US3102101A

US3102101A - Deodorant compositions and the methods of use

Info

Publication number: US3102101A
Application number: US115074A
Authority: US
Inventors: Hawley Harold Kenneth; Jr Thomas Bently Laycock
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1961-06-06
Filing date: 1961-06-06
Publication date: 1963-08-27
Anticipated expiration: 1980-08-27
Also published as: GB1005194A

Description

United States Patent DEODURANT CQMPGSHIGNS IVETHODS (BF USE Ann "nan Harold Kenneth Hawley, Woodlawn, and Thomas Bently common approaches to controlling odors have been oxidation of the odoriferous material by means of such oxidizingagents as sulfur dioxide, free chlorine, ozone, and

' hydrogen peroxide and masking by means of perfumes and other pleasantly odoriferous compounds. The oxi dation method is complicated by the corrosiveness of the oxidizing agents which makes it difiicult to store and use them. In sufiiciently large concentrations in air, these agents can corrode metal and are "annoying and even harmful to people. The masking method simply pollutes the air to a greater extent, and a substantial portion of the public finds perfumes themselves objectionable in the concentrations needed to mask objectionable odors. The ideal material for treating odor-containing air is one that leaves little residue and is non-corrosive, odorless, nonstaining, non-toxic, non-irritating, and effective.

Accordingly, it is an object of this'invention to provide a pressurized deodorant composition for treating air containing objectionable odors.

It is another object of this invention to provide a process for treating air containing objectionableodors.

It is a further object of this invention to provide a preferred pressurized deodorant composition, for treating air containing objectionable odors, which will leave the treated air substantially odorless.

It is a still further object of this invention to provide a pressurized deodorant composition for treating air containing objectionable odors, which is non-toxic and noncorrosive and which leaves lit-file residue.

The pressurized deodorant compositions of this invention comprise from. about 0.3% by weight to about 15% by Weight of the composition of a deodorant material selected from the group consisting of aliphatic unsaturated hydrocarbons containing from one to three multi-bond carbon to carbon linkages, aliphatic saturated hydrocarbons, and mixtures thereof, said saturated and unsaturated hydrocarbons containing from 12 to 18 carbon atoms, the balance of the composition being an aerosol propellant capable of providing. a pressure from about 30 pounds per square inch absolute to about 115 pounds .per square inch absolute in the aerosol container, under either straight or branched chain, preferably the former.

Examples of suitable compounds are: dodecene; tetradecene; hexadecene; octadecene; dodecane; tetradecane; hexadecane; octadecane; oct-ene-l dimer; propylene tetraan odor of their own.

chain, there should not be more than about four branch this invention is presumed to be odor cancellation.

ice

. 2 mer; 3,6-dimethyldecane; 2,4,5,7-tetramethyloctane; octadecyne; and 1,3-tetradecadiene.

Lower homologs (C and lower) of these deodorant hydrocarbons are also efiective at controlling o'dors, but they have odors of their own. The higher homologs (C and above) are much less effective than the C C deodorant hydrocarbons of this invention. In the saturated hydrocarbonseries, for instance, the compounds are relatively odorless from octadecane down to and in cluding dodecane. Decane has a positive odor of its own and octane and hexane are objectionable in this re- 1 gard. On the other hand, homologs higher than octadecane (melting point -30 C.) tend to solidify, particularly under the evaporative cooling eliect of an aerosol propellant, and this solidificationminimizes theirelfectiveness in controlling odors, and may clog the valve or orifice of the aerosol container.

Branched chain structures, such as octene-l dimer and propylene tetramer are also efiective at controlling odors. Excessively branched structures, however, tend to have In addition to the longest carbon chains having from about one to about two carbon atoms. Structures containing aromatic or ring configurations have very strong natural odors, and are therefore unac ceptable. Olfactory desensitization may also be induced by aromatics, e.g., it is believed that the aromatics in gasoline are responsible for its desensitization power.

