Note: Descriptions are shown in the official language in which they were submitted.
52SO
" ANTI-ODORANT COMPOSITIONS
SPECIFICATION:
This invention relates to a composition and method
for eliminating or reducing odors.
It has become extremely important in our society to
eliminate unpleasant odors from our environment, in the
home, in the office and from factories, especially those
factories whic~ manufacture or utilize inherently odoriferous
chemicals. One method for eliminating unpleasant odors
has been to merely mask the odors with other, more power-
ful odors. This, however, has been found to be insuf-
ficient ~nd/or inefficient, because at best, the maskingis highly transitory, and at worst, the masking odor it-
self results in a certain pollution of the atmosphere and
may, in fact, in turn, be unpleasant to certain persons.
Obtaining a strong, but pleasant odor, which is found to
be pleasant by substantially all individuals, is an extremely
difficult, if not impossible, consideration.
Thére are several different mechanisms of odor-
generation. In a first mechanism, organic matter, includ-
ing portions or natural by-products of living organisms,
such as me~ator fecal matter or urine, generally become un-
desirably odoriferous by virtue of microbial action. Such
microbial actionr or bio-degradation, results in the gener-
ation of undesirably odoriferous by-products as a result of
such degradation. Although such degradation is desirable in
certain circumstances, for example in sewage disposal systems,
such bio-degradation in the home , as in the bathroom or kitchen,
or in the office, is particularly unpleasant to ~e inhabiting
the surroundings. A secondtype of odoriferous material is the
so-called chemical odor, where the material itself is inherent-
ly odoriferous. There is no requirement for any type of bio-
degradation or other chemical change, microbial or otherwise,
25~
in order to form the undesirable odor.
The precise functionality of odor-causing substances is not
clearly understood; however, it is believed that the first type of odor
problem can be substantially reduced if not completely eliminated, by merely
preventing microbial action for an extended period of time. This prevents
the formation of the undesirable odoriferous compounds and thus avoids
completely the formation of the unpleasant odor. The second type of odor
is possibly prevented by a binding effect, which prevents the discharge,
dissemination or distribution of the odor particles from the main body of
material into the atmosphere, from whence it can be sensed by an individual's
olfactory organ Furthermore, where the anti-odorant composition is dis-
persed into the atmosphere, as by spraying, the dispersed odor particles
are possibly bonded to the dispersed anti-odorant material, and thereby its
odor rendered insensible.
In accordance with the present invention, there is provided a
method for reducing the odor of an inherently odoriferous material comprising
a chemical or mixture of chemicals, the method comprising admixing with the
odoriferous material an anti-odorant composition comprising a substituted
phenolic anti-oxidant, the anti-oxidant being capable of retarding rancidity
in natural fats and oils, and an aliphatic hydroxycarboxylic acid compound
having a general graphic formula selected from the group consisting of:
- ,~[ R] T~ ~,[R] n
~c o=c c c=o
n
L~ o Y o Y
X X
/[R] n ~R] n \
,~ c-- -- !C= ~c o=cl
O Y O Y
X X
wherein R is an aliphatic organic group, or a plurality of such groups
52~0
connected by the "C-O-X" group; N is O or l; OX is an hydroxy group (-OH),
an ether group or an ester group; and O=C-Y can be a carboxyl group (OCOH)~
a thioacid group (OCSH), an ester group OCOR' a thioester group (SOCR'),
or an amide group (OCN " R" ').
The present invention also provides an anti-odorant composition
for reducing the perceived odor of an inherently odoriferous material the
composition comprising a substituted phenolic anti-oxidant, the anti-oxidant
being capable of retarding rancidity in natural fats and oils, and an
aliphatic hydroxycarboxylic acid compound, having a general graphic formula
selected from the group consisting of:
~ [R] ~ ~R]n
~, HF o=cl ~f Ic=o
, jo Y o Y
X X
jR]n / [R~n
HC C=O CH O=C
1 2
O Y O Y
X X
wherein R is an aliphatic organic group, or a plurality of such groups
r2o connected by the "C-0-X" group; ~ is O or l; OX is an hydroxy group (-OH),
an ether group or an ester group; and O=C-Y can be a carboxyl group (OCOH),
~,,
a thioacid group (OCSH), an ester group OCOR' a thioester group (SOCR'), or
an amide group (OCN" R "').
In a most preferred embodiment of the above composition the
hydrocarboxylic acid is sulfate free and contains at least 8 carbon atoms
and has at least one unsaturated carbon-carbon linkage.
The present invention also provides an aqueous anti-odorant com-
position comprising an aqueous medium, and dispersed therein the combination
of a substituted phenolic anti-oxidant, the anti-oxidant being capable of
- 2a -
` ll~SZSO
retarding rancidity in natural fats and oils, and an aliphatic hydroxy-
carboxylic acid compound having a general graphic formula selected from the
group consisting of:
R]n \ ~ [R]n
~ HC 0=C ~HC -- C=0
,., i O Y Y
X X
/ [R]n / [R] ~
- HC -C=0 CH 0=C
1 2
f Y o y
X X
wherein R is an aliphatic organic group, or a plurality of such groups
connected by the "C-0-X" group; ~tis O or l; OX is an hydroxy group (-OH),
an ether group or an ester group; and O=C-Y can be a carboxyl group (OCOH)
a thioacid group tOCSH), an ester group OCOR' a thioester group (SOCR'),
or an amide group (OCN " R"'), and an emulsifying agent moiety, the
emulsifying agent being capable of maintaining a stable dispersion of the
combination in water, the phenolic anti-oxidant being dispersed in water
in an amount of at least 0.05% by weight of the total dispersion and
wherein the hydroxycarboxylic acid compound is present in an amount of at
least about 50% by weight of the phenol.
