CA2197440C - Uncomplexed cyclodextrin solutions for odor control on inanimate surfaces - Google Patents

Abstract

The present invention relates to a stable, aqueous odor-absorbing composition, for use on inanimate surfaces. The composition comprises from about 0.1 % to about 5 % by weight of the composition, of solubilized, water-soluble, uncomplexed cyclodextrin, from about 0.01 % to about 1 % by weight of the composition of low molecular weight polyols. Optionally, but preferably, an effective amount of solubilized, water-soluble, antimicrobial preservative, having a water-solubility of greater than about 0.3 % and perfume. The composition is essentially free of any material that would soil or stain fabric.

Description

WO 96109358 PCTlUS95I09086 UNCOI\IPLEXEI) CYCLUDEVTR.IN SOLI?TIONS
FOR ODOR CONTROL UN INANLMATE SURFACES
TECHNICAL FIELD
The present invention relates to stable, preterably clear, aqueous odor-absorbing compositions, articles of manufacture, andr'or method of use on inanimate surfaces, i.e., not for use directly on human skin, comprising solubilized, water-soluble uncompiexed cyciodextrin, low molecular weight polyols, and preferably, a solubilized, water-soluble antimicrobial presen~ative for said aqueous cyclodextrin solution. The odor-absorbing composition is designed to control odors caused by a broad spectrum of organic odariferous materials, which may, or may not, contain reactive functional groups, and to preferably remain shelf stable for a substantial period of time.
Preferably, the aqueous odor-absorbing compositions are for use on inanimate surfaces, especially fabrics, and more specifically, clothes, in order to restore and/or maintain freshness by reducing malodor without the need for washing or dry cleaning.
BACKGROUND OF TFIE INVENTION
The present invention relates to stable, preferably clear, aqueous odor absorbing compositions, articles of manufacture and/or method for use on inanimate surfaces, i.e., not for use directly on human skin, as an odor-absorbing composition.
Such compositions can aptionally provide a "scent signal" in the form of a pleasant odor which signals the removal of the malodor. Preferably, the compositions are sprayed onto fabrics, particularly clothes, to restore their freshness by reducing malodor without washing or dry cleaning. The compositions are preferably not used directly on human skin because the preferred preservative may cause skin irritation Fabrics treated with some preferred campositions of the present invention can also optionally provide release of fragrance upon rewetting, such as when the wearer perspires. This phenomenon provides an added benefit to fabrics treated with the 3C> composition of the present invention in that the fabrics will stay fresher longer.
A wide variety of deodorizing compositions are known in the art, the most common of which contain perfumes to mask malodor. Odor masking is the intentional concealment of one odor by the addition of another. The control of odor tin fabrics, in , particular clothes, has been accomplished by using perfumes, colognes, etc.
However, preference to perfume is greatly varied and high levels are needed to ensure that the malodor is no longer noticeable.

