyst (e.g., chloroplatinic acid) and a solvent
(e.g.,
toluene).
Water-soluble anionic surfactant
Still suitable wetting agents are the anionic surfactants. Noniimiting
examples of
cyclodextrin-compatible anionic surfactants are the alkyldiphenyl oxide
disulfonate, having the general formula:
SO3Na SO}Na
R
wherein R is an alkyl group. Examples of this type of surfactants are
available
from the Dow Chemical Company under the trade mark Dowfax wherein R is a
linear or branched C6-C16 alkyl group. An example of these cyclodextrin-
compatible anionic surfactant is Dowfax 3B2 with R being approximately a
linear
Clp group. Still other preferred anionic surfactants for use herein are the
alkyl
sulphosuccinates (R'OOCCH2CH(SO3M)COOR') wherein R' is a hydrophobic
chain (Ce-C 18, preferably Cg-C 12) linear or branched alkyl or alkenyl, and M
is
as defined hereinbefore. Preferred alkyl sulphosuccinates are commercially
available from CYTEC Industries under the trade mark Aerosol OT, and Aerosol
AOT. Preferred among the above described anionic surfactants are selected
from the alkyl sulphate surfactants, alkyl sulphosuccinate surfactants, and
mixtures thereof. These anionic surfactants are preferably not used when the
antimicrobial active or preservative, etc., is cationic to minimize the
interaction
with the cationic actives, since the effect of both surfactant and active are
diminished.
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Still further nonionic surfactants which may be of use herein are the
polyhydroxyfatty acid surfactants as described in EP-A-659870.
The above ethoxylated nonionic surfactants are useful in the present process
invention alone or in combination, and the term "nonionic surfactant"
encompasses mixed nonionic surface active agents.
Preferred surfactants for use herein among the above disclosed water-soluble
surfactants are the nonionic surfactants, more preferably the nonionic
surfactants
selected from polyalkyleneoxide polysiloxane surfactant, a block copolymer of
ethylene oxide and propylene oxide based on ethylene glycol, propylene glycol,
glycerol, trimethylolpropane, or ethylenediamine, and mixtures thereof.
The wetting agent is present in the composition in a sufficient amount to
result in
an amount of from 0.001 % to 5%, preferably from 0.01 % to 3%, more preferably
from 0.01 % to 1.50% by weight of active per weight of dry fabrics.
Accordingly, typical levels of the water-soluble wetting agent in the
composition
are from 0.1 to 10% by weight, preferably from 0.1 to 5%, more preferably from
0.1 % to 1.5% by weight of the composition.
3- Nonionic polyhydric alcohol humectant
A nonionic humectant of the polyhydric alcohol type is a preferred optional
ingredient of the composition of the present invention. Typical of these
compounds are the low molecular weight polyols.
Low molecular weight polyols with relatively high boiling points, as compared
to
water, are essential ingredients of the composition of the present invention.
By "low molecular weight", it is meant that the compounds preferably have a
molecular weight below 1000, preferably from 50 to 500, more preferably from
55
to 200.
Preferably, these polyols are short chain. By "short chain ", it is meant that
the
compounds have a carbon chain length of less than 10 carbon atoms, preferably
less than 8 carbon atoms.
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Not to be bound by theory, it is believed that the incorporation of a small
amount
of nonionic polyhydric alcohol humectant into the compositions containing the
solubilising agent reinforces the hydrogen breaking process as well as
reducing
the fabric drying rate, thereby allowing more time to the fabric to relax, and
also
deliver a basic level of lubrication and plasticizing of the polymer.
Preferred polyols for use herein are selected from polyols having from 2 to 8
hydroxy groups.
Preferably the glycol used is glycerol, ethylene glycol, propylene glycol,
diethylene glycol, dipropylene glycol, sorbitol, erythritol or mixtures
thereof, more
preferably diethylene glycol, ethylene glycol, propylene glycol, dipropylene
glycol
and mixtures thereof.
Some polyols, e.g., dipropylene glycol, are also useful to facilitate the
solubilization of some perfume ingredients in the composition of the present
invention. Both diethylene glycol and dipropylene glycol are favored for use
herein as it provides non-stickiness properties on hard surfaces and/or
fabrics.
Further, the incorporation of such polyol provides an improved odor control
performance of the composition of the present invention comprising said
cyclodextrin. In this respect, diethylene glycol has been found particularly
useful
in the presence of the uncomplexed cyclodextrin. Indeed, it has been found to
enhance the removal of small malodour molecules.
!t is further 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. It is further
believed that a small amount of low molecular weight polyol as defined herein
before into the composition comprising the uncomplexed cyclodextrin enhances
the formation of the cyclodextrin inclusion complexes as the fabric dries.
Accordingly, cyclodextrins prepared by processes that result in a level of
such
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polyols are highly desirable, since they can be used without removal of the
polyols.
The preferred weight ratio of low molecular weight cyclodextrin to polyol is
from
about 50:1 to about 1:11, more preferably from about 20:1to about 1:1, even
more preferably from about 10:1 to about 1:1, and most preferably from about
5:1 to about 1:1.
The humectant is present in the composition in a sufficient amount to result
in an
amount of from 0.005% to 5%, preferably from 0.01% to 3%, more preferably
from 0.01 % to 1.50% by weight of active per weight of dry fabrics.
Typically, the humectant is added to the composition of the present invention
at a
level of from about 0.01 % to about 10%, by weight of the composition,
preferably
from about 0.1% to about 3%, more preferably from about 0.1% to about 1.5%,
by weight of the composition.
4-Lubricant
In addition to the above humectants which can impart a lubrication property to
the fabrics, the composition may also optionally employ typical lubricating
compounds. Lubricants have also been found beneficial in. providing "wrinkles
resistance" of dry-cleaned fabrics.
Typical lubricants are those conventionally known as softeners and include the
cationic softener and nonionic softeners.
Cationic softeners
Typical of the cationic softening components are the quaternary ammonium
compounds or amine precursors thereof as defined hereinafter.
A)-Quaternary Ammonium Fabric Softening Active Compound
(1) Preferred quatemary ammonium fabric softening active compound have
the formula
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[(R)4m= N (CH2)n-Q-R] X '
m
(1)
or the formula:
(R)~m N (CH~ - CH - CK - Q -- R' )C
I m
Q W (2)
5 wherein Q is a functional unit having the formula:
0 0 O 0 R2 O O R2
-O-C- , -C--O- , -O-C-O-, -N-C- , -C-N-
each R unit is independently hydrogen, C1-C6 alkyl, C1-C6 hydroxyalkyl, and
mixtures thereof, preferably methyl or hydroxy alkyl; each R1 unit is
10 independently linear or branched C11-C22 alkyl, linear or branched C11-C22
alkenyl, and mixtures thereof, R2 is hydrogen, C1-C4 alkyl, C1-C4
hydroxyalkyl,
and mixtures thereof; X is an anion which is compatible with fabric softener
actives and adjunct ingredients; the index m is from 1 to 4, preferably 2; the
index
n is from 1 to 4, preferably 2.
An example of a preferred fabric softener active is a mixture of quaternized
amines having the formula:
+ 0
11
R2-N (CH2)n-O-C-RI X -
2
wherein R is preferably methyl; R1 is a linear or branched alkyl or alkenyl
chain
comprising at least 11 atoms, preferably at least 15 atoms. In the above
fabric
softener example, the unit -R1 represents a fatty alkyl or alkenyl unit which
is
typically derived from a triglyceride source. The triglyceride source is
preferably
derived from tallow, partially hydrogenated tallow, lard, partially
hydrogenated
lard, vegetable oils and/or partially hydrogenated vegetable oils, such as,
canola
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31
oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall
oil, rice bran
oil, etc. and mixtures of these oils.
