Note: Descriptions are shown in the official language in which they were submitted.
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LIQUID LAUNDRY DETERGENTS CONTAINING CATIONIC HYDROXYETHYL
CELLULOSE POLYMER
FIELD OF THE INVENTION
The present invention relates to the use of cationic hydroxyethyl celluloses
in liquid
laundry detergent compositions for the laundering of textiles (e.g. clothing,
linens, fabric).
BACKGROUND OF THE INVENTION
A large number of liquid laundry detergents are available to today's
consumers. While
many of the detergents adequately remove dirt, soil and odors, effectively
cleaning textiles (for
example, clothing items) very well in traditional horizontal axis and/or
vertical access washing
machines, there is an ongoing desire to provide consumers with additional
fabric care benefits
resulting from their laundry detergent and through the wash cycle, such as
softening, color
protection, protection from fabric wear, and gentle treatment of fine textiles
(such as wool and
silk).
Cationic polymers such as cationic hydroxyethyl cellulose polymers are
traditionally
commercially supplied for inclusion in detergent compositions, particularly
hair products such as
shampoos. More recently, such cationic polymers have been experimented with in
heavy duty
liquid laundry detergents to enhance deposition of other known materials that
provide softening
benefits to laundered textiles but do not deposit well during traditional
washing machine cycles.
It has now been surprisingly discovered that such cationic polymers may in
combination
with surfactant and fatty acid provide fabric care benefits to laundered
textiles, when included in
selected aqueous liquid laundry detergent compositions.
SUMMARY OF THE INVENTION
The present invention relates to aqueous liquid laundry detergent compositions
useful for
cleaning delicate fabrics comprising from about 0.05% to about 0.4%, by weight
of the
composition, of a cationic hydroxyethyl cellulose polymer having a degree of
substitution of the
cationic charge of from about 0.01 to about 0.20; from about 5% to about 30%,
by weight of the
composition, of a surfactant comprising at least one anionic surfactant and at
least one nonionic
surfactant; and from about 2% to about 15%, by weight of the composition, of
fatty acid. The
composition may also contain a benefit agent containing delivery particle
wherein the delivery particle is a
perfume microcapsule. The composition comprises less than 0.001% by weight of
the composition of
enzymes having cellulytic activity and less than 0.0001% by weight of the
composition of optical
brightener.
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The present invention further relates to aqueous liquid laundry detergent
compositions
useful for cleaning delicate fabrics, comprising from about 0.15% to about
0.2%, by weight of
the composition, of a cationic hydroxyethyl cellulose polymer having a
molecular weight of from
about 200,000 to about 800,000 and a degree of substitution of the cationic
charge of from about
0.01 to 0.20; from about 7% to about 15%, by weight of the composition, of a
surfactant
comprising an alkyl ethoxylate sulfate surfactant and at least one nonionic
surfactant; from about
2% to about 10%, by weight of the composition, of fatty acid; wherein the
composition is
substantially free of optical brightener; and wherein the composition is
substantially free of
enzymes having cellulytic activity.
The present invention also relates to the above compositions wherein the
cationic
hydroxyethyl cellulose polymer has a degree of substitution of the cationic
charge of from about
0.01 to about 0.1.
The present invention also relates to the above compositions wherein the
cationic
hydroxyethyl cellulose polymer has a degree of substitution of the cationic
charge of from about
0.01 to less than 0.1.
The present invention also relates to the above compositions wherein the
cationic
hydroxyethyl cellulose polymer has a molecular weight of from about 200,000 to
about 800,000.
The present invention also relates to the above compositions wherein the
composition is
substantially free of enzymes having cellulytic activity.
The present invention also relates to the above compositions wherein the
composition is
substantially free of optical brightener.
The present invention also relates to the above compositions wherein the
composition
comprises from about 0.1 % to about 0.3%, by weight of the composition, of the
cationic
hydroxyethyl cellulose polymer.
