Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
IN THE UNITED STATES PATENT AND TRADEMARK OFFICE
PROVISIONAL PATENT APPLICATION
Title: METHOD AND PRODUCT FOR MITIGATING PET MALODORS
Inventors: Sheila E. Ali, David Peterson, Gregory M. Piche and Roger V. Lee
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a method and product for mitigating or eliminating
pet
malodors, particularly those which arise from feline urine. The method
provides for the
contacting of the malodors) with an aqueous liquid deodorizing composition,
the
composition containing about at least 0.02% to about 10% of an alkali metal
tetraborate n-
hydrate (with n being an integer from 1 to 10), 0.1-3% water
soluble/dispersible polymer, 1-
20% water soluble/dispersible volatile solvent, at least 75% water and various
aesthetic and
functional additives.
2. Brief Statement of the Related Art
One of the most common and distressing household odors is caused by pets, such
as cats, who must void or eliminate in the home in discrete areas, such as
litter boxes or other
containment devices. However, since replacement or replenishment of the litter
box is left to
individual discretion, some home environments may succumb to a perceived
higher level of
malodor than others. Additionally, the individual pet may, depending on its
health and the
amount of water and/or feed it intakes, produce more liquid and solid wastes
than others.
Further, some pets because of instinctive need or other such motivation,
"mark" or spray
surfaces outside of the litter box, perhaps as a means of establishing
territory or some other
behavioral idiosyncracy. In all such events, there is thus a need for a
deodorizer or malodor
mitigator which is specially formulated to deal with these particular
malodors.
Stanislowski et al., U.S. Patent 5,183,655 (of common assignment and
incorporated herein by reference), discloses and claims an animal waste
deodorizer
comprising a mixture of pine oil and a borate-based compound selected from
polyborate,
borax and a boric acid/borax mixture, carried in a liquid dispersion.
Stanislowski, however,
does not teach, disclose or suggest the presence of a water
soluble/dispersible polymer in its
deodorizer.
On the other hand, there are many references to animal litters which are
pretreated
with boron-containing compounds, especially boric acid, which have been
identified as
effective additives. These are discussed in, for example, Ratcliffet al., U.S.
Patents
4,949,672 and 5,094,190, Jenkins et al., U.S. Patent 5,176,108, and
Stanislowski et al., U.S.
Patents 5,018,482, 5,135,743 and 5,183,655, all of which are of common
assignment and
incorporated herein by reference thereto. Of course, these types of litters
cannot suppress
CA 02329218 2000-12-20
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malodors indefinitely. Moreover, even the best animal litter cannot guarantee
that the
household pet, especially the domesticated feline, will be adequately trained
to use the litter
box or other containment means, will be sufficiently accurate in its private
duties to make
sure that its wastes are retained in
the litter box, or will not be behaviorally motivated to mark or spray other
surfaces in the
household.
There are presently some liquid household malodor counteractants, such as
aerosols and spray-dispensed liquid compositions. None, however, appear to
disclose, teach
or suggest that borax in a liquid deodorizing composition is especially
effective at mitigating
or eliminating pet malodors, particularly those which arise from feline urine.
SUMMARY AND OBJECTS OF THE INVENTION
The invention provides a method and product for contacting of pet malodors)
with an aqueous liquid deodorizing composition, the composition containing
about at least
0.02% to about 10% of an alkali metal tetraborate n-hydrate (with n being an
integer from 1
to 10), 0.1-3% water soluble/dispersible polymer, I-20% water
soluble/dispersible volatile
solvent, at least 75% water. In alternative embodiments, various aesthetic and
functional
additives may be added in low levels, such as surfactants/emulsifiers,
fragrances, and
preservatives.
It is therefore an object of this invention to provide a method for the
counteracting
of pet malodors by contacting them with an aqueous liquid deodorizing
composition
It is another object of this invention to provide a convenient product for
mitigating
or eliminating pet malodors, particularly those caused by domestic felines.
It is a further object of this invention to provide a trigger sprayer, pump
sprayer,
aerosol or other consumer-friendly means for delivering the malodor
counteractant of this
invention.
It is also an object of this invention to provide a long lasting means for
malodor
control, especially when compared to what is presently commercially available.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a bar graph depicting the performance of the inventive malodor
counteractant versus a control.
Fig. 2 is bar graph depicting the performance of the invention versus
commercially available surface deodorizers and water (as a control).
Fig. 3 is a bar graph demonstrating the performance of the invention in
combating
ammonia production from cat spray swatches versus a commercially available
surface
deodorizer and water (as a control).
CA 02329218 2000-12-20
DETAILED DESCRIPTION OF THE INVENTION
The invention provides a method and product for contacting of pet malodors)
with an aqueous liquid deodorizing composition, the composition containing
about at least
0.5% to about 5% of an alkali metal tetraborate n-hydrate (with n being an
integer from 1 to
10), 0.1-3% water soluble/dispersible polymer, 1-20% water soluble/dispersible
volatile
solvent, at least 75% water. In alternative embodiments, various aesthetic and
functional
additives may be added in low levels, such as surfactants/emulsifiers,
fragrances, and
preservatives.