Preferably, the invention provides a water-dispersible, odor-
reducing composition comprising the phenolic anti-oxidant and the aliphatic
hydroxycarboxylic acid compound together with
~ - 2b -
S25~
an emulsifying surfactant moiety, and the composition dispersed
in an aqueous medium. In one embodiment, the surfactant
moiety can be part of the same compound as the phenolic anti-
oxidant or the hydroxycarboxylic acid compound.
The phenolic anti-oxidant compounds useful in accord-
ance with the present invention include any of that class of
compounds which retard oxidation, deterioration and rancidity.
These compounds are well-known, and have been used in the past,
for example, to protect natural fats and oils, soaps, petro-
leum products/ vulcanized rubber and other such organic sub-
stances. Generally, those antioxidants which are non-toxic,
and thus, have been especially useful in food products, includ-
ing those especially useful for natural fats and oils, are
believed to be most useful in the present inventions. Ac-
cordin~ly, such food antioxidants which are non-toxic to humans,
are especially suitable for use where the anti-odorant compo-
sition may be sprayed into the atmosphere, and thus inhaled
by human beings, or otherwise come into direct contact with an
animal or human being. Where the anti-odorant composition is
to be applied directly to an inanimate surface, such as
floors, as by use of a brush or sponge application, antioxi-
dants which could be toxic to human beings can be used, such
materials especially including those which are useful anti-
oxidants for petroleum products.
Antioxidants include the polyphenols, such as the
hydroquinones, especially the ortho- and para-polyphenols, such
as pyrocatechol and pyrogallol; poly-substituted "masked",
or "hindered" phenols, especially those which are substituted
in the 2, 4, and 6-positions, such as 2-, 4-,6-trialkylphenolsi
neutral esters of hydroxybenzoic acids, such as, alkylhydroxy-
benzoic acids, p-hydroxybenzoic acid, gallic acid, and salicylic
~l~SZ50
acid; bisphenols; aminophenols; and condensed hydroxyaromatics,
such as naphthols.
Useful such antioxidant compounds include, for example:
butylated hydroxyanisole; di-tert butyl-para-cresol; alkyl
gallate esters, such as ethyl gallate, propyl gallate, butyl
gallate, octyl gallate and dodecyl gallate; ethyl toluate;
butyl toluate; ethyl p-hydroxybenzoate; propyl salicylate;
bisphenol A; bisphenol F; sesamol; alpha-naphthol, eugenol,
quercetin, catechol, osagin, pomiferin; 2, 2, 5, 7, 8-
penta-methylhydroxychromane ; 6-quinone; gossypol; 4-tert.
phenol;
butyl-m-cresol; o-phenyl~ p-chloro-m-zylenol; o-cresol;
o-aminophenol; p-aminophenol; and 4-amino-salicylic acid.
The hydroxycarboxylic acid compound useful in the
present combination can contain one or more of each of the
hydroxy groups, or the organic derivatives thereof, and of
the carboxyl groups, or the organic derivatives thereof.
The term "aliphatic", as most generally used herein
includes both closed ring compounds, commonly referred to as
cycloaliphatic compounds, as well as the open chain, both
straight-and branched-chain, compounds. However, the open
chain compounds are preferred. The term "aliphatic" also
includes saturated groups and groups containing at least one
olefinically or acetylenically unsaturated carbon-carbon link;
the unsaturated groups are preferred.
The most common aliphatic hydroxycarboxylic acid
compounds can be graphically defined by the following
formula:
1~5ZS0
~R~
n~
C---------------- , C = O (1)
O Y.
X
wherein R is an aliphatic organic group, or a plurality of
such groups connected by the "C-0-X" group; the dashed lines
indicate alternative possible linkages between the R and the
COX and OCY groups, or between the COX and OCY groups directly;
n is 0 or 1; OX is an hydroxy group t-OH), an ether group or
an ester group; and 0=C-Y can be a carboxyl group (OCOH), a
thioacid group (OCSH), an ester group (OCOR'), a thioester
group (OSCR'), or an amide group (OCNR"R"). R" and R"'can be
the same or different, and can each be hydrogen or an organic
group. The R group can contain one or more additional COX
and OCY groups, as defined above. Preferably, the "aliphatic"
group R contains at least about three carbon atoms, and more
preferably at least about eight carbon atoms.
