WO2011037923A1

WO2011037923A1 - Malodor control

Info

Publication number: WO2011037923A1
Application number: PCT/US2010/049664
Authority: WO
Inventors: Eric John Lind
Original assignee: Vantage Specialties, Inc.
Priority date: 2009-09-24
Filing date: 2010-09-21
Publication date: 2011-03-31

Abstract

A composition for use in treating a malodor comprising a carboxylic acid having covalently bonded to one or more hydroxyl groups of the carbon chain of the acid 1 to about 400 alkoxy groups in which the alkyl portion of the alkoxy group has one to about six carbon atoms, wherein the carbon chain of the acid can be saturated or unsaturated, can be linear or branched, and can have about 4 to about 22 carbon atoms or a saponified form of the alkoxylated carboxylic acid, preferably the source of the carboxylic acid being castor oil, and the composition including preferably a metal having odor-control properties, for example, zinc.

Description

MALODOR CONTROL

Field of the Invention

This invention relates to compositions, including novel compositions, which are effective in reducing or eliminating malodors which are associated with inanimate objects or animate beings, to the preparation of such compositions, and to the use thereof to reduce malodors, even to the extent of eliminating them.

It is recognized that there are odors (smells) which are considered to be unpleasant or otherwise offensive or even noxious to the extent that they can cause sickening of an individual. Such odors are referred to conventionally as "malodors" and they are so referred to herein.

Compositions have been developed to reduce malodors by treating the sources thereof with "malodor-treating" compositions. Such compositions can function in one or more ways to reduce the malodor. For example, the malodor can be masked by the treating with a composition that has a more dominant, but acceptable odor, for example, a perfume. A malodor-treating composition can function also by absorbing or adsorbing the malodor or by having one or more ingredients that react with one or more materials that are the source of the malodor to form one or more products of reaction that have an acceptable odor. The term "odor-control composition" is used herein to identify a composition which is effective in reducing one or more malodors, even possibly to the extent of eliminating the malodor(s) and irrespective of how the composition functions to reduce the malodor. Reported Developments

The following patents disclose compositions for treating malodor, including, for example, deodorants. U.S. Patent No. 4,968,496 discloses a deodorant composition containing zinc ricinoleate. U.S. Patent No. 5,783,544 discloses a composition for treating malodors associated with inanimate surfaces; the composition contains a particular type of perfume among other ingredients, including, for example, a water and soluble zinc salt. U.S. Patent No. 6,528,047 discloses a composition which is said to have enhanced odor-absorbing capabilities; the composition contains zinc ricinoleate and a particular alkoxylatedamine for solubilizing the zinc ricinoleate. U.S. Patent No. 6,458,469 discloses a deodorizing composition that includes as an active ingredient, an alcohol ethoxycarboxylate, for example, one having a terminal end group comprising

Summary of the Invention

In one embodiment of the invention, there is provided a composition for use in treating a malodor comprising a carboxylic acid having covalently bonded to one or more hydroxyl groups of the carbon chain of the acid 1 to about 400 alkoxy groups in which the alkyl portion of the alkoxy group has one to about six carbon atoms, wherein the carbon chain of the acid can be saturated or unsaturated, can be linear or branched, and can have about 4 to about 22 carbon atoms. The composition can be used in solid form of in the form of an aqueous solution. In preferred form, the composition contains a metal which has odor-control properties, preferably zirconium or copper, and most preferably zinc.

In another embodiment of the invention, a composition of the present invention comprises a saponified product of the aforementioned carboxyated acid. Preferably, there is used a saponified product of alkoxylated castor oil which comprises mixture of triglycerides of a plurality of fatty acids, including a major amount of the triglyceride of alkoxylated ricinoleic acid, in which the alkoxy group of the alkoxylated castor oil is a C₂- C₆ alkoxy group, preferably an ethoxy group, and the number of alkoxy group(s) is 1 to about 400. A preferred composition of the saponified product includes also a metal which has odor-control properties.

In still another embodiment of the invention, there is provided a method for reducing malodor associated with an inanimate object or an animate being comprising treating the malodor with an odor-control composition of the present invention.

In another embodiment of the invention, there is provided a method for increasing the water-solubility of a carboxylic acid having attached to one or more carbon atoms of the carbon chain of the acid a hydroxyl group, wherein the carbon chain of the acid can be saturated or unsaturated, can be linear or branched, and can have about 4 to about 22 carbon atoms, the method comprising:

(A) providing a glyceride of the carboxylic acid in which the hydroxyl group(s) of the acid has/have been alkoxylated with 1 to about 400 alkoxy groups in which the alkyl portion of the alkoxy group(s) has/have one to about six carbon atoms; and

(B) saponifying in liquid form the glyceride to convert it to glycerol and a salt(s) of the alkoxylated acid. Detailed Description of Invention

The present invention provides a carboxylic acid having covalently bonded to one or more hydroxyls of the carbon chain of the acid 1 to about 400 alkoxy groups in which the alkyl portion of the alkoxy group has one to about six carbon atoms, wherein the carbon chain of the acid can be saturated or unsaturated, can be linear or branched, and can have about 4 to about 22 carbon atoms. In preferred form, the alkoxy group has two carbon atoms, that is, an ethylene oxide group (-CH₂-CH₂-0-). A malodor- treating composition containing the aforementioned carboxylic acid can be in solid form or in the form of an aqueous solution and includes preferably metal which has odor- control properties, preferably zirconium or copper, and most preferably zinc.

In a particularly preferred embodiment, products of the present invention are made from castor oil which is alkoxylated and thereafter saponified. Castor oil (known also as ricinus oil) includes a mixture of triglycerides. The chemical composition of castor oil can very depending on the source of the castor oil. By way of example, a castor oil referred to in the literature is described as containing the following eight fatty acids which are present in the castor oil in the amounts (weight %) indicated below and which vary in carbon (C) content and hydroxyl (OH) groups and ethylenic unsaturation, as indicated below also.

(1) 89.5% ricinoleic acid 18C, 1 OH, and monounsaturated

(2) 4.2% linoleic acid 18C, no OH, and diunsaturated

(3) 3.0% oleic acid 18C, no OH, and monounsaturated

(4) 1.0% stearic acid 18C, no OH, and saturated

(5) 1.0% palmitic acid 16C, no OH, and saturated

(6) 0.7% dihydroxystearic acid 18C, 2 OH's, and saturated

(7) 0.3% linolenic acid 18C, no OH, and triunsaturated

(8) 0.3% eicosanoic acid 20C, no OH, and saturated

In the particularly preferred embodiment of the invention, the odor-control composition of the present invention includes ethoxylated ricinoleic acid and ethoxylated

dihydroxystearic acid which is prepared by saponifying the alkoxylated glyceride form of the acids and which is substantially free of the other fatty acids identified above, that is, they comprise no more than about 15 wt. % of the composition. Examples of other alkoxylated acids that can be used in the practice of the present invention are glycolic acid and lactic acid. To the extent that such acids need to be synthesized, they can be prepared in any suitable way, for example, by the alkoxylation of one or more hydroxyl groups which are present on the backbone of the acid or on the backbone of the glyceride form of the acid (followed by saponification).

The term "ethoxylation" appears in the literature in connection with the reaction of ethylene oxide with a fatty acid to increase the water-solubility of the acid. The term "alkoxylating" appears also in the literature in reference to the reaction of an

"alkoxylating compound" (for example, ethylene oxide, propylene oxide, and buytlene oxide) with a fatty alcohol to form a fatty alcohol polyglycol ether which is a nonionic surfactant.

