WO1996024387A1

WO1996024387A1 - Deodorizing and anti-soiling composition

Info

Publication number: WO1996024387A1
Application number: PCT/US1995/014256
Authority: WO
Inventors: Robert D. Harris
Original assignee: Harris Research, Inc.
Priority date: 1995-02-09
Filing date: 1995-11-06
Publication date: 1996-08-15
Also published as: CO4650224A1; AU4101196A; PE37496A1; ZA961028B

Abstract

A composition for removing odors from fabrics and hard surfaces and inhibiting soiling of these surfaces is made up of a combination of a water soluble deodorizing component comprising an essential oil fragrance, a surfactant and a water soluble low molecular weight polymeric component in an aqueous carrier. The deodorizing component and polymeric component are both soluble in the aqueous carrier and compatible with each other such that when the aqueous carrier is removed following application to a material surface as by drying or evaporation, the deodorizing component is retained within the polymeric component and the fragrance and mal-odor agent, if present, are slowly released therefrom. The composition can be applied as sprays, such as from aerosol cans, or can be admixed with other solutiosn such as for cleaning and/or stain removal and then applied in any conventional manner. The preferred polymer is a styrene maleic anhydride copolymer.

Description

DEODORIZING AND ANTI-SOILING COMPOSITION

This invention relates to compositions that function to deodorize confined spaces and materials and impart anti-soiling properties to surfaces of such materials. More particularly this invention relates to water based liquid room and surface deodorizers and anti-soiling compositions that have a sustained release effect particularly when applied to materials such as textile fibers, and carpeting, drapery or upholstery in particular.

In the past, most deodorants for carpets or other surfaces of materials having a porous or permeable nature, were in the form of powders. These have to be applied to the carpet or other similar permeable material and let stand for some time in order to absorb odor forming materials and/or emit a fragrance. In the case of carpets, the carpets then have to be vacuumed to remove the powders and prevent buildup of the powder in the textile fibers, backing or other porous materials. This is time consuming and requires at least two steps with a time lapse in between i.e., applying the powder, letting it remain for a time interval and then vacuuming it up.

Liquid based deodorizers and/or reodorizers have not heretofore been effective nor efficient for use on porous materials. Most liquid fragrances are based on essential oils and require the presence of organic solvents such as alcohols, ketones, aliphatic and aromatic hydrocarbons and the like in order to keep the essential oil in solution until it is applied to a material surface. Once the solvent has evaporated, leaving the essential oil fragrance, it tends to become sticky and form a residue on the surface to which it was applied. Such a residue actually contributes to the resoiling of the surface of the material to which it adheres .

Some liquid deodorizers, in the place of or in addition to an organic solvent, contain a surfactant. By "surfactant" is meant a synthetic amphipathic molecule having a large non-polar hydrocarbon end that is oil- soluble and a polar end that is water soluble. Soap is also an amphipathic molecule made up of an alkali salt, or mixture of salts, of long-chain fatty acids wherein the acid end is polar or hydrophilic and the fatty acid chain is non-polar or hydrophobic. Surfactants are further classified as non-ionic, anionic or cationic. Anionic or nonionic surfactants are the most common.

The use of surfactants enables essential oils to become soluble, or at least emulsifiable, in water. Hence, a water based deodorizer of sorts can be prepared. Surfactants and soaps function because the hydrophobic ends of the molecules are soluble in the essential oils and the water soluble hydrophilic (polar) ends are soluble in water and help to solubilize or disperse the essential oils in an aqueous environment . One problem associated with the use of surfactants is that, once water is removed, they generally leave an oily hydrophobic coating on surface to which they have been applied. The inherent oily nature of the hydrophobic end of the surfactants causes premature resoiling of a textile fiber or other permeable surface even when the material surfaces have a surfactant coating which is only a molecule thick. The greater the concentration of surfactants used, the greater the potential for resoiling. Hence, the indiscriminant application of surfactants and essential oils to a porous material surface can promote resoiling properties to the surface to which they have been applied. When a powdered deodorant has been applied to a carpet surface and then removed, such as by vacuuming, the effectiveness of the deodorant is limited because of the very nature of its application and subsequent removal. It would be desirable to have a deodorant that would remain on a porous surface over an extended period of time without contributing to the resoiling of such surface and which would continuously act to counteract and remove odors and provide the surface and surrounding atmosphere with a pleasant, fresh, natural fragrance.

OBJECTS AND SUMMARY OF THE INVENTION It is an object of the present invention to provide an aqueous odor removing, deodorizing, soil inhibiting compositions that can be applied to permeable material surfaces such as textiles as well as to hard surfaces.

It is also an object of this invention to provide a water based deodorizing and soil inhibiting composition containing essential oils and surfactants that can be applied as a liquid to a porous material surface and which simultaneously counteracts malodorous properties and inhibits soiling on such surfaces. Another object of this invention is to provide a water based deodorizing and anti-soiling composition containing no organic solvents which is suitable for application to porous substrates.

Yet another object of the invention is to provide a water based composition for application to textile fibers which provides anti-soiling properties, counteracts malodorousness and has a sustained release of fragrance.

These and other objects may be accomplished by means of a composition comprising a combination of a water soluble deodorizing component comprising an essential oil fragrance, a surfactant and an optional mal-odor agent and a water soluble low molecular weight polymeric component in an aqueous carrier. The deodorizing component and polymeric component are both soluble in the aqueous carrier and are compatible with each other such that when the aqueous carrier is removed following application to a material surface, as by drying or evaporation, the deodorizing component is retained within the polymeric component and the fragrance and mal-odor agent, if present, are slowly released therefrom.