The preferred fabric softening actives of the present invention are the
Diester
and/or Diamide Quaternary Ammonium (DEQA) compounds, the diesters and
diamides having the formula:
[R4-m N (wherein R, R1, X, and n are the same as defined herein above for
formulas (1)
and (2), and Q has the formula:
0 H O
-O-C- or -N-C-
These preferred fabric softening actives are formed from the reaction of an
amine
with a fatty acyl unit to form an amine intermediate having the formula:
R N (CH2)n-Q-R] 2
wherein R is preferably methyl, Q and R' are as defined herein before;
followed
by quaternization to the final softener active.
Non-limiting examples of preferred amines which are used to form the DEQA
fabric softening actives according to the present invention include methyl
bis(2-
hydroxyethyl)amine having the formula:
CH3
HO,~N "-~OH
methyl bis(2-hydroxypropyl)amine having the formula:
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CH3
N
HO OH
methyl (3-aminopropyl) (2-hydroxyethyl)amine having the formula:
CH3
HON NH2
methyl bis(2-aminoethyl)amine having the formula:
CH3
H2N _---__~NH2
triethanol amine having the formula:
(oH
HO
di(2-aminoethyl) ethanolamine having the formula:
(oH
H2N
The counterion, X(-) above, can be any softener-compatible anion, preferably
the anion of a strong acid, for example, chloride, bromide, methylsulfate,
ethylsulfate, sulfate, nitrate and the like, more preferably chloride or
methyl
sulfate. The anion can also, but less preferably, carry a double charge in
which
case X(-) represents half a group.
Tallow and canola oil are convenient and inexpensive sources of fatty acyl
units
which are suitable for use in the present invention as R1 units. The following
are
non-limiting examples of quaternary ammonium compounds suitable for use in
the compositions of the present invention. The term "tallowyl" as used herein
below indicates the Rl unit is derived from a tallow triglyceride source and
is a
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33
mixture of fatty alkyl or alkenyl units. Likewise, the use of the term canolyl
refers
to a mixture of fatty alkyl or alkenyl units derived from canola oil.
In the following table are described non-limiting examples of suitable fabric
softener according to the above formula. In this list, the term "oxy" defines
a
0
-8- unit, whereas the term "oxo" defines a-O- unit.
Table II
Fabric Softener Actives
N,N-di(tallowyl-oxy-2-oxo-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium
chloride;
N,N-di(canolyl-oxy-2-oxo-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium
chloride;
N,N-di(tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride
N,N, N-tri(tallowyl-oxy-2-oxo-ethyl)-N-methyl ammonium chloride;
N,N,N-tri(canolyl-oxy-2-oxo-ethyl)-N-methyi ammonium chloride;
N-(tallowyioxy-2-oxo-ethyl)-N-(tallowyl)-N,N-dimethyi ammonium chloride;
N-(canolyloxy-2-oxo-ethyl)-N-(canolyl)-N,N-dimethyl ammonium chloride;
1,2-di(tallowyloxy-oxo)-3-N,N,N-trimethylammoniopropane chloride; and
1,2-di(canolyloxy-oxo)-3-N,N,N-trimethylammoniopropane chloride;
and mixtures of the above actives.
Other examples of quatemay ammoniun softening compounds are
methylbis(tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate and
methylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)ammonium
methylsulfate; these materials are available from Witco Chemical Company
under the trade marks Varisoft 222 and Varisoft 110, respectively.
Particularly preferred is N,N-di(tallowyl-oxy-2-oxo-ethyl)-N-methyl, N-(2-
hydroxyethyl) ammonium chloride, where the tallow chains are at least
partially
unsaturated.
The level of unsaturation contained within the tallow, canoia, or other fatty
acyl
unit chain can be measured by the Iodine Value (IV) of the corresponding fatty
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34
acid, which in the present case should preferably be in the range of from 5 to
100
with two categories of compounds being distinguished, having a IV below or
above 25.
Indeed, for compounds having the formula:
[(R)4m N (CH2)ri Q-R] X
m
derived from tallow fatty acids, when the Iodine Value is from 5 to 25,
preferably
to 20, it has been found that a cisltrans isomer weight ratio greater than
about
10 30170, preferably greater than about 50/50 and more preferably greater than
about 70/30 provides optimal concentrability.
For compounds of this type made from tallow fatty acids having a Iodine Value
of
above 25, the ratio of cis to trans isomers has been found to be less critical
unless very high concentrations are needed.
15 Other suitable examples of fabric softener actives are derived from fatty
acyl
groups wherein the terms "tallowyl" and canolyl" in the above examples are
replaced by the terms "cocoyl, palmyl, lauryl, oleyl, ricinoleyl, stearyl,
palmityl,"
which correspond to the triglyceride source from which the fatty acyl units
are
derived. These alternative fatty acyl sources can comprise either fully
saturated,
or preferably at least partly unsaturated chains.
As described herein before, R units are preferably methyl, however, suitable
fabric softener actives are described by replacing the term "methyl" in the
above
examples in Table 11 with the units "ethyl, ethoxy, propyl, propoxy,
isopropyl,
butyl, isobutyl and t-butyl.
The counter ion, X, in the examples of Table II can be suitably replaced by
bromide, methylsulfate, formate, sulfate, nitrate, and mixtures thereof. In
fact,
the anion, X, is merely present as a counterion of the positively charged
quaternary ammonium compounds. The scope of this invention is not considered
limited to any particular anion.
Mixtures of actives of formula (1) and (2) may also be prepared.
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2)-Stitt other suitable quaternary ammonium fabric softening compounds for use
herein are cationic nitrogenous salts having two or more long chain acyclic
aliphatic C8-C22 hydrocarbon groups or one said group and an arylalkyl group
which can be used either alone or as part of a mixture are selected from the
5 group consisting of:
(i) acyclic quatemary ammonium salts having the formula:
R4 +
R8-N-Rs A
i8
wherein R4 is an acyclic aliphatic C8-C22 hydrocarbon group, R5 is a Cl-C4
saturated alkyl or hydroxyalkyl group, R8 is selected from the group
consisting of
R4 and R5 groups, and A- is an anion defined as above;
(ii) diamino alkoxylated quatemary ammonium salts having the formula:
+
0
0 O Rs t)
R'-C-NH-R2-N-R2-NH-C-RI A
(CH2CHZO)nH
wherein n is equal to I to about 5, and Ri, R2, R5 and A- are as defined
above;
(iii) mixtures thereof.
Examples of the above class cationic nitrogenous salts are the well-known
dialkyldi methylammonium salts such as ditallowdimethylammonium chloride,
ditallowdimethyiammonium methylsulfate,
di(hydrogenatedtallow)dimethylammonium chloride, distearyidimethylammonium
chloride, dibehenyidimethylammonium chloride. Di(hydrogenatedtallow)di
methylammonium chloride and ditallowdimethylammonium chloride are preferred.
Examples of commercially available dialkyldimethyl ammonium saits usable in
the present invention are di(hydrogenatedtaliow)dimethylammonium chloride
(trade mark Adogen 442), ditallowdimethylammonium chloride (trade mark
Adogen 470, Praepagen 3445), distearyl dimethylammonium chtoride (trade
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36
mark Arosurf TA-100), all available from Witco Chemical Company.