As used herein: (a) the term "alkoxylating" or the term "alkoxylation" refers to reacting a one to six-carbon alkylene oxide (methylene, ethylene, propylene, butylene, pentylene, or hexylene oxide or a mixture of two or more of the aforementioned oxides) with at least one hydroxyl group that is (are) attached to the backbone of the acid or to the backbone of a glyceride of a carboxylic acid (alkoxylation increases the water- solubility of the carboxylic acid or salt thereof that is used in the odor-control

composition of the present invention); (b) the term "alkylene oxide" encompasses within its meaning any one of the aforementioned six oxides referred to in (a) hereof; and (c) the term "alkoxylated" refers to the product formed by alkoxylating (alkoxylation).

Preferably, one or more hydroxyl groups that are attached to the backbone of the acid portion of a glyceride are in alkoxylated form. Speaking generally, a glyceride is an ester formed between one or more acids (which can be the same or different) and glycerol, which includes three hydroxyl groups (C3H₅-(OH)₃), and, accordingly, a glyceride can be a monoglyceride, a diglyceride or a triglyceride. For the purpose of the present invention: (a) the acid portion of a monoglyceride must have at least one hydroxyl group that is capable of being alkoxylated; (b) at least one of the two acid portions of a diglyceride must have at least one hydroxyl group that is capable of being alkoxylated; and (c) at least one of the three acid portions of a triglyceride must have a hydroxyl group that is capable of being alkoxylated. Preferably, a triglyceride in which each of the acid portions of the three acids that comprise the "triester" is in alkoxylated form.

The alkoxylation of the hydroxyl group(s) with an alkylene oxide can be carried out in any suitable way. As described in detail, hereinafter, an example of a reaction involves effecting the alkoxylation of a water-free reaction mixture which includes a catalyst, for example, potassium hydroxide, in a pressurized and heated reactor at a temperature at which the reactants are liquid. As described hereinbelow, the product of reaction can be in a liquid form which is water-miscible or in a water-soluble solid form depending on variables associated with the reaction, e.g., the extent of the alkoxylation. In accordance with the present invention, a glyceride in which its acid portions include 1 to about 400 alkoxy groups is saponified to form a salt of the involved acid and glycerol. At room temperature, the product of the saponification can be a water-miscible liquid or a water-soluble solid depending on the number of alkoxy groups in the said acid portions as discussed hereinbelow. The saponification can be carried out in any suitable way, for example, in the presence of alkali or in the presence of steam. As described in detail hereinafter, an example of a suitable reaction involves effecting the saponification by heating an aqueous solution of the glyceride in the presence of alkali to provide an aqueous solution in which a normally solid saponified product is dissolved or in which normally liquid saponified product is miscible; as mentioned above, whether the product is in solid or liquid form depends on the number of alkoxy groups in the product; this is discussed in more detail below. A saponified product comprising an aqueous solution of the acid salt and glycerol has typically a pH of about 2 to about 5 and has odor-control properties; as discussed below, the pH of the solution can vary over a broader range. As will be evidenced by compositions of the Examples herein, the odor-control properties of the composition can be improved by adding to the solution a soluble metal which has odor-control properties and adjusting, as may be needed, the pH of the solution to about 2 to about 5.

In another embodiment of the saponification, the reaction mixture is non-aqueous and comprises alkali and a liquid glyceride, the acid portion of which includes the aforementioned alkoxy groups. In an embodiment in which the "alkoxylated" glyceride is normally a solid at room temperature, the saponification is conducted at a

temperature sufficiently high to convert the glyceride to a liquid. As discussed hereinbelow, a solid saponified product can be recovered upon cooling the reaction mixture.

As stated above, a particularly preferred embodiment of the invention comprises saponifying an alkoxylated castor oil. In the castor oil exemplified above, the

triglyceride of rincinoleic acid is the triglyceride that comprises the highest proportion of glycerides present in the castor oil, that is, almost 90 wt.%, as indicated above; its formula is set forth below.

Saponification of one mole of the above alkoxylated triglyceride of ricinoleic acid results in 3 moles of the alkoxylated ricinoleic acid and one mole of glycerol which is soluble in an aqueous solution of the saponified product. From the above description, it should be appreciated the odor-control compositions of the present invention can comprise either:

(A) an aqueous solution of the aikoxylated carboxylic acid described above, preferably an aikoxylated carboxylic acid prepared by saponifying a triglyceride form of the acid, most preferably a triglyceride of ricinoleic acid present in castor oil; such aqueous solution has typically a pH of about 2 to about 5; or

(B) an aqueous solution of (A) above and including also a dissolved metal which has odor-control properties.

For convenience: (1) the solution of (A) above is referred to herein as "the aikoxylated solution"; (2) the solution of (B) above is referred to herein as "the alkoxylated/metal solution"; and (3) the solutions of (A) and (B) are referred to collectively herein as "the odor-control solutions hereof.

For effective and trouble-free use in applications in which the odor-control composition is applied in liquid form, the odor-control solutions hereof should be true solutions, that is, all of the ingredients of the solutions should be water-soluble at room temperature, and the solutions should be stable, for example, for a period of time, of at least about one month. With respect to stability, the solution should not contain ingredients which decompose into one or more constituents which affect adversely the odor-control properties of the composition or which affect adversely the ability to apply the liquid composition in a trouble-free way. Thus, in preferred form, the solution should not contain dissolved ingredients which over a period of time come out of solution and form solids, even solids in the form of fine particles. Such solids can clog the holes of a spray device through which the liquid composition is discharged, for example, in the form of a fine spray by an atomizer.

Accordingly, an important aspect of the present invention is the use of an aikoxylated carboxylic acid or salt thereof which is water-soluble and stable. There are various factors which should be taken into account in producing the aforementioned. For example, the number of moles of alkylene oxide used in the alkoxylation will depend on the alkylene oxide used and the particular carboxylic acid being alkoxylated. Thus, for the alkoxylation of any particular carboxylic acid, there may need to be adjustments made in the number of moles of alkylene oxide used in the alkoxylation or even the particular alkylene oxide used if the alkoxylated product is not sufficiently water-soluble.

As evidence of the above, there follows a description of the preparation of ethoxylated ricinoleic acid that is derived from castor oil and recovered from a glyceride- containing reaction product by saponification thereof.

In the preparation of ethoxylated ricinoleic acids that contained varying amounts of ethylene oxide groups, it was observed that the use of up to about 30 moles of ethylene oxide (EtO) in the ethoxylation resulted in an ethoxylated ricinoleic acid that, at room temperature is a liquid which is miscible with water, forming therewith a solution that has a translucent and milky appearance.

As the number of moles of EtO are increased, the resulting ethoxylated castor oil becomes more and more solid like at room temperature, and upon the use of about 150 moles, a solid ethoxylated ricinoleic acid with good water solubility can be produced. Aqueous solutions of ethoxylated ricinoleic acids that are produced by ethoxylation with greater than about 30 to less than about 150 moles of EtO are translucent and milky in appearance. In the particularly preferred embodiment of the present invention, ricinoleic acids that contain about 200 to about 300 EtO groups, most preferably about 240 to about 260 EtO groups are more water-soluble, as evidenced by their ability to form clear aqueous solutions which are stable. On the other hand, ricinoleic acids that are produced by ethoxylation with greater than about 300 moles of EtO are, at room temperature, solids which when dissolved in water form an aqueous solution that is not clear in appearance in that it is cloudy. In the event that a precursor solution of the odor-control solutions hereof contain one or more materials that affect adversely the stability properties of the odor-control composition, they should be removed from the precursor solution. For example, in the alkoxylation of castor oil, the reaction product thereof and the saponified product which is derived therefrom can include materials which are desirably removed from the precursor solutions by purifying them, for example, by treatment with a suitable ion exchange material, such as an ion exchange resin, or by filtering. Examples of such materials are fatty acids that are water-insoluble and sodium and potassium ions.