The present invention provides a method and product for contacting of pet
malodors) with an aqueous liquid deodorizing composition in which ammonia
fonmation due
to decomposition of urea present in animal waste may be affected by one or
more
mechanisms: (1) Urease Inhibition. Urease is an enzyme which is produced by
many
bacteria and other microflora. Urease acts as a catalyst to break down urea
into ammonia via
the following chemical pathway:
O
HZNCNHZ + HZO ~ 2NH3 + COz
Control of crease, via competition, denaturation, or enzyme poisoning, would
therefore
significantly reduce the formation of ammonia. (2) Bacterial Inhibition. As
previously
discussed, bacteria and other microflora appear to be sources for crease.
Thus, reduction of
bacteria through antimicrobial action of the odor control agents would also
significantly
control odor formation.
It has been surprisingly discovered that a dramatic reduction in malodor
formation
caused by domestic animals occurs if the animal's liquid waste is contacted
with the inventive
aqueous liquid deodorizing composition, the composition containing about at
least 0.5% to
about 5% of an alkali metal tetraborate n-hydrate (with n being an integer
from 1 to 10), 0.1-
3% water soluble/dispersible polymer, 1-20% water soluble/dispersible volatile
solvent, at
least 75% water.
In the application, effective amounts are generally those amounts listed as
the
ranges or levels of ingredients in the descriptions which follow here to.
Unless otherwise
stated, amounts listed in percentage ("%'s") are in weight percent of the
composition, unless
otherwise noted.
The ingredients constituting the novel liquid pet malodor mitigating
composition
are described hereinbelow.
1. Boron-Based Odor Control Agent:
Borax, or, more accurately, di-alkali metal tetraborate n - hydrate
(preferably,
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Na2B40, x nHzO, where n=1-10, most preferably, 4, 5 or 10), is the preferred
compound for
use in the invention. The alkali metal counterion may be selected from sodium,
potassium or
lithium, or a combination thereof. Borax decahydrate is the most commonly
found form of
borax and is the compound assumed when one discusses borax. Borax pentahydrate
is
another preferred compound. Other boron-based compounds potentially suitable
for use are
disclosed in Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed., Vol.
4, pp. 67-109
(1978), said pages being incorporated herein by reference. Borax can be
obtained from such
vendors as U.S. Borax and North American Borax.
Borax appears to provide multiple benefits in odor control by: ( 1 ) acting as
a
unease inhibitor, which controls odors by preventing enzymatic breakdown of
urea; (2)
having bacteriostatic properties, which appear to help control odor by
controlling the growth
of bacteria which are responsible for production of the unease enzymes.
An alternative odor control animal litter additive is boric acid. See, Kirk-
Othmer,
Encyclopedia Chemical Technology, 3rd Ed., Vol. 4, pp. 71-77 (1978),
incorporated herein
by reference. Boric acid has the structure H3BO3. Boric acid is available from
such suppliers
as Kerr-McGee
Corporation. Polyborate, tetraboric acid, sodium metaborate and other forms of
boron are
also appropriate alternative materials.
An odor controlling effective amount is defined as at least about 0.02%
equivalent
boron, more preferably at least greater than 0.03%. The preferred range varies
from about
0.02 to about 10%, by weight of the composition. The more preferable range is
about 0.02 to
5% by weight of the composition. Those skilled in the art will adjust the
compositional
levels to ensure effective odor control and cost effectiveness.
In the following discussion, percent boron is defined as the amount of atomic
boron delivered in wt.%. Percent boron is determined by calculating the amount
of atomic
boron in a boron-containing compound. So, for boric acid, borax decahydrate
and borax
pentahydrate, percent boron is:
1 g boric acid' 10.81 BZ) = 0.1748 x 100% = 17.48%
61.84g boric acid
1 g borax3 43.24 BZ) = 0.1134 x 100% = 11.34%
381.37g borax
1 g borax4 43.24 BZ) = 0.1484 x 100% = 14.8%
291.37 g borax
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Molecular weight of boric acid (H,BO,) is 61.84.
=Atomic weight of boron is 10.81. In boric acid, there is only one atom of
boron; in borax, there are four.
'Molecular weight of borax (Na,B,O, x I OH=O) is 38137, assuming borax
decahydrate.
Molecular weight of borax (Na,B,O, x 5 H,O) is 291.37, assuming borax
pentahydrate.
CA 02329218 2000-12-20
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2. The Water Soluble/Dispersible Polymer(s)
The polymer is another key component of the invention. It is necessary to
provide
substantivity via a transparent to slightly visible residue or film which
results after
application of the inventive liquid composition to a surface.
The polymer is generally speaking a water soluble to dispersible polymer
having a
molecular weight of generally below 2,000,000 daltons. The polymers will also
be not
damaging to fabrics, carpets, and other soft surfaces. They should have enough
tack or
stickiness, when applied and dried, to provide a matrix in which the boron
additive and
materials and the animal waste may be entrapped, but not so much that to the
human touch
the film or residue feels or imparts an obvious sticky feel. Preferably, the
polymer will also
not itself have an obvious or offensive odor, although that attribute can be
mitigated by
judicious selection of fragrance.