Odor modiIicanon. m which the .odor p chanced. a ~ . by ~hemmai modiucation. has also been used Current malodor moditication methods I:now,~, ~r, the art are o.~idative de<~radation. which uses oaidizin~ agents such as ow ~_en.
bleaches.
chlorine. chlorinated materials such as sodium hvpochlorite, chlorine diode.
et~ . and potassium permanganate to reduce malodor. and reductive degradation which uses reducing agents such as sodmm bisulfate to reduce malodor Both of these methods are unacceptable for general use on fabric because they can damage colored fabrics.
specifically, they can bleach and; or discolor colored fabrics Other methods of odor control utilize actives that are targeted to react with l a malodors having specific chemical functional groups Examples of such acw es are.
biauanide polymers, which complex with organic compounds containing organically bound N and,or S atoms and tatty alcohol esters of methyl methacrylic acid which react with thiols, amines, and aldehydes. Such actives are limited in the scope of protection which they afford because they only react with limited types of malodor .~
1 ~ more detailed description of these methods can be found in U S. Pat. Nos..
'_.44.093, 3,074,891; 4,818,524; and 4,946.672; and U.K. Pat. App. No. 941,105.
Other types of deodorizing compositions known in the art contain antibacterial and antifungal agents which regulate the malodor-producing microorganisms found on 20 the surface to which the deodorizing composition is directed. Many skin deodorant products use this technology. These compositions are not effective on malodors that have already been produced and malodors that do not come from bacterial sources.
such as tobacco or food odors.
Fabric malodor is most commonly caused by environmental odors such as 'S tobacco odor, cooking and/or food odors, or body odor. The unpleasant odors are mainly organic molecules which have different structures and functional groups, suct, as amines, acids, alcohols, aldehydes, ketones, phenoGcs, polycyclics.
indoles.
aromatics, polyaromatics, etc They can also be made up of sulfur-containing functional groups, such as, thiol. mercaptan, sul5de and/or disulfide groups.
30 It is preferable to apply an odor absorbing material, preferably a broad spectrum odor absorbing material, to fabrics rather than a masking or chemical reaction material for odor control between washing and dry cleaning operations .as opposed to a masking or chemical reaction material, an odor absorbing material can eliminate a broad spectrum of odoriferous molecules and usually does not contribute 35 an odor of its own. The commonly known solid odor absorbers such as activated charcoal and zeolites can be harmful to fabrics and therefore are not preferred as an odor controlling agent under these circumstances. Activated charcoal easily stains 21~~440 WO 96!05358 PCTlU995/09086 -;_ light colored fabrics and zeolites are seen as a light colored stain an dark colored fabrics. Furthermore, zcolites can cause "harsh" feel if too much is deposited.
Uncomplexed cycladextrin molecules, which are made up of varying numbers of glucose units provzde the absorbing advantages of known absorbent deodorizing compositions without harmful effects to fabrics. While cyclodextrin is an effective odor absorber, some small molecules are not sufficiently absorbed by the cyclodextrin molecules because the cavity of the cyclodextrin molecule may be too large to adequately hold the smaller organic molecule. if a small sized organic odor molecule is not suffciently absorbed into the cyelodextrin cavity, a substantial amount of I O malodor can remain. In order to alleviate this problem, low molecular weight palyals can be added to the composition to enhance the formation of cyclodextrin inclusion complexes.
Uncomplexed cycladextrin molecules, which are made up of varying numbers of glucose units provide the absorbing advantages of known absorbent deodorizing compositions without harmful effects to fabrics. The current teachings in the art suggest that cyclodextrin does not contribute to the growth of microorganisms despite the fact that they are made up of varying numbers of glucose units. See Effect of Hvdrox4~orapvl-B-cvclodextrin on the Antimicrobial Action of Preservatives, S.
J.
Lehner, B. W. Miller and J. K. Seydel, J. Pharm. Pharmacol 1994, 46:p.188 and Interactions Between P-Hydroxvbenzoic acid Esters and H~ro~cvoroRyl-B-Cyclodextrin and Their Antimocrobial Effect Against Candida Albicans, S. J.
Lehner, B. 41r. l4Jiller and J. K. Seydel. It has been discovered, however, that cyclodextrin is a prime breeding ground for certain microorganisms, especially when in aqueous compositions. This growth problem leads to a problem with storage stability of ZS cyclodextrin solutions for any significant length of time. Contamination by certain microorganisms, can cause microbial growth resulting in an unsightly and/or malodorous solution. Because microbial growrth in cyclodextrin solutions can occur, it is preferable to include a water-soluble antimicrobial preservative, which is effective for inhibiting and/or regulating microbial growth, to increase storage stability of clear, aqueous odor-absorbing solutions containing water-soluble cyclodextrin.

The present invention relates to a stable, aqueous odor-absorhing composition , for use on inanimate surfaces, comprising:
A. from about 0.1% to about 5%, by weight of the composition, of solubilized, water-soluble, uncomplexed cyclodextrin;

tfOm 300Ut ~J ~~ 1 ° o t0 3DOUt i ° o. hV w et~ht Of the COmpO5ltIOn JI iu~~
molecular wmht polvols.
C opoonallv. but preferably. an etFecme amount of polubii~zed. wtef-soluble. antimicrobial preservative hawn_ a water-solubilm of __reater than about 0 3°%0, D optional perfume.
E aqueous carrier: and wherein said composition is essentially free of any material that would soil or stain fabric 10 The composition can be incorporated into a spray dispenser to create an article of manufacture that can facilitate treatment of articles and/or surfaces with uncompiexed cyclodextrin solution of a level that is effective vet is not discernible when dried on the surfaces.