Most preferably, the hydroxycarboxylic acid compounds
most useful in this invention are the hydroxy fatty acids,
especially those hydroxycarboxylic acids having at least about
13 carbon atoms; not greater than about 30 carbon atoms need
be present, and even more preferably not more than 21 carbon
atoms, with optimally from about 15 to about 21 carbon atoms,
and the ether, ester and amide derivatives thereof, that is,
where all of some of the hydroxyl groups and carboxyl groups
are so substituted with organic groups. Even more preferred,
the acid is an unsaturated acid containing at least one
olefinically unsaturated linkage. Useful such acid compounds
include the naturally occurring ricinoleic acid compounds,
5ZSV
ricinelaidic acid compounds, dihydroxyoctadecenoic acid
compounds, aleuritic acid (trihydroxypalmitic acid) compounds,
dihydroxystearic acid compounds, trihydroxystearic acid com-
pounds, tetrahydroxystearic acid compounds, abietic acid com-
pounds, cholic acid compounds, and desoxycholic acid com-
pounds.
Other useful hydroxycarboxylic acids are: ascorbic
acid, lactic acid, malic acid, tartaric acid, citric acid,
glycolic acid, ~-hydroxybutyric acid, hydracrylic acid,
cyclohexaneglycolic acid, gluconic acid,galactonnic acid,
mannuronic acid, and other sugar acids.
As stated above, althouqh the free acid can be used,
it has been found that the ester and amide derivatives of the
carboxyl group, that is where "Y" is an ester group or an amine
group, are most effective; especially most preferred are the
esters of both polyhydric and monohydric alcohols. Useful such
ester groups, Y, can therefore be derived from either an ali-
phatic or an aromatic alcohol, such as esters of alkanols,
alkenols, alkynols, cyclic such compounds and benzyl alcohols.
Examples of such esters are derived from methanol, ethanol,
isopropanol, n-propanol, propargyl alcohol, propenol, ricinoleyl
alcohol, stearyl alcohol, lauryl alcohol, 3-buten-1-ol, allyl
alcohol, propylene glycol, glycerine, n-butanol, isobutanol,
ethylene glycol, cyclohexanol, benzyl alcohol, butene-1,4-diol,
and diethylene glycol.
Also extremely useful are the amides (O-CNR'R")
derived from both monoamines and polyamines. Useful such amine
groups can be derived from, for example, preferably the aliphatic
amines, such as ethylamine, propylamine, isopropanolamine,
ethanolamine, hydroxyethylethylenediamine, and the aromatic
11C~5ZSO
amines, such as aniline, phenylene diamine, triaminobenzene,
- naphthylamine, ~-naphthylamine.
It is preferred that the hydroxyl group not be sub-
stituted, i.e., that X be a hydrogen atom. However, the ether
or ester derivatives of the hydroxyl groups can be utilized
if desired. Generally such groups can contain from one to about
six carbon atoms, or higher if desired, and include aliphatic
and aromatic groups, such as for example, methyl, ethyl, propyl,
ethyloxyethyl, cyclohexyl, and methylbenzyl, and ester groups
such as acetyl. Polyether groups are also useful.
As stated above, the various R groups, and X and Y
groups, can each contain additional hydroxyl or carboxyl groups,
as well as oxygen linkages, amino groups, and other groups
which do not interfere with the odor-destroying activity of the
anti-odorant combinations, for example, halogen atoms, such as
chlorine and bromine. In addition, although R is defined as an
aliphatic group, the presence of an aromatic ring substituent
on a long aliphatic chain, it is understood, need not destroy
the aliphatic nature of the compound. Specifically, depending
upon the location of the aromatic group, in most cases it has no
effect on the odor-destroying capacity of the claimed combina-
tion. Accordingly, such an "inert" aromatic substituent can
be present on a hydroxycarboxylic acid compound within the
scope of the present invention.
The use of metal salts of the hydroxycarboxylic acid
compounds does not provide the same desired effect as the present
invention, when used in combination with a phenolic antioxidant.
Thus, a metal salt of ricinoleic acid, for example, the sodium
ricinoleate obtained by the saponification of castor oil, does
not fully provide the same desired effect as the use of either
--7--
Z50
the free acid or one of the organic derivatives thereof, e.g.,
an ester or an amide.
Similarily, the presence of sulfate groups, as in
the so-called "sulfonated castor oil", does interfere with
the activity of the claimed combination. The sulfate-free
hydroxycarboxylic acid compounds are thus preferred.
The active combination of the phenolic and the
aliphatic hydroxycarboxylic acid com~ounds in accordance with
the present invention is preferably dispersed in a carrier or
diluent before application. For use by the ultimate consumer,
it is preferred that the diluent be water, or an aqueous solu-
tion. Accordingly, it is possible that the active combination
can be itself soluble, or dispersible in water, or that it
at least be able to be dispersed in water with the assistance
of a surface active emulsifying agent.