The present invention also relates to the above compositions wherein the
composition
comprises from about 0.15% to about 0.2%, by weight of the composition, of the
cationic
hydroxyethyl cellulose polymer.
The present invention also relates to the above compositions wherein the
composition
comprises from about 7% to about 15%, by weight of the composition, of the
surfactant.
The present invention also relates to the above compositions wherein the
composition
comprises from about 2.5% to about 7%, by weight of the composition, of the
fatty acid.
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The present invention also relates to the above compositions wherein the
composition
further comprises an opacifying agent.
The present invention also relates to the above compositions wherein the
anionic
surfactant is selected from alkyl ethoxylate sulfates and linear alkyl benzene
sulfonates.
The present invention also relates to the above compositions wherein the
anionic
surfactant is selected from alkyl ethoxylate sulfates having a chain length of
from about 12 to
about 14 and a degree of ethoxylation of from about 1 to about 8.
The present invention also relates to the above compositions wherein the
composition
further comprises a suds suppressor.
The present invention also relates to the above compositions wherein the
composition is
substantially free of enzymes.
The present invention also relates to the above compositions wherein the
composition
further comprises a laundry adjunct ingredient selected from soil release
polymers, dye transfer
inhibiting polymers, chelants, performance boosting polymers, preservatives,
stabilizers,
structurants, viscosity modifiers, and citric acid.
The present invention also relates to the above compositions wherein the
composition
further comprises from about 0.01 to about 1 % of a structurant that is
selected from
hydrogenated castor oil.
The present invention further relates to use of the above compositions for
handwashing
delicate fabrics.
The present invention further relates to use of the above compositions for
machine
washing of delicate fabrics, wherein the machine washing occurs at a delicate
machine setting.
DETAILED DESCRIPTION OF THE INVENTION
The citation of any document is not to be construed as an admission that it is
prior art with
respect to the present invention. To the extent that any meaning or definition
of a term in this written
document conflicts with any meaning or definition of the term in a document
referred to, the meaning
or definition assigned to the term in this written document shall govern.
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All percentages, ratios and proportions herein are on a weight basis unless
otherwise
indicated.
The present invention relates to aqueous liquid laundry detergent compositions
comprising a surfactant containing at least an anionic and an nonionic
surfactant, fatty acid, and
a cationic hydroxyethyl cellulose polymer having a degree of substitution of
the cationic charge
of from about 0.01 to about 0.20 and a molecular weight of from about 200,000
to about
800,000.
Without being limited by theory, it is now believed that the lower charge
density of the
cationic hydroxyethyl cellulose polymer is important in providing a liquid
laundry detergent
product containing relatively low levels of surfactant (at least an anionic
surfactant and a
nonionic surfactant) that is capable of offering both fabric care benefits and
good cleaning to
laundered textiles.
The compositions and methods of the present invention are advantageous in
providing
low cost liquid laundry detergents compositions offering good cleaning along
with softening
benefits through the wash to textiles such as clothing and fabrics. Additional
objects'and
advantages will be apparent in view of the detailed description of the
invention.
Cationic Hydroxyethyl Cellulose Polymers
The aqueous liquid laundry detergent compositions of the present invention
contain from
about 0.05% to about 0.4%, by weight of the composition, of a cationic
hydroxyethyl cellulose
polymer. In one embodiment, the composition contains from about 0.1% to about
0.3%, by
weight of the composition, alternatively from about 0.15% to about 0.2%, of
the cationic
hydroxyethyl cellulose polymer.
The cationic hydroxyethyl cellulose polymers useful herein have a degree of
substitution
of the cationic charge of from about 0.01 (one cationic charge per 100 polymer
repeating units)
to about 0.20 (two cationic charges per 10 polymer repeating units).
Preferably, the cationic
hydroxyethyl cellulose polymers useful herein have a degree of substitution of
the cationic
charge of from about 0.01 to about 0.1, more preferably a degree of
substitution of the cationic
charge of less than 0.1, in one embodiment from about 0.01 to less than 0.1.
The positive
charges could be on the backbone of the polymers or the side chains of
polymers.