Examples of suitable classes of polymers include:
a. Polysaccharides
Suitable polymers may comprise polysaccharide polymers, which include
substituted cellulose materials like carboxymethylcellulose, ethyl cellulose,
hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose,
succinoglycan and
naturally occurring polysaccharide polymers like xanthan gum, guar gum, locust
bean gum,
tragacanth gum or derivatives thereof. Particularly useful polysaccharides are
xanthan gum
and derivatives thereof. Some of these are thickeners which may have too much
tack, from a
performance and aesthetic standpoint. Additional suitable polysaccharide
polymers may
include sodium caseinate and gelatin. Other suitable polysaccharide polymers
may include
cationic derivatives, such as the cationic cellulose ether, Polymer JR.
b. Polycarboxylates
Polycarboxylates can also be used which contain amounts of nonionizable
monomers, such as ethylene and other simple olefins, styrene, alpha-
methylstyrene, methyl,
ethyl and C3 to C8 alkyl acrylates and methacrylates, isobornyl methacrylate,
acrylacnide,
hydroxyethyl acrylate and methacrylate, hydroxypropyl acrylate and
methacrylate, N-vinyl
pyrrolidone, butadiene, isoprene, vinyl halides such as vinyl chloride and
vinylidine chloride,
alkyl maleates, alkyl fumarates. Other suitable polymers include other
polycarboxylates, such
as homopolymers and copolymers of monomeric units selected FROM the group
consisting
of unsaturated carboxylic acids such as acrylic acid, methacrylic acid,
polycarboxylic acids,
sulfonic acids, phosphoric acids and mixtures thereof. Copolymerization of the
above
monomeric units among them or with other co-monomers such as malefic
anhydride, ethylene
or propylene are also suitable.
c. Polystyrenesulfonates
Other suitable polymers are polystyrenesulfonates such as Flexan 130 and Versa
CA 02329218 2000-12-20
TL501 from ALCO Corporation. Polystyrenesulfonates are also useful as
copolymers, for
example Versa TL-4 also from ALCO Corporation.
d. Acrylate Polymers
Other suitable polymers are acrylic emulsion polymers used as floor polish
coatings. These are generally copolymers of one or more acidic monomers, such
as acrylic
acid, methacrylic acid or malefic anhydride, with at least one other
ethylenically unsaturated
monomer selected from a group consisting of ethylene and other simple olefins,
styrene,
alpha-methylstyrene, methyl, ethyl and C3 to C8 alkyl acrylates and
methacrylates, isobornyl
methacrylate, acrylamide, hydroxyethyl acrylate and methacrylate,
hydroxypropyl acrylate
and methacrylate, N-vinyl pyrrolidone, butadiene, isoprene, vinyl halides such
as vinyl
chloride and vinylidine chloride, alkyl maleates, alkyl fumarates, fumaric
acid, malefic acid,
itaconic acid, and the like. It is also frequently desirable to include minor
amounts of other
functional monomers, such as acetoacetoxy methacrylate or other acetoacetate
monomers and
divinyl or polyvinyl monomers, such as glycol polyacrylates, allyl
methacrylate, divinyl
benzene and the like. The preferred polymers have an acid number from about 75
to about
500 and a number average molecular weight of about 500 to about 20,000. These
polymers
may also be crosslinked with metal ions or modified for crosslinking with
silane functionality
as described, for example, in U.S. Patent 5,428,107. Examples of such acrylic
emulsion
polymers include those available under the Rhoplex tradename from Rohm & Haas,
such as
Rhoplex AC-33, Rhoplex B-924, and Rhoplex MC-76. There are also polymers from
Alco,
such as Balance CR, Balance 47 and Balance 055. Other suitable polymers are
copolymers
of acrylic and/or methacrylic acid with acrylate and methacrylate esters. For
example, a
copolymer of 51 % methyl methacrylate, 31 % butyl acrylate, and 18% acrylic
acid is
available from Rohm & Haas as Emulsion Polymer E-1250.
Other suitable polymers may include cationic acrylic water soluble polymers
that
are copolymers of cationic quaternized acrylates, methacrylates, acrylamides,
and
methacrylamides, for example trimethylammoniumpropylmethacrylate, and
acrylamide or
acrylonitrile.
e. Polyethyleneimines
Other suitable polymers are polyethyleneimines and copolymers with other
polyalkyleneimines. These amino-functional polymers can also be modified by
ethoxylation
and propoxylation. These amino-functional polymers can also be quanternized
with methyl
groups or oxidized to amine oxides.
f. Polyvinylpyrrolidones
Other suitable polymers include vinylpyrrolidone homopolymers and copolymers.
Suitable vinylpyrrolidone homopolymers have an average molecular weight of
from 1,000 to
100,000,000, preferably from 2,000 to 10,000,000, more preferably from 5,000
to 1,000,000,
and most preferably from 30,000 to 700,000. Suitable vinyl pyrrolidone
homopolymers are
CA 02329218 2000-12-20
_g_
commercially available from ISP Corporation, Wayne, New Jersey under the
product names
PVP K-15 (average molecular weight of 8,000), PVP K30 (average molecular
weight of
38,000), PVP K-60 (average molecular weight of 216,000), PVP K-90 (average
molecular
weight of 630,000), and PVP K-120 (average molecular weight of 2,900,000).