The odor-control solutions hereof can contain other materials (additives) which are dissolved in the solution, in addition to the alkoxylated acid and preferably one or more metals which have odor-control properties. Examples of such other materials include: perfumes, dyes, anti-static agents, surfactants, biocides, and preservatives. Such materials are typically used as ingredients of odor-control compositions and collectively comprise typically about 0.1 to about 30 wt.% of the composition. In the application of the odor-control composition in liquid form, the composition should not contain a material which is capable of reacting with another ingredient of the

composition to form a material which is water-insoluble.

As mentioned above, an aqueous solution of the alkoxylated carboxylic acid or of the saponified product has typically a pH of about 2 to about 5. The pH of the solution can be broadened to, for example, about 1 to about 12 by adding thereto one or more compounds which have an effect on insolubles which may be present in the solution, for example, by rendering them soluble by the use of solubilizers, for example, surfactants, buffers, solvents, and chelating agents. The amount used will depend on various factors, for example, the particular solubilizer used and the concentration of the active (typically the source of the insolubles). An amount of about 0.1 to about 50 wt.% of the solubilizer is exemplary, with an amount of about 0.1 to about 15 wt% being more typical.

The odor-control composition of the present invention can be applied as a liquid or a solid to the surface which is the source of the malodor.

A liquid composition can be applied in the form of an aqueous concentrate of the odor-control solution or it can be applied in dilute form which can be prepared, for example, by adding additional water to the concentrate. The active ingredient(s) of the odor-control solution should be present therein in an amount(s) which is effective in treating effectively the malodor. This will depend, for example, on the particular material which is the source of the malodor and the amount thereof.

Generally speaking, it is believed that an aqueous concentrate of the odor-control solution will comprise: (A) about 20 to about 50 wt.% of the alkoxylated carboxylic acid; (B) optionally, but preferably about 0.1 to about 50 wt.% of a metal having odor-control properties; and (C) about 50 to about 80 wt.% of water. It is likely that a dilute form of the aqueous odor-control composition will be used more widely than the "concentrate" in the treatment of malodors, for example, the following dilute aqueous solution:

(A) about 1 to about 30 wt.% of the alkoxylated carboxylic acid;

(B) optionally, but preferably about 0.04 to about 30 wt.% of a metal having odor-control properties; and

(C) about 70 to about 99 wt.% of water.

Other constituents (for example, as identified above) can be included in the concentrate or dilute form of the composition.

With respect to the use of the odor-control composition of the present invention in solid form, dissolved solids of the odor-control solutions hereof can be recovered in solid form by evaporating the aqueous solvent of the solution. Alternatively, a solid form of the odor-control composition can be synthesized directly by not using water in the synthesis, as described above. In a preferred embodiment, a metal having odor-control properties is incorporated into the solid form of the composition.

The solids can then be fabricated according to available techniques into any suitable form for treatment of a malodor, for example, into a deodorant stick. In an application in which the alkoxylated carboxylic acid, optionally, but preferably in admixture with a metal having odor-control properties, is a liquid at room temperature, the liquid can be combined with a solid material according to available techniques and used in solid form, for example, by impregnating a powdery carrier with the liquid and forming the resulting solid composition into a form suitable for application to the source of the malodor.

The odor-control composition of the present invention should be applied to the surface treated in an "odor-reducing" amount, that is, an amount at least sufficient to reduce the malodor to the degree that an individual can discern that the malodor associated with the source of the treated surface is not as strong as that of the untreated surface. The amount of odor-control composition used for a particular application will depend on many factors, including, for example, the nature of the odor involved, its intensity, the particular odor-control composition used (for example, with or without a metal having odor-control properties), and the amount of the actives (odor- control ingredients) in the composition. More than one application of the odor- composition may be needed to reduce the malodor to the desired degree.

The composition, whether in liquid or solid form, can be applied in any suitable way, for example, by use of a spray device or a pad or a roller.

The odor-control composition of the present invention can be used: (A) to reduce many types of malodors, including, for example, kitchen odors, bathroom odors, household odors, food odors, human body odors, pet and animal odors, and sulfur- or amine-based odors; and (B) in many types of applications involving treatment of malodors, including, for example, spray deodorizers, carpet cleaning, air-care, personal care, diapers, furniture, building materials, fabric cleaning, laundry, garbage, hotels, hospitals, agriculture, litter boxes, fabric detergents, fungicides, hard surface cleaning, plastics, polymers, paints, floor cleaning, deodorant, sports equipment, car interiors, landfills, manufacturing plants, water-treatment and waste-water treatment, garbage and other trash cans, and shoe cavities.

An exemplary synthesis for preparing products of the present invention utilizing castor oil as a starting material is described hereafter. The first step of the synthesis is the alkoxylation of the castor oil which is mixed with an aqueous solution of KOH catalyst or other suitable "alkoxylation" catalyst, for example, NaOH and LiOH, in a suitable reactor, for example, a Parr Reactor which is sealed. The contents of the Parr reactor are vacuum purged while heating up to about 150°C to remove water. An alkylene oxide is added slowly, with stirring, to the contents of the reactor which is maintained at about 40 psig pressure and a temperature of about 150°C. After the hydroxyl groups of the castor oil and the alkylene oxide have reacted, the contents of the reactor are maintained at a temperature of about 150°C under vacuum for an additional period of time to strip off volatiles, for example, about one to about four hours. Then the reactor is cooled and the product of reaction is collected; it comprises, at room temperature, a solid or liquid depending on the alkylene oxide used and the degree of alkoxylation.

In preparation for the saponification, an aqueous solution of the alkoxylated castor oil product is prepared and filtered to remove insolubles. The solution is somewhat alkaline, for example, having a pH of about 7.5 to about 8.

In an embodiment in which the castor oil is ethoxylated with about 200 to about 300 moles of ethylene oxide, the resulting aqueous solution of ethoxylated castor oil is diluted by adding thereto deionized (Dl) water to form, for example, an aqueous solution having an alkaline pH, for example, about 7.5 and containing about 25 wt.% solids of dissolved ethoxylated (200 to 300 EtO) castor oil (hereafter "200 to 300 EtO castor oil").

Saponification of the 200 to 300 EtO castor oil can be effected in any suitable way. In preferred form, it is saponified at about 70°C to reflux temperature with caustic, preferably by adding thereto an aqueous solution of NaOH or KOH. The resulting saponified product comprises an aqueous solution of a salt of: (A) ethoxylated ricinoleic acid; and (B) the other acids comprising castor oil, as exemplified above, and (C) also glycerol. The "saponified" solution is alkaline; for example, it has a pH of about 9 to about 13. In preferred form, the product is filtered to remove insolubles. Then the pH of the resulting solution (about 9 to about 13) is adjusted with an aqueous solution of HCI or of H₂S0₄, or of lactic acid or it can be subjected to an acidic ion exchange resin. The purified product comprises an aqueous solution having an acidic pH, for example, a pH of about 2 to about 5.

The aforementioned purified product has odor-control properties which, however, can be improved by adding thereto a water soluble metal in the form of a water-soluble metal salt, for example, a zinc, zirconium, or copper salt; a zinc salt is preferred, for example, ZnCI₂, ZnS0₄, ZnO, Zn acetate, and a mixture of ZnC0₃ and Zn(OH)₂.

Examples of other salts that can be used are zirconium hydroxide and copper. The pH of the resulting solution is typically about 2 to about 5 and is filtered to remove insolubles and to produce a clear solution.

The product produced by the alkoxylation of castor oil with an alkylene oxide in an amount in excess of about 300 moles is also a solid which can be saponified to produce an odor-control composition in the manner described above for the 200 to 300 EtO castor oil and its odor-control properties can be improved by treating the saponified product with the aforementioned soluble metals. The resulting saponified products are aqueous solutions which tend to be less than clear. The product produced by the alkoxylation of castor oil with 1 to less than about 50 moles of an alkylene oxide is a liquid which is miscible in water and comprises a less than clear solution; it can be saponified in the manner described above.