Preferably, the most useful emulsifying agents for
water dispersal of the antioxidants are the non-ionic surfac-
tants, including, e.g., the alkoxylated phenols and the oxy-
alkoxylated glycerides~ such as oxyalkoxylated natural oils,
including, e.g., castor oil and tall oil, and any of the
available synthetic glycerides of organic acids. Particularly
use~ul non-ionic surfactants are the alkoxylated alkyl phenols,
which combine in a single compound an effective water-dispers-
ing, emulsifying activity with a small, but effective, anti-
odor activity, to assist the antioxidant in reducing oreliminating odors cause, e.g., by microbial degradation of
organic material. One preferred alkyl phenol surfactant
includes an alkyl group containing at least about six carbon
atoms, preferably, in the range of from about eight to
about thirty-two carbon atoms, and optimally, about eight
to about 24 carbon atoms. The alkyl phenol is reacted with
5250
an alkylene oxide, e,g " ethylene oxide, to form a surface
active compound having the general formula:
R ~ O~RlO)nRlOH (2)
wherein R is an alkyl group containing at least about
six carbon atoms and Rl is an alkyl group containing
from about two to about six carbon atoms. If desired, ;
additional alkyl groups (R) can be substituted onto each
phenyl ring. However, preferably, there should not be more
than two alkyl groups per ring, and optimally, only one alkyl
group.
A second group of highly preferred surfactant are
the oxyalkoxylated glycerides which combine in a single com-
pound the effective water-dispersing, emulsifying activity
with the antiodor activity of an aliphatic hydroxycarboxylic
acid ester. Commercially availahle such compounds are generally
derived from castor oil, which is primarily a natural source
of glycerides of ricinoleic acid. This glyceride is reacted
with an alkylene oxide, e.g., ethylene oxide, to form a surface
active compound having the general formula:
C3H503 oC-cloHl8-cH-c H13
! (3)
L (R'O)nR'OH 3
wherein R' is as defined above for formula (2), and [3(n+1)] can
range from about three up to about 50, or higher, depending upon
the surface activity required. The minimum value ofn should be
used to obtain the desired emulsifying activity for the amount
of the antiodor-activity required from the hydroxy carboxylic
acid compound portion of the emulsifier.
l~SZSO
Other hydroxycarboxylic acid compounds which can be
alkoxylated in this manner can also be utilized as the emulsi-
fying agent if desired.
Other hydroxycarboxylic acid compounds which have
inherent emulsifying properties for the phenol antioxidant
in water includes the amides, such as diethanolamine ricino-
leate.
When utilizing the non-ionic surfactants, and specif-
ically, the alkoxylated type, the hydrophilic property of the
compound, e.g., the alkoxylated alkylphenol or oxyalkoxylated
triglyceride, is increased as the number (n) of oxyalkyl
groups is increased in each molecule. Usually, the oxyalkyl
groups are, as commercially available, oxyethylene groups,
although more generally, oxypropylene or mixed oxyethylene-
oxypropylene groups have been utilized. The oxyalkyl groupcan generally contain from about 2 to about 6 carbon atoms,
but preferably, from about two to about four carbon atoms,
and optimally, 2 or 3 carbon atoms. These compounds are
available commercially, and their emulsifying properties are
well-known to the art. The surface active compounds themselves,
and their specific applicability as emulsifying agents, does
not per se form a part of the present invention.
Useful such non-ionic surfactants include, for
example, ethoxylated n-octylphenol, ethoxylated decylphenol,
ethoxylated laurylphenol, ethoxylated stearylphenol, propoxyl-
ated n-octylphenol, ethoxy-propoxylated n-decylphenol, ethoxyla-
ted glyceryl monoricinoleate, ethoxypropoxylated castor oil,
ethoxylated castor oil, ethoxylated tall oil.
--10--
iZ50
Other useful dispersing agents include ethoxyla-
ted aliphatic alcohols; ethoxylated carboxylic acid esters
of polyols; ethoxylated esters of fatty acids, rosin acids
and tall oil acids; carboxylic amides, such as diethanolamine
laurate; and polyoxyalkylene oxide block copolymers.
Alternatively, if desired, the anti-odorant combina-
tion can be dispersed in an organic solvent, such as aliphatic
solvent, cycloa~iphaticor aromatic, cycloaliphat~aromatic,
aliphatic-aromatic or chlorinated such hydrocarbons. Prefer-
ably, the active anti-odorant combination of compounds is
soluble in such solvent liquid. The liquid should be inert,
that is, non-reactive with the antioxidant or hydroxycarboxylic
acid compound.
Preferably, the organic solvent is also relatively
volatile, having approximately the same vapor pressure as water,
or a higher vapor pressure, at usual ambient temperatures.
Useful such organic solvents include, for example,
benzene, toluene, xylene, aliphatic and aromatic petroleum
fractions, such as low flash-point kerosene and hexane-
h~ptane mixtures. Non-hydrocarbon solvents which can be
utilized include alcohols, phenol, ketones, such as acetone,
esters, and terpenes.
Generally, surface active agents, or emulsifiers
are not necessary to disperse the active anti-odorant com-
ponents into an organic solvent, which should be selectedto be a solvent for the particular active ingredients uti-
lized.