Suitable
copolymers of vinylpyrrolidone include copolymers of N-vinylpyrrolidone with
one or more
alkylenically unsaturated monomers. Suitable alkylenically unsaturated
monomers include
unsaturated
dicarboxylic acids such as malefic acid, chloromaleic acid, fumaric acid,
itaconic acid,
citraconic acid, phenylmaleic acid, aconitic acid, acrylic acid, methacrylic
acid, N-
vinylimidazole, vinylcaprolactam, butene, hexadecene, and vinyl acetate. Any
of the esters
and amides of the unsaturated acids may be employed, for example, methyl
acrylate,
ethylacrylate, acrylamide, methacryamide, dimethylaminoethylmethacrylate,
dimethylaminopropylmethacrylamide, trimethylammoniumethylmethacrylate, and
trimethylammoniumpropylmethacrylamide. Other suitable alkylenically
unsaturated
monomers include aromatic monomers such as styrene, sulphonated styrene, alpha-
methylstyrene, vinyltoluene, t-butylstyrene and others. Copolymers of
vinylpyrrolidone with
vinyl acetate are commercially available under the trade name PVP/VA from ISP
Corporation. Copolymers of vinylpyrrolidone with alpha-olefins are available,
for example,
as P-904 from ISP Corporation. Copolymers of vinylpyrrolidone with
dimethylaminoethylmethacrylate are available, for example, as Copolymer 958
from ISP
Corporation. Copolymers of vinylpyrrolidone with
trimethylammoniumethylmethacrylate
are available, for example, as Gafquat 734 from ISP Corporation. Copolymers of
vinylpyrrolidone with trimethylammoniumpropylmethacrylamide are available, for
example,
as Gafquat HS-100 from ISP Corporation. Copolymers of vinylpyrrolidone with
styrene are
available, for example, as Polectron 430 from ISP Corporation. Copolymers of
vinylpyn olidone with acrylic acid are available, for example, as Polymer ACP
1005 (25%
vinylpyrrolidone/75% acrylic acid) from ISP Corporation.
g. Methylvinyl ether
Other suitable polymers include methylvinylether homopolymers and copoymers.
Preferred
copolymers are those with malefic anhydride. These copolymers can be
hydrolyzed to the
diacid or derivatized as the monoalkyl ester. For example, the n-butyl ester
is available as
Gantrez ES-425 from ISP Corporation.
h. Polyvinyl alcohols
Other suitable polymers include polyvinyl alcohols. Preferably, polyvinyl
alcohols which are at least 80.0%, preferably 88-99.9%, and most preferably
99.0-99.8%
hydrolyzed are used. For example, the polyvinyl alcohol, Elvanol 71-30 is
available from E.
I. DuPont de Nemours and Company, Wilmington, Del.
Mixtures of any of the foregoing polymers may be possible or desirable.
CA 02329218 2000-12-20
_4_
3. The Volatile Organic Solvents)
The solvents useful in this invention are organic solvents with a vapor
pressure of
at least 0.001 mm Hg at 25°C and soluble to the extent of at least
lg/100m1 water. The upper
limit of vapor pressure appears to be about 100 mm Hg at 25°C. Vapor
pressure is a useful
measure for determining the applicability of the given solvent, since one
would select a
solvent which will volatilize sufficiently so as to leave no visible residue.
The organic
solvent of the invention is preferably selected from C,~ alkanol, C~_24
alkylene glycol ether,
and mixtures thereof. The C~,~ alkanol solvents are preferred for use. The
alkanol can be
selected from methanol, ethanol, n-propanol, isopropanol, butanol, pentanol,
hexanol,
their various positional isomers, and mixtures of the foregoing. In the
invention, it has been
found most preferable to use ethanol, which has particularly good
volatilization and
solubilization characteristics. It may also be possible to utilize in addition
to, or in place of,
said alkanols, the diols such as methylene, ethylene, propylene and butylene
glycols, and
mixtures thereof. Other solvents, such as amines, ketones, ethers,
hydrocarbons and halides
may be useful. Other examples of solvents can be found in Kirk-Othmer,
Encyclopedia of
Chemical Technology 3rd, Vol.21, pp. 377-401 (1983), incorporated by reference
herein.
The alkylene glycol ether solvents can include ethylene glycol monobutyl
ether,
ethylene glycol monopropyl ether, propylene glycol monopropyl ether, propylene
glycol
monobutyl ether, and mixtures thereof. It is preferred to limit the total
amount of solvent to
no more than 20%, more preferably no more than 15%, and most preferably, no
more than
10%, of the cleaner. Moreover, in some of the compositions of this invention,
no solvent
may be present. A preferred range is about I-15%.
4. Water
The third principal ingredient is water, which should be present at a level of
at
least about 75%, more preferably at least about 80%, and most preferably, at
least about 85%.
Deionized water is most preferred. Water forms the predominant, continuous
phase in which
the ingredients are solubilized or dispersed.
5. Aesthetic/Functional Additives
Various desirable Actives include:
a. Surfactants
The surfactants used in the invention may be one or more nonionic surfactants
which have a HLB of about 3-16. For a further discussion of HLB measurements,
one should
consult Popiel, Introduction to Colloid Science (1978), pp. 43-44 and
Gerhartz, Ullmann's
Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A9 (1985), pp. 322-23,
both of which are
incorporated by reference thereto.