The following examples are illustrative of the practice of the present invention. Comparative examples are included also.

Examples

Example No. 1 (247 moles of ethylene oxide)

This example describes a preferred synthesis for the preparation of a saponified ethoxylated castor oil water-soluble salt solution in which 247 moles of ethylene oxide were used in the ethoxylation. The first step of the synthesis involved the use of a starting material that was a partially ethoxylated castor oil, namely, a castor oil that was ethoxylated with 40 moles of ethylene oxide. (It was prepared from a reaction mixture that comprised 34.3 wt.% castor oil, 65.3 wt.% of purified ethylene oxide, 0.2 wt.% of an aqueous solution of 45 wt.% KOH, and 0.2 wt.% of an aqueous solution of 50 wt.% sulfuric acid.) The following constituents were added, as described hereafter, to a two- liter Parr Reactor to form a reaction mixture comprising: (A) 24.1 wt.% castor oil ethoxylate (40 moles EtO); (B) 75.7 wt.% of purified ethylene oxide; and (C) 0.2 wt.% of an aqueous solution of 45 wt.% potassium hydroxide catalyst. The partially ethoxylated castor oil and potassium hydroxide solution were added to the reactor and mixed. The reactor was sealed and purged with N2. Then the reactor was vacuum purged while heating up to a temperature of 150°C to remove volatiles, including water. Two hundred seven moles of ethylene oxide were added slowly as the mixture was stirred and maintained under a pressure of 40 psig pressure and a temperature of 150°C. Once all of the 207 moles of ethylene oxide were consumed, the reaction mixture was heated to a temperature of 150°C under vacuum for an additional period of time to strip off volatiles. The reactor was then cooled and a solid reaction product was recovered; it comprised solid ethoxylated (247 EtO) castor oil and by-products. An aqueous solution of the product was prepared and its Saponification Number was determined to be 14.25 mg KOH/g. In anticipation of saponifying this product, an aqueous solution of deionized water containing 25 wt.% solids of the product was prepared and then filtered through filter aid/filter paper under a pressure of 20 psi to remove insolubles from the solution.

Saponification was effected by refluxing the purified solution with 0.5 wt.% of 50 wt.% NaOH solution to give the corresponding carboxylate salts. The pH of the saponified product is then adjusted with 6N HCI to a pH of about 4 to provide a pH adjusted saponified "247" ethoxylated castor oil product which has odor-control properties. The product comprised an aqueous solution containing 25 wt.% of the saponified "247" ethoxylated castor oil. The odor-control properties of this product are improved by addition to the aqueous solution of zinc in the form of an aqueous solution of 5 wt.% of ZnCI₂ based on the wt.% of the actives to provide a clear aqueous solution in which the zinc comprises about 0.6 wt.% of the solution based on the total weight of the solution.

Example No. 2 (250 moles of ethylene oxide)

This example is similar to Example No. 1 , but describes the preparation of compositions of the present invention in which 250 moles of ethylene oxide were used in the ethoxylation of the castor oil. The first step of the synthesis involved the use of a starting material that was a partially ethoxylated castor oil, namely, a castor oil that was ethoxylated with 89 moles of ethylene oxide. The procedure described in Example No. 1 for preparing the ethoxylated castor oil was followed except that 161 moles of purified ethylene oxide were used in the further ethoxylation of the castor oil and the reaction mixture comprised: (A) 41.8 wt.% castor oil ethoxylate (89 moles EtO); (B) 58 wt.% of purified ethylene oxide; and (C) 0.2 wt.% of an aqueous solution of 45 wt.% potassium hydroxide catalyst. A solid reaction product was recovered from the cooled reactor; it comprised solid ethoxylated (250 EtO) castor oil and by-products. An aqueous solution of the product was prepared and its Saponification Number was determined to be 14.1 mg KOH/g.

In anticipation of saponifying this product, an aqueous solution of deionized water containing 25 wt.% solids of the product was prepared and then filtered through filter aid/filter paper under a pressure of 20 psi to remove insolubles from the solution.

Saponification of the "250" ethoxylated castor oil was effected in the manner described in Example No. 1. The pH of the saponified product is then adjusted with a strong acid ion exchange resin (Purolite C-150 H) to a pH of about 4 to provide a pH adjusted saponified "250" ethoxylated castor oil product which has odor-control properties. The product comprised an aqueous solution containing 25 wt.% of the saponified "250" ethoxylated castor oil. The odor-control properties of this product were improved by addition to the aqueous solution of zinc in the form of an aqueous solution of 5 wt.% of ZnCI₂ based on the wt.% of the actives to provide a clear aqueous solution in which the zinc comprises about 0.6 wt.% of the solution based on the total weight of the solution.

Example No. 3 (205 moles of ethylene oxide)

This example is similar to Example No. 1 also, but describes the preparation of compositions of the present invention in which 205 moles of ethylene oxide were used in the ethoxylation of the castor oil. The first step of the synthesis involved the use of a starting material that was a partially ethoxylated castor oil, namely, a castor oil that was ethoxylated with 40 moles of ethylene oxide (like in Example No. 1 ). The procedure described in Example No. 1 for preparing the ethoxylated castor oil was followed except that the reaction mixture comprised: (A) 27.6 wt.% castor oil ethoxylate (40 moles EtO); (B) 72.2 wt.% of purified ethylene oxide; and (C) 0.2 wt.% of an aqueous solution of 45 wt.% potassium hydroxide catalyst. After the reactor was cool, a solid reaction product was recovered; it comprised solid ethoxylated (205 EtO) castor oil and by-products. An aqueous solution of the product was prepared and its Saponification Number was determined to be 16.9 mg KOH/g.

In anticipation of saponifying this product, an aqueous solution of deionized water containing 25 wt.% solids of the product was prepared and then filtered through filter aid/filter paper under a pressure pf 20 psi to remove insolubles from the solution.

Saponification of the "205" ethoxylated castor oil was effected in the manner described in Example No. 1. The pH of the saponified product was then adjusted, like in Example No. 2, with a strong acid ion exchange resin (as identified in Example No. 2) to a pH of about 4 to provide a pH adjusted saponified "205" ethoxylated castor oil product which has odor-control properties. The product comprised an aqueous solution containing 25 wt.% of the saponified "205" ethoxylated castor oil. The odor-control properties of this product were improved by addition to the aqueous solution of zinc in the form of an aqueous solution of 8.2 wt.% of ZnCI₂ based on the wt.% of the actives to provide a clear aqueous solution in which the zinc comprises about 1 wt.% of the solution based on the total weight of the solution.

Example No. 4 (287 moles of ethylene oxide)

This example is similar to Example No. 2, but describes the preparation of compositions of the present invention in which 287 moles of ethylene oxide were used in the ethoxylation of the castor oil. The first step of the synthesis involved the use of a starting material that was a partially ethoxylated castor oil, namely, a castor oil that was ehtoxylated with 79 moles of ethylene oxide. The procedure described in Example No.

2 for preparing the ethoxylated castor oil was followed except that 208 moles of purified ethylene were used in the further ethoxylation of the castor oil and the reaction mixture comprised: (A) 35.3 wt.% castor oil ethoxylate (79 moles EtO); (B) 64.5 wt.% of purified ethylene oxide; and (C) 0.2 wt.% of an aqueous solution of 45 wt.% potassium hydroxide catalyst. After the reactor was cool, a solid reaction product was recovered; it comprised solid ethoxylated (287 EtO) castor oil and by-products. An aqueous solution of the product was prepared and its Saponification Number was determined to be 12.4 mg KOH/g.