The polymeric component dries to a crystalline structure which adheres to the surface to which it has been applied and the surfactant, essential oil fragrance and mal-odor agents are contained by the polymer and do not display the conventional tacky or sticky residue characteristics traditionally found in these components.

As a result, the surface containing the composition actually resists soiling because the polymer attaches to the surface of the material and prevents soil from coming into contact with and adhering to such a surface .

This is particularly important in the case of carpet or other textile fibers.

The compositions can be applied as sprays, such as from aerosol cans, or can be admixed with other solutions such as used for cleaning and/or stain removal and then applied in any conventional manner. In either event, a single application is all that is required to impart both deodorizing and anti-soiling characteristics to the surface to which the compositions have been applied and there is no need to remove residue following the application as in the case of deodorizing powders and the like.

DETAILED DESCRIPTION OF THE INVENTION

It will be appreciated that the invention disclosed herein can be useful in deodorizing and imparting soil resistant properties to any material surface. However, it is particularly suited to application to textile fibers such as carpeting, drapery and upholstery.

As used herein, "porous material surface", "permeable material surface", "carpet", "textile fibers", "upholstery", "drapery" and any other similar term refers to a material or object having a large surface to mass or size ratio and is therefore capable of containing soil, odor producing particles, and the like within the confines of said material or object. The invention is particularly suited for the treating of carpets and that will be illustrated as the preferred embodiment. However, any other types of materials such as upholstery or drapery could be treated in an equally effective manner.

The term "hard surface" will refer to objects which are relatively non porous such as tiles, vinyl flooring, lavatories and kitchen appliances, doors, and similar types of objects. The term "polymer", "copolymer", "water soluble polymer" or "water soluble copolymer" means any polymer having a low molecular weight, is water soluble and is compatible with the deodorizing components as described herein and, when applied as an aqueous solution with the deodorizing components, dries to a crystalline coating on the surface to which it is applied. The preferred polymer is a water soluble styrene maleic anhydride copolymer which had been rendered water soluble by converting the anhydride functionalities to ammonium salts by the addition of ammonia. It is technically referred to as 2,5-furanidone, polymer with ethenylbenzene, ammonium salt and will be described more in detail below.

The term "odor controlling agent" means an essential oil, mal-odor agent or a combination of both.

The terms "essential oil", "essential oil fragrance", "fragrance", "perfume" or the like refers to a single olfactory ingredient or combination(s) of olfactory ingredients, which may be natural or synthetic, which are generally oleophilic in nature and which convey a scent or fragrance pleasing to the smell and which preferably mimic or duplicate the scent of flowers, plants, fruits, trees, sea breeze, mountain air, and any other favorable smell. "Mal-odor agents", "odor destroying agents" or similar terms refer to components which are similar in some respects to essential oils and which either function to destroy unpleasant odors by means of masking, neutralizing, the chemical breakdown of or attaching to or blocking the olfactory sites in an individual which detect unpleasant odors. Surfactants are as defined above. However, for purposes of the present invention nonionic or anionic surfactants or detergents are preferred with nonionic surfactants being particularly preferred. Deodorizing Component: The deodorizing component contains a balanced mixture of an essential oil fragrance, a surfactant and, optionally, a mal-odor agent which is preferred but is not required.

Surfactants:

The surfactant functions to solubilize the essential oil fragrance and render it compatible with the polymer component. The only limit as to the surfactant is one of functionality. Therefore cationic, nonionic and anionic surfactants may all be utilized within the scope of the invention. Nonionic and anionic surfactants are preferred with nonionic surfactants being particularly preferred.

Suitable classes of nonionic surfactants are alkyl phenol-ethylene oxide condensates, polyoxyalkylene alkanols and condensation products of a fatty alcohol with ethylene oxide.

The alkyl phenol-ethylene oxide condensates have the general formula: R-Ar-0- (-CH₂CH₂0-)_nCH₂CH₂OH where R is an alkyl moiety having from nine to twelve carbon atoms, Ar represents an o, or p-phenylene group, and n is an integer of from eight to fourteen. Representative surfactants in this group are dodecyl phenol condensed with an average of ten moles of ethylene oxide (R is C₁₂, n is 9) sold under the tradename "Sterox DF", nonyl phenol condensed with an average of nine or ten moles of ethylene oxide (R is ₉, n is 8 or 9) sold under the tradnames Triton N101, Igepal CO-630 and Tergitol NPX, and dodecyl phenol condensed with an average of fifteen moles of ethylene oxide (R is C₁₂, n is 14) .

Another nonionic surfactant class, which is low sudsing, is represented by the polyoxyalkylene alkanols of the formula:

HO- (CH₂CH₂0), (CH₂CH₂CH₂0)_b(CH₂CH₂0) _CH wherein b is an integer from 26 o 30 and a plus c is an integer such that the molecule contains from about 0 to 20 percent ethylene oxide groups. Representative examples include a surfactant sold commercially as Pluronic L-61 where b is an integer from about 26 to 30 and a plus c is an integer such that the molecule contains from 10 to 20 percent of ethylene oxide. Another example is Pluronic L-60 where b is an integer from about 26 to 30 and a and c are zero such that the polyoxyalkylene alkanol is entirely polyoxypropylene propanol .