- 4a -In accordance with another aspect of the present invention there is provided an aqueous odor absorbing composition, comprising:
A. from about 0.1% to about 5%, by weight of the composition, of solubilized, water-soluble, uncomplexed cyclodextrin;
B. from about 0.01% to about 1%, by weight of the composition of low molecular weight polyol selected from the group consisting of propylene glycol, ethylene glycol, glycerol, and mixtures thereof;
C. aqueous carrier; and D. additional ingredient selected from the group consisting of:
(a) from about 0.0001% to about 0.5%, by weight of the composition of solubilized, water-soluble, antimicrobial preservative having a water-solubility of greater than about 0.3%;
(b) perfume at a level of from about 0.003% to about 0.3%, by weight of the composition;
(c) metallic salt selected from the group consisting of water-soluble zinc salts, water-soluble copper salts, and mixtures thereof; and (d) mixtures of (a), (b), and (c), D. being optional when the cyclodextrin is selected from the group consisting of (a) methylated-alpha-cyclodextrin (b) methylated-beta-cyclodextrin;
(c) hydroxypropyl beta-cyclodextrin; (d) hydroxypropyl alpha-cyclodextrin; and (e) mixtures thereof.
In accordance with another aspect of the invention, the cyclodextrin derivatives are selected from the group consisting of methyl substituted cyclodextrins, ethyl substituted cyclodextrins, hydroxyl alkyl substituted cyclodextrins, branched - 4b -cyclodextrins, cationic cyclodextrins, quaternary ammonium cyclodextrins, anionic cyclodextrins, amphoteric cyclodextrins, cyclodextrins wherein at least one glucopyranose unit has as 3-6-anhydro-cyclomalto structure, and mixtures thereof.
In accordance with another aspect of the present invention, there is provided a stable, aqueous odor absorbing composition, for use on inanimate surfaces, comprising:
A. from about 0.5% to about 5%, by weight of the composition, of a mixture of methylated-beta-cyclodextrin and alpha-cyclodextrin;
B. from about 0.02% to about 0.5%, by weight of the composition of propylene glycol;
C. from about 0.0001% to about 0.01%, by weight of the composition, of a water-soluble, antimicrobial preservative comprising a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one;
D. from about 0.003% to about 0.3%, by weight of the composition, of perfume; and 1 S E. water; and wherein said composition is free of any material that would soil or stain fabric.
In accordance with yet another aspect of the present invention, there is provided a stable, aqueous odor absorbing composition, for use on inanimate surfaces, comprising:
A. from about 0.5% to about 2%, by weight of the composition, of a mixture of methylated-alpha-cyclodextrin and methylated-beta-cyclodextrin;
B. from about 0.03% to about 0.3%, by weight of the composition, of propylene glycol;
C. from about 0.0001 % to about 0.01 %, by weight of the composition of a water-soluble, antimicrobial preservative comprising a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one;

- 4c -D. from about 0.1 % to about 10%, by weight of the composition, of ZnCl2 ;
E. from about 0.005% to about 0.2%, by weight of the composition, of perfume; and F. water; and wherein said composition is free of any material that would soil or stain fabric and has a pH of from about 4 to about 5.5.
In accordance with yet another aspect of the present invention there is provided, a stable, aqueous odor absorbing composition, for use on inanimate surfaces, comprising:
A. from about 0.5% to about 2%, by weight of the composition, a mixture of hydroxyethyl alpha-cyclodextrin and hydroxy ethyl beta-cyclodextrin;
B. from about 0.03% to about 0.3%, by weight of the composition, of ethylene glycol;
C. from about 0.0004% to about 0.002%, by weight of the composition, of a water-soluble, antimicrobial preservative comprising a mixture of S-1 S chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one;
D. from about 0.005% to about 0.2%, by weight of the composition of perfume; and E. water; and wherein said composition is free of any material that would soil or stain fabric and has a pH of greater than about 3.
In accordance with even yet another aspect of the present invention there is provided, a stable, aqueous odor absorbing composition, for use on inanimate surfaces, comprising:
A. from about 0.5% to about 2%, by weight of the composition, of a mixture of alpha-cyclodextrin and hydroxypropyl-beta-cyclodextrin;