Dibehenyldimethylammonium chloride is sold under the trade mark Kemamine
Q-2802C by Humko Chemical Division of Witco Chemical Corporation.
Dimethylstearylbenzyl ammonium chloride is sold under the trade marks Varisoft
SDC by Witco Chemical Company and Ammonyx 490 by Onyx Chemical
Company.
B)-Amine Fabric Softening Active Compound
Suitable amine fabric softening compounds for use herein, which may be in
amine form or cationic form are selected from:
(i)- Reaction products of higher fatty acids with a polyamine selected from
the
group consisting of hydroxyalkylalkylenediamines and dialkylenetriamines and
mixtures thereof. These reaction products are mixtures of several compounds in
view of the multi-functional structure of.the polyamines.
The preferred Component (i) is a nitrogenous compound selected from the group
consisting of the reaction product mixtures or some selected components of the
mixtures.
One preferred component (i) is a compound selected from the group consisting
of substituted imidazoline compounds having the formula:
N
R7-'
N
I
Rg-NH-C-R7
II
0
wherein R7 is an acyclic aliphatic C15-C21 hydrocarbon group and R8 is a
divalent CI-C3 alkylene group.
Component (i) materials are commercially available as: Mazamide(D 6, sold by
Mazer Chemicals, or Ceranine HC, sold by Sandoz Colors & Chemicals; stearic
hydroxyethyl imidazoline sold under the trade marks of Alkazine ST by Alkaril
Chemicals, Inc., or Schercozoline S by Scher Chemicals, Inc.; N,N"-
ditallowalkoyldiethylenetriamine; 1-tallowamidoethyl-2-tallowimidazoline
(wherein
in the preceding structure Rl is an aliphatic C15-C17 hydrocarbon group and R8
is a divalent ethylene group).
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37
Both N,N"-ditallowalkoyldiethylenetriamine and 1-tallow(amidoethyl)-2-
tallowimidazoline are reaction products of tallow fatty acids and
. diethylenetriamine, and are precursors of the cationic fabric softening
agent
methyl-l-tallowamidoethyl-2-tallowimidazolinium methylsulfate (see "Cationic
Surface Active Agents as Fabric Softeners," R. R. Egan, Joumal of the American
Oil Chemicals' Society, January 1978, pages 118-121). N,N"-ditallow
alkoyldiethylenetriamine and 1-tallowamidoethyl-2-tallowimidazoline can be
obtained from Witco Chemical Company as experimental chemicals. Methyl-1-
tallowamidoethyl-2-tallowimidazolinium methylsulfate is sold by Witco Chemical
Company under the trade mark Varisoft 475.
=(ii)-softener having the formula:
N
R~ I
= C
\ +
O
N CI-2 7C4-)
I / \ Rs
C G ~
wherein each R2 is a C1-6 alkylene group, preferably an ethylene group; and G
is an oxygen atom or an -NR- group; and each R, Ri, R2 and R5 have the
definitions given above and A' has the definitions given above for X-.
An example of Compound (ii) is 1-oleylamidoethyl-2-oleylimidazolinium chloride
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 chloride anion.
(iii)- softener having the formula:
H H 29
N-R2-N
NI N 2AG 25
wherein R, R1, R2, 'and A- are defined as above.
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38
An example of Compound (iii) is the compound having the formula:
p
1V-CH2CH2__N1 H H\
ci e
NRl ~ =N
wherein R1 is derived from oleic acid.
Nonionic softeners
Nonionic softener include compounds such as the fatty acid esters, preferably
a
partial ester, of mono- or polyhydric alcohols or anhydride thereof containing
from
1 to 8 carbon atoms.
It is preferred that the fatty acid ester has at least 1 free (i.e.
unesterified)
hydroxyl group and at least 1 fatty acyl group.
The mono- or polyhydric alcohol portion of the ester can be represented by
methanol, isobutanol, 2-ethyl hexanol, isopropanol, ethylene glycol and
polyethylene glycol with a maximum of 5 ethylene glycol units, glycerol,
diglycerol, xylitol, sucrose, erythritol, penta-erythritol, sorbitol or
sorbitan.
Ethylene glycol, glycerol and sorbitan esters are particularly preferred.
The fatty acid portion of the ester normally comprises a fcltty acid having
from 12
to 22 carbon atoms, typical examples being lauric acid, myristic acid,
paimitic
acid, stearic acid and behenic acid.
One highly preferred group of lubricant for use in the present invention is
the
sorbitan esters, which are esterified dihydration products of sorbitol.
Sorbitol,
itself 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 Brown, U.S. Pat. No. 2,322,821, issued June 29,
1943). The foregoing type 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.
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39
The lubricants of the type employed herein can be prepared by esterifying the
"sorbitan" mixture with a fatty acyl group in standard fashion, e.g. by
reaction with
a fatty acid halide or fatty acid. The esterification reaction can occur at
any of the
available hydroxyl groups, and various mono-, di-, etc., esters can be
prepared.
In fact, mixtures of mono-, di-, tri-, etc., esters almost always result from
such
reactions, and the stoichiometric ratios of the reactants can be simply
adjusted to
favor the desired reaction product.
For commercial production of the sorbitan ester materials, etherification and
esterification are generally accomplished in the same processing step by
reacting
sorbitol directly with fatty acids. Such a method of sorbitan ester
preparation is
described more fully in MacDonald; "Emulsifiers: Processing and Quality
Control:", Journal of the American Oil Chemists' Society, Volume 45, October
1968.
The mixtures of hydroxy-substituted sorbitan esters useful herein contain,
inter
alia, compounds of the following formulae, as well as the corresponding
hydroxy-
substituted di-esters:
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HO OH H
I
C -.- CH2O C(O)R
/L- O 1
OH
O :: C(O)R
OH OH
HO p
0 C(O)R
O
wherein the group R is a C10-C26, and higher, fatty alkyl residue. Preferably
this
fatty alkyl residue contains from 16 to 22 carbon atoms. The fatty alkyl
residue
5 can, of course, contain non-interfering substituents such as hydroxyl
groups.
Esterified hydroxyl groups can, of course, be either in terminal or internal
positions within the sorbitan molecule.
The foregoing complex mixtures of esterified dehydration products of sorbitol
10 (and small amounts of esterified sorbitol) are collectively referred to
herein as
"sorbitan esters". Sorbitan mono- and di-esters of lauric, myristic, palmitic,
stearic
and behenic (docosanoic) acids are particularly useful herein as softening
agents
and also can provide an anti-static benefit to fabrics. Mixed sorbitan esters,
e.g.
mixtures of the foregoing esters, and mixtures prepared by esterifying
sorbitan
15 with fatty acid mixtures such as the mixed tallow fatty acids, are useful
herein
and are economically attractive. Unsaturated C10-C22 sorbitan esters, e.g.
sorbitan monooleate, usually are present in such mixtures in low
concentration.
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The term "alkyl" as employed herein to describe the sorbitan esters
encompasses both the saturated and unsaturated hydrocarbyl ester side chain
groups.
Certain derivatives of the sorbitan esters herein, especially the '9ower"
ethoxylates thereof (i.e. mono-, di- and tri-esters) wherein one or more of
the
unesterified -OH groups contain one to about 20 oxyethylene moieties
(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.