Yet another class of nonionic surfactant are condensation products of a fatty alcohol with ethylene oxide having the formula:

R' -O- (CH₂CH₂0)_nH where R' is a C₁₀ to C₂₀ alkyl group, preferably straight chained, and m is an integer of from about 5 to 14. The alkyl group of these surfactants can vary from a C₁₀ to a C₂₀ within the same mixture due to method of manufacture. Such surfactants usually contain both a mixture of alkyl groups and a mixture of ethylene oxide chains, e.g. where m is also a mixture. Representative products are sold under the tradenames Neodol 27-5 and Neodol 41-11 where R' is mixed alkyl from 12 to 15 and 14 to 15 carbon atoms respectively and m is an average of about 11. Another surfactant, also containing (CH₂CH₂CH₂0) groups, is sold under the tradename Plurofac 8 B-26 and is a linear alcohol reacted with a mixture of both ethylene and propylene oxides .

Anionic surfactants which can be used include straight and branched chain alkylaryl sulfonates wherein the alkyl group contains from about 8 to 15 carbon atoms; the lower aryl or hydrotropic sulfonates such as sodium dodecyl benzene sulfonate and sodium xylene sulfonate; the olefin sulfonates, such as those produced by sulfonating a C₁₀ to C ₂₀ straight chained olefin; hydroxy C₁₀ to C₂₄ alkyl sulfonates; water soluble alkyl disulfonates containing from about 10 to 24 carbon atoms, the normal and secondary higher alkyl sulfates, particularly those having about 8 to 20 carbon atoms in the alkyl residue; sulfuric acid esters of polyhydric alcohols partially esterified with higher fatty acids; the various soaps or salts of fatty acids containing from 8 to 22 carbon atoms, such as the sodium, potassium, ammonium and lower alkanol-amine salts of fatty acids and sarcosinates of fatty acids.

Preferred anionic surfactants are those having the formula:

R\AM' wherein R¹ is C₈ to C₂₀ alkyl, aralkyl, or alkaryl; A is a sulfate (S0₄) , sulfonate (S0₃) , or sarcosinate

(CON(CH₃)CH₂COO) radical; M' is a positive ion selected from the group consisting of sodium, potassium or R"₄N wherein R" is H, methyl, ethyl or hydroxyethyl . Typical alkyl groups include decyl, lauryl (dodecyl) , myristyl

(tetradecyl) , palmityl (hexadecyl) and stearyl

(octadecyl) . Typical aralkyl groups include 2- phenylethyl, 4-phenylbutyl and up to 8-phenyloctyl and the various isomers thereof. Alkaryl groups include all ortho-, meta- and para- alkyl substituted phenyl groups such as p-hexylphenyl, 2,4, 6-trimethylphenyl and up through p-dodecylphenyl . Specifically included are alkylbenzene sulfonates, alkyl sarcosinates and alkyl sulfates. Particularly preferred are sodium, potassium, ammonium and lower alkyl or aryl amine salts of C₈ to C₂₀ alkyl sulfates. The most preferred surfactants are the salts of lauryl sulfate, i.e. sodium lauryl sulfate, ammonium lauryl sulfate, potassium lauryl sulfate, and the mono-, di- and tri-ethanolamine salts of lauryl sulfate.

Odor Controlling Agents:

As noted above, odor controlling agents may consist of essential oils, mal-odor agents or combinations thereof.

Essential Oils:

Most fragrances were initially derived as extracts from plants and were called "essential oils", because they contain the essence, i.e. the odor or flavor, of the plant. They are volatile oleophilic substances which provide the plant with its fragrance and flavor. Hence, they have been uses extensively in perfumery and as flavoring agents. Today, many fragrances are synthetically produced but most are related to the "essential oil" structure and/or chemistry.

Compounds generally known as terpenes or terpenoids are major constituents of essential oils. Most terpenes have a carbon skeleton of ten (monoterpenes) , fifteen (sesquiterpenes) , twenty (diterpenes) or thirty

(triterpenes) atoms. Another class of compounds extracted as essential oils from plants include certain phenols and phenolic ethers. Another group of compounds extracted from plants are volatile alkyl esters having a fruitlike fragrance.

Representative of various terpenes or terpenoids are myrcene (from bayberry oil) , d-limonene (from oil of lemon or orange) , citronellol (from rose oil) , linalool

(flowers of ylang-ylang) , geraniol (from roses, gingergrass and other plants) , menthol (from peppermint oil) , citral (oil of lemon grass) , a- and -S-pinenes (from terpentine oil) , camphor (from camphor tree) , ascaridole (chenopodium oil) , α-irone (oil of violets) , farnesol (ambrette-seed oil or lilly of the valley scent) , bisabolene (widely found in many plants) , caryophyllene (oil of cloves) , cedrol (cedar-wood oil) , α-farnesene (from oil of citronella) , guaiazulene (geranium oil) , zingiberene (from oil of ginger) .

Representative of various phenols and phenol ethers are eugenol (oil of cloves) , isoeugenol (oil of nutmeg) , anethole (oil of aniseed) , vanillin (oil of vanilla bean) , thymol (oil of thyme and mint) and safrole (oil of sassafras) .

Representative volatile aliphatic esters are n- butyl acetate (oil of bananna) , n-octyl acetate (oil of orange) , methyl n-butyrate (oil of pineapple) , n-amyl butyrate (oil of apricot) , isoamyl butyrate (oil of pear) and isoamyl isovalerate (oil of apple) .

The essential oil and fragrance industry is highly complicated and proprietary. Many fragrances are blends of various essential oils, the identity of which is regarded as being eminently confidential. It is not the purpose of this invention to claim any novel fragrance. However, it is noteworthy that almost all fragrances are designated as "oil of (plant name)". In other words, such fragrances are primarily oleophilic or hydrophobic (oil soluble) in nature and are not easily utilized except in the presence of an organic or hydrocarbon based solvent or carrier. This is not conducive to their use in water based systems.