- 4d -B. from about 0.03% to about 0.3%, by weight of the composition, of propylene glycol; and C. from about 0.0001 % to about 0.01 %, by weight of the composition of a water-soluble, antimicrobial preservative comprising a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one;
D. water; and wherein said composition is free of any material that would soil or stain fabric and has a pH of greater than about 3.
In yet another aspect of the present invention there is provided a method of controlling odor on inanimate surfaces, the method comprising spraying an effective amount of a composition of the present invention onto a fabric using a trigger-spray device wherein the trigger-spray device comprises a bottle made of clear polyethyleneterephthalate.

- 4e -DETAILED DESCRIPTION OF THE LVYEYTIOH
The present invention relates to a stable, aqueous odor-absorbing composition.
for use on inanimate surfaces, comprising:
A. from about 0.1% to about 5%, by weight of the composition, of solubiliied, water-soluble, uncomplexed cyclodextrin:
B. from about 0.01% to about 1%, by weight of the composition of low molecular weight polyols:
C. optionally, but preferably, an effective amount of solubilized, water-soluble, antimicrobial preservative having a water-solubility of greater than about 0.3%:
D. optional perfume;
E. aqueous carrier; and wherein said composition is essentially free of any material that would soil or stain fabric.
I. COMPOSITION
(A). CYCLODEXTRIN
As used herein, the term "ryciodextrin" includes any of the known cyclodextrins such as unsubstituted cyclodextrins containing from six to twelve glucose units, especially, alpha-cyclodextrin. beta-cyclodextrin, gamma-cyclodexcrin andlor their derivatives and/or mixtures thereof. The alpha-ryclodextrin consists of sir glucose units, the beta-ryclodextrin consists of seven glucose units, and the gamma-cyclodextrin consists of eight glucose units arranged in a donut-shaped ring.
The W0 96lD5358 PCT/US95I04(186 -5_ specific coupling and conformation of the glucose units give the cycladextrins a rigid, conical molecular structure with a hollolv interior of a specific volume. The "lining" of the internal cavity is formed by hydrogen atoms and glycosidic bridging oxygen atoms.

therefore, this surface is fairly hydrophobic. The unique shape and physical-chemical properties of the cavity enable the cyclodextrin molecules to absorb (farm inclusion complexes with) organic molecules or parts of organic molecules which can fit into the cavity. Many odorous molecules can fit into the cavity including many malodorous molecules and perfume molecules. Therefore, cyclodextrins, and especially mixtures of cycladextrins with different size cavities, can be used to control odors caused by a bread spectrum of ar~,anic odoriferous materials, which may, or may not, contain reactive functional groups. The complexation between cyclodextrin and odorous molecules occurs rapidly in the presence of water. However, the extent of the complex formation also depends on the polarity of the absorbed molecules. In an aqueous solution, strongly hydrophilic molecules (these which are highly water-I 5 soluble) are only partially absorbed, if at all. Therefore, cyclodextrin does not complex effectively with some very low molecular weight organic amines and acids when they are present at low levels on wet fabrics. As the water is being removed however, e.g., the fabric is being dried off, some law molecular weight organic amines and acids have mare affutity and will complex with the cyclodextrins more readily.

The cavities within the cyclodextrin in the solution of the present invention should remain essentially unfilled (the cyalodextrin remains uncomplexed) while in solution, in order to allow the cyclodextrin to absorb various odor molecules when the solution is applied to a surface. Non-derivatised (normal) beta-cyclodextrin can be present at a level up to its solubility limit of about 1.85%
(about I .85g in 100 grams of 2i water) at room temperature. Beta-cycladextrin is not preferred in compositions which call for a level of cyclodextrin higher than its water solubility limit. Nan-derivatised beta-cyclodextrin is further not preferred when the composition contains optional perfiAme material and a clear solution is preferred. When non-derivatised beta-cyclodextrin is used in either of these situations the aqueous solution becomes cloudy and is not clear. Not to be limited by theory, it is believed that some beta-cyclodextrin andlor beta-cyclodextrinlperFume complexes solidify and!or precipitate out producing an undesirable cloudy aqueous solution.