Saponification of the "287" ethoxylated castor oil was effected and the pH of the saponified product was adjusted in the manner described in Example No. 2 to provide a pH adjusted saponified "287" ethoxylated castor oil product which has odor-control properties. The product comprised an aqueous solution containing 25 wt.% of the saponified "287" ethoxylated castor oil. The odor-control properties of this product were improved by addition to the aqueous solution of zinc in the form of an aqueous solution of 8.2 wt.% of ZnCI₂ based on the wt.% of the actives to provide a clear aqueous solution in which the zinc comprises about 1 wt.% of the solution based on the total weight of the solution.

Example No. 5 (241 moles of ethylene oxide)

This example is similar to Example No. 1 , but describes the preparation of compositions of the present invention in which 241 moles of ethylene oxide were used in the ethoxylation of the castor oil. The first step of the synthesis involved the use of a starting material that was a partially ethoxylated castor oil, namely, a castor oil that was ethoxylated with 40 moles of ethylene oxide, like in Example No. 1. The procedure described in Example No. 1 for preparing the ethoxylated castor oil was followed except that 201 moles of purified ethylene were used in the further ethoxylation of the castor oil and the reaction mixture comprised: (A) 24.7 wt.% castor oil ethoxylate (40 moles EtO); (B) 75.1 wt.% of purified ethylene oxide; and (C) 0.2 wt.% of an aqueous solution of 45 wt.% potassium hydroxide catalyst. After the reactor was cool, a solid reaction product was recovered; it comprised solid ethoxylated (241 EtO) castor oil and by-products. An aqueous solution of the product was prepared and its Saponification Number was determined to be 14.6 mg KOH/g.

Saponification of the "241" ethoxylated castor oil was effected in the manner described in Example No. 1. The pH of the saponified product was then adjusted with a strong acid ion exchange resin (as identified in Example 2 hereof) to a pH of about 4 to provide a pH adjusted saponified "241" ethoxylated castor oil product which has odor- control properties. The product comprised an aqueous solution containing 25 wt.% of the saponified "241" ethoxylated castor oil. The odor-control properties of this product were improved by addition to the aqueous solution of zinc in the form of an aqueous solution of 5 wt.% of ZnCI₂ based on the wt.% of the actives to provide a clear aqueous solution in which the zinc comprises about 0.6 wt.% of the solution based on the total weight of the solution.

As mentioned above, the stability of aqueous solutions of odor-control

composition is of particular importance in applications where the composition is applied by spray. The stability of an odor-control composition of the present invention and of commercially available compositions was evaluated at room temperature and at an elevated temperature (50°C). Table 1 below shows the results of testing a dilute form of the Zn-containing composition of Example No. 2 hereof which contains 0.6 wt.% of dissolved Zn and 25 wt.% of the saponified ethoxylated castor oil (241 moles of EtO); the composition does not contain a solubilizer. The testing included also the evaluations of commercially available odor-control compositions, namely SYNGARD WD-A or TEGO® SORB A 30 sold respectively by Lambent Technologies and

DeGussa. The concentration of the actives in each of the compositions was 1 wt.%

Table 1

Odor-Control Temp. Time

Composition CO 1 week 1 month

Example No. 2/Zn room temperature clear to slight haze clear to slight haze SYNGARD WD-A room temperature variable cloudiness variable cloudiness

TEGO SORB A 30 room temperature cloudy (sediment) cloudy (sediment)

Example No. 2/Zn 50 clear clear

SYNGARD WD-A 50 variable cloudiness variable cloudiness

TEGO SORB A 30 50 cloudy (sediment) cloudy (sediment) With reference to Table 1 , the compositions of Example No. 2 hereof were all transparent. In contrast, those compositions having variable cloudiness were not transparent; they were translucent and the cloudiness disappeared and returned. The compositions which were cloudy (sediment) were opaque and solids tended to form therein and precipitate.

Tests were conducted also to evaluate the comparative effectiveness of the odor- control compositions of the present invention. As indicated below, all of the evaluations, except one, involved the use of the aforementioned commercially available odor-control compositions (hereafter "test compositions"). The malodors that were involved in the evaluations were those associated with onions, smoke, garlic, ammonia and body odor. The evaluations involved the preparation of substrates which were impregnated with the malodor (hereafter "test samples"). Test methods were developed to determine odor- control characteristics of the test compositions by a panel of individuals. Panelists were provided with coffee grounds to clear the nasal passages and prevent saturation between evaluations of the test samples. The performance characteristics of the test compositions were determined by comparatively ranking, according to an odor-intensity scale (see below), the odor intensity of the test sample to a control sample that was treated with deionized water.

Evaluation/Onion Malodor

Panelists evaluated the capability of test compositions within the scope of the present invention to reduce the smell of onion. The test compositions which were evaluated included saponified castor oil ethoxylates (pH = 4), some of which included dissolved zinc salts and others of which did not, as identified in Table 2 below. Test samples were prepared by applying 1/8" yellow onion slices to swatches of cotton fabric. Within 15 minutes before the panelist began evaluation, the onion-treated swatches were treated with Dl water to provide control samples or with 0.5 gram of a test composition that contained 1 wt.% of actives. Each of the test compositions was contained in a vial. Each test sample was evaluated by a panelist at time intervals of 15 minutes, 4 hours, and 24 hours after the test sample was treated with the test composition. Ten panelists participated in the evaluations.

The results of the testing are reported in Table 2 below which includes numerical values that are the average of the odor-intensity scale values of the ten panelists.

Table 2

Onion Odor

Control Test Compositions

Time Interval Dl Water Example No. 3, Example No. 3, Example No. 4, Example No. 4,

No Zinc Zn No Zinc Zn

15 minutes 3.0 2.2 2.1 2.1 2.0 4 Hours 3.0 2.4 1.4 2.4 2.3 24 Hours 3.5 3.2 2.2 3.0 2.7 As can be seen from the results reported in Table 2, the compositions of the present invention were more effective than the control composition in reducing the odor of the onion and those compositions which included dissolved zinc were more effective in reducing the onion odor than those which did not contain zinc.

Evaluation/Cigarette smoke Malodor

Panelists evaluated also the capability of test compositions within the scope of the present invention to reduce the smell of cigarette smoke. The test compositions which were evaluated included saponified castor oil ethoxylates (pH = 4), some of which included dissolved zinc salts (zinc chloride) and others of which did not, as identified in Table 3 below. Test samples were prepared by impregnating 100% cotton swatches with cigarette smoke. Sixty of the cotton swatches were cut into 1.5"x 4" strips for ease of handling. Each swatch was impregnated with cigarette smoke at the same time to reduce variability in the testing. A method for impregnating the cotton swatches with smoke without directly contacting the swatch with cigarette ash or butt and with equal distribution of smoke odor involved the use of chamber which was constructed from cardboard and lined with aluminum foil. The chamber was vented to allow airflow through a narrow rectangular slit in its top and back. In addition, the front of the chamber was provided with a flap to contain the smoke in the environment around the swatches. Three lines of thread were strung through the top of the chamber and swatches were hung equidistance along the threads. Three disposable aluminum ashtrays were placed equidistant along the middle bottom of the chamber. One burning cigarette was placed in each of the three ashtrays; it released smoke onto the swatches that were in the chamber. After the initial three cigarettes were consumed, additional cigarettes were burned to consumption in the ashtrays in the same manner; a total of twenty cigarettes were so burned in the chamber.

After all the cigarettes were consumed in the chamber, the swatches were placed in a single sealed quart jar for three days to allow thorough penetration of the smoke throughout the swatches. Individual swatches (hereafter "test samples") were rolled into a 1.5" long cylindrical shape and placed into a two-ounce sealed plastic vial. The vials were labeled with an ID that did not identify the particular test composition that was used to treat the test sample. Within 15 minutes before panelist began evaluation, each of the test samples was treated with 0.5 gram of a test composition that contained 1 wt.% of the active. A control test sample was prepared by treating it with 0.5 gram of deionized water.