Mal-odor agents:

Not all fragrances are pleasant to the smell . An odor is registered by a subject, i.e. human or other animal, only when the agent or chemical compound particular to that odor (e.g. terpene, phenol, ester, etc.) comes into contact with an olfactory receptor in the membrane in the upper part of the nasal cavity and is communicated to the brain by stimulation of an olfactory sensory nerve. If that agent or chemical compound is (1) chemically destroyed, (2) overpowered or masked by more potent or different olfactory agents or

(3) blocked from reaching the olfactory receptor site, it will not be "smelled" or sensed by that subject. For example, when one has a "cold" or the "flu", the sense of smell is often lost or diminished because of the swelling in nasal cavity that prevents such agents from reaching the olfactory membrane. It is believed that many mal-odor agents either chemically react with objectional odor causing agents to render them innocuous or preferentially attach to olfactory receptors in the olfactory membrane thereby preventing objectional odor agents from adhering to such receptors. Mal-odor agents are also regarded as being highly proprietary and are therefore generally referred to by tradename only. However, it is thought that such mal-odor agents are comparable to essential oils in being oleophilic in nature. Alternatively, such agents may neutralize or break down the objectionable odor in which case they could be either hydrophilic or oleophilic. One commercial mal-odor agent useful in the present invention is a formulation containing a metal salt of a C₁₈ carboxylic acid which additionally contains solubilizers that are considered proprietary to the manufacturer, AFF, Inc. of Marietta, Georgia and is sold under the tradename, VALEX.

It is therefore essential to the deodorizing component of present invention that the essential oils and mal-odor agents, if used, be combined with a surfactant which is compatible with both the essential oil and/or mal-odor agent and the polymeric component so as to be useful for application in water based systems.

The amount of surfactant to use is quite empirical and will depend on a great extent on the particular surfactant and the strength of the fragrance in the essential oil or amount of mal-odor agent. Some surfactants function better than others. For example, the nonionic surfactants appear to be more compatible with the essential oils than are the anionic surfactants. In the tests conducted thus far it appears to take more anionic surfactant to solubilize the same amount of essential oil than it does for a nonionic surfactant . The only necessary criteria seems to be that sufficient surfactant must be used to take the essential oil fragrance and the mal-odor agent into an aqueous solution. Preferable the essential oil and mal-odor agent will be dissolved in solution. However, emulsions and/or suspensions, can also be used provided that they are compatible with the polymeric component in an aqueous solution and can be incorporated into the polymeric component to form an overall crystalline structure on a substrate after the water carrier has been removed, i.e by evaporation or drying.

In tests conducted it has been found that about a 1:1 weight ratio of surfactant to essential oil/mal-odor agent is about optimal in solubilizing the essential oil/mal-odor ingredients. When using certain anionic surfactants that ratio may increase to something like 2:1 surfactant to essential odor/mal-odor agent ratio. Again, the only limitation to the relative amounts of surfactant to essential oil and mal-odor agent is that which is functional in meeting the criteria stated above. Such criteria might be met by ratios as broad as 5:1 to 1:3 surfactant to essential oil/mal-odor agent. Generally, that range will be between about 3:1 and 1:2.

Polymeric Component:

The polymer component can be any polymer which meets the functional characteristics of being low molecular weight, water soluble, compatible with the deodorizer component, adheres to the material to which it is applied, dries to a crystalline state on the 13 material surface retaining within the polymer matrix the deodorizer component but is sufficiently flexible on the surface to continue to adhere thereto even in the event of certain distortion or bending. In other words, when the polymer adheres to textile fibers, e.g., on a carpet, foot traffic may cause certain cracking or fracturing to the polymer but it will remain on the fiber surface. Such cracking or fracturing serves to increase the polymer surface area allowing additional volatile fragrance or mal-odor agents to be released. It is believed that such a polymer functions in protecting the textile fiber from soiling because the sites on the fiber to which soil or residue could attach or adhere are already blocked because that site on the fiber has been attached to the polymer. Preferably such a polymer will have a molecular weight which is below about 3000 and above about 400 and will preferably be between about 1400 to 1800. It will have hydrophilic sites or be primarily hydrophilic in order to be water soluble but, at the same time, must be compatible with the surfactant, and essential oil fragrance and, if used, the mal-odor agent.

One such polymer meeting these characteristics is a styrene maleic anhydride copolymer wherein the anhydride groups are hydrolyzed and the resulting carboxylic acid functionalities are reacted with a base to form a salt, such as an ammonium salt. A preferred water soluble polymer contains between about one to three styrene units and one to three maleic anhydride units and is reacted in an aqueous solution with ammonia or an amine which neutralizes the carboxylic acid functionalities and forms a soluble ammonium or primary, secondary or tertiary amine salt. Preferably, the ratio of styrene unites to maleic anhydride units will be about 1:1 but some variance either direction, i.e. from 3 : 1 to 1 :3 may occur. Ammonia (ammonium hydroxide) is the preferred reactant. A particularly preferred polymer contains about 35 to 60% by weight maleic anhydride, 35 to 60% styrene and 10 to 25% ammonium salt functionalities and is technically named as a 2,5- furandione polymer with ethenylbenzene, ammonium salt. This polymer, referred to herein as "SMACAMS" (styrene maleic anhydride copolymer ammonium salt) , will be utilized in demonstrating the preferred embodiment. This copolymer is commercially available under the tradename SMA 1000 from Atochem, Inc. in Malvern, PA.