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Cationic hydroxyethyl cellulose polymers useful include those which may or may
not be
hydrophobically-modified and have a molecular weight of from about 200,000 to
about 800,000.
These cationic materials have repeating substituted anhydroglucose units that
correspond to the
general Structural Formula I as follows:
ORl
72o4
ORZ
R4
STRUCTURAL FORMULA I
Wherein R~, R2, R3 are each independently H, CH3, C8-24 alkyl (linear or
branched),
R5
-E-CH2CH-O). Rx
n or mixtures thereof; wherein n is from about 1 to about 10; Rx is H, CH3,
OH R7
-CH2CHCH2- N - R9 Z
a
C8-24 alkyl (linear or branched), R or mixtures thereof, wherein Z is a
water soluble anion, preferably a chlorine ion and/or a bromine ion; R5 is H,
CH3, CH2CH3, or
mixtures thereof; R7 is CH3, CH2CH3, a phenyl group, a C8-24 alkyl group
(linear or
branched), or mixture thereof; and
R8 and R9 are each independently CH3, CH2CH3, phenyl, or mixtures thereof:
--I - P- j3 H
R4 is H, , or mixtures thereof wherein P is a repeat unit of an addition
polymer formed
Z
\3Qq
by radical polymerization of a cationic monomer such as wherein Z' is a
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water-soluble anion, preferably chlorine ion, bromine ion or mixtures thereof
and q is from about
1 to about 10.
Water-soluble anions useful herein include C8-C24 alkyl sulfates, C8-C24 alkyl
alkoxy
sulfates, preferably alkyl ethoxy sulfates, C8-C24 alkyl sulfonates, C8-C16
alkyl benzene
sulfonates, xylene sulfonates, toluene sulfonates, cumene sulfonates, fatty
alkyl carboxylates,
chlorine ions, bromine ions, or mixtures thereof, while chlorine and/or
bromine ions are
preferred.
The cationic hydroxyethyl cellulose may have alkyl substitution on the
anhydroglucose
rings of the polymer ranges. When such alkyl substitution is present, it may
be from about 0% to
5% per glucose unit, more preferably from about 0% to 2% per glucose unit, of
the polymeric
material.
The cationic cellulose may lightly cross-linked with a dialdehyde such as
glyoxyl to
prevent forming lumps, nodules or other agglomerations when added to water at
ambient
temperatures.
The cationic hydroxyethyl cellulose ethers of Structural Formula I likewise
include those
which are commercially available and further include materials which can be
prepared by
conventional chemical modification of commercially available materials.
Commercially
TM
available cellulose ethers of the Structural Formula I type useful herein
include the LR 400 and
TM
LK 400 polymers, preferably the LK 400 polymers, which are marketed by Dow
Chemical.
Surfactant
The aqueous liquid laundry detergent products of the present invention
comprise from
about 5% to about 30%, by weight of the composition, of surfactant. In one
embodiment, the
aqueous liquid laundry detergent products of the present invention comprise
from about 5% to
about 20%, alternatively from about 7% to about 15%, by weight of the
composition, of
surfactant.
The surfactant of the detergent products of the present invention includes at
least one
anionic surfactant and at least one nonionic surfactant. The detergent
products of the
present invention may also include other surfactants such as zwitterionic,
ampholytic or cationic
type or can comprise compatible mixtures of these types in conjunction with
the anionic
surfactant and nonionic surfactant.
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In one embodiment, the anionic surfactant is selected from alkyl ethoxylate
sulfates and
linear alkyl benzene sulfonates. In another embodiment, the anionic surfactant
is selected from
alkyl ethoxylate sulfates having a chain length of from about 12 to about 14
and a degree of
ethoxylation of from about 1 to about 8.
Detergent surfactants useful herein include those described in U.S. Patent
3,664,961,
Norris, issued May 23, 1972, U.S. Patent 3,919,678, Laughlin et al., issued
December 30, 1975,
U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent
4,239,659,
Murphy, issued December 16, 1980.