In accordance with this invention, it has further
been found that the addition of a terpene, to the anti-
odorant composition, results in a further improvement in itsanti-odorant effectiveness. For purposes of this invention,
~l~,'SZS~
it has been found that the terpenoids, i.e., the oxygenated
derivatives of the terpene hydrocarbons, including the al-
cohols, ~etones, aldehydes, acids and esters derived from
the terpenes can also be used and are to be included within
the general term "terpene". Useful terpenes include the
acyclic, monocyclic and bicyclic terpenes. Although the
C10- terpenes have been found to be most effective, sesqui-
terpenes and diterpenes are also useful. Examples of such
compounds include A- pinene, ~ - pinene, phellandrene, myri-
cene, ocimene, tricyclene, terpinolene, terpinoyl acetate,isoborneol, dipentene, menthol, menthone, carene, limonene,
sylvestrene, sabinene, camphene, C~- farnesene, zingiberene,
caryophyllene, gerniol, geranial, nerol linalool, neral,
citronellal, ~ - terpineol, 1,8-cineole, ascaridole, camphor,
thujone, verbenone, fenchone, isobornyl acetate, farnesol,
abietic acid and its salts and esters. A variety of naturally-
occurring terpene mixtures, derived from various plant sources,
have also been found useful, for example from citrus fruits,
the lemon terpenes, orange terpenes, lemon glass oil and lime
oil distillate. Although the higher terpenes, e.g., the di-
terpenes and sesqui-terpenes, can be utilized, the terpene
hydrocarbons and terpenoids, including the basic terpene -C10
group are preferred. Generally, mixtures of terpenes, includ-
ing terpenoids, are used in admixture with an antioxidant for
purposes of this invention.
It has further been found, in accordance with the
present invention, that alkylated aromatic compounds, and
their inertly-substituted derivatives, provide desirable anti-
odorant characteristics~ especially when dispersed in an
aqueous medium. Preferably the alkylate~ aromatic compounds
are monocyclic aromatic compounds containing at least about
-12-
two alkyl substituents on the aromatic ring and most prefer-
ably not more than about four alkyl groups~ Each alkyl group
preferably contains up to abbut eight carbon atoms, and
most preferably~ up to about four carbon atoms.
Such compounds preferably have the empirical
formulae: '
n ~ R or R ~ ~ R
wherein R and Rl are alkyl groups having from one to
about eight, and preferably, from one to about four carbon
atoms, and n is an integer from 1 to 3 and, most preferably
1. When n is greater than one, the plurality of Rl groups can
each be the same or different alkyl groups. Examples of
suitable alkyl groups include methyl, ethyl, n-propyl, iso-
propyl, n-butyl, sec-butyl, tert.-butyl, and l,l-dimethyl-
propyl.
Useful such compounds for example, include ,
especially, the polyalkylated benzene compounds, such as
para-isopropyl toluene, meta-isopropyl toluene, xylene,
1, 3,5-mesitylene, 1,4-methylethylbenzene and 1-methyl~4-tert.-
butylbenzene.
Many of the above polyalkyl aromatic compounds can
be utilized as, or part of, an organic solvent, ~f one is
used, for the antioxidant material, and thus serves a double
purpose of a dispersant for the antioxidant and terpene, if
present, and as an active odor suppressor.
In preventing odors in accordance with the present
invention, wherein the odor-reducing composition is to be
applied to a solid surface, as in a toilet area or kitchen,
the phenolic antioxidant is preferably dispersed in an inert
diluent, such as water, in an amount of at least about 0.005
`52SV
percent by weight of the total liquid, and preferably, in
an amount of at least about 0~01 percent by weight. More
preferably~ the phenolic antioxidant is present in the diluent
in an amount of from about 0.01 to about 1 percent by weight
of thé total mixture, and optimally, from about 0.02 to about
0.2 percent by weight. The hydroxycarboxylic acid compound
is preferably present in an amount of at least about 50 per-
cent by weight of the phenolic antioxidant present, more
preferably at least about lO0 percent by weight of the anti-
oxidant, most preferably from about 100 percent to about
2000 percent by weight of the antioxidant and optimally from
about 200 percent to about 1000 percent by weight of the
antioxidant~
When the polyalkylated aromatic compounds are
used for their odor-absorbing properties, they can be prefer-
ably present in am amount of at least about 0.005 percent
by weight of the total composition. Because these compounds
can be used as the diluent, or organic solvent for the anti-
oxidant, there is no practicable upper limit. The terpenes
can be present in an amount of at least about 20 percent by
wt. of the phenolic antioxidant, and most preferably from
about 25 to about 300 percent by weight of the phenolic
antioxidant.
For the above active agents, the outer limits
merely define proportions above which it is considered waste-
ful to use the material. However, greater amounts of any can
be used if desired. It must be added that when any material
is inherently undesirably odoriferous, this could result in
an undesirable situation. The composition used is prefer-
ably nontoxic to human beings.
-14-
i250
The surface active agents useful for dispersing
the antioxidants, terpenes and/or polyalkyl aromatic com-
pounds in water should be present in an amount sufficient
to maintain the emulsion of the organic compounds in water.
Generally, surface active agents can be present in an amount
of at least about 200 percent by weight of the water-insoluble
organic compounds to be dispersed, e.g., the phenolic anti-
oxidant, and the hydroxycarboxylic acid compound, if desirable,
compound to be dispersed. Preferably, the emulsifier is
present in an amount of at least about 400 percent by weight,
most preferably from about 400 to about 2000 percent by weight
and optimally from about 500 to about 1000 percent by weight
of the antioxidant and other insolubles.