The copolymer is prepared by the free radical copolymerization of styrene and maleic anhydride to form a styrene-maleic anhydride (2, 5-furandione ethenylbenzene) copolymer of the formula:

where x represents about 1 to 3 styrene units, y represents about 1 to 3 maleic anhydride units and n is an integer or from about 1 to 10. The numbers represented by x and y are not necessarily whole integers . The copolymer thus prepared is not water soluble but upon being reacted with an aqueous base, such as ammonium, sodium or potassium hydroxide, the anhydride is hydrolyzed to the maleic acid unit and the corresponding salt of the base is formed having the formula: r I

-CH-CH₂-—- -CH- -CH-

C₆H₅ 0=C c=o

O. o. z* z⁺ n where Z is a member selected from the group consisting of NH₄, Na and K and x, y and n are as represented above. Preferably the base will be ammonium hydroxide, in which case a water soluble styrene maleic anhydride copolymer ammonium salt (SMACAMS) is formed having the formula:

where x, y and n are as represented above.

In the above formula, the ratio between x (styrene units) and y (maleic acid ammonium salt units) is preferably between about 3:1 and 1:3 with a ratios of about 1:1 being most preferred. This SMACAMS copolymer salt will preferably have a molecular weight in the range of about 1400 and 1800 and contain between about 35 and 60% by weight styrene units, 35 and 60% by weight maleic acid units and 10 and 25% by weight ammonium salt cations. Such a copolymer is sufficiently water soluble and is fully compatible with the deodorant components of this invention. Combined Deodorizing and Polymeric Component Compositions:

The water soluble copolymer component is prepared and utilized as an aqueous solution containing between about 20 to 50% solids or copolymer content. The relative amounts of deodorizing component and copolymer component to be combined is again limited only by that which is functional. There must be sufficient copolymer present to contain the deodorizing component once the aqueous carrier is removed from the substrate to which the composition has been applied. Weight ratios of between about 2:1 to 1:2 deodorizing component to copolymer are considered to be adequate. However, while less preferable ratios outside these ranges are also intended to be within the scope of this invention to the extent that they are functional.

The compositions containing the combined deodorizing/polymeric components are prepared and applied in an aqueous solution. Typically a polymer solution having a solids content as described above will be admixed along with the deodorizing component in a water carrier such that the solids content of the deodorizing component and actual copolymer solids in the copolymer component solution are in the range of about 0.5 to 25% by weight. The upper limit is dictated only by the solubility of the components in the aqueous phase and the viscosity of the solution. It must be sufficiently fluid to be applied to a substrate as a spray and to coat the material surface. When applied to textile fibers, such as a carpet, the solution must be able to penetrate the fibers so as to form a polymeric coating which contains the deodorizing component on the fibers once the solution has evaporated or otherwise removed from the fibers.

When being applied as a pressurized spray, as from an aerosol can, it is most economical to have as concentrated a solution as will exit the spray nozzle and thoroughly coat the textile fiber before it dries. It has been found that concentrations of up to 25% by weight can be utilized in this manner. On the other hand, when being used as an additive to a cleaning solution containing natural cleaning ingredients, or synthetic surfactants, such as disclosed in pending patent applications Serial Numbers 335,113 and 335,114, both filed November 7, 1994, a concentrate of the solution may be diluted to have a solids content, attributable to the deodorizing component and soluble copolymer, as low as 0.5% by weight of the overall solution.

For some applications, it may be advisable to adjust the concentration of polymer in the solution to provide antisoiling properties similar to that of the fabric before being treated. This is particularly true when the composition is being applied for deodorizing purposes and a uniform application is not necessary. If the composition is applied in an erratic or variable pattern, the portions of the carpet or other fabric receiving the treatment may have antisoiling properties which are superior to that of the untreated portion resulting in an inconsistent appearance when the carpet other is soiled, or further soiled. For example if the composition is to be applied to a surface, with or without being cleaned, it may be desirable to apply the composition such that the polymer, containing the essential oils and surfactant, essentially match the soiling or antisoiling properties of the untreated portions of the surface. On the other hand, if the carpet or other fabric being treated is being cleaned simultaneously with the treatment, it will be desirable to uniformly apply the composition and adjust the concentration of the polymer to provide optimal antisoiling properties. The following examples illustrate the invention but are not intended to be limitations thereof. Example 1

An aqueous solution was prepared by mixing 3 parts by weight of a combined fragrance (oil of mulberry) and mal-odor agent (VALEX) , 3 parts by weight of a nonionic surfactant sold under the tradename Triton N101 (a nonyl phenol condensed with an average of nine to ten moles of ethylene oxide in 94 parts by weight of water. Duplicate compositions were prepared using as fragrance a mixture containing essential oils designated as wildflower and strawberry.

Example 2 An aqueous solution was prepared by mixing 5 parts by weight of a combined fragrance (oil of mulberry) and mal-odor agent as in Example 1, 5 parts by weight of Triton N101 in 90 parts by weight of water. Duplicate compositions were prepared using as fragrance a mixture containing essential oils designated as wildflower and strawberry.

Example 3

An aqueous solution was prepared by mixing 3 parts by weight of a combined fragrance (oil of mulberry) and mal-odor agent (VALEX) , 3 parts by weight of Triton N101, and 15 parts by weight of the SMA 1000 brand SMACAMS copolymer solution having a solids content of about 38% with the copolymer containing about 44% by weight maleic anhydride, 41% styrene and 15% ammonium s a l t f u n c t i o n a l i t i e s . T h i s copolymer/surfactant/essential oil solution was then diluted with 79 parts by weight of water. Duplicate compositions were prepared using as fragrance a mixture containing essential oils designated as wildflower and strawberry.