Preparation of the sorbitan esters can be achieved by dehydrating sorbitol to
form a mixture of anhydrides of the type set forth above, and subsequently
esterifying the mixture using, for example, a 1:1 stoichiometry for the
esterification reaction. The esterified mixture can then be separated into the
various ester components. Separation of the individual ester products is,
however; difficult and expensive.
Accordingly, it is easier and more economical not to separate the various
esters,
using instead the esterffied mixture as the sorbitan ester component. Such
mixtures of esterified reaction products are commercially available under
various
trade marks e.g. Span . Such sorbitan ester mixtures can also be prepared by
utilizing conventional interesterification procedures.
For the purposes of the present invention, it is preferred that a significant
amount
of di- and tri-sorbitan esters are present in the ester mixture. Ester
mixtures
having from 20%-50% mono-ester, 25% to 50% di-ester and 10%-35% of tri- and
tetra-esters are preferred. The material which is sold commercially as
sorbitan
mono-ester (e.g. mono-stearate) does in fact contain significant amounts of di-
and tri-esters and a typical analysis of sorbitan monostearate indicates that
it
comprises ca.27% mono-, 32% di- and 30% tri- and tetra esters. Commercial
sorbitan mono-stearate therefore is a preferred material.
Mixtures of sorbitan stearate and sorbitan palmitate having stearate/palmitate
weight ratios varying between 10:1 and 1:10, and 1,5-sorbitan esters are
useful.
Both the 1,4- and 1,5- sorbitan esters are useful herein. Other useful alkyl
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sorbitan esters for use in the softening compositions herein include sorbitan
monolaurate, sorbitan monomyristate, sorbitan monopolmitate, sorbitan mono-
behenate, sorbitan monooleate, sorbitan dilaurate, sorbitan dimyristate,
sorbitan
dipaimitate, sorbitan
distearate, sorbitan dibehenate, sorbitan dioleate, and mixtures thereof, and
mixed tallowalkyl sorbitan mono- and di-esters. Such mixtures are readily
prepared by reacting the foregoing hydroxy-substituted sorbitans, particularly
the
1,4- and 1,5-sorbitans, with the corresponding acid or acid chloride in a
simple
esterification reaction, It is to be recognized, of course, that commercial
materials
prepared in this manner will comprise mixtures usually containing minor
proportions of uncyclized sorbitol, fatty acids, polymers, isosorbide
structures,
and the like.
It is also to be recognized that the sorbitan esters employed herein can
contain
up to about 15% by weight of esters of the C20 -C26, and higher, fatty acids,
as
well as minor amounts of C8, and lower, fatty esters.
Other fatty acid partial esters useful in the present invention are xylitol
monopalmitate, pentaerythritol - monostearate, sucrose monostearate, glycerol
monostearate and ethylene glycol monostearate. As with the sorbitan esters,
comrbercially available mono-esters normally contain substantial quantities of
di-
or tri-esters.
The glycol esters are also highly preferred. These are the mono-, di- or tri-
esters
of glycerol and fatty acids of the class described above.
Commercial glyceryl monostearate, which may contain a proportion of the di-
and
tristearates, is especially preferred.
Another class of suitable nonionic lubricants are the cyclomethicones such as
described in EP636356.
The above-discussed nonionic compounds are correctly termed "lubricating
agents", because, when the compounds are correctly applied to a fabric, they
do
impart a soft, lubricious feel to the fabric.
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Additional fabric softening agents useful herein are described in U.S. Pat.
No.
4,661,269, issued April 28, 1987, in the names of Toan Trinh, Errol H. Wahl,
Donald M. Swartley, and Ronald L. Hemingway; U.S. Pat. No. 4,439,335, Burns,
issued March 27, 1984; and in U.S. Pat. Nos.: 3,861,870, Edwards and Diehl;
4,308,151, Cambre; 3,886,075, Bemardino; 4,233,164, Davis; 4,401,578,
Verbruggen; 3,974,076, Wiersema and Rieke; 4,237,016, Rudkin, Clint, and
Young; and European Patent Application publication No. 472,178, by Yamamura
etal. %
Of course, the term " lubricating agent " can also encompass mixed softening
active agents.
Preferred lubricating agent among the one disclosed above are the quaternary
ammonium compound disclosed under (A) and the cyclomethicones.
The lubricating agent is present in the composition in a sufficient amount to
result
in an amount of from 0.005% to 5%, preferably from 0.01% to 3%, more
preferably from 0.01 % to 1.50% by weight of active per weight of dry fabrics.
Typically, the lubricating agent is added to the composition of the present
invention at a level of from about 0.01% to about 10%, by weight of the
composition, preferably from about 0.1% to about 3%, more preferably from
about 0.1 % to about 1.5%, by weight of the composition.
5- Salt
A salt is another optional ingredient. When used, it will both contribute to
the
hydrogen bond breaking process produces by the water and to the reinforcement
of the wetting power of the wetting agent. The salt is further believed to
facilitate
the dewrinkling action by maintaining a residual humidity of fibers.
The salt useful in the present invention is a compound made of alkaline and/or
earth alkaline metal, and that can form hydrates upon crystallization.
Typically,
the salt for use in the present invention have the following formula: AM;
wherein A is a cation. This cation is an alkaline and/or earth alkaline metal,
preferably selected from sodium, calcium, potassium, magnesium; more
preferably sodium and calcium, and
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wherein M is a couteranion selected from sulfate, chloride, nitrate,
carbonate,
borate, and carboxylates.
Preferred salts are salts selected from sodium, calcium, potassium, magnesium
and mixtures thereof; more preferably salt of sodium, calcium, and mixtures
thereof.
Particularly preferred salts for use herein are selected from sodium sulphate,
sodium bicarbonate, sodium chloride, sodium borate, potassium sulphate,
calcium chloride, sodium citrate, magnesium sulphate, and mixtures thereof,
more preferably are selected from sodium sulphate, sodium bicarbonate,
potassium sulphate, calcium chloride, and mixtures thereof.
The salt is present in the composition in a sufficient amount to result in an
amount of from 0.005% to 5%, preferably from 0.01% to 3%, more preferably
from 0.01 % to 1.50% by weight of active per weight of dry fabrics.
Accordingly, typical levels of the salt in the composition are from 0.01% to
about
10%, by weight of the composition, preferably from about 0.1% to about 3%,
more preferably from about 0.1 % to about 1.5%, by weight of the composition.
6. Polyolefin
The compositions of the present invention can also include an optional
dispersible polyolefin. When used this will provide a further wrinkle
reduction.
Preferably, the polyolefin is a polyethylene, polypropylene or mixtures
thereof.
The polyolefin may be at least partially modified to contain various
functional
groups, such as carboxyl, alkylamide, sulfonic acid or amide groups. More
preferably, the polyolefin employed in the present invention is at least
partially
carboxyl modified or, in other words, oxidized. In particular, oxidized or
carboxyl
modified polyethylene is preferred in the compositions of the present
invention.
For ease of formulation, the dispersible polyolefin is preferably introduced
as a
suspension or an emulsion of polyolefin dispersed by use of an emulsifying
agent. The polyolefin suspension or emulsion preferably has from about 1 to
about 50%, more preferably from about 10 to about 35% by weight, and most
preferably from about 15 to about 30% by weight of polyolefin in the emulsion.
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The polyolefin preferably has a molecular weight of from about 500 to about
15,000 and more preferably from about 4,000 to about 10,000.