Each sample was screened by the panelists at 15 minutes, 4 hours and 24 hours after the swatches were treated with the test composition. Each test sample was then compared to the control sample treated with Dl water. Between testing, samples were stored in the sealed vials at room temperature.

The test compositions which were evaluated were compositions of the Examples identified in Table 2 above. Ten panelists participated in the evaluations.

The results of the testing are reported in Table 3 below which includes numerical values that are the average of the odor-intensity scale values of the ten panelists.

Table 3

Cigarette Odor

Control Test Compositions

Time Interval Dl Water Example No. 3, Example No. 3, Example No. 4, Example N

No Zinc Zinc No Zinc Zinc

15 minutes 2.9 2.4 2.1 2.6 2.6

4 Hours 3.0 2.1 2.0 2.3 2.1

24 Hours 3.0 2.2 2.3 2.3 2.5 As can be seen from the results reported in Table 3, the compositions of the present invention were more effective than the control composition in reducing the odor of the smoke and those compositions which included dissolved zinc were in general more effective in reducing the smoke odor than those which did not contain zinc.

A second cigarette smoke test was performed to compare the results of testing compositions of the present invention with those of commercially available odor-control compositions. In this evaluation, six cigarettes were used rather than twenty as were used in the first evaluation described immediately above. The chamber described above was used for the evaluations. The commercially available compositions that were used in the evaluations were those identified in Table 1 hereof and also

FORESTALL which is sold by Uniqema. The compositions of the present invention that were evaluated were zinc-containing compositions, as identified in Table 4 below which includes numerical values that are the average of the odor-intensity scale values of the eight panelists who participated in the evaluations.

Table 4

Cigarette Odor/Comparative Testing

Test Compositions

Time Interval Dl Water FORESTALL TEGOSORB SYNGARD Example No. 5, Example

A-30 WD-A Zn Zn

15 minutes 3 1 .6 2.3 1.9 1.8 1.6 4 Hours 3 2.1 2.5 1.9 1.6 1.4

24 Hours 3 2.1 2.4 1.8 1.5 1.1

As can be seen from the results reported in Table 4, the compositions of the present invention were more effective than the control composition and the commercially available compositions in reducing the odor of the smoke. Evaluation/Garlic Malodor

Panelists evaluated also the capability of compositions within the scope of the present invention to reduce the smell of garlic, the odors of which are composed of a variety of sulfur-containing compounds such as, for example, sulfides. The evaluation included also the use of commercially available odor-reducing compositions to compare their performances with those of compositions within the scope of the present invention.

A chamber was used to treat 100% cotton fabric swatches with garlic odor without actual contact of the swatches with the garlic to prevent molding or rotting of the swatches prior to testing. Sixty cotton swatches were cut to 1.5"x4" strips. Each swatch was treated at the same time to reduce variability in the testing. The chamber was made of plastic. Holes were drilled into handles of the chamber and thread was strung through the holes up each side of the chamber and across the length of the top of the chamber in two parallel lines. The swatches were hung equidistant on the thread lines to allow vapor to penetrate all surfaces of the swatches.

Chopped garlic in water was spread evenly across the bottom of the chamber out of contact with the swatches in that they were hung above the chopped garlic. A lid was then placed on the chamber sealing it shut to allow the swatches to become

impregnated with the odor of the garlic. The chamber was stored in a 5° C refrigerator for 24 hours prior to the swatches being submitted to the panelists.

The swatches were removed from the chamber prior to one hour of the evaluation and each individual swatch was rolled into a 1.5" long cylindrical shape (test sample) which was placed into a two-ounce plastic vial with a snap-on lid. Each vial was labeled with a sample ID number to prevent bias. Within 15 minutes prior to submission to the panelists, each test sample was treated with 0.5 gram of a 1% active solution of the odor-control composition to be evaluated. A control sample was treated with 0.5 gram of deionized water. The control sample and each test sample were evaluated by the panelists at intervals of 15 minutes, 4 hours, and 24 hours after the swatches were treated with the compositions being evaluated. Between evaluations, the samples were stored at room temperature in the vials which were sealed.

The compositions which were evaluated are identified in Table 5 below which includes also numerical values that are the average of the odor-intensity scale values of the ten panelists who participated in the evaluations.

Table 5

Garlic Odor

Control Test Compositions

Time Dl FORESTALL TEGOSORB SYNGARD Example No. 5, Example No. 4,

Interval Water A-30 WD-A Zn Zn

15 minutes 3 2.1 1.7 1 .4 1.8 1.2

4 Hours 3 2.0 1.8 2.3 1.3 1.5

24 Hours 3 1.8 1.9 2.2 1.1 1.4

The test results reported in Table 5 show that the compositions comprising saponified castor oil ethoxylates with ZnCI₂ (Example Nos. 4 and 5 of the present invention) showed a greater reduction in garlic odor relative to that of the commercial compositions (FORESTALL, TEGOSORB A-30, and SYNGARD WD-A) and the Dl water control composition. Evaluation/Ammonia Malodor

Panelists evaluated also the capability of compositions within the scope of the present invention to reduce the smell of ammonia. The evaluation included also the use of commercially available odor-reducing compositions to compare their performances with those of compositions within the scope of the present invention. The compositions are identified in Table 6 below; they each contained 1 wt.% of the active odor-control constituents. An ammonia containing-formulation was prepared from a six gram sample of a wax emulsion comprising a blend of waxes, of nonionic and anionic surfactants, and of ammonium stearate (Kahl PE-359). For each evaluation, the formulation was weighed into the bottom of a two-ounce plastic vial which was sealed with a snap-on lid and labeled with a sample ID number to prevent bias.

As each composition was evaluated, it was added to the ammonia-containing formulation in the vial in an amount of 0.6 gram and hand-mixed to a uniform

consistency within 20 seconds. A control composition comprised 0.6 gram of deionized water. The vials were closed and kept at room temperature for one hour to allow the headspaces therein to fill with ammonia. Upon opening a vial, each test composition was compared to the control composition for changes in intensity of the odor of the ammonia. The five panelists who were involved in the testing evaluated the intensity of the ammonia odor 15 minutes after the vial was opened.

The results of the evaluation are reported in Table 6 below which includes numerical values that are the average of the odor-intensity scale values of the five panelists who participated in the evaluations.

Table 6

Ammonia Odor

Control Test Compositions

PI Water FORESTALL TEGOSORB SYNGARD Example No. 5, Example No. 4,

A-30 WD-A Zn Zn 3.0 3.0 3.0 2.7 2.3 2.3

The test results in Table 6 show that the compositions of the present invention

(Examples Nos. 4 and 5) reduced the odor of the ammonia to a greater extent than that of the commercially available compositions (FORESTALL, TEGOSORB A-30, and SYNGARD WD-A) and the control composition. Evaluation/Body Odor

Panelists evaluated also the capability of a composition within the scope of the present invention to reduce the smell of body odor. Test fabric swatches (100% cotton) were dosed with 0.1 g of a body-malodor blend that was acquired form Bell Flavors and Fragrances, Inc. and that contained 0.03 g of body-odor fragrance #6100403, 5.0 g Dl water and 5.0 g of isopropylalcohol. The swatches were treated with either 0.5 g of Dl water (control) or with 0.5 g of a 3 wt. % active solution of a malodor-treating

composition of the present invention (hereafter "test sample") in which the active was a saponified "266" ethoxylated castor oil that was prepared similarly to the saponified product of Example No. 1 hereof, but in a scaled-up reactor. The saponified product included about 0.55 wt. % zinc which was added to the product in the form of zinc chloride. The saponification number of an aqueous-solution of the product was determined to be 13.3 mg KOH/g. Three panelists evaluated the control and the test sample according to the odor intensity scale described herein, above. The scale value of the control was 2.0 and that of the test sample was 1.0, thus illustrating that the odor- control composition of the present invention is more effective at reducing body odor than the control. Effects of Applying Odor-Control Compositions to Fabric

As stated hereinabove, the odor-control compositions of the present invention can be used effectively to reduce malodors that are associated with fabrics. In general, it is important that the application to the fabric of the composition, indeed any odor- control composition, does not affect the fabric in an adverse way.