Anionic surfactants which are suitable for use herein include the water-
soluble salts,
preferably the alkali metal, and ammonium salts, of organic sulfuric reaction
products having in
their molecular structure an alkyl group containing from about 10 to about 20
carbon atoms and
a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is
the alkyl portion of
acyl groups.) Examples of this group of synthetic surfactants are a) the
sodium, potassium and
ammonium alkyl sulfates, especially those obtained by sulfating the higher
alcohols (Cg-C18
carbon atoms) such as those produced by reducing the glycerides of tallow or
coconut oil; b) the
sodium, potassium and ammonium alkyl polyethoxylate sulfates, particularly
those in which the
alkyl group contains from 10 to 22, preferably from 12 to 18 carbon atoms, and
wherein the
polyethoxylate chain contains from 1 to 15, preferably 1 to 6 ethoxylate
moieties; and c) the
sodium and potassium alkylbenzene sulfonates in which the alkyl group contains
from about 9 to
about 15 carbon atoms, in straight chain or branched chain configuration,
e.g., those of the type
described in U.S. Patents 2,220,099 and 2,477,383. Also useful are linear
straight chain
alkylbenzene sulfonates in which the average number of carbon atoms in the
alkyl group is from
about 11 to 13, abbreviated as C11-13 LAS.
In one embodiment, nonionic surfactants useful herein include those of the
formula
R1(OC2H4)nOH, wherein R1 is a C10-C16 alkyl group or a C8-C12 alkyl phenyl
group, and n
is from 3 to about 80. In one embodiment, the nonionic surfactants are
condensation products
of C12-C1 5 alcohols with from about 5 to about 20 moles of ethylene oxide per
mole of alcohol,
e.g., C12-C13 alcohol condensed with about 6.5 moles of ethylene oxide per
mole of alcohol.
Additional suitable nonionic surfactants include polyhydroxy fatty acid amides
of the
formula: .
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11 1`
R-C-N-Z
wherein R is a C9_17 alkyl or alkenyl, Rl is a methyl group and Z is glycidyl
derived from a
reduced sugar or alkoxylated derivative thereof. Examples are N-methyl N-1-
deoxyglucityl
cocoamide and N-methyl N-1-deoxyglucityl oleamide. Processes for making
polyhydroxy fatty
acid amides are known and can be found in Wilson, U.S. Patent 2,965,576 and
Schwartz, U.S.
Patent 2,703,798.
Fatty Acid
The aqueous liquid detergent compositions of the present invention contain
from about
2% to about 15%, by weight of the composition, of fatty acid. In one
embodiment, the
compositions contain from about 2% to about 10%, alternatively from about 2.5%
to about 7%,
by weight of the composition, of fatty acid.
A used herein, "fatty acids" refers to a range of fatty acids including those
that contain
from about 8 to about 24 carbon atoms, alternatively from about 12 to about 18
carbon atoms.
The fatty acids useful herein include those that are both saturated and
unsaturated, as well as
mixtures thereof.
Free of Optical Brightener
In one embodiment, the aqueous liquid detergent compositions of the present
invention
are substantially free of optical brightener. As used herein, "substantially
free of optical
brightener" means that the aqueous liquid detergent composition contains less
than 0.0001% of
optical brightener, preferably no detectable amount of optical brightener.
Enzymes having Cellulytic Activity
In one embodiment, the aqueous liquid detergent compositions of the present
invention are
substantially free of enzymes containing cellulytic activity. The aqueous
liquid detergent
compositions of the present invention may comprise an enzyme that is free of
cellulytic activity.
As used herein, "substantially free of enzymes containing cellulytic activity"
means that the
aqueous liquid detergent composition contains less than 0.001% of an enzyme
containing
cellulytic activity, preferably no detectable amount of enzyme containing
cellulytic activity.
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Without being limited by theory, it is believed that the cellulase present in
certain enzymes
will hydrolyze the cationic hydroxyethyl cellulose polymer molecule, thereby
destroying the
fabric care benefits otherwise associated with the cationic hydroxyethyl
cellulose polymer.