Surfactants may be selected from linear and branched alkoxylated alcohols,
alkoxylated alkylphenols and alkylpolyglycosides, among others. The
alkoxylated alcohols
include ethoxylated, propoxylated, and ethoxylated and propoxylated CS_ZO
alcohols, with
CA 02329218 2000-12-20
_1O_
about I-5 moles of ethylene oxide, or about 1-5 moles of propylene oxide, or 1-
S and 1-5
moles of ethylene oxide and propylene oxide, respectively, per mole of
alcohol. There are a
wide variety of products from numerous manufacturers, such as the Neodol
series from
Texaco Chemical Co., to wit, Neodol 25-3, a linear C,z_,5 alcohol ethoxylate
with 3 moles of
ethylene oxide ("EO") per mole of alcohol, HLB of 7.8, and Neodol 91-2.5,a
linear C9_"
alcohol ethoxylate with 2.5 moles of EO; Alfonic 1412-40, a C,z_,4 ethoxylated
alcohol with 3
moles of EO from Conoco; Surfonic L12-2.6, a C,0.,z ethoxylated alcohol with 3
moles of
EO, and Surfonic L24-3, a C,z_,4 ethoxylated alcohol with 3 moles of EO from
Huntsman
Chemical; and Tergitol 25-L-3, a C,z_~5 ethoxylated alcohol with 3 moles of
EO, from Union
Carbide. The secondary ethoxylated alcohols include Tergitol 15-S-3, a C"_,s
secondary
ethoxylated alcohol, with 3 moles of EO, from Union Carbide.
The branched surfactants, especially preferred of which are tridecyl ethers,
include Trycol TDA-3, a tridecyl ether with 3 moles of EO, from Henkel KGaA
(formerly,
Emery), and Macol TD 3, a tridecyl ether with 3 moles of EO, from PPG
Industries. See,
also, McCutcheon's Emulsifiers and Detergents, 1987. The sparingly soluble
nonionic
surfactant can also be selected from alkoxylated alkylphenols, such as: Macol
NP-4, an
ethoxylated nonylphenol with 4 moles of EO, and an HLB of 8.8, from PPG;
Triton N-57, an
ethoxylated nonylphenol with an HLB of 10.0, Triton N-42, an ethoxylated
nonylphenol with
an HLB of 9.1, both from Rohm & Haas Co.; and Igepal CO-520, with an HLB of
10.0, an
ethoxylated nonylphenol from GAF Chemicals Corp.; Alkasurf NP-5, with an HLB
of 10.0,
and Alkasurf NP-4, with an HLB of 9.0, both of which are ethoxylated
nonylphenols from
Alkaril Chemicals; Surfonic N-40, with an HLB of 8.9, an ethoxylated
nonylphenol from
Huntsman. See, McCutcheon's Emulsifiers and Detergents (1987), especially page
282,
incorporated herein by reference thereto. The nonionic surfactant can be
chosen from, among
others: Alfonic surfactants, sold by Conoco, such as Alfonic 1412-60, a C,z_,4
ethoxylated
alcohol with 7 moles of EO; Neodol surfactants, sold by Shell Chemical
Company, such as
Neodol 25-7, a C,z_,5 ethoxylated alcohol with 7 moles of EO, Neodol 45-7, a
C,~,s
ethoxylated alcohol with 7 moles of EO, Neodol 23-5, a linear C,z_,3 alcohol
ethoxylate with 5
moles of EO, HLB of 10.7; Surfonic surfactants, also sold by Huntsman Chemical
Company,
such as Surfonic L12-6, a C,a,z ethoxylated alcohol with 6 moles of EO and L24-
7, a C,z_,4
ethoxylated alcohol with 7 moles of EO; and Tergitol surfactants, both sold by
Union
Carbide, such as Tergitol 25-L-7, a C,z_~5 ethoxylated alcohol with 7 moles of
EO, and
Tergitol S-15-7, a C"_,5 ethoxylated alcohol with 7 moles of EO. Macol NP-6.
an
ethoxylated nonylphenol with 6 moles of EO, and an HLB of 10.8, Macol NP-9.5,
an
ethoxylated nonylphenol with about 11 moles EO and an HLB of 14.2, Macol NP-
9.5, an
ethoxylated nonylphenol with about 9.5 moles EO and an HLB of 13.0, both from
Mazer
Chemicals, Inc.; Triton N-101, an ethoxylated nonylphenol with 9-10 moles of
ethylene
oxide per mole of alcohol ("EO") having a hydrophile-lipophile balance ("HLB")
of 13.4,
CA 02329218 2000-12-20
-1 1 -
Triton N-11 l, an ethoxylated nonylphenol with an HLB of 13.8, both from Rohm
& Haas
Co.; Igepal CO-530, with an HLB of 10.8, Igepal CO-730, with an HLB of 15.0,
Igepal CO-
720, with an HLB of 14.2, Igepal CO-710, with an HLB of 13.6, Igepal CO-660,
with an
HLB of 13.2, Igepal CO-620, with an HLB of 12.6, and Igepal CO-610 with an HLB
of 12.2,
all polyethoxylated nonylphenols from GAF Chemicals Corp.; Alkasurf NP-6, with
an HLB
of 11.0, Alkasurf NP-15, with an HLB of 1 S, Alkasurf NP-12, with an HLB of
13.9, Alkasurf
NP-11, with an HLB of 13.8, Alkasurf NP-10, with an HLB of 13.5, Alkasurf NP-
9, with an
HLB of 13.4, and Alkasurf NP-8, with an HLB of 12.0, all polyethoxylated
nonylphenols
from Alkaril Chemicals; and Surfonic N-60, with an HLB of 10.9, and Surfonic N-
120, with
an HLB of 14.1, Surfonic N-102, with an HLB of 13.5, Surfonic N-100, with an
HLB of
13.3, Surfonic N-95, with an HLB of 12.9, and Surfonic N-85, with an HLB of
12.4, all
polyethoxylated nonylphenols from Huntsman.