Evaluations were performed to determine the extent to which, it at all, the application of odor-control compositions of the present invention to various types of fabric modified adversely the appearance of the fabrics, for example, by discoloring or staining the fabrics, or modified adversely the soil-attraction properties of the fabrics. The evaluations included also the use of commercially available odor-reducing compositions to compare their performances with those of compositions of the present invention. The odor-control compositions involved in the evaluations were tested on white, blue, and red fabrics to determine if they caused a discoloration of the fabric compared to the use of a water-control composition. The fabrics that were used in the evaluation included the following: (A) machine-washable white fabric comprising 60% cotton/40% polyester and 200 thread count; (B) machine-washable red fabric comprising 60% cotton/40% polyester and 250 thread count; and (C) machine-washable blue fabric comprising 60% cotton/40% polyester and 250 thread count. Swatches (2" square) were prepared from each fabric for testing (fabric sample). Fabrics were used as-is to mimic upholstery or decorative pillow-type fabrics, which are not typically cleaned after purchase.

Each test composition which was evaluated comprised 1 % active in a dilute solution of Dl water and was applied to the fabric sample from a spray bottle having a trigger spray mechanism. (All bottles were from the same manufacturing lot.) The test compositions were shaken thoroughly in the bottles and the triggers primed prior to each application. Each fabric sample was treated by spraying from a distance of one foot for uniform coverage. Fabric samples were dosed with either one spray, five sprays or ten sprays of the test composition or with one drop of concentrate (undiluted) that was applied directly on the fabric sample (concentrated drop). Dl water was used as a control.

The treated fabric samples were evaluated for discoloration and for soil attraction. Discoloration

Fabric samples that were treated with the test and control compositions were stored in three different environments, as set forth below.

(1) room temperature (ranging from 20-30°C), with humidity of 45% or lower, and stored on a shaded interior shelf to prevent access to direct sunlight;

(2) a controlled-temperature 40°C oven for accelerated aging; or

(3) direct sunlight on a windowsill facing west at room temperature (ranging from 20-30°C), with humidity of 45% or lower.

The storing of the fabric samples started at the same time in their environments, hereafter "Room Temperature", "40°C Oven" and "Sunlight". After five weeks, the fabric samples were removed from their respective environments and compared visually for discoloration using the scale below.

After the evaluations, all fabric samples were rinsed under running tap water at a temperature of 60-80°F to determine if the running water had an effect on the appearance of the fabric sample.

Table 7

Discoloration/Evaluation

In addition to the "test" information in Table 7, the following additional information is provided based on observations of the fabric samples treated with each of the test compositions. Composition of the Invention (Example No. 4)

The presence on the surface of the blue fabric samples that were treated with the test composition comprising the drop of concentrated composition (cone.) was evidenced in the form of a dry film that was slightly opaque and stiff to the touch; the presence of such a film was less prominent on the white and red fabric samples and even less prominent when the white and red fabrics were stored in the oven. When rinsed and dried at the end of the study, there was no evidence of a film; the

composition was completely washed out with no residue or discoloration detected on the fabric samples. No discoloration was observed on any of the sprayed fabric samples. SYNGARD WD-A Comparative Composition

The fabric samples treated with one drop of the concentrated composition (cone.) showed a slight darkening oily shadow around the edges of the drop on the white and red fabric samples and a slight opaque drop on the blue fabric sample. When rinsed at the end of the study and dried, the composition was completely washed out with no residue or discoloration detected on the fabric sample. No discoloration was observed on any of the sprayed fabric samples.

TEGOSORB A-30 Comparative Composition

All fabric samples that were treated with one drop of the concentrated composition (cone.) were stained with an obvious dark yellow, stiff film similar to a shiny wax. When rinsed and dried, residual shadowing around the edges of the drop was detected and the fabric sample was still stiff. The fabric samples treated with 10 sprays of 1 % active solution were stiff to the touch. White fabric samples showed increasing yellowing at 5 sprays and 10 sprays both at room temperature and in sunlight. In addition, white fabric samples that were stored in the oven showed discoloration, ranging from an off-white (1 and 5 sprays) to yellowing (10 sprays) and deep yellowing/staining with the "drop" application. Red swatches treated with 10 sprays at room temperature and 5 sprays in the sunlight were dingy in appearance. Fabric samples that were dosed with 10 sprays and stored in sunlight and in the oven were darker in color. Blue fabric samples that were dosed with ten sprays and stored at room temperature and in the oven were a dingy yellow color. Soil-Attraction

The term "soil-attraction" as used herein means the measure of how fabric treated with an odor-control composition attracts soil, for example, dust, lint, dander, and other particles. Odor-control compositions are used often on fabrics, for example, carpeting or fabric-covered furniture that is soiled with dust, lint, pet hair, dander, and other undesirable materials. A composition of the present invention was evaluated to determine its level of soil-attraction (lower better than high soil-attraction), as were commercially available odor-control compositions.

The fabric samples that were used in the evaluations were machine-washable black fabric (60% cotton/40% polyester, 250 thread count). Baby powder (soil) was used to provide a good visual depiction of soil attraction. Fabric samples (2 inches square) were prepared. Each fabric sample was labeled. The fabric was not cleaned and was used as-is. Fabric samples were either sprayed with "dilute" test compositions or with one drop of each test composition in concentrated form that was applied directly onto the fabric sample as described below.

Test compositions which were evaluated included those comprising 1% actives in a dilute solution of Dl water; they were applied to the fabric samples from spray bottles having a trigger spray mechanism. (All bottles were from the same manufacturing lot.) The test compositions were shaken thoroughly in the bottles and the triggers primed prior to each application. Each fabric sample was treated by spraying from a distance of one foot for uniform coverage. Fabric samples were dosed with either one spray, five sprays or ten sprays of the test compositions or with one drop of concentrate (undiluted) that was applied directly on the fabric sample (concentrated drop). Dl water was used as a control composition. The fabric samples were stored at room temperature away from direct sunlight for three days to fully dry and set. After three days, the fabric samples were dusted with a uniform layer of baby powder to completely cover each sample. The samples were then individually lifted by their label, inverted and tapped five times on their untreated side to remove the excess baby powder. For the water-control compositions, the majority of the powder was removed by the fifth tap.

The fabric samples were rated on a scale of 0-4 with 0 having no additional buildup compared to the water control, and 4 showing a complete coating with little removal of the soil.

Table 8

Soil-Attraction/Evaluation

Sample Conc.drop 1 spray 5 sprays 10 sprays

Example No. 4/Zn 0.5 0 0 0

SYNGARD WDA 3 1 0 0.5

TEGO SORB A-30 1.5 0 1.5 0.5

FORESTALL 4 1 1.5 1.5

DEIONIZED WATER 0 0 0 0

With reference to Table 8, the composition of the present invention (Example No. 4) showed very little soil-attraction or no soil-attraction on any of the fabric samples evaluated.

As regards the commercially available compositions, SYNGARD WDA showed a high affinity to soil-attraction for the fabric sample treated with the drop of concentrate. TEGO SORB A-30 showed some soil attraction for the fabric sample treated with the drop of concentrate and at the 5- and 10-spray applications. FORESTALL showed the highest affinity for soil attraction, with the powder coating barely being removed from the fabric sample after tapping the sample that was treated with the drop of concentrate and some soil deposition at every dosage level. These results indicate that the fabric sample treated with the zinc-containing composition of Example No. 4 exhibited less build-up of powder over time compared to the other compositions that were used in the tests of the study.