Preferably, the odor absorbing solution of the present invention is clear. The term "clear" as defined herein means transparent or translucent, preferably transparent as in "water clear," when observed through a layer having a thickness of less than about 10 cm.

Pre:erablv. the cvclode~trins used in the present invention are 'tu~hiv ester soluble such as. alpha-cvclodewnn and or derivatives thereot. gamma-cvclodextrm and. or derivatives thereof, derivatised beta-cvclode~ctnns, and, or mixtures thereof The derivaoses of cvclodertrin consist mainly of molecules wherein some of the OH
Qroups are converted to OR groups Cvclodextrin derivatives include. a ~ .
those with short chain allcvl groups such as methvlated cyciode~ctrins, and ethylated cvclodextnns.
wherein R is a methyl or an ethyl group: those with hvdroxyali.-~~I
substituted groups.
such as hvdroxypropyl cvclodextrins and/or hydroxyethvl cvclodextrins. wherein R is a -CHI-CH(OH)-CH3 or a 'CH~CH~-OH group; branched cvclode~ctrins such as 10 maltose-bonded cvciodextrins: cationic cyclodextrins such as those contairuno =
hvdroxv-3(dimethvlamino)propyl ether, wherein R is CH2-CH(OHl-CH=-'fCH;)_ which is cationic at low pH; quaternary ammonium, e.g.. =-hvdroxv~-~-(tnmethylammonio)propyl ether chloride groups, wherein R is CH,-CH(OH)-CH=-~'-(CH3)3C1-: anionic cyclodextrins such as carboxvmethyl cyclodextrins.
15 cyclodextnn sulfates, and cyciodextrin succinyiates; amphoteric cyciodextrins such as carboxymethyUquaternary ammonium cyclodextrins: cyclodextrins wherein at least one glucopyranose unit has a 3-6-anhydro-cyclomalto structure, e.g., the mono-anhydrocyclodextrins, as disclosed in "Optimal Performances with Minimal Chemical Modification of Cyclodextrins". F. Diedaini-Pilard and B. Perly, The 7th International 20 Cvclodextrin Symposium Abstracts, April 1994, p. 49, a n a m i x t a r a s t n a r a o t . Other cyciodextrin derivatives are disclosed in C,' S
Pat. yos: 3,426,011. Parmerter et al., issued Feb. 4, 1969: 3,453,257:
3,453.358:
3,.53.259; and 3.453,260, all in the names of Parmerter et al., and all issued July I.
1969; 3,459,731, Gramera et al., issued Aug. 5. 1969; 3,553,191. Parmerter et al .
25 issued Jan. 5, 1971; 3.565,887, Parmerter et al., issued Feb. 23, 1971;
4.535.152.
Szejtli et al., issued Aug. 13, 1985; 4,616,008, Hirai et al., issued Oct. 7.
1986, 4,678,598, Ogino et al., issued Jul. 7. 1987; 4.638,058, Brandt et al., issued Jan. 20.
1987; and 4,746,734, Tsuchiyama et al., issued May 24, 1988 .
30 Highly water-soluble ryclodextrins are those having water solubility of at least about 10 g in 100 ml of water at room temperature, preferably at least about 20 g in 100 ml of water, more preferably at least about 25 g in 100 ml of water at room temperature. The availability of solubilized, uncomplexed cyclodextrins is essential for an effective and efficient odor control performance. Solubilized, water-soluble 35 cyclodextrin can exhibit more efficient odor control performance than non-water-soluble cyclodextrin when deposited onto surfaces, especially fabric.

2i~~r~~
WO 96!05358 PG°fltJS9510908G
-7_ Examples of preferred water-soluble cyclodextrin derivatives suitable for use herein are hydroxypropyl alpha-cyclodextrin, methylated alpha-cyclodextrin.