The glycosides, particularly the alkyl polyglycosides, may also be used as a
surfactant for purposes of the aerosol formulation of the present invention.
These glycosides
include those of the formula:
RO(C~H~O)y(Z)x
wherein R is a hydrophobic group (e.g., alkyl, aryl, alkylaryl etc., including
branched or
unbranched, saturated and unsaturated, and hydroxylated or alkoxylated members
of the
foregoing, among other possibilities) containing from about 6 to about 30
carbon atoms,
preferably from about 8 to about 15 carbon atoms, and more preferably from
about 9 to about
13 carbon atoms; n is a number from 2 to about 4, preferably 2 (thereby giving
corresponding units such as ethylene, propylene and butylene oxide); y is a
number having
an average value of from 0 to about 12, preferably 0; Z is a moiety derived
from a reducing
saccharide containing 5 or 6 carbon atoms (e.g., a glucose, fructose, mannose,
galactose,
talose, gulose, allose, altrose, idose, arabinose, xylose, lyxose, or ribose
unit, etc., but most
preferably a glucose unit); and x is a number having an average value of from
1 to about 10,
preferably from 1 to about 5, and more preferably from 1 to about 3.
It would be apparent that a number of variations with respect to the makeup of
the glycosides
are possible. For example, mixtures of saccharide moieties (Z) may be
incorporated into
polyglycosides. Also, the hydrophobic group (R) can be attached at the 2-, 3-,
or 4-positions
of a saccharide moiety rather than at the 1-position (thus giving, for
example, a glucosyl as
opposed to a glucoside). In addition, normally free hydroxyl groups of the
saccharide moiety
may be alkoxylated or polyalkoxylated. Further, the (C"HZpO)y group may
include ethylene
oxide and propylene oxide in random or block combinations, among a number of
other
possible variations.
An exemplary glycoside surfactant is APG 325n, which is manufactured by the
CA 02329218 2000-12-20
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Henkel Corporation. APG 325n is a nonionic alkyl polyglycoside in which R is a
mixture of
C9, C,o and C" chains in a weight ratio respectively of 20:40:40 (equivalent
to an average of
C,o.2), with x of 1.6, and an HLB of 13.1.
The amine oxides, referred to as mono-long chain, di-short chain, trialkyl
amine
oxides, have the general configuration:
R2
R~-N~O
R3
wherein R' is C~z, alkyl, and RZ and R3 are both C,~ alkyl, or C,~
hydroxyalkyl, although RZ
and R3 do not have to be equal. These amine oxides can also be ethoxylated or
propoxylated.
The preferred amine oxide is Iaury1 amine oxide. The commercial sources for
such amine
oxides are Barlox 10, 12, 14 and 16 from Lonza Chemical Company, Varox by
Witco and
Ammonyx by Stepan Company.
A furkher semi-polar nonionic surfactant is alkylamidoalkylenedialkyl-
amine oxide. Its structure is shown below:
p Rz
R'-C-NH-(CHZ)o N~O
R3
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O
wherein R' is CS_2° alkyl, RZ and R3 are C,~ alkyl, R1-C-NH-(CHZ)~- or -
(CHZ)P OH, although
RZ and R3 do not have to be equal or the same substituent, and n is 1-5,
preferably 3, and p is
1-6, preferably 2-3. Additionally, the surfactant could be ethoxylated (1-10
moles of
EO/mole) or propoxylated (1-10 moles of PO/mole). This surfactant is available
from
vanous sources as a cocoamidopropyldimethyl amine oxide; it is sold by Lonza
Chemical
Company under the brand name Barlox C. Additional semi-polar surfactants may
include
phosphine oxides and sulfoxides.
It is possible that other surfactants may be suitable for use herein: anionic
surfactants, such as, without limitation, alkali metal alkyl sulfates,
alkylarylsulfonates,
primary and secondary alkane sulfonates (also referred to as paraffin
sulfonates), alkyl
diphenyloxide disulfonates, and mixtures thereof; cationic surfactants, such
as, without
limitation, quaternary ammonium, imidazolinium, morpholinium, and other such
surfactants;
amphoteric surfactants, such as, without limitation,an alkylbetaine, an
amidobetaine
(especially alkylpropylamidodialkylbetaines, eg., Velvetex AB, from Henkel
KGaA), or a
sulfobetainedialkylbetaines; and zwitterionic surfactants can be found
described in Jones,
U.S. 4,005,029, at columns 11-15, which are incorporated herein by reference.