Example 4 An aqueous solution was prepared by mixing 5 parts by weight of a combined fragrance (oil of mulberry) and mal-odor agent (VALEX) , 5 parts by weight of a Triton NlOl, and 20 parts by weight of the SMA 1000 brand SMACAMS copolymer solution having a solids content of about 38% with the copolymer containing about 44% by weight maleic anhydride, 41% styrene and 15% ammonium s a l t f u n c t i o n a l i t i e s . T h i s copolymer/surfactant/essential oil solution was then diluted with 70 parts by weight water. Duplicate compositions were prepared using as fragrance a mixture containing essential oils designated as wildflower and strawberry.

There follows a series of examples showing the antisoiling properties of the compositions of the present invention as compared with untreated controls.

A virgin light, cream colored, level loop, nylon carpet was selected for purposes of testing. Before any tests were begun, the carpet was scanned by a Photovolt

577 Reflectance and Gloss Meter with a "D" search unit. The reflectometer was set at 99.9% using the virgin carpet sample. The carpet was divided into two sections for each comparative test recorded in the following examples. One section of the carpet was the control. The second section was treated with a composition as indicated in each example for purposes of comparison with the corresponding control. The solutions were placed in a pressurized container and sprayed, through a spray wand, lightly but uniformly on the carpet section. Treated sections were allowed to air dry for 24 hours. Each control and treated section, measuring approximately 12" x 6", was soiled by being strapped to the soles of the shoes of a person, pile side down with the jute backing being against the soles of the shoe of the wearer, who then walked through a warehouse having a cement floor for a period of ten minutes. The samples were then removed and a reflectometer reading was taken comparing both the control and treated samples . In some instances, the samples were vacuumed before the reflectometer reading was taken.

Example 5 Carpet samples treated with the compositions of

Examples 1 and 2, not containing any of the SMACAMS copolymer, dried slowly and were tacky. They also soiled readily indicating that the soil was adhering to the essential oil and carpet fibers. The reflectometer reading of the control samples varied between about 44 and 48 whereas the treated samples using the mulberry, wildflower and strawberry essential oils showed a much lower reading in the neighborhood of between about 30 and 40. The samples treated with the composition of Example 2, containing higher amounts of essential oils, were inferior to the samples treated with the composition of Example 1. Because the carpets treated without any SMACAMS polymer present were clearly inferior when viewed by the eye, no attempt was made to get an accurate reflectometer reading.

Example 6

Carpets were treated with the composition of

Example 3 and allowed to dry. A reflectometer reading was taken 24 hours after application and a comparison was made with a control . Table 1 shows an average of numerous reflectometer readings taken of the sample.

Table 1 Reflectometer Reading Average

Treated Control

44.03% mulberry 42.43% 45.10% wildflower 41.10%

46.70% strawberry 46.16%

It can be noted that the percentage of reflectance, as compared with the virgin carpet, was only marginally better in the treated as compared with the control. This was done deliberately to bring the antisoiling properties into line with that of the untreated carpet. In this regard, any partial or erratic treatment would not be noticeable when the composition was applied only for purposes of odor control . The odor on and about the treated carpet was pleasant and natural and lasted for a number of days .

Example 7 The carpet samples of Example 6 were then vacuumed and a reflectometer reading was again taken with the results being as shown in Table 2.

Table 2 Reflectometer Reading Average

Treated Control

56.25% mulberry 53.30%

58.00% wildflower 54.40% 57.30% strawberry 55.60%

As in Example 6, it can be noted that the percentage of reflectance, as compared with the virgin carpet, was somewhat better in the treated as compared with the control. Again, this was because the polymer content of composition 3 was selected to match the soiling or antisoiling properties of the virgin carpet being treated. The odor control properties were similar to those obtained in Example 6 indicating that the odor is contained within the polymer and was not removed during vacuuming.

Example 8 Carpets were treated with the composition of Example 4 and allowed to dry. A reflectometer reading was taken 24 hours after application and a comparison was made with a control. Table 3 shows an average of numerous reflectometer readings taken of the sample. 5 Table 3

Reflectometer Reading Average

Treated Control

0 42.19% mulberry 43.15%

41.62% wildflower 42.30% 46.02% strawberry 45.70% It can be noted that the percentage of reflectance, as compared with the virgin carpet, was again comparable 5 with the control. It is evident that the raising of the copolymer content along with the raising of the essential oil content mitigated soiling which might be expected by the higher essential oil content. The odor on and about the treated carpet was pleasant and natural 0 and lasted for a number of days.

Example 9 The carpet samples of Example 8 were then vacuumed and a reflectometer reading was again taken with the 25 results being as shown in Table 4.

Table 4 Reflectometer Reading Average

30. Treated Control

54.73% mulberry 55.95%

51.14% wildflower 53.80% 56.52% strawberry 56.10%

35 As in Example 6, it can be noted that the percentage of reflectance, as compared with the virgin carpet, was comparable to that obtained with the control. The antisoiling properties attributable to the raising the copolymer content, when the essential oil

40 content is raised are evident. The odor control properties were similar to those obtained in Example 8 again indicating that the odor is contained within the polymer and was not removed during vacuuming. Example 10

This example illustrates the use of the composition of Example 4 being used as an additive to a cleaning solution containing natural cleaning ingredients, as disclosed in copending patent application Serial Number 335,113 filed November 7, 1994. A solution containing 2.6 parts by weight citric acid, 1.3 parts by weight urea and 2 parts by weight of the undiluted composition of Example 4 (wildflower fragrance) in 94.1 parts by weight water was heated to 180 °F. Another solution containing 2.6 parts by weight sodium carbonate in 97.4 parts by weight water was also heated to 180 °F. A 90 ml sample of each heated solution was mixed and metered immediately onto a carpet as a sheet of liquid at ambient pressure. This provides a combined carbonating solution containing about 0.5% weight of the deodorizing component (surfactant and essential oil) and SMACAMS copolymer. There was noticeable effervescence as the solution reached the carpet fibers. Following application, the carpet was buffed with a dry towel to remove any excess moisture and allowed to dry for 24 hours.