When an emulsion is employed, the emulsifier may be any suitable
emulsification
5 agent. Preferably, the emulsifier is a cationic or nonionic surfactant or
mixtures
thereof. Most any suitable cationic or nonionic surfactant may be employed as
the emulsifier of the present invention. Preferred emulsifiers of the present
invention are cationic surfactants such as the fatty amine surfactants and in
particular the ethoxylated fatty amine surfactants. In particular, the
cationic
10 surfactants are preferred as emulsifiers in the present invention when the
pH of
the iiquid composition is formulated in the preferred range of from about 2 to
about 7. The dispersible polyolefin is dispersed by use of an emulsifier or
suspending agent in a ratio of emulsifier to polyolefin of from about 1:10 to
about
3:1. Preferably, the emulsion includes from about 0.1 to about 50%, more
15 preferably from about 1 to about 20% and most preferably from about 2.5 to
about 10% by weight of emulsifier in the polyolefin emulsion. Polyethylene
emulsions suitable for use in the present invention are available under the
trade mark VELUSTROL from HOECHST Aktiengesellschaft of Frankfurt am
Main, Germany. In particular, the polyethylene emulsions sold under the
20 trade marks VELUSTROL PKS, VELUSTROL KPA and VELUSTROL P-40 may
be employed in the compositions of the present invention.
The compositions of the present invention may contain from about 0.01% to
about 50% by weight of the polyolefin. More preferably, the compositions
include
25 from about 0.1% to about 20% by weight polyolefin and most preferably from
about 0.1% to about 10% by weight polyolefin. When the dispersible polyolefin
is
added as an emulsion or suspension of polyolefin as described above, from
about 0.1 % to about 90%, and more preferably from about 0.5% to about 25% by
weight of the emulsion or suspension may be added.
7. Hydroxy-capped polydimethyl siioxane emulsion (sifanoi)
When a polyolefin emulsion as described above under (6) is present in
combination with a polymer such a polyvinyl alcohol, it has been found
desirable
to add a hydroxy-capped polydimethyl siloxane emulsion (silanol). Such
addition
will further increses the wrinkles neduction present on fabrics.
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Typical of hydroxy-capped polydimethyl siloxane emulsion (sitanol) also called
Dimethiconols according to INCI and the CTFA, are SM2725 and SM2068A
commercially available from General Electric, Q2-1403 from Dow Coming; Abil
OSWTM series from Goldschmidt; and SandopermTM FE from Sandoz. A preferred
silanol for use herein, especially when used in combination with a
polyvinylalcohol and polyolefin emulsion is SM2725 because of its film forming
properties.
The compositions of the present invention may contain from about 0.01% to
about 25% by weight of the hydroxy-capped polydimethyl siloxane emulsion.
More preferably, the compositions include from about 0.01 % to about 20% by
weight hydroxy-capped polydimethyl siloxane emulsion and most preferably from
about 0.1% to about 10% by weight hydroxy-capped polydimethyl siloxane
emulsion.
8- Antimicrobiai active
The composition may suitably use an optionai solubilized, water-soluble
antimicrobial active, useful in providing protection against organisms that
become
attached to the treated materiai. 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, quatemary compounds, and phenolic compounds.
Biguanides. Some of the more robust 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'-hexamethyiene bis(5-(p-chlorophenyl)biguanide),
commonly known as chlorhexidine, and its saits, 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 0.01 % to about 0.1%, by weight of
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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 CosmociO 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, phenyisulfonates 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; 1,6-di-(N1,N1'-phenyidiguanido-
N5,N5')-hexane tetrahydrochloride; 1,6-di-(N1,Nl'-phenyl-N1,N1'-
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(N 1,N 1'-
.alpha.-methyl-.beta.-phenyldiguanido-N5,N5')-hexane dihydrochloride; 1,6-
di(N1,N 1'-p-nitrophenyldiguanido-N5, N5')hexane
dihydrochloride;.omega.:.omega.'-di-(N1,N1'-phenytdiguanido-N5,N5')-di-n-
propyl
ether' dihydrochloride;.omega:omega'-di(N1,N1'-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-
.25 trichlorophenyldiguanido-N5,N5') hexane tetrahydrochloride; 1,6-di[N1,N1'-
.alpha.-(p-chlorophenyl) ethyldiguanido-N5,N5'] hexane
dihydrochloride;.omega.:.omega.'di(Nl, N1'-p-chlorophenyl diguanido-N5,N5')m-
xylene dihydrochloride; 1,12-di(N1,N1'-p-chlorophenyl diguanido-N5,N5')
dodecane dihydrochloride; 1,10-di(N 1,N 1'-phenyldiguanido-N5,N5')-decane
tetrahydrochloride; 1,12-di(N1,N1'-phenyldiguanido-N5,N5') dodecane
tetrahydrochloride; 1,6-di(N1,N1'-o-chlorophenyldiguanido-N5,N5') hexane
dihydrochloride; 1,6-di(N 1, N 1'-p-chlorophenyld iguanido-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-
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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-
coconutalkyisarcosinates; 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-(NI,N1'-phenyldiguanido-
N5, N5')-hexane tetrahydrochloride; 1 ,6-di(N 1,N 1'-o-chlorophenyldiguanido-
N5,N5')-hexane dihydrochloride; 1,6-di(N1,N1'-2,6-dichiorophenyldiguanido-
N5,N5')hexane dihydrochloride; 1,6-di(N1,N1'-2,4-dichlorophenyldiguanido-
N5,N5')hexane tetra hydrochloride; 1,6-di[N1,N1'-.alpha.-(p-chlorophenyl)
ethyldiguanido-N5,N5'] hexane dihydrochioride;.omega.:.omega.'di(N1, N1'-p-
chlorophenyldiguanido-N5,N5')m-xylene dihydrochloride; 1,12-di(N1,N1'-p-
chlorophenyldiguanido-N5,N5') s dodecane dihydrochloride; 1,6-di(N1,N1'-o-
chlorophenyldiguanido-N5,N5') hexane dihydro chloride; 1,6-di(N1,N1'-p-
chlorophenyldiguanido-N5,N5')-hexane tetrahydrochloride; and mixtures thereof;
more preferably, 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,Nl'-2,4-dichlorophenyldiguanido-N5,N5')hexane
.25 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(N1,N1'-o-chlorophenyldiguanido-
N5,N5') hexane dihydrochioride; 1,6-di(N1,N1'-p-chlorophenyldiguanido-N5,N5')-
hexane tetrahydro chloride; and mixtures thereof. As stated hereinbefore, the
bis
biguanide of choice is chlorhexidine its salts, e.g., digluconate,
dihydrochloride,
diacetate, and mixtures thereof.
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 that do not contain cyclodextrin. Non-
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limiting examples of useful quatemary compounds include: (1) benzalkonium
chlorides. and/or substituted benzalkonium chlorides such as commercially
available Barquat (available from Lonza), Maquat (available from Mason),
V.ariquat (available from Witco/Sherex), and HyamineOD (available from
Lonza);
(2) dialkyl quatemary such as Bardac products of Lonza, (3) N-(3-chloroallyi)
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 10X supplied by Rohm
& Haas, (6) cetylpyridinium chloride such as CepacolTM chloride available from
of
Merrell Labs. Typical concentrations for biocidal effectiveness of these
quatemary 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.
Other preservatives which are conventional in the art, such as described in US
5,593,670 may also by used herein.
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.