. methylated beta-cyclodextrin, hydroxyethyl beta-cyclodextrin, and hydroxypropyl beta-cyclodextrin. Hydroxyalkyl cyclodextrin derivatives preferably have a degree of substitution of from about 1 to about 14, more preferably from about I S to about 7, wherein the total number of OR groups per cyclodextrin is defined as the degree of substitution. Mfethylated cyclodextrin derivatives typically have a degree of substitution of from about 1 to about 18, preferably from about 3 to about 16. A

known methylated beta-cyclodextrin is heptakis-2,6-di-O-methyl-(3-cyclodextrin, commonly known as DIME, in which each glucose unit has about

2 methyl groups with a degree of substitution of about 14. A preferred, more commercially available, methylated beta-cyclodextrin is a randomly methylated beta-cyclodextrin having a degree of substitution of about 12.6. The preferred cyclodextrins are available, e.g., from .American Niaize-Products Company and blacker Chemicals (USAj, Inc.

I~ It is also preferable to use a mixture of cyclodextrins.
Such mixtures absorb odors more broadly by complexing with a wider range of odoriferous molecules having a wider range of molecular sizes. Preferably at least a portion of the cyclodextrins is alpha-cyclodextrin and its derivatives thereof, gamma-cyclodextrin and its derivatives thereof, andlor derivatised beta-cyclodextrin, more preferably a mixture of alpha-cyclodextrin, or an alpha-cyclodextrin derivative, and derivatised beta-cyclodextrin, even more preferably a mixture of derivatised alpha-cyclodextrin and derivatised beta-cyclodextrin, most preferably a mixture of hydroxypropyl alpha-cyclodextrin and hydroxypropyl beta-cyclodextrin, andlor a mixture of methylated alpha-cyclodextrin and methylated beta-cyclodextrin.

For controlling odor on fabrics, the composition is preferably used as a spray.

It is preferable that the composition of the present invention contain low levels of cyclodextrin so that a visible stain does not appear on the fabric at normal usage levels.

Preferably, the solution is virtually not discernible when dry. Typical levels of cyclodextrin are from about 0.1% to about 5,%, preferably from about 0.2io to about 4ro, more preferably from about 0.3% to about 3.~0, most preferably from about 0.4%

to about 2io. Compositions with higher concentrations can leave unacceptable visible ' stains on fabrics as the solution evaporates off of the fabric. This is especially a problem on thin, colored, synthetic fabrics. In order to avoid or minimize the ' occurrence of fabric staining, it is preferable that the fabric be treated at a level of less than about 5 mg ofcyclodextrin per mg of fabric, more preferably less than about 2 mg of cyclodextrin per mg of fabric.

wo ~~rossss ~ ~ ~ ~ ~ ~ ~ ecTrt~s~srayosc~
_g_ Concentrated compositions can also be used in order to provide a Icss expensive product. When a concentrated product is used, i.e., w°hen the level of cyc(odextrin used is from about 3°.o to about 5"-m, it is preferable to dilute the composition before treating fabrics in order to avoid staining. Preferably the cycladextrin is diluted with about 50°~o to about 2000°ro, more preferably with about 60°o to about 1000°~~, most preferably with about 75°ro to about 500°o by~ weight of the composition of water.
(B). L.OfY MOLECULAR WEIGHT POLYOLS
Low molecular weight polyols with relatively high boiling points, as compared to water, such as ethylene glycol, propylene giyco! and/or glycerol are preferred optional ingredients far improving odor control performance of the composition of the present invention. Not to be bound by theory, it is believed that the incorporation of a small amount of low molecular weight glycols into the composition of the present invention enhances the formation of the cyclodexttin inclusion completes as the fabric dries.
It is believed that the polyals' ability to remain on the fabric far a longer period of time than water, as the fabric dries allows it to form ternary complexes with the cyclodextrin and same malodorous molecules. The addition of the glycols is believed to fill up void space in the cyclodextrin cavity that is unable to be filled by some malodor molecules of relatively smaller sixes. Preferably the glycol used is ethylene glycol, andlor propylene glycol. Cyclodextrins prepared by processes that result in a level of such polyols are highly desirable, since they can be used without removal of the polyols.
Typically, glycol is added to the composition of the present invention at a level of from about O.OI°,r° to about 7°ro, by weight of the composition, preferably from about 0.02°ro to about 0.5°1°, more preferably from about 0.03°,r° to about 0.3°ro, by weight afthe composition. The preferred weight ratio allow molecular weight polyal to cyclodextrin is from about 2:1,000 to about 20:100, more preferably from about