Although the total solids concentration of the deodorizer/copolymer composition only about 0.5%, the wildflower fragrance lingered for several days. The antisoiling properties of the composition were compared with a sample treated without the addition of the composition of this invention and were found to be comparable. That would be expected since the hot carbonating natural component surfactant claimed in copending application Serial No. 335,113 in and of itself possesses excellent antisoiling properties.

Example 11 A commercial carpet cleaning solution containing anionic surfactants, builder salts, antifoaming agents, and optical brighteners was prepared by admixing 170 g of a commercial concentrate with 4.5 gallons of water. The solution was externally carbonated by pressurizing from a C0₂ cylinder and shaking the solution to provide uniform carbonation. This formulation has been compared with hundreds of other compositions and has been found to have a superior balance of cleanability, and resistance to resoiling and yellowing. This carbonated cleaning composition has been used by an international franchise to clean millions of square feet of carpet. This solution was used as a control for comparative purposes.

A second solution was prepared which was identical with the first except that 4 ounces of the undiluted composition of Example 4 was added. Both compositions were applied uniformly to identical soiled carpet samples, buffed with a dry towel and allowed to stand for several hours. The cleaned carpet samples appeared identical to the naked eye and were then subjected to soiling by being strapped to the soles of shoes and worn in a warehouse in the manner as described above and then vacuumed. Although a reflectometer was not used to measure antisoiling properties, it was evident to the eye that the carpet sample cleaned containing the SMACAMS copolymer composition possessed superior antisoiling properties. Also, the wildflower fragrance was present on the carpet for period of several days.

Example 12 Another commercial carpet cleaning composition comprising a mixture of 200 g (1.04 moles) of citric acid with 200 g (1.89 moles) of sodium carbonate and 100 g (1.67 moles) of urea was prepared. This solid mixture was added to 4 gallons of water. Upon mixing the generation of carbon dioxide was extensive. This internally carbonated solution was pressurized with air using a compressor and sprayed onto soiled carpet samples to compare cleanability and resoiling. A second solution was prepared which was identical with the first except that 4 ounces of the undiluted composition of Example 4 was added. Both compositions were applied uniformly to identical soiled carpet samples, buffed with a dry towel and allowed to stand for several hours. The cleaned carpet samples appeared identical to the naked eye and were then subjected to soiling by being strapped to the soles of shoes and worn in a warehouse in the manner as described above and then vacuumed. Although a reflectometer was not used to measure antisoiling properties, it was evident to the eye that the carpet sample cleaned containing the SMACAMS copolymer composition possessed superior antisoiling properties although the difference was not as great as noted in the comparison of Example 11. As in Example 11, the wildflower fragrance was present on the carpet for period of several days.

Example 13 A section of a new commercial stain resistant carpet was divided into two sections. One section served as a control. The other section was treated with the composition of Example 3 and allowed to dry for 24 hours. Each section was then subjected to possible staining by pouring a red fruit flavored beverage on it. The beverage was allowed to remain for about 15 minutes after which is was absorbed onto a piece of toweling and the sections were allowed to dry. Neither section showed evidence of staining which indicates that the compositions of this invention do not negatively affect the antistaining characteristics of carpeting treated with stain resistant chemicals. Example 14

In this example, the composition of Example 4 was used with the exception that the essential oil was that of a tropical fruit . A lavatory having a faulty vent pipe causing the backup of sewer gases into the room was selected as a test site. The odor in the room was sufficiently objectionable that the room was uninhabitable. The composition was sprayed into the room and on the hard surfaces of the urinal, toilet and basin. Five minutes after spraying the only odor detectable was that of the tropical fruit essence. Ten days after spraying, and without additional spraying, the tropical fruit essence was still detectable and was the dominating odor. This indicates that the composition not only provides a long lasting pleasant odor but also eliminates objectionable odors.

Example 15 In this example, the composition of Example 4 was used with the exception that the essential oil was strawberry. A small carpeted unvented room was selected. A group involving pipe, cigarette and cigar smokers where then invited to smoke in the room and leave the room with the air saturated with smoke to the extent possible. A few minutes later the room was sprayed with the composition. Although not timed, within less than a half hour the odor of smoke was completely eradicated from the room. The room was examined each day for the next week and only the odor of strawberry could be detected. A similar experiment was conducted using a commercial carpet reodorizer powder containing baking soda. The powder was sprinkled on the carpet and allowed to remain for a period of time according to instructions on the package. The carpet was then vacuumed. The smell of smoke was less noticeable than prior to application but could still be detected. The 27 day following application, the odor of tobacco smoke in the room was more prominent than the odor of the powdered reodorizer.

While it is not known for a certainty, it is believed that, when applied, the copolymer on the composition adheres to the textile surface and contains the deodorizing component . The polymer dries to a crystalline coating which allows the volatile fragrance and odor inhibiting reagents to permeate the surrounding atmosphere to provide a pleasant fragrance. The polymer is a thin coating which cracks or fractures when distorted, such as walking on the carpet, sitting on upholstery, drawing drapery, etc., thereby releasing additional fragrance and mal-odor agents. Reapplication of the composition causes a buildup of the polymer on the textile surface which improves the anti-soiling properties. However, in the event that the polymer builds to a thickness that it cannot be retained on the fiber surface, it breaks into particles or is sloughed off the fiber and removed by vacuuming or other means.