-25
9- Perfume
The composition of the present invention can also optionaHy provide a "scent
signal" in the form of a pleasant odor which signals the removal of malodor
from
fabrics. The scent signal is designed to provide a fleeting perfume scent, and
is
not designed to be overwhelming or to be used as an odor masking ingredient.
When perfume is added as a scent signal, it is added only at very low levels,
e.g.,
from about 0% 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.
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Perfume can also be added as a more intense odor in product and on surfaces.
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.
5
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
10 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).
15 (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
20 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
25 partition coefficients of the perfume ingredients normally have high
values, they
are more conveniently given in the form of their logarithm to the base 10,
logP.
Thus the preferred perfume hydrophilic perfume ingredients of this invention
have IogP of about 3.5 or smaller, preferably of about 3.0 or smaller.
30 The logP of many perfume ingredients have been reported; for example, the
Pomona92 database, available from Daylight Chemical Information Systems, Inc.
(Daylight CIS), Irvine, California, contains many, along with citations to the
original literature. However, the IogP values are most conveniently calculated
by
the "CLOGP" program, also available from Daylight CIS. This program also lists
35 experimental logP values when they are available in the Pomona92 database.
The "calculated logP" (ClogP) is determined by the fragment approach of Hansch
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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, allyl 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, Cycial 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, flor acetate (tricyclo decenyl
acetate),
fructone, frutene (tricyclo decenyl propionate), geraniol, geranyl
oxyacetafdehyde, heliotropin, hexenol, hexenyl acetate, hexyl acetate, hexyl
formate, hinokitiol, hydratropic alcohol, hydroxycitronellal,
hydroxycitronellal
diethyl acetal, hydroxycitroneliol, 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 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,
para-
cresol, para-cresyl methyl ether, para hydroxy phenyl butanone, para-methoxy
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acetophenone, para-methyl acetophenone, phenoxy ethanol, phenoxyethyl
propionate, phenyl acetaidehyde, phenylacetaidehyde diethyl ether, phenylethyl
oxyacetaidehyde, phenyl ethyl acetate, phenyl ethyl alcohol, phenyl ethyl
dimethyl
carbinol, prenyl acetate, propyl butyrate, pulegone, rose oxide, safrole,
terpineol,
vanillin, viridine, and mixtures thereof.
Noniimiting examples of other preferred hydrophilic perfume ingredients which
can be used in perfume compositions of this invention are allyl heptoate, amyl
benzoate, anethole, benzophenone, carvacrol, citral, citroneliol, 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,
isobomyl acetate, isobutyl benzoate, isononyl alcohol, isomenthol, para-
isopropyl phenylacetaidehyde, isopulegol, linalyl acetate, 2-methoxy
naphthalene, menthyl acetate, methyl chavicol, musk ketone, beta naphthol
methyi ether, neral, nonyl aidehyde, 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 Ingredient
The odor detection threshold of an odorous material is the lowest vapor
concentration of that material which can be olfactoriiy detected. The odor
detection threshold and some odor detection threshoid 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.
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The use of small amounts of perfume ingredients that have low
odor detection threshold values can improve perfume odor character,
even though they are not as hydrophilic as perfume ingredients of group (a)
which are given hereinabove. Perfume ingredients that do not belong to group
(a) above, but have a significantly low detection threshold, useful in the
composition of the present. invention, are selected from the group consisting
of
ambrox, bacdanol, benzyl salicylate, butyl anthranilate, cetalox, damascenone,
alpha-damascone, gamma-dodecalactone, ebanol, herbavert, cis-3-hexenyl
salicylate, alpha-ionone, beta-ionone, alpha-isomethylionone, 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
16%, 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, Cycial C,
cymal, 4-decenal, dihydro isojasmonate, ethyl anthranilate, ethyl-2-methyl
butyrate, ethyl methylphenyl glycidate, ethyl vanillin, eugenol, flor acetate,
florhydral, fructone, frutene, heliotropin, keone, indole, iso cyclo citral,
isoeugenol, lyral, methyl heptine carbonate, linalool, methyl anthranilate,
methyl
dihydrojasmonate, methyl isobutenyl tetrahydropyran, methyl beta naphthyl
ketone, beta naphthol methyl ether, nerol, para-anisic aidehyde, 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.
10-Salt to absorb amine and sulfur-containing compounds
Optionally, but preferably, salts to absorb amine and sulfur-containing
compounds, preferably water-soluble zinc salts, can be added to the
composition
of the present invention. The salt can be used as an odor control agent. The
water-soluble metallic salt can be present in the composition of the present
invention to absorb amine and sulfur-containing compounds. Furthermore, they
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usually do not contribute an odor of their own. Preferably the water-soluble
metallic salts are selected from the group consisting of copper salts, zinc
salts,
and mixtures thereof.
Metallic safts of use herein are described in US 5670475 column 9 line 8 to
43.
Examples of preferred water-soluble zinc salts are zinc chioride, zinc
gluconate,
zinc lactate, zinc maleate, zinc salicylate, zinc sulfate, etc. Highly-ionized
and
soluble zinc salts such as zinc chloride, provide the best source of zinc
ions.
Examples of preferred copper salts are copper chloride and copper -gluconate.
Preferred metallic salts are zinc chloride and copper chloride.
Salts to absorb amine and sulfur-containing compounds are added to the
composition of the present invention typically at a level of from about 0.1%
to
about 10%, preferably from about 0.2% to about 7%, more preferably from about
0.3% to about 5%, by weight of the composition.
11-Soil Release Agent
Soil Release agents are desirably used in compositions of the instant
invention.
Any polymeric soil release agent known to those skilled in the art can
optionally
be employed in the compositions of this invention. Polymeric soil release
agents
are characterized by having both hydrophilic segments, to hydrophilize the
surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic
segments, to deposit upon hydrophobic fibers and remain adhered thereto
through completion of washing and rinsing cycles and, thus, serve as an anchor
for the hydrophilic segments. This can enable stains occurring subsequent to
treatment with the soil release agent to be more easily cleaned in later
washing
procedures. If utilized, soil release agents will generally comprise from
about 0.01 % to about
10.0%, by weight, of the detergent compositions herein, typically from about
0.1 k to about 5%, preferably from about 0.2% to about 3.0%.
The following describe soil release polymers suitable for use in the present
invention. U.S. 3,959,230 Hays, issued May 25, 1976; U.S. 3,893,929
Basadur, issued July 8, 1975; U.S. 4,000,093, Nicol et al., issued
December 28, 1976; U.S. Patent 4,702,857 Gosselink, issued October
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27, 1987; U.S. 4,968,451, Scheibel et al., issued November 6; U.S. 4,702,857,
Gosselink, issued October 27, 1987; U.S. 4,711,730, Gosselink et al., issued
December 8, 1987; U:S. 4,721,580, Gosselink, issued January 26, 1988; U.S.
4,877,896, . Maldonado et al., issued October 31, 1989; U.S. 4,956,447,
5 Gosselink et al., issued September 11, 1990; U.S. 5,415,807 Gosselink et
al.,
issued May 16, 1995; European Patent Application 0 219 048, published April
22, 1987 by Kud, et al..
Further suitable soil release agents are described in U.S. 4,201,824, Violland
et
10 a/.; U.S. 4,240,918 Lagasse et al.; U.S. 4,525,524 Tung et al.; U.S.
4,579,681,
Ruppert et al.; U.S. 4.240,918; U.S. 4,787,989; U.S. 4,525,524; EP 279,134 A,
1988, to Rhone-Poulenc Chemie; EP 457,205 A to BASF (1991); and DE
2,335,044 to Unilever N. V., 1974.