It has been found that the addition of a polyol,
and especially glycerine, and a carboxylic acid, such as a
fatty acid or lactic acid, into the water-dispersible compo-
sition together with the antioxidant, results in a further
improvement in the anti-odorant properties. The carboxylic
acid and polyol act as coupling agents solubilizing in the
usual manner.
The anti-odorant composition of the invention is
preferably used dispersed in an aqueous medium, in the propor-
tions discussed above. However, the composition can be formu-
lated and shipped in a concentrated form without water, wherein
the phenolic antioxidant, and hydroxycarboxylic compounds,
and any other present, can be dispersed or dissolved in the
other organic ingredients, principally the relatively large
amount of surface active agent.
The water-dispersible concentrate can be readily
dispersed into water at the desired concentration by merely
5Z50
agitating a mixture of the water and non-aqueous concentrate.
However, it is ~metimes even more preferred to provide the
anti-odorant com~osition in a concentrated aqueous dispersion,
which can then be further diluted by merely pouring the de~
sired quantity into additional water and gently stirring.
For certain purposes, as for deodorizing large amounts of
aqueous liquids, or water-immiscible liquids, the non-aqueous
concentrate is most useful.
The anti~odorant composition of this invention
can be used, for example, for the elimination of odor
from animal fecal matter, for example, manure, by mere ap-
plication to the surface of the collected feces. Sewage
effluent can be rendered odor-free, and therefore, less ob-
jectionable during storage, without interfering with further
sewage digestion~ Similarly, paper pulp liquor can be sub-
stantially deodorized by the addition of the anti-odorant
composition of this invention without substantially affect-
ing the digestion of the pulp.
A fuel for house heating purposes in certain areas
is formed from dried animal fecal matter. Such material
burns well, but has a powerful odor. The addition of a
small amount, e.g. 1% by wt. of the anti-odorant of the in-
vention to a dried animal waste substantially eliminates
odor during combustion.
The anti-odorant composition of this invention
is also useful as a deodorant for animals, including humans,
when applied to the body in a dilute aqueous solution, for ex-
ample, in a bath. The addition of the anti-odorant composi-
tion of this invention to the premoisturized packaged towel-
ettes, moistened with an alcohol solution greatly enhances
the ability of the towelette to remove unpleasant odors from,
-16-
~szso
e.g., the hands, or from other parts of the body.
It has been found to be preferable to add a
relatively strong biocide to the anti-odorant composition
of the present invention to prevent biodegradation of the
ingredients, especially of the surface active agents during
storage. The greatest problem, it has been found, is fungal
attac~; however, other organisms also need to be protected
against. ~hen the material is to be used in contact with
humans or other living organisms, nontoxic biocides, es-
pecially fungicides, should be used. Useful such nontoxic
materials include, for example, the alkali and alkaline earth
metal salts of known fungistatic acids, such as sodium sorbate,
sodium benzoate, sodium propionate and calcium propionate;
carboxylic acids and théir esters, such as sorbic acid, ben-
zoic acid, ethyl sorbate, dipropionic acid, ethylidene di-
! propionate, propionic acid, ethyl propionate, lactic acid.
Other, more powerful biocides, which can be used include
quaternary ammonium compounds, such as didecyl dimethyl am-
monium chloride, chlorinated phenols, such as pentachloro-
phenol, and formaldehyde-generating agents. These biocides are
generally added in an amount of from about 0.02% to about 5~
by weight of the surface active agent present and more prefer-
ably from about 0.05 to about 0.5% by weight.
The antiodorant composition of the present inven-
tion is effective against both odors of putrefaction, where
the biocidal properties of the composition are effective,
and inherent chemical odors, where any biocidal properties
of the antiodorant composition are not relevant.
This latter property is the most surpxising
aspect of the combination of this invention,as the mechanism
5~
by which this is accomplished is not known. The composition
is effective against a variety of odoriferous chemical materi-
als, especially the sulfides, both inorganic sulfides, such
as hydrogen sulfide and its aqueous solutions, and organic
sulfides, such as the mercaptans and mercaptides, but also
including the organic amines. It is noted, however, that free
ammonia may interfere with the antiodorant activity of the
combination of this invention.
The composition can be admixed with, or applied
to the surface, or surfaces, of a mass of odoriferous chemical
material, or to a container which the chemical had contami-
nated with its odor, or as a spray to remove the chemical
odor present as a liquid aerosol, gas or vapor in the air,
from the atmosphere. Such bulk chemicals include pure or
mixed chemicals. Other chemically odoriferous materials,
include for example, chemical reaction products, such as from
pulping mixture or sewage digestion plants, wherein the ac-
tive antiodorant combination is added in concentrations too
low to affect the reactions occurring, e.g., to prevent mi-
crobial degradation of sewage, but in sufficient quantity
to eliminate or substantially reduce the evolution of un-
desirable odors.
The following Examples are intended to describe
the preferred methods for carrying out the present inven-
tion. The Examples are merely exemplary of the scope of
the present invention, and are not intended to be exclusive
thereof. A variety of equivalent materials can be utilized
in the composition, including those antioxidants which may
in the future become available on the market.