3:1,0(70 to about 15:100, even more preferably from about 5:1,000 to about 10:100, and mast preferably from about i :100 to about 7:100.
(C). OPTIONAL ANT114IICROBIAL PRESERVATIVE
Optionally, but preferably, solubilized, water-soluble, antimucrobiai presen~ative can be added to the composition of the present invention because cycladextrin molecules are made up of varying numbers of glucose units which can make them a prime breeding ground for certain microorganisms, especially when in aqueous 21974.0 W'O 9G1053iS PCT/US95109056 -g_ compositions. This problem, that certain organisms grow extremely well on cyclodextrin, has not been previously disclosed. This drawback can lead to the problem of storage stability of cyclodextrin solutions for any significant len~rth of time.
contamination by certain microorganisms with subsequent microbial grow ~th can result , 5 in an unsightly and/or malodorous solution. Because microbial growth in cyclodextrin solutions is highly objectionable when it occurs, it is highly preferable to include a solubilized, water-soluble, antimicrobial preservative, which is effective for inhibiting and/or regulating microbial growth in order to increase storage stability of the preferably clear, aqueous odor-absorbing solution containing water-soluble cyclodextrin Typical microorganisms that can be found in cyclodextrin supplies and whose growth can be found in the presence of cyclodextrin in aqueous cyclodextrin solutions include bacteria, e.g., Bacillus thurin~iensis (cereus group) and Bacillus sphaericus;
and fungi, e.g., .Aspereillus ustus. Bacillus s~haericus is one of the most numerous members of Bacillus species in soils. Aspergillus ustus is common in grains and flours which are raw materials to produce cyclodextrins. Microorganisms such as Escherichia toll and Pseudomonas aeruginosa are found in some water sources, and can be introduced during the preparation of cyclodextrin aqueous solutions.
It is preferable to use a broad spectrum preservative, e.g., ono that is effective on both bacteria (both gram positive and gram negative) and fungi. A limited spectrum preservative, e.g., one that is only effective on a single group of microorganisms, e.g., fungi, can be used in combination with a broad spectrum preservative or other limited spectrum preservatives with complimentary andtor supplementary activity. A mixture of broad spectrum preservatives can also be used.
2S Antimicrobial preservatives useful in the present invention include biocidal compounds, i.e., substances that kill microorganisms, or biostatic compounds, i.e , substances that inhibit and/or regulate the growth of microorganisms.
Preferred antimicrobial preservatives are those that are water-soluble and are effective at low levels because the organic preservatives can form inclusion complexes with the cyclodextrin molecules and compete with the malodorous molecules for the cyclodextrin cavities, thus rendering the cyclodextrins ineffective as odor controlling actives. Water-soluble preservatives usefulin the present invention are those that have a solubility in water of at least about 0.3 g per 100 ml of water, i.e., greater than about 0.3% at room temperature, preferably greater than about 0.5% at room temperature.
These types of presen~atives have a lower atflnity to the cycladextrin cavity, at least in the aqueous phase, and are therefore mare available to provide antimicrobial activity.
Preservatives with a water-solubility of less than about 0.3% and a molecular structure PCTlUS95lOJOS6 WO 9Cr105358 _l0_ that readily fits into the cyclodextrin cavity, have a greater tendency to form inclusion complexes with the cyclodextrin molecules, thus rendering the preservative Iess etFective to coniral microbes in tire cycladextrin solution. Therefore, many well know°n preservatives such as sham chain alkyl esters of p-hydraxybenzaic acid, commonly known as parabens; N-(4-chlorophenyl)-N'-{3,4-dichlorophenyl) urea, also known as 3,4,4'-trichlorocarbanilide or triclocarban; 2,4,4'-trichloro-2'-hydraxy diphenyl ether, commonly known as triclasan are not preferred in the present invention since they are relatively ineffective when used in conjunction with cycladexrtrin.