However, where desirable, it is possible to formulate aqueous liquid detergent
compositions of the present invention that do contain enzymes having
cellulytic activity as long
as the composition also contains an effective amount of a cellulase inhibitor.
Enzymes
When incorporated into the formulations of the present invention, enzymes are
included at
levels sufficient to provide a "cleaning-effective amount". The term "cleaning-
effective
amount" refers to any amount capable of producing a cleaning, stain removal,
soil removal,
whitening, deodorizing, or freshness improving effect on substrates such as
fabrics. In one
embodiment, the aqueous liquid detergent compositions of the present invention
may contain up
to about 5 mg by weight, more typically from about 0.01 mg to about 3 mg, of
active enzyme
per gram of the detergent composition. Stated otherwise, the compositions
herein will typically
comprise from about 0.001% to about 5%, preferably from about 0.01% to about
1% by weight
of the composition, of a commercial enzyme preparation. Protease enzymes are
preferably
present in such commercial preparations at levels sufficient to provide from
0.005 to 0.1 Anson
units (AU) of activity per gram of composition. Higher active levels may be
desirable in highly
concentrated detergent formulations.
Selected proteases which are useful herein include the subtilisins which are
obtained from
particular strains of B. subtilis and B. licheniformis. A preferred protease
is obtained from a
strain of Bacillus, having maximum activity throughout the pH range of 8-12,
developed and
sold as ESPERASE by Novo Industries A/S of Denmark, hereinafter "Novo". The
preparation
of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo.
Other suitable
proteases include ALCALASE and SAVINASE from Novo and MAXATASE from
International Bio-Synthetics, Inc., The Netherlands. When desired, a protease
having decreased
adsorption and increased hydrolysis may be included in the compositions
herein, as described in
WO 9507791 to Procter & Gamble. Another, recombinant trypsin-like protease for
detergents
suitable herein is described in WO 9425583 to Novo.
Any known amylase may be included in the compositions of the present
invention.
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Suitable lipase enzymes for use herein include those produced by
microorganisms of the
Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in
GB
1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open
Feb. 24, 1978.
This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan,
under the trade
mark Lipase P "Amano," or "Amano-P." Other suitable commercial lipases include
Amano-
CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
lipolyticum NRRLB
3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from
U.S.
Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex
Pseudomonas
gladioli. LIPOLASE enzyme derived from Humicola lanuginosa and commercially
available
from Novo, see also EP 341,947, is a preferred lipase for use herein.
When the compositions of the present invention contain a compatible enzyme,
the
compositions preferably also contain an effective enzyme stabilizing system.
The enzyme-
containing aqueous liquid laundry detergent compositions herein may therefore
optionally also
comprise from about 0.001% to about 10%, preferably from about 0.005% to about
8%, most
preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing
system. The
enzyme stabilizing system can be any stabilizing system which is compatible
with the enzymes
useful herein. Such a system may be inherently provided by other formulation
actives, or be
added separately, e.g., by the formulator or by a manufacturer of enzymes.
Such stabilizing
systems can, for example, comprise calcium ion, boric acid, propylene glycol,
short chain
carboxylic acids, boronic acids, or mixtures thereof, and are designed to
address different
stabilization problems depending on the type and physical form of the
detergent composition.
Where enzymes having cellulytic activity are included into the aqueous liquid
laundry detergent
compositions herein, the enzyme stabilizing system should also include the
cellulase inhibitor.
Builder
The compositions may also comprise from about 0.1% to 80% by weight of a
builder. In
one embodiment, the compositions of the present invention contain from about
1% to 20% by
weight of the builder component. Detergent builders are well known in the art
and can
comprise, for example, phosphate salts as well as various organic and
inorganic nonphosphorus
builders.