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EX~PLE 1
A water dispersible mixture is formed h~ving
the following composition:
Part ~y
Ingredients ~ eight
Ethoxylated Castor Oil
(Surfact~1~365~* 16
Ethoxylated Nonyl Phenol
(Igepal CO-73Q~ 70
Glyceryl Tri-Oleate 6
Calcium Propionate 0.2
* - approximately 40 mols of ethylene oxide (EtO) per mol
of triglyceride of ricinoleic acid.
Part By
Ingredients Weight
Glycerine 2
Butylated Hydroxyotoluene (2,6-di-
tert. butyl-4-methoxylphenol 3.4
Butylated ~ydroxyanisole (2,4-di-
methyl-6-tert. butylphenol) 1.6
Lactic Acid 3
A portion of the above mixture, 10 parts by
weight, is dispersed in 990 parts water to form a stable
emulsion of the antiodorant materials with the emulsifiers
listed. An odor-causing test sample is formed comprising
10 ml. of tap water and 3 grams of filet of fish. The mixture
is blended together and 2 ml. of the above anti-odorant
emulsion is added thereto. An identical second odor-causing
sample is formed in the same manner, but 2 ml. of additional
tap water is added in place of the above anti-odorant emul-
sion. The two test compositions were permitted to incubate
at a temperature maintained in the range of from 37 to 40C.
The relative strength of the odor was measured after 24 hours,
48 hours, 72 hours and 168 hours. The composition containing
only the tap water was found to be substantially completely
putrified within 24 hours. The composition containing the
~ f~3~P~J~
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anti-odorant emulsion of the present invention did not
generate an odor of putrefaction until some time after the
72-hour test period.
EXAMPLE 2
The test procedures of Example 1 are repeated,
with the addition of 0.5 parts by weight of a mixture of
terpenes having the following ingredients:
- pinene
~i-pentene
Lemon Terpenes
Lemon Grass Oil
Para-Cymene
Phellandrene
Terpinolene
Terpincyl Acetate
Orange Terpines
Lime Oil (Distilled)
The same odor test is carried out, and the fish-
water composition containing the deodorant composition in
accordance with the present invention, including the anti-
oxidant and the hydroxycarboxylic acid compound and the
terpenes shows a satisfactory low odor level up to the
168-hour level.
As a comparative Example, the procedures of
Example 2 were repeated, but with the elimination of the two
phenols, i.e., butylated hydroxytoluene and butylated hydroxy-
anisole. The test solution was found to have an odor approach-
ing that of putrefaction after only 72 hours, and to have gone
well beyond putrefaction by the 168-hour period.
In a second comparative test, the procedures of
Example 2 were repeated, except that the hydroxycarboxylic
acid compound, i.e., the ethoxylated castor oil, was omitted.
The test solution has an odor approaching that of putrefaction
after only 72 hours and to have gone well beyond putrefaction
by the 168~hour period.
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EXAMPLE 3
The anti~odorant test composition of Example 2,
1 cc was floated as a thin film on the surface of a beaker
containing ethyl mercaptan, 100 cc. The odor of the mercap-
tan was found to be substantially completely eliminated.
EXAMPLE 4
An aqueous anti-odorant emulsion as prepared in
Example 2 was applied by a sponge around the outside of a
toilet, on the floor and on the walls in the vicinity sur-
rounding the toilet. The toilet room was found to have a
pleasant odor even after seven days. Substantially the same
results were obtained when the aqueous emulsion was applied
with a conventional spray bottle.
EXAMPLE 5
An aqueous anti-odorant emulsion, as prepared in
Example 2, was sprayed, to a total amount of 100 gallons, over
100 cubic feet of animal fecal matter (cow manure). The mass
of manure was found to produce substantially no odor for a
period of 96 hours after the application of the anti-odorant
composition.
; EXAMPLE 6
Highly odoriferous sewage effluent in a primary
digester, in a quantity of approximately 500,000 gallons, was
treated by dripping the non-aqueous concentrate of Example 2
into the sewage at the rate of one drop per minute for a
period of 96 hours. During this time, the evolution of odor
from the primary digester liquid was substantially eliminated,
substantially without affecting, or in any way inhibiting,
the further digestion of the sewage effluent to any measur-
able extent.
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EXAMPLE 7
The aqueous anti-odorant emulsion, as prepared in
Example 2, was sprayed, in a total amount of 20 gallons, over
unburned refuse held in a container, with a cross-sectional
area of 700 square feet, and found to inhibit odor substan-
tially completely when stored overnight. The addition of the
emulsion was found not to impair, to any measurable extent,
the burning of the refuse on the following day.
EXAMPLE 8
An aqueous anti-odorant emulsion, as prepared in
Example 2, was added to the recirculating water supply in a
spray-type unit air conditioner used for conditioning the
odoriferous air in a sulfite pulp processing plant. The
thus-conditioned air was substantially deodorized.
EXAMPLE 9
The sulfite pulp liquor, in a sulfite pulp manufac-
turing plant, was directly deodorized, without substantially
affecting the digestion of the pulp, by adding the aqueous
anti-odorant emulsion, as prepared in Example 6, directly to
the pulp mixture. The odor evolved from the pulp was sub-
stantially completely eliminated.