15 Commercially available soil release agents include the METOLOSETM SM100,
METOLOSE SM200 manufactured by Shin-etsu Kagaku Kogyo K.K., SOKALANTM
type of material, e.g., SOKALAN HP-22, available from BASF (Germany),
ZELCONTM 5126 (from Dupont) and MILEASE T (from ICI).
20 12-Pro-perfume
The composition may also comprises ingredient useful for providing a long and
lasting release of a perfume material. Typical disclosure can be found in
W095/04809, W096/02625, W098/07811 and EP-A-0,752,465.
25 Typical level of incorporation of the perfume are from 0.01 % to 15% by
weight of
the composition.
13-pH
An optional requirement of the compositions according to the present invention
is
30 that the pH is greater than 7, preferably between 7 and 12, more preferably
between 8 and 11, most preferably between 9 and 10.5. This is achieved by the
addition of a caustic alkali. Suitable caustic alkalis for use herein include
sodium
and potassium hydroxide.
35 14- Other Optional Ingredients
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The present invention can include optional components conventionally used in
textile treatment compositions, for example, colorants, preservatives,
bactericides, optical brighteners, opacifiers, anti-shrinkage agents,
germicides,
fungicides, anti-oxidants, dye fixing agent, enzymes, chelating agents, color
protectors like polyethylene imine and its alkoxylated derivatives and the
like.
The compositions are preferably free of any material that would soil or stain
fabric, and are also substantially free of starch. Typically, there should be
less
than about 0.5%, by weight of the composition, preferably less than about
0.3%,
more preferably less than about 0.1%, by weight of the composition, of starch
and/or modified starch.
E. Form of the composition and compounds
The composition or its individual components can be provided in any suitable
form such as spray, foam, gel or any other suitable form for liquid aqueous
compositions, preferably the composition is in the form of a spray.
Preferably,
when sprayed, the liquid composition which is applied on the fabric will have
particle sizes in the range of 8 to 100 m, preferably from 10-60 m (more
preferably from 20-60 m) for automatic sprayer, and preferably from 50-100 m
for manually activated sprayer. Accordingly, there is provided a packaged
composition comprising the composition or compounds, preferably in a spray
dispenser.
F. Packaginq
In another aspect of the invention, a packaged composition is provided that
comprises a packaged composition comprising a wrinkle reducing composition
comprising a wrinkle reducing active which contains a polymer, a cyclodextrin,
a
liquid carrier, and a spray dispensing device.
The dilute compositions, i.e., compositions containing from about 0.1% to
about
5%, by weight of the composition, of wrinkle reducing active, of the present
invention are preferably sprayed onto fabrics and therefore are typically
packaged in a spray dispenser. The spray dispenser can be any of the manually
activated means for producing a spray of liquid droplets as is known in the
art,
e.g. trigger-type, pump-type, electrical spray, hydraulic nozzle, sonic
nebulizer,
high pressure fog nozzle, non-aerosol self-pressurized, and aerosol-type spray
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means. Automatic activated means can also be used herein. These type of
automatic means are similar to manuaqy activated means with the exception that
the propellant is- replaced by a compressor. It is preferred that at least
about
70%, more preferably, at least about 80%, most preferably at least about 90%
of
the droplets have a particle size of smaller than about 200 microns.
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 intemal pressure in the range of from about 5 to about
100 p.s.i.g., more preferably from about 10 to about 60 p.s.i.g. The one
important
requirement conceming the dispenser is that it be provided with a valve member
which will permit the wrinkle reducing 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 wrinkle reducing 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, are not preferred. Halogenated
hydrocarbon propellants such as chlorofluoro hydrocarbons have been alleged to
contribute to environmental problems. 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.
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 essentialiy cylindrical elastomeric sleeve. The liner/sleeve is
capable of
holding a substantial quantity of odor-absorbing fluid product and of causing
said
product to be dispensed. A more complete description of self-pFessurized 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.
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Another type of aerosol spray dispenser is one wherein a barrier separates the
wrinkle reducing composition from the propellant (preferably compressed air or
nitrogen), as is 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 wrinkle reducing 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. Other materials can include
stainless steel. A more complete disclosure of commercially available
dispensing
devices appears in: U.S. Pat. Nos.: 4,895,279, Schulttr, issued January 23,
1990; 4,735,347, Schultz et al., issued April 5, 1988; and 4,274,560, Carter,
issued June 23, 1981õ
Most preferably, the spray dispenser is a manually activated trigger-spray
dispenser. Said trigger-spray dispenser comprises a container and'a trigger
both
of which can be constructed of any of the conventional material employed in
fabricating trigger-spray dispensers, including, but not limited to:
polyethylene;
polypropylene; polyacetal; polycarbonate; polyethyleneterephthalate; polyvinyl
chloride; polystyrene; blends of polyethylene, vinyl acetate, and rubber
elastomer. Other materials can include stainless steel and glass. The trigger-
spray dispenser does not incorporate a propellant gas. The trigger-spray
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dispenser herein is typically one which acts upon a discrete amount of the
wrinkle reducing 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
aNows the
:product to be forced through the swirl chamber and out the nozzle to form a
discharge pattem. 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, Caiifomia; 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., the Calmar TS800-1A sprayers, available from
Calmar Inc., or the CSI T7500 available from Continental Sprayers, Inc.,
because of the fine uniform spray characteristics, spray volume, and pattern
size.
5 Any suitable bottle or container can be used with the trigger sprayer, the
preferred bottle is a 17 fl-oz. bottle (about 500 mi) 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
10 made of high density polyethylene or polyethylene terephthalate.
For smaller four fl-oz. size (about 118 ml), 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.
Regardless of the particular commercial spray nozzle used, it is preferable
for the
atomization spray nozzle to have an orifice diameter of from about 0.1 mm to
about 2 mm, and most preferably from about 0.15 mm to about 1 mm. The
spraying step is conducted for a period of time of from about 5 minutes to
about
30 minutes, more preferably from about 5 minutes to about 20 minutes. Spraying
times will vary depending upon the various operating parameters selected as
described herein.
For use herein, it is preferred that said spray dispenser comprises a trigger
spray
device. More preferably, the spray dispenser should be capable of providing
droplets with a weight average diameter of from 8 to 100 m, preferably from
10-
60 m (more preferably from 20-60 m) for automatic sprayer, and preferably
from 50-100 m for manually activated sprayer.
G. Method of use
An effective amount of the liquid composition of the present invention is
preferably sprayed onto fabrics, particularly clothing. When the composition
is
sprayed onto fabric an effective amount should be deposited onto the fabric
without causing saturation of the fabric, typically from 3 % to 85%,
preferably
from 5 % to 50%, more preferably from 5 % to 25 %, by weight of the fabric.
The
amount of total active typically sprayed onto the fabric is from 0.01% to 3%,
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preferably from 0:1 % to 2 %, more preferably from 0.1 % to 1%, by weight of
the
fabric. 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 interface sewn into them, or on the hem of clothing. Once
the
fabric has been sprayed and optionally, but preferably, stretched, it is hung
until
dry.
Accordingly, there is provided a method for reducing wrinkles and malodours on
fabrics which comprises the steps of contacting the fabrics with a composition
of
the invention, as defined herein before.