The amount of the surfactants is generally between about 0.1 to about 5%, of
the
aqueous composition.
b. Fragrances
Fragrances, which are usually lipophilic oils, such as, without limitation,
materials
which can also function as solvents, such as terpenes and their derivatives,
Representative
examples for each of the above classes of terpenes with functional groups
include but are not
limited to the following: Terpene alcohols, including, for example, cis-2-
pinanol, pinanol,
thymol, 1,8-tenpin, dihydro-terpineol, tetrahydromyrcenol, tetrahydrolinalool,
and tetrahydro-
alloocimenol; and terpene ethers, including, for example, benzyl isoamyl
ether, 1,8-cineole,
1,4-cineole, isobornyl methylether, methyl hexylether. Further, other tertiary
alcohols are
useful herein. Additional useful solvents include alicyclic hydrocarbons, such
as
methylcyclohexane. Terpene hydrocarbons with functional groups which appear
suitable for
use in the present invention are discussed in substantially greater detail by
Simonsen and
Ross, The Terpenes, Volumes I-V, Cambridge University Press, 2nd Ed., 1947
(incorporated
herein by reference thereto). See also, co-pending and commonly assigned Choy,
U.S. Patent
5,279,728, incorporated herein by reference thereto. Other fragrances are
found amongst
combinations of aldehydes, esters, essential oils, and the like. See, Bertrand
et al., U.S.
Patent 4,938,416, and Swatting et al, U.S. Patent 5,227,366, both of which are
incorporated
herein by reference. Fragrances are available from such vendors as Givaudan-
Rohre,
International Flavors and Fragrances, Firmenich, Norda, Bush Boake and Allen,
Quest and
others.
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c. Dyes and Colorants
Dyes and colorants which can be solubilized or suspended in the formulation. A
wide variety of dyes or colorants can be used to impart an aesthetically and
commercially
pleasing appearance. The amounts of these aesthetic adjuncts should be in the
range of 0-2%,
more preferably 0-1%.
d. Antimicrobials
Additionally, because the surfactants in liquid systems are sometimes subject
to
attack from microorganisms, it is advantageous to add a preservative, i.e.,
mildewstat or
bacteristat. Exemplary mildewstats (including non-isothiazolone compounds)
include
Kathon GC, a 5-chloro-2-methyl-4-isothiazolin-3-one, Kathon ICP, a 2-methyl-4-
isothiazolin-3-one, and a blend thereof, and Kathon 886, a 5-chloro-2-methyl-4-
isothiazolin-
3-one, all available from Rohm and Haas Company; Bronopol, a 2-bromo-2-
nitropropane
1,3-diol, from Boots Company Ltd.; Proxel CRL, a propyl-p-hydroxybenzoate,
from ICI
PLC; Nipasol M, an o-phenyl-phenol, Na+ salt, from Nipa Laboratories Ltd.;
Integra from
ISP; Dowicide A, a 1,2-benzoisothiazolin-3-one, from Dow Chemical Co.; and
Irgasan DP
200, a 2,4,4'-trichloro-2-hydroxydiphenylether, from Ciba-Geigy A.G. See also,
Lewis et al.,
U.S. 4,252,694 and U.S. 4,105,431, incorporated herein by reference. Other
actives include,
without limitation, quaternary ammonium compounds, "polyquats," which are
reaction
products/mixtures of anionic polymer or prepolymers with quaternary ammonium
compounds, phenols, 3-isothiazolones, methyl and propyl parabens, and the
like. These
antimicrobial materials may be desirable to be delivered to a particular
surface, such as
fabrics, or hard surfaces, so as to deliver residual antimicrobial activity.
Especially preferred
are the polyquats which are referred to in Zhou, U.S. Patent Application
Serial No.
08/833,276, filed April 4, 1997, and Zhou et al., U.S. Patent Application
Serial No.
09/116,190, filed July 15, 1998, both of common assignment, and incorporated
herein by
reference thereto.
e. Miscellaneous Adiuncts
Small amounts of adjuncts can be added for improving aesthetic qualities of
the
invention. Other desirable additives may include chelating agents (without
limitation, such as
alkali metal salts of EDTA, preferably tetrapotassium EDTA; See Robbins et
al., U.S. Patent
5,972,876, incorporated herein by reference; or tetraammonium EDTA ; see Mills
et al., U.S.
Patent 5,814,591, incorporated herein by reference) salts, pigments, colorants
and the like.
Additional surfactants (anionic, nonionic, cationic, amphoteric, zwitterionic
and mixtures),
hydrotropes, solvents, and other dispersing aids may also be added in discrete
amounts,
taking into account their individual performance attributes and whether their
addition may
affect the product stability.
In the following Experimental section, examples of the inventive composition
are
provided.
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EXPERIMENTAL
In the following section, examples of various embodiments of the invention are
depicted. Where ingredients are repeated in some of the Examples, and have
been previously
identified in footnotes in prior Examples, those footnotes are not repeated.
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EXAMPLE I
Aqueous Liquid Pet Malodor Mitigating Composition
Ingredient Wei t
Deionized Watery 90.70 (q.s. to
100%)
Acrylic Polymer Emulsion2 1.08
Ethanol3 5.00
Polyether modified Polydimethylsiloxane'0.03
Preservatives 0.10
Nonionic Surfactantb 0.50
Fragrances 0.20
Dipotassium tetraborate decahydrateg0.70
Total: 100.00%
~ May not necessarily need to be deionized
2 Carboset polymer, BF Goodrich
3Solvent, Midwest Grain
4BYK Chemie
SIntegra
6Union Carbide.