The double and triple bonds in the hydrocarbons of this invention can be in the alpha position, conjugated, or otherwise, since it appears that the effectiveness of these compounds depends upon number of carbon atoms in the chain and not upon reactivity or location of the double or triple bond. it will be realized that a selection of the specific deodorant hydrocarbon for the compositions of this invention can be made on the basis of considerations other than those relating to deodorization, such as, cost, availability, odor, and amount of residue.

The deodorant hydrocarbons of this invention are very effective against a wide variety of odois. Some of the more common odors which can be controlled by these compounds are bathroom odors, frying odors, cabbage odors, fish odors, onion odors, ethyl mercaptan, and ciga-.

rette odors. The treated air is substantially odorless if the propellant selected is odorless and if no perfume is added to the product.

The compositions of this invention have a. very low level of toxicity, and are not irritating to the eyes, nose, or throat. They do not leave a noticeable residue or stain furniture, clothes, etc., under ordinary usage.

The term deodorization is a broad one comprising several mechanisms for controlling odors. It is not limited to destruction of the odoriferous materials by chemical reaction, but includes control by adsorption or absorption of the odorifero-us material, desensitization of the olfactory nerve, and odor cancellation. The latter mechanism is the phenomenon which occurs when the effects of two separate compounds, at least one of which is odoriferous, cancel out, resulting in an apparent destruction of the odor.

Although it is not desired to be bound by theory, the mechanism of deodorization for the hydrocarbons of A vapor phase chromatography study of air treated by the compositions of this invention failed to detect any reaction products, Which seems to eliminate chemical interaction as the mechanism for odor control. the human nose with the deodorant hydrocarbon dispersion prior to an exposure to objectionable odors failed to control the odors, which seems to eliminate the possibility that the mechanism for odor control is desensiti zation of the olfactory nerve. Positive evidence tor the Also, treatment of with the compositions of this invention. By virtue of the fact that the deodorant hydrocarbons I of this invention are not reactive, a wider range of perfumes, sanitizers and other minor additives, can be in-:

proposed theory of odor cancellation includes the results of a test in which an objectionable odor was introduced into one nostril of a subject at the same time that a dis- .per-sion in air of the deodorant hydrocarbons'of this invention was introduced into the other nostril of the same subject. The odor was controlled (cancelled) as far as the subject was concerned although the odorous air and theair containing the hydrocarbons never came in contact. i I I I .The deodorant hydrocarbons of this invention solve many problems. Since they are extremely non-reactive and substantially odorless, it is possible to formulate a wide variety of aerosol compositions. Corrosion has always been a problem in aerosol oans, particularly those made of metal,. as for instance, iron, aluminum and the like. Thedeodorant hydrocarbons of this invention are not corrosive to metals, and therefore, permit a wider selection of materials for an aerosol container than would be possible with conventional oxidizing deodorizing agents. Even the more non-reactive conventional deodorizing agents, such as strong perfumes, often require somekind of anti-oxidant to prevent corrosion and degradation of the deodorizing agent. This is not necessary cluded in theformulation than can be included with the conventional deodorizing agents. With conventional deodorizing agents, and especially oxidizing agents, many perfumes are ruined upon prolonged storage.

The odorless nature of the deodorant hydrocarbons of p this invention also contributes to their utility (although cancellation of an objectionable odor with the substitution of a less objectionable odor may be desirable in some situations). This permits the torrnulation of an odorless product or the use of a perfume in a deodorant product without having to consider the effect of the odor of the deodorizing agent. Therefore, the deodorant hydrocarbons of this invention are especially suited for use in an I aerosol whereas conventional masking deodorizing agents are not. These deodorant. hydrocarbons are unique in combining effective odor control, low odor, and low chemical reactivity.

The concentration range of about 0.3% to about 15% by weight of the product for the hydrocarbons of this invention in an aerosol is set on the basis of performance. With lower concentrations than about 0.3%, the cost to the consumer of using the product would be prohibitively expensive, since to achieve adequate performance, a relatively large amount of the product would have to be used. With larger concentrations than 15%, the residue tends to become objectionable and the odor of some hydrocarbon' cornpoundsmay become noticeable. Solubility of large concentrations of the hydrocarbons in the propellant may also become a problem with certain propellants such as the chloroiluoromethanes and ichlorofluoroethanes.