EXAMPLE 10
A one-pound compressed fuel "log" formed of dried
animal fecal matter, commonly referred to as "cow chips" or
"buffalo chips", was formed by admixing the dried animal fecal
matter with one percent by weight of the aqueous anti-odorant
emulsion, as prepared in accordance with Example 2. When
burned, the log containing the anti-odorant composition was
found to evolve substantially no odor.
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EXAMPLE 11
- A pre-moistened towelette, of the type commonly
marketed, for example, under the designation "WASH N DRI",
generally comprises a paper napkin substantially saturated
with an alcohol-water solution. A commercially available
such product was utilized to clean the hands of a person
who had previously rubbed a mixture of onion and smoked
salmon ("lox") on his hanas. The odor was slightly dimin-
ished, following the rubbing with the moistened towel,
but still strongly noticeable. The hands were again rubbed
with the mixture of onions and smoked salmon, and again im-
mediately thereafter, wiped with a towelette moistened with
alcohol~ and with the anti-odorant emulsion as prepared in
Example 2. Upon wiping with this second moistened towelette,
the odor of the onions and smoked salmon was substantially
completely removed, leaving the hands substantially odor-free.
EXAM2LE 12
A ba~h was prepared by placing aboutll ounces of an
aqueous solution of the anti-odorant composition of Example 2
into approximately ten gallons of water. A long-haired dog,
weighing approximately seventy pounds, was washed in the bath,
removed from the bath and towelled dry. The dog was found to
have substantially no body odor for a period of five days
thereafter, even when the animals's fur became wet.
EXAMPLE 13
The anti-odorant aqueous emulsion, as prepared in
Example 2, was utilized to aid in the housebreaking of dogs.
The effectiveness of the anti-odorant composition is apparently
sufficiently great to not only eliminate odors which are
sensible to human beings, but also sufficiently effective to
eliminate even the residual odors that the far more sensitive
~ t ~ ~ -23-
~szso
noses of dogs can detect. The anti-odorant composition, in
accordance with the present invention, was placed over areas
where young puppies had previously urinated or defecated. It
was found that the dogs were completely unable to sense the
scent from their previous activities, and thus, were not induced
or urinate or defecate subsequently in the same spots.
EX~PLE 14
The procedures of Example 1 were repeated utilizing
the following odor-dispersable composition:
Ingredients Parts by Weight
Ethoxylated castor oil
(Surfactol 318-5~mols EtO) 11
Ethoxylated nonyl~henol
(Igepal C0-730~ 55
Butylated hydroxyanisole 1.3
Butylated hydroxytoluene 2.7
Glycerine 1.5
Soya oil 4
Oleic acid 2.5
Terpene mixture of Example 2 20
Water 15
Propyl Paraben 2
A portion of the above mixture, 10 parts by weight,
is dispersed in 990 parts by weight water to form a stable
emulsion of the anti-odorant composition. The same tests as
are set forth in Example 1 were carried out and greater effec-
tiveness in destroying the odor of putrefaction was obtained,
wherein the odor at 72 hours was slightly less than in Ex-
ample 1, and even after 200 hours, substantially no odor of
putrefaction was sensed.
EXAMPLES 15 - 23
The procedure of Example 14 was repeated, using the
same composition set forth therein, except that the hydroxy-
carboxylic acid compound, i.e., Surfactol 318, was substituted
for by the same amount of the materials listed in the Table
below.
~ fr~ 24-
1~525(~
EX~PLE NO. HYDROXYCARBOXYLIC ACID COMPOUND
Sulfated castor oil
16 Isopropanolamine amide of ricinoleic acid
17 Aminoethylethanolamine amide of castor oil
18 Aminoethylethanolamine diamide of ricin-
oleic acid
19 Aminoethylethanolamine mono amide of ricin-
oleic acid
Ethanolamine amide of ricinoleic acid
21 Butyl acetyl ricinoleate
22 Polymerized castor oil
23 ~ethyl ester of ricinoleic acid
24 Ascorbic acid
Ricinoleic acid
26 Tartaric acid :
27 Hydroxystearic acid
In all cases, the anti-odorant composition of the
afore-said examples was capable of preventing the sensing of
any odor of putrefaction after 72 hours and was in all cases
capable of substantially decreasing the sensing of any such
odor even after 200 hours. The compositions of Examples 17,
18, 19 and 23 substantially completely eliminated any such
odor putrefaction even after 200 hours.
EXAMPLES 28 - 29
The procedures of Example 14 are again repeated ex-
cept that the phenolic antioxidants set forth in Example
14 are substituted for by equal quantities by weight of the
phenolic antioxidant or antioxidants listed in the following
table:
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EXAMPLE NO. PHENOLIC ANTIOXIDANT
28 Bisphenol A
29 octyl gallate
alpha-napthol
31 ethyl-p-hydroxybenzoate
32 p-hydroxyaniline
33 propyl salicylate
34 ethyl toluate
In each of the tests set forth in the Table above,
substantially no odor putrefaction is sensible after 72
hours of testing and the odor putrefaction is maintained com-
pletely eliminated or substantially reduced for a substantial
period thereafter in all cases.
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