By "contacting", it is meant any steps that is suitable for providing a
contact of the
composition with the fabric. This can include by soaking, washing, rinsing,
and/or
spraying as well as by means of a dryer sheet onto which is adsorbed the
composition.
The composition of the present invention can also be used as an ironing aid.
An
effective amount of the composition can be sprayed onto fabric, wherein said
fabric should not be sprayed to saturation. The fabric can be ironed at the
normal
temperature at which it should be ironed. The fabric can be sprayed with an
effective amount of the composition, allowed to dry and then ironed, or
sprayed
and ironed immediately.
In a still further aspect of the invention, the composition can be sprayed
onto
fabrics by means of an in-home de-wrinkling apparatus containing the fabric to
be dewrinkled, thereby providing ease of operation. Conventional personal as
well as industrial de-wrinkling apparatus are suitable for use herein.
Traditionally,
these apparatus act by a steaming process which provides a relaxing of the
fibers. The spraying of the composition or compounds on the fabrics can then
occurs within the chamber of the apparatus or before placing the fabrics into
the
chamber. Again, the spraying means should preferably be capable of providing
droplets with a mean diameter of from 3 to 50 m, preferably from 5-30 m for
automatic sprayer, and preferably from 50-100 m for manually activated
sprayer. Preferably, the loading of moisture on fabrics made of natural and
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synthetic fibers is from 5 to 25%, more preferably from 5 to 10% by weight of
the
dried fabric. Other conventional steps for the dewrinkling apparatus can be
applied such as heating and drying. Optionally, for optimum dewrinkling
benefit,
the temperature of the conditioning composition can be heated to enhance
distribution and deposition of the conditioning composition on the garments.
In
that regard, the temperature of the conditioning composition can be as low as
room temperature, and preferably is from 35 C to 80 C, more preferably from 40-
70 C. By having the conditioning composition at the aforementioned elevated
temperatures, it has been found that superior de-wrinkling benefits are
achieved.
It should be understood that the temperature of the conditioning composition
can
be from about ambient (15 C) temperature to about 80 C, and higher
temperatures generally improve de-wrinkling performance.
It has also been found that effective softening composition distribution on
the
garments, e.g inside the cabinet, can be further enhanced by optimally
selecting
the fluid surface tension of the softening composition. For example, it is
preferable for the softening composition to have fluid surface tension of from
about 5 dynes/cm to about 60 dynes/cm, more preferably of from about 20
dynes/cm to about 55 dynes/cm, and most preferably, from about 20 dynes/cm to
about 30 dynes/cm. The lower surface tension of the softening composition
improves effective distribution by improving surface absorption and spreading
of
the softening composition on the garment fabric.
Furthermore, it is preferable for the softening composition to have a fluid
viscosity
of from about 1 cps to about 100 cps, more preferably from about 1 cps to
about
50 cps, and most preferably of from about 1 cps to about 20 cps as measured by
a standard Brookfield viscometer.
In the examples, the abbreviated component identifications have the following
meanings:
Wetting agent 1: N,N dimethyl-N-(2-hydroxyethyl)-N-dodecyl/tetradecyi
ammonium bromide
Wetting agent 2: C12/C14 Choline ester
Wetting agent 3: C8/C12 dimethyl, hydroxyethyl quatemary ammonium salt
Wetting agent 4: Silwet L-7600 commercially available from OSi Specialties
Lubricant: N,N-di-(canolyi-oxy-ethyl)-N-methyl-N-(2-hydroxyethyl)
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ammonium methyl sulfate
Cyclodextrin: Hydroxypropyl beta-cyclodextrin
preservative: KathonTM
Dye fixative: Cationic dye fixing agent (50% active) available under the
trade mark Tinofix Eco from Ciba-Geigy
VELUSTROLTM P-40: Nonionic polyethylene emulsion available from HOECHST
Aktiengesellschaft
Silanol: Hydroxy-capped polydimethyl siloxane emulsion
commercially available from General Electric under the
trade mark SM2725
CarezymeTM: Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO
Industries A/S and of activity mentioned above unless
otherwise specified
~TABLE 1
The following table defines the adhesive polymers used in the examples.
The following are copolymers used in the examples. Synthesis of the 2 first
compounds is made according the synthesis of US 5,120,532.
Copolymer #1 25/75 by weight of acrylic acid to tert-butyl acrylate of
molecular weight of about 70,000 to 100,000.
Copolymer #2 35/65 by weight of acrylic acid/tert-butyl acrylate of molecular
weight of about 60,000 to 90,000
Copolymer #3 ethyl acrylate/metacrylic acid/methyl methacrylate/acrylic
acid copolymer commercially available from Union Carbide
under the trade mark Amerhold DR-25
Copolymer #4 poiyvinyl acetate commercially available from Clariant under
the trade mark APPRETAN
Copolymer #5 polyacrylate dispersion commercially available from BASF
under the trade mark Poligen A
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Copolymer #6 polyvinyl alcohol commercially available from Clariant under
the trade mark MOWEOL
Copolymer #7 polyvinylpyrrolidone/acrylic acid commercially available from
BASF under the trade mark SOKALAN EG 310
The invention is illustrated in the following non limiting examples, in whch
all
percentages are on a weight basis unless otherwise stated.
Example I
The following compositions are in accordance with the present invention.
A B C D E F G
Co-polymer # 1 0.35% - - - - -
Co-polymer # 2 - - - 1.50% - -
Co-polymer # 3 - - - - - 0.50%
Co-polymer #4 - 0.35% - - -
Co-polymer #5 - - - - 0.50%
Co-potymer #6 - - 1.50% - - -
Co-polymer #7 - - - - - 0.50%
-
Dipropylene - - - - 0.50% 0.50%
glycol
Diethylene 0.35% 0.35% 0.75% 0.75% - - 0.50%
glycol
Wettlng agent 4 0.25% 0.25% 0.25% 0.25% 0.35% 0.35% 0.25%
Cyctodextrin 1.00% 1.00% 1.00% 1.00% 1.20% 1.20% 1.00%
Preservative 3 ppm 3 ppm 3 ppm 3 ppm 3ppm 3ppm -
Perfume 0.10% 0.10% 0.10% 0.10% 0.10% 0.10% -
Sodium 0.10% 0.10% 0.10% 0.10% 0.10% 0.10% 0.10%
hydroxide
Water Balance Balance Balance Balance Balance Balance Balance
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5
H I J K L
co-polymer #1 1.0% - - - -
co-polymer #2 - - - 1.0% -
co-polymer #3 - - 1.5% - -
co-polymer #4 - 2.0% - - -
co-polymer #6 - - - - 0.75%
VELUSTROL P-40 - - - - 0. 5%
Silanol - - - - 0.25%
Wetting agent 4 - - - - 0.25%
Diethylene Glycol - - - - 0.25%
Cyclodextrin 1.0% 1.0% 1.20% 1.0% 1.0%
Sodium dodecyl sulphate - - 1.5% - -
Sorbitol 0.7% - - - -
Propylene glycol - 3.0% -
Sodium borate - - - 1.0% 1.0%
Sodium citrate - 2.0% - - -
Isopropanol 30.0% - - - -
Ethanol - - 20.0% - -
Dye fixative - 0.5% - - -
Polyethyleneimine - - - 2.0% -
Carezyme - 0.1% - - -
Perfume 0.15% 0.3% 0.1% 0.4% 0.1%
Potassium hydroxide 0.1% 0.1% 0.1% 0.1% -
Water Balance Balance Balance Balance Balance