' This concentration range is especially important based upon the normal usage of aerosol room deodorants which is about two to three grams per usage.

The aerosol propellant should be selected with care.

First it must provide the proper amount of pressure in order to achieve an adequate dispersion of the active deodorant material in air. From 0 to 115 pounds per square inch absolute (at about 70 C.) is preferred. Ideally, the propellant is not flammable. From this standpoint, the halogenated hydrocarbons and inorganic propellants are preferred whereas such propellants as N butane, isob-utane, and propane are not. However,

some halogenated hydrocarbons such as methylene chlor'id-e tendto cause corrosion in metal cans in the presence of waterwhere they-react to dorm hydrochloric acidwhile N-butane, isobutane, and propane do not. Some halogenated hydrocarbons also have odors of their own which would beunacceptable in an odorless-product but which could betolerate'd in some I can also pose a toxicity problem. The inorganic prolants.

perfumed products, and some pellants such as nitrogen gas are not suitable from the standpoint-that a single phase product is desirable and; p the deodorant hydrocarbons of this invention cannot form a single phase with the compressed gas inorganic propel However, two phase products can be used, although they may requireagitation prior to use. From the standpoints of odor, corrosiveness, chemicalinertness, flammability, and toxicity, a mixture of-trichlorofluoromethane and dichlorodifluoromethane is preferred.

if flammability is not a problem and if lower cost is desirable, the saturated hydrocarbon propellants areuserul. Isobu-ta'ne and-N-butane are best from the standpoint of a propervapor-pressure, but propane and'pentane are also useful and in mixture s can provide the same vapor pressures as isobutaneand N-butane. Mixtures of these hydro-carbon propellants with chloroand/or fluoro substi-t-uted hydrocarbons can give the proper vapor pres,-

sure and eliminate flammability While lowering cost as I compared with the pure chloroand/ or fluor o-substituted 7 suitable vapor pressure when used alone, butthey can be used in mixtures so long as the mixture has a proper vapor pressure and the mixture is compatible.

It will be understood that the propellant must be chosen in view of the finished product, and that suchf'considerations as odor, flammability, toxicit chemical reactivity,

corrosiveness, availability,cost, and vapor pressure of the individual propellantwill determine whether his selected,

either aloneor as part of a mixture, for a given-product. Once a suitable propellant has been selected, the loading of the aerosol container is carried out by conventional procedures which will not be described here in :detail I but which may be found in Pressurized Packaging, Herska, I

A., and Pickthall 1;, chapter V, pp. 106-123, Academic Press,- Inc.' (1958). j v I i T Suitable additives to the compositions of this invention, but which are not necessary, include perfumes and such anti-bacterial agents as quaternary ammonium compounds (e.g., benzethonium chloride), propylene glycol, tr-iethylone glycol, and halogenated hydrocarbons (e.g., hexachloro-phene). A normally solid anti-bacterial agent is preferably used with anon-volatile solvent to prevent the formation of an irritating dust when the composition is sprayed into the atmosphere. I

v The following examples illustrate the practice of this invention and the advantages which accrue from the com:

positions and process of this invention Example I The tollowing table' compares compositions comprising the various ,deodoranthydrocarbons or this invention and certain lower homologs based upon the following test method. I

Ethyl mercaptan, chopped onions, and cigarette butts I were placed, respectively, in three separate one gallon jars. Suflicient odoriferous air from these jars was placed in three similar one gallon jars'to create odors of a su fficient strength that it took six 1 to 10 dilutions (one part I of the odoriferous air plus nine partsfresh air) to reach a dilution where the odor was not detectable (threshold) in the case of ethyl mercaptan and live such dilutions in the case of the onions and cigarettes. This odoriferous air provided the standard concentrations of odors for this test 0.5 -gm.. of pressurized aerosolcompositions ,convtaining 1% of the testmaterials listed below and the tially odorfree.

balance propellant, were these-standard concentrations of odors. (The propellant was a 50/50 mixture of trichlonofiuoromethane and dichlorodi-fluoromethane.) The IlLlIIlbfiP-Of to dilu-' T tions with :fresh air needed to reach a 'thresholdodor for each of the jars was then determined. The same procedure was followed withan aerosol containing only propellant, which served as a blank.

sprayed into jars'containing 1-hexadecene, 1.0% denatured alcohol, 0.21% of a perfume and the rest a 50/50 mixture of trichlorofluoro- Another set of jars with the same three standard concentrations of odors were injected with 0.5 gm. samples of the aerosol composition-s until the threshold odor was reached. This procedurewas also followed using the propellant blank. 1 V Y Thus, in this test there were u ee numbers obtained for each compound and three. numbers for the blanks.