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Water-soluble, nonphosphorus organic builders useful herein include the
various alkali
metal, ammonium and substituted ammonium polyacetates, carboxylates,
polycarboxylates and
polyhydroxy sulfonates. Examples of polyacetate and polycarboxylate builders
are the sodium,
potassium, lithium, ammonium and substituted ammonium salts of ethylene
diamine tetraacetic
acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene
polycarboxylic acids, and
citric acid. Other suitable polycarboxylates for use herein are the polyacetal
carboxylates
described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et
al, and U.S. Patent
4,246,495, issued March 27, 1979 to Crutchfield et al. Polycarboxylate
builders useful herein
include the oxydisuccinates and the ether carboxylate builder compositions
comprising a
combination of tartrate monosuccinate and tartrate disuccinate described in
U.S. Patent
4,663,071, Bush et al., issued May 5, 1987.
Examples of suitable nonphosphorus, inorganic builders include the silicates,
aluminosilicates, borates and carbonates.
Aqueous liquid laundry detergents
The aqueous liquid detergent compositions of the present invention may be made
by any
known process, including those processes disclosed in U.S. Patent Nos.
6,274,540 and
6,306,817; WIPO Publication Nos. WO 01/16237 published March 8, 2001; and WO
01/16263
published on March 8, 2001.
The laundry detergent compositions herein are formulated as aqueous liquid
laundry
detergents. The detergent compositions herein therefore comprise from about 3%
to about 98%,
alternatively from about 15 lo to about 95%, by weight of the liquid detergent
composition, of an
aqueous liquid carrier which is preferably water. Preferably, the liquid
laundry compositions
according to the present invention should provide a wash solution pH from
about 6 to about 10,
more preferably from about 7 to about 9, in order to maintain a preferred
cleaning and fabric care
performance by the aqueous liquid detergents according to the present
invention. If needed, the
cleaning compositions may contain alkalinizing agents, pH control agents
and/or buffering
agents.
Laundry Adjunct Ingredients
The laundry detergents herein may further comprise a laundry adjunct
ingredient.
Suitable laundry adjuncts are known in the art and include soil release
polymers, dye transfer
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inhibiting polymers, chelants, performance boosting polymers, preservatives,
stabilizers,
structurants, viscosity modifiers, citric acid, and benefit agent containing
delivery particles.
Benefit agent containing delivery particles useful herein comprise a core
material and a
wall material that at least partially surrounds said core material. As used
herein, the phrase
"benefit agent containing delivery particle" encompasses microcapsules,
including perfume
microcapsules (where the core material includes perfume). As used herein, the
terms "particle",
"benefit agent containing delivery particle" J"capsule" and "microcapsule" are
synonymous.
EXAMPLES 1-4
The following example aqueous liquid detergent formulations may be made by
traditional methods and means as known to one of ordinary skill in the art.
1 2 3 4
Ingredient
Wt.% Wt% Wt% Wt%
Nonionic surfactant 4.0 4.0 7.0 4.0
Anionic surfactant 7.0 3.0 8.0 3.0
Citric Acid 2.0 3.0 2.5 3.0
Fatty acid 4.5 3.0 6.0 3.0
PVPVI 0.02 0.03 0.05 0.03
Performance Boosters 0.3 0.5
Cationic hydroxyl ethyl 0.18 0.15 0.25 0.15
cellulose
Ethanol 0.85 1.00 1.2 1.00
Boric acid 1.2 0.85 1.00 0.85
DB 110 A 0.0025 0.0025 0.0025 0.0025
Sodium hydroxide 3.0 3.0 3.5 3.0
Perfumes and Dyes 0.6 0.5 0.7 0.5
Opacifier 0.100 0.040 0.040
Preservative 0.002 0.001 0.0018 0.001
Perfume Microcapsules 1.3
Water Remainder Remainder Remainder Remainder
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While particular embodiments of the present invention have been illustrated
and described, it
would be obvious to those skilled in the art that various other changes and
modifications can be
made without departing from the spirit and scope of the invention. It is
therefore intended to
cover in the appended claims all such changes and modifications that are
within the scope of this
invention.