Additional evaluations were conducted to determine the extent to which, if at all, odor-control compositions of the present invention and a commercially available composition could be cleaned from treated fabric samples of the type used in the evaluations of soil-attraction. The fabric samples were subjected to a benchtop "terge" test. This involved loading fabric samples into a beaker that contained 2000 ml of tap water and 0.8 g of a mild, liquid laundry detergent (2x Concentrated Xtra Liquid Laundry Detergent); the contents of the beaker were heated to 125°F and were agitated for 10 minutes, drained, and individually rinsed under running tap water at a temperature of 60-80°F. The fabric samples were then air dried on a rack and compared visually for soil (powder) removal.

For fabric samplers that were treated with TEGOSORB A-30, soil remained on the fabric sample treated with the drop of concentrated composition; the fabric sample was brittle and discolored. The fabric sample was subjected unsuccessfully to an additional "terge" test in that soil remained on the fabric after completion of the test. On the other hand, there was complete removal of soil from all of the other fabric samples and no discoloration or fading of the black fabric comprising the samples. There follows a description of an additional example of an aqueous odor-control composition within the scope of the present invention and one which contains a fragrance, a material which is used often in odor-control compositions. Example No. 6

The fragrance constituent of the composition was a fabric fragrance sold by Arylessence, Inc. as "Dapioni Silk." A water-soluble fragrance formulation was prepared initially by blending the fragrance with the following emulsifiers: (a) PEG - 50

(hydrogenated castor oil); (b) Polysorbate 80; and (c) Polysorbate 60.

The above fragrance-containing aqueous formulation was mixed with the ethoxylated (287 moles of ethylene oxide) and saponified product of Example No. 4 hereof which included also zinc chloride. The odor-control composition comprised the following ingredients (wt.% based on the total weight of the composition).

Ingredients wt.%

(A) Zn-containing product of Example No. 4 2.02

(B) fragrance 0.42

(C) Peg 50 0.07

(D) Polysorbate 80 0.42

(E) Polysorbate 60 0.07

(F) water 97.00

The above composition was an aqueous solution of the ingredients and had a clear appearance, with all of the ingredients being compatible with each other. The composition is suitable for application by spray.

In summary, the present invention can be used to reduce malodors of many types and in many types of "malodor" applications, including applications involving restoring and/or maintaining the freshness of various types of fabric articles without subjecting them to dry-cleaning, washing, or other cleaning operation.

Claims

1. A composition for use in treating a malodor comprising a carboxylic acid having covalently bonded to one or more hydroxyl groups of the carbon chain of the acid 1 to about 400 alkoxy groups in which the alkyl portion of the alkoxy group has one to about six carbon atoms, wherein the carbon chain of the acid can be saturated or unsaturated, can be linear or branched, and can have about 4 to about 22 carbon atoms.

2. A composition according to Claim 1 in solid form.

3. A composition according to Claim 1 in the form of an aqueous solution in which said carboxylic acid is dissolved, said solution being purified and free of solids and dissolved ingredients which over a period of time tend to come out of solution and form solids.

4. A composition according to Claim 3 wherein said solution has a pH of about 2 to about 5.

5. A composition according to Claim 3 or 4 including also a dissolved metal which has odor-control properties, preferably dissolved zirconium or copper, and most preferably dissolved zinc.

6. A composition according to Claim 2 including also a metal which has odor- control properties, preferably zirconium or copper, and most preferable zinc.

7. The saponified product of alkoxylated castor oil which comprises mixture of triglycerides of a plurality of fatty acids, including a major amount of the triglyceride of alkoxylated ricinoleic acid, in which the alkoxy group of the alkoxylated castor oil is a C₂- C6 alkoxy group, preferably an ethoxy group, and the number of alkoxy group(s) is 1 to about 400.

8. The product of Claim 7 in solid form.

9. The product according to Claim 8 including also a metal which has odor- control properties, preferably zirconium or copper, and most preferably zinc.

10. The product according to Claim 7 in the form of an aqueous solution and in which the alkoxy group is an ethoxy group and the aqueous solution has a pH of about 2 to about 5.

1 1. The product of Claim 7, 8, 9, or 10 wherein the number of ethoxy groups is about 200 to about 300, preferably about 240 to about 260 groups.

12. The product according to Claim 10 or 1 1 and including also a dissolved metal having odor-control properties, preferably dissolved zirconium or copper, and most preferably dissolved zinc.

13. A composition according to Claim 3 in the form of an aqueous concentrate of the aqueous solution and comprising: (A) about 20 to about 50 wt.% of the alkoxylated carboxylic acid; (B) optionally, but preferably about 0.1 to about 50 wt.% of dissolved metal having odor-control properties; and (C) about 50 to about 80 wt.% of water.

14. A composition according to Claim 3 in the form of a dilute aqueous solution comprising:

(A) about 1 to about 30 wt.% of the alkoxylated carboxylic acid;

(B) optionally, but preferably about 0.04 to about 30 wt.% of dissolved metal having odor-control properties; and

(C) about 70 to about 99 wt.% of water.

15. A product according to Claim 10 in the form of an aqueous concentrate of the aqueous solution and comprising: (A) about 20 to about 50 wt. % of salts of the alkoxylated castor oil; (B) optionally, but preferably about 0.1 to about 50 wt. % of dissolved metal having odor-control properties; and (C) about 50 to about 80 wt. % of water.

16. A product according to Claim 10 in the form of a dilute aqueous solution comprising:

(A) about 1 to about 30 wt.% of the alkoxylated carboxylic acid;

(C) about 70 to about 99 wt.% of water.

17. A product according to Claim 15 or 16 wherein the alkoxylated castor oil includes about 200 to about 300 ethoxy groups, preferably about 240 to about 260 ethoxy groups.

18. A process for preparing the product of Claim 7 comprising saponifying said alkoxylated castor oil in the presence of alkali or in the presence of steam.

19. A method for reducing malodor associated with an inanimate object or an animate being comprising treating the malodor with an odor-control composition or product defined in any preceding claim and containing zinc.

20. A composition comprising an aqueous, alkaline, purified solution in which there is dissolved a glyceride of a carboxylic acid having attached to one or more hydroxyl group(s) of the carbon chain of the acid portion of the glyceride 1 to about 400 alkoxy groups in which the alkyl portion of the alkoxy group has one to about six carbon atoms, wherein the carbon chain of the acid can be saturated or unsaturated, can be linear or branched, and can have about 4 to about 22 carbon atoms.

21. A composition according to Claim 20 wherein said solution has a pH of about 7.5 to about 8 and said glyceride is a triglyceride of the carboxylic acid and wherein the alkoxy groups are ethoxy groups.

22. A composition according to Claim 20 or 21 in which the source of the glyceride is castor oil.

23. A composition according to Claim 20, 21 , or 22 which includes mainly a triglyceride of ricinoleic acid having about 200 to about 300 ethoxy groups, preferably about 240 to about 260 ethoxy groups.

24. A method for increasing the water-solubility of a carboxylic acid having attached to one or more carbon atoms of the carbon chain of the acid a hydroxyl group, wherein the carbon chain of the acid can be saturated or unsaturated, can be linear or branched, and can have about 4 to about 22 carbon atoms, the method comprising:

(B) saponifying in liquid form the glyceride to convert it to glycerol and a salt(s) of the alkoxylated acid.

25. A method according to Claim 24 wherein the source of the glyceride of the carboxylic acid is castor oil which comprises mainly a triglyceride of ricinoleic acid in which each of the ricinoleic acid portions of the triglyceride contains 1 to about 400 ethoxy groups.

26. A method according to Claim 25 wherein said ricinoleic acid portion contains about 200 to about 300 ethoxy groups, preferably about 240 to about 260 ethoxy groups.