The first number was the sumof the number of dilutions required to reduce all three odors (standard concentrations) to a threshold level. The second number was the sum ofthe number of dilutions required to reduce all three odors to ath-reshold level after the standard odor concentration had been treatedwith 0.5 gm. of the test material or blank. The third :figure was the sum of the number of 0.5 gm.--injections of the test material or blank required to reduce the standard odor concentration to the threshold level.

These three numbers were combined arbitrarily to give a single performance number which reflects the de-.

odoran-t performance of the individualoompound. The

sum of the last two numbers .of the three is subtracted .fir-om the first number to give this performance number.

The slight deodorization effect of the propellant is acmethane and diehlorodifluoromethane. The product had onlythe pleasant odor of the perfume.

This composition was used on the usual home odors and was found to be an effective deodorant.

Example I V An aerosol air deodorizzing composition was prepared with 2.0% l-hex-adecene, 0.0004% pine needle oil, andthe rest a 50/ 5'0 mixture of trichlorofluoromethane and t i The composition was packed dichlorodifiuoromcthane. in aconventional aerosol can. The product itself was substantially odor free to observers.

This composition was usedwith the usual home odors and found to be an effective deodorant.

counted for by computing the performance number for the blank and then subtracting this from the performance number of the test material to give a corrected performance number. This has the efieot of making the performance number of the blank equal to -zero. All figores in the following table are corrected performance numbers.

Compound Oct ne Decene Dodecene Tefiradet'sno Hexadecene Octadpr'smp Decane Dodecane l Theseexamples were part of the screening test and roughly indicate the relative deodorant performance of some of the representative individual compounds of the O -C aliphatic hydrocarbons of the compositions of this invention. The good performance numbers of the lower homologs are accounted for in part by the masking effect of their own odor.

Example II A pressurized aerosol air deodorizing composition was prepared which contained 1.4% l-hexadecene, 1.0% denatured alcohol, 0.07% lhexachlorophene, and the balance a 50/50 mixture of trichlorofiuoromethane and dichlorodifluoromethane. The product was packed in a conventional aerosol container. The product itself was substan- This product was .used on the usual cooking, cigarette and bathroom odors found in the home to provide concentrations of l-hexadecene ranging from 0.1 to 10 p.p.m. in the air; the product was found to be an effective, odorless deodorant. t. i

Example Ill An aerosol air deordorizing composition, packed "in a conventional aerosol can. Was prepared containing 1.4%

Number chlorodifiuoromethane, methylene. chloride, N-butane,'

Example V An odorless aerosol air deodorizing composition was prepared with 1.5% hexadecane, 0.5% deodorized kerosene, and the rest a 50/50mixture of triohlorofluoromethane and dichlorodifluoromethane. The composition was packed in a conventional aerosol can.

This composition was used with the usual home odors and was found to be an effective deodorant.

Example VI An odorless aerosol air deodorizing composition was prepared with 3.0 gm. l hexadecene, 1.4 gm. denatured ethyl alcohol, 0.1 gm. hexachlorophene, and 136 gm. of-a 50/50 mixture of trichlorofluoromethane and diclhlorodifluoromethane and packed in a conventional aerosol container. The product was substantially odor free.

This composition was used on the usual home odors and was found to be an efiective deodorant.

Example Vll An odorless aerosol air deodorizing composition was prepared with 4.0% ootene-l dimer and the rest .a50/50 mixture of tr-ichlorofluor'omethane and .dichlorodifiuoromethane. The composition was packed in a conventional aerosol container. The product itself was substantially odor free.