Bush Boake and Allen.
sU.S. Borax
These ingredients are merely admixed together, with gentle stirring. The
preferred order of addition is to disperse the fragrance via the surfactant
and to neutralize the
polymer (although one can purchase versions that are already neutralized. So,
to disperse the
fragrance adequately, a preblend of water, surfactant and fragrance, and then
this preblend is
added to the bulk of the product. The finished liquid pet malodor mitigating
composition
can then be loaded into trigger or pump sprayers. It may also be possible to
load them into
cans for aerosol delivery. However, cost, the presence of an additional
solvent (the
propellant) and the ensuing reduction in water content, are considerations in
aerosol delivery.
If aerosol delivery is practiced, there are preferred systems described in co-
pending patent
application Serial No. 09/116,190, of Boli Zhou et al, filed July 15, 1998,
and incorporated
herein by reference. Preferably, but by no means limiting to the invention,
the composition
is delivered in a trigger sprayer made of high density polyethylene (HDPE) or
polypropylene,
although it may also be desirable to use transparent polyethylene
terephthalate (PET) or
polyvinyl chloride (PVC), and other transparent or translucent thermopolymers.
Examples
of such sprayers are depicted in Hefter et al., U.S. D-404,650, Bolliger et
al., U.S. D-
401,504, and Malmquist, U.S. D-372,428, all of which are incorporated herein
by reference.
In application, a fine spray or mist is applied to a surface having the
wastes)
giving rise to the malodor thereon. It has been determined that after the
wastes) have been
wetted, and then allowed to dry, the wastes) are thus entrapped in the minute,
transparent
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residue or film, said film containing the borax active. This has been observed
to be especially
effective at malodor mitigation or elimination. Because the quantity of
product used is very
sparing, the invention presents an extremely cost-effective solution to the
elimination or
mitigation of these particularly noxious malodors in enclosed living, working
and gathering
spaces.
EXAMPLE 2
Cat Litter Deodorizer Test
In this test, the inventive malodor counteractant was blind tested on soiled
litter
boxes to demonstrate the efficacy of the invention. This test was meant to
assay not only
immediate odor control, but residual odor control as well.
In the test, full sized cat litter boxes which have been preinnoculated with a
standard amount of cat urine are evaluated by an expert panel of about 30 in-
house panelists
on a 0 to 60 scale, with 60 being the highest in malodor. These boxes are,
over time,
additionally re-soiled with additional liquid and solid cat wastes to
replicate the domestic
animal's standard pattern of elimination. No to low odor typically is scaled
at a score of
below 15, while high malodor is from 35-50. This was a blind test, meaning the
samples
were unlabeled so the panelists were not influenced by the identity of the
product tested.
In the test, the invention (which, in Fig. l, is labeled the POP Prototype and
is the
darker of the two bars) significantly outperformed the control, which is a
commercially
available surface deodorizer and is labeled Control, the lighter of the two
bars) over a period
of up to 76 hours. The results are depicted in Fig. 1.
EXAMPLE 3
Cat Spray Deodorizing Tests
In this next experiment, the effect of the inventive product against Cat
Spray,
which again is the finely divided spray cats produce (mostly constituted of
urine) which cats
use to mark territory, is considered. Consumers have identified Cat Spray as
one of the
strongest and most difficult odors to remove. In this test, to simulate cats
marking, fabric
(upholstery) swatches were used to test efficacy of both the invention and a
number of
commercially available surface deodorizers and water. These swatches, being of
standardized sizes, can be dosed with a consistent amount of a simulated cat
spray (an
artificial cat spray developed internally by sensory experts, which was
created by using
pooled cat urine), which is applied to the swatches according to a specially
developed
protocol. Generally speaking, the simulated cat spray is dosed by a
specialized doser. The
innoculated swatches are then stored in standardized plastic covered
containers and left at
room temperature for up to one week or until ready to be tested. Prior to
evaluation, the
containers are opened and left open over night. Prior to sensory evaluation,
the swatches are
removed from the containers and treated with, respectively, the invention, the
commercial
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products and water (as a control), in a standardized amount of about less than
3 grams of
products each. A group of expert panelists again rated each swatch according
to a 0 to 60
scale. Again, this was a blind test. In the time frame of assessment (about 48
hours), it was
determined that the invention (labeled "Proto") in the bar graph of Fig. 2 was
numerically
superior to each the remaining commercial products (labeled CP1, CP2 and CP3)
and water
(Control). The results are depicted in Fig. 2 graphically.
EXAMPLE 4
Comparison of Ammonia Generation
In this test, saturation of swatches in accordance with the directions of one
particular competitive product was tested. The products tested were the
invention, the
competitive product CP-3 and water (as a control). The times tested were after
48 hours (2
days) and 216 hours (9 days) incubation at room temperature (70°F, 21
°C). The ammonia
generation was determined by using a Kitegawa toxic gas detector with Matheson
ammonia
detector tubes. Naturally, a score that is higher in ppm NH3 is less
preferred. In this test, the
invention, labeled POP Prototype, vastly
outperformed both CP-3 and water. The results are depicted in Fig. 3.
The invention is further defined without limitation of scope by the claims
which
follow hereto.
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