A thorough vacuuming and/or cleaning of the fibers before the application of the composition exposes the binding sights on the fibers so that treatment with the composition enables the polymer in the solution to attach to such binding sites and regenerate or restore the deodorizing and anti-soiling properties to the fiber surfaces.

The above examples clearly demonstrate the ability of the compositions of this invention, when applied to textile fibers, to emit a sustained release pleasant fragrance and function as an anti-soiling agent over a sustained period of time. It has not heretofore been possible to provide a water soluble polymer deodorizing composition which functions both to deodorize a surface and, at the same time, inhibit or prevent resoiling.

Claims

1. An aqueous odor removing, soil inhibiting polymeric composition comprising:

(a) a water soluble deodorizing component comprising (i) a surfactant, and

(ii) an odor controlling agent containing an essential oil,

(b) a low molecular weight water soluble polymeric component compatible with said deodorizing component such that said deodorizing component is contained within the copolymer matrix when water is removed; and

(c) sufficient water to maintain said deodorizing and copolymer components an homogeneous liquid state.

2. A composition according to Claim 1 wherein said low molecular weight polymeric component has a molecular weight in the range of between about 400 and 3000.

3. A composition according to Claim 2 wherein the weight ratio between said surfactant and odor controlling agent in said deodorizing component is between about 5:1 to 1:3.

4. A composition according to Claim 3 wherein the weight ratio between said deodorizing component and said polymeric component is between about 2:1 to 1:2.

5. A composition according to Claim 4 wherein the solids contents of said water soluble deodorizing component and said polymeric component in said aqueous solution is between about 0.5 to 25 percent by weight.

6. A composition according to Claim 5 wherein the polymeric component is a styrene maleic anhydride copolymer wherein the anhydride groups have been hydrolyzed and the resulting carboxylic acid functionalities have been reacted with a base to form a salt.

7. A composition according to Claim 6 wherein said salt has the formula:

where Z is a member selected from the group consisting of NH₄, Na and K and x and y is each a number of between about 1 and 3 and n is an integer of between 1 and 10 with the proviso that the numbers represented by x and y need not be whole integers.

A composition according to Claim 7 wherein Z is NH₄.

9. A composition according to Claim 8 wherein said surfactant is a member selected from the group consisting of nonionic and anionic surfactants.

10. A composition according to Claim 9 wherein said surfactant is an anionic surfactant.

11. A composition according to Claim 9 wherein said surfactant is a nonionic surfactant.

12. A composition according to Claim 11 wherein said nonionic surfactant is a member selected from the group consisting of alkyl phenol-ethylene oxide condensates, polyoxyalkylene alkanols and condensation products of a fatty alcohol with ethylene oxide.

13. A composition according to Claim 11 wherein said polymeric component contains between about 35 to 60% by weight styrene, 35 to 60 % by weight maleic acid and 10 to 25% by weight ammonium salt cations.

14. A composition according to Claim 13 wherein said odor controlling agent containing an essential oil additionally contains an odor destroying agent.

15. A method for removing objectionable odors and inhibiting soiling of a surface which comprises contacting said surface with an effective amount of an aqueous polymeric composition comprising:

(a) a water soluble deodorizing component comprising

(i) a surfactant, and (ii) an odor controlling agent containing an essential oil,

16. A method according to Claim 15 wherein said low molecular weight polymeric component has a molecular weight in the range of between about 400 and 3000.

17. A method according to Claim 16 wherein the weight ratio between said surfactant and odor controlling agent in said deodorizing component is between about 5:1 to 1:3.

18. A method according to Claim 17 wherein the weight ratio between said deodorizing component and said polymeric component is between about 2:1 to 1:2.

19. A method according to Claim 18 wherein the solids contents of said water soluble deodorizing component and said polymeric component in said aqueous solution is between about 0.5 to 25 percent by weight.

20. A method according to Claim 19 wherein said composition is applied in the form of a spray.

21. A method according to Claim 20 wherein the polymeric component is a styrene maleic anhydride copolymer wherein the anhydride groups have been hydrolyzed and the resulting carboxylic acid functionalities have been reacted with a base to form a salt .

22. A method according to Claim 21 wherein said salt has the formula:

23. A method according to Claim 22 wherein Z is

NH₄.

24. A method according to Claim 23 wherein said surfactant is a member selected from the group consisting of nonionic and anionic surfactants.

25. A method according to Claim 24 wherein said surfactant is an anionic surfactant.

26. A method according to Claim 24 wherein said surfactant is a nonionic surfactant.

27. A method according to Claim 26 wherein said nonionic surfactant is a member selected from the group consisting of alkyl phenol-ethylene oxide condensates, polyoxyalkylene alkanols and condensation products of a fatty alcohol with ethylene oxide.

28. A method according to Claim 26 wherein said polymeric component contains between about 35 to 60% by weight styrene, 35 to 60 % by weight maleic acid and 10 to 25% by weight ammonium salt cations.

29. A method according to Claim 28 wherein said odor controlling agent containing an essential oil additionally contains an odor destroying agent.

30. A method according to Claim 20 wherein said surface is a fabric.

31. A method according to Claim 20 wherein said fabric is carpeting.

32. A method according to Claim 20 wherein said surface is a hard surface.

33. A method according to Claim 32 wherein said hard surface is a lavatory.

34. A method according to Claim 31 wherein the polymeric component content of said composition is adjusted such that, when said composition is applied to said carpeting, the antisoiling properties of said carpeting following application will be essentially the same as before application.