All percentages in the preceding examples were by weight of the total product. i

Carbon dioxide, nitrous oxide, argon, nitrogen, difluoroethane, isobutane, trichloroiiuoromethane, chlorodifiuoroethane, octafluorocyclobutane, isopentane, N-pentane, di-

propane, vinyl chloride, and mixtures of the above can be substituted for the propellantin the preceding ex-' ceding examples with substantially equivalent results.

hydrocarbons, and mixtures thereof, the balance being an aerosol propellant capable of providing a pressurefrom What [is claimed is:

l. A pressurized deodorantcomposition comprising from about 0.3% to about 15% by weight of the composition or a deodorant hydrocarbon containing from 12 to 18 carbon atoms, said hydrocarbon containing not more than about our branched chains having from about one to about two carbon atoms, and said hydrocarbon. being selected from the group consisting of aliphatic on saturated hydrocarbons containing from one to three multi-bond carbon to carbon linkages, aliphatic saturated methane;

pounds per square inchabsolute in the aerosol container under conditions ofznormal use." p 2. The compositionofclaim l in which the deodorant ,hydrocarbon is a straightohain compound and the aerosol propellant isJselectedl-from the group consisting of isobutane, trichlorofluoromethane, dichlorodiiiuoromethane,

and mixtures thereof.

mixture of trichlorofluorome-thane and dichloro difiuoroa methane.

'. The composition ofclaim 1 in which the'hydrt Q.;1 ;part per million of said air 'and in a concentration :sufficie'nt to control the odor in said air of deodoranthy 31The composition of'clairn 1 in which the hydrocar- :b'on is hexadecane and the aerosolpropellant isv a mixture jg "o f trichlorofluoromethane and dichlorodifluorornethane.

carbon is l-hexadecene and the aerosol propellant is a.

imixtu'retof trichlorofluorornet'hane and dichlorodifluorot 6. The" composltlon of claim 5 containing a minor 4 amountof pine-needle oil.

drocarbons containingflfrom 12'to 1l8lcarbon'eitoms, said i hydrocarbons containingnot rnore than about iour' branched jchains having from about one'to; about two carbon atoms, and saidhydrocarbons being selected from the' group consisting of aliphatic-unsaturatedhydrocar bons containingfrom one to three multi-bond carbon to carbon linkages, aliphatic saturated .hydroc' iarbons, and

mixtures thereof. 8. 'T'he'pro'cess of cla' A 7 in the hydrocarbons are dispersed in ainbyjneansto f an aerosol propellant. V

Referencesfliterl in the file 'of this patent UNITED STATES PATENTS 588,766 Ekenberg tAu .-24, 1897 Joy et a1. 5"

about pounds per square inch absolute to about I p t 7. The process of 'deodorizing' odor containing air comprising thestep of dispersing inair, not less-than-about'

Claims

1. A PRESSURIZED DEODORANT COMPOSITION COMPRISING FROM ABOUT 0.3% TO ABOUT 15% BY WEIGHT OF THE COMPOSITION OF A DEODORANT HYDROCARBON CONTAINING FROM 12 TO 18 CARBON ATOMS, SAID HYDROCARBON CONTAINING NOT MORE THAN ABOUT FOUR BRANCHES CHAINS HAVING FROM ABOUT ONE TO ABOUT TWO CARBON ATOMS, AND SAID HYDROCARBON BEING SELCTED FROM THE GROUP CONSISTING OF ALIPHATIC UNSATURATED HYDROCARBONS CONTAINING FROM ONE TO THREE MULTI-BOND CARBON TO CARBON LINKAGES, ALIPHATIC SATURATED HYDROCARBONS, AND MIXTURES THEREOF, THE BALANCE BEING AN AEROSOL PROPELLANT CAPABLE OF PROVIDING A PRESSURE FROM ABOUT 30 POUNDS PER SQUARE INCH ABSOLUTE TO ABOUT 115 POUNDS PER SQUARE INCH ABSOLUTE IN THE AREOSOL CONTAINIER UNDER CONDITIONS OF NORMAL USE.