The water-soluble antimicrobial preservative in the present invention is included at an effective amount. The term "effective amount" as herein defined means a level sufficient to prevent spoilage, or present growth of inadvertently added microorganisms, 1°ar a specific period of time. In other wards, the preservative is not being used to kill microorganisms on the surface onto which the composition is deposited in order to eliminate odors produced by microorganisms. Instead, it is preferably being used to prevent spoilage of the cyclodextrin solution in order to increase the shelf Tile of the composition. Preferred levels of presen.~ative are from about 0.0001% to about 0.5°,i°, more preferably from about 0,0002°.'° to about 0.2°ia, most preferably from about 0.0003°Jo to about 0.1°J°, by weight of the composition.
In order to reserve mast of the cyclodextrins far odor control, the cyclodextrin to preservative molar ratio should be greater than about 5:1, preferably greater than about iO:I, mare preferably greater than about 50:1, even mare preferably greater than about 100:1.
The preservative can be any organic preservative material which will not cause damage to fabric appearance, e.g., discoloration, coloration, bleaching.
Preferred water-soluble preservatives include organic sulfur compounds, haiagenated compounds, cyclic organic nitrogen compounds, low molecular weight aldehydes, quaternary ammonium compounds, dehydroacetic acid, phenyl. and phenaxy compounds, and mixtures thereof The follot~ing are non-limiting examples of preferred water-soluble preservatives for use in the present invention.
(I) Oreanic Suifnr Compounds ' Preferred water-soluble preservatives for use in the present invention are organic sulfur compounds. Some non-limiting examples of organic sulfur compounds suitable for use in the present invention are:
(aj 3-Isothiazotone Compounds 219i~40 W0 96105358 PCT/CTS9510y08G
-Il-A preferred preservative is an antimicrobial, organic preservative containing _>-isothiazolone groups having the formula:
R~ O
N
R S~ ~Y
wherein Y is an unsubstituted alkyl, alkenyl, or alkynyl group of from about 1 to about 1 R
carbon atoms, an unsubstituted ar substituted cycloalkyl group having from about a 3 to about a b carbon ring and up to 12 carbon atoms, an unsubstituted or substituted aralkyl group of up to about 10 carbon atoms, or an unsubstituted or substituted aryl group of up to about 10 carbon atoms;
RI is hydrogen, halogen, or a (CI-C4) alkyl group; and R2 is hydrogen, halogen, or a (C I-C4) alkyl group.
Preferably, when Y is methyl or ethyl, RI and R2 should not both be hydrogen.
Salts of these compounds formed by reacting the compound with acids such as hydrochloric, nitric, sulfuric, etc. are also suitable.
This class of compounds is disclosed in U.S. Pat. No. 4,265,899, Lewis et al., issued May 5, 1981, and incorporated herein by reference. Examples of said compounds are: 5-chloro-2-methyl-4-isothiazolin-3-one; 2-n-butyl-3-isothiazolone; 2-benzyl-3-isothiazolone; 2-phenyl-3-isothiazolone, 2-methyl-4,5-dichloroisothiazolone;
; 5-chloro-2-methyl-3-isothiazolone; 2-methyl-4-isothiazolin-3-one; and mixtures thereof A preferred preservative is a water-soluble mi.~cture of 5-chlora-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isathiazolin-3-one, more preferably a mixture of about 77°% 5-chloro-2-methyl-4-isothiazolin-3-one and about 23°io 2-methyl-4-isothiazolin-3-one, a broad spectrum preservative available as a 1.5% aqueous solution under the trade name Kathon~ CG by Rohm and Haas Company.
When Kathon~ is used as the preservative in the present invention it is present at a level of from about 0.0001% to about 0.01%, preferably from about 0.0002°rb to about 0.005°ro, more preferably from about 0.0003% to about 0.003%, most preferably from about 0.0004% to about 0.002%, by weight of the composition.
(b) Sodium Pvrithione Another preferred organic sulfur preservative is sodium pyrithione, with water solubility of about 50°io. W hen sodium pyrithione is used as the preservative in the present invention it is typically present at a level of from about 0.0001°~o to about 2~~744~
W~D ~36I05358 PCT/U895/0~08G

O.OI°~~, preferably from about 0.0002°.'n to about 0.005°~0, more preferably from about 0.000 3~~o to about 0 003°0, by weight afthe composition.
Mixtures of the preferred organic sulfur compounds can also be used as the presen ative in the present invention.
(2) Halo~enated Compounds Preferred preservatives far use in the present invention are halogenated compounds. Some non-limiting examples of halogenated compounds suitable far use in the present invention are:
S-bromo-5=vitro-1,3-dioxane, available under the trade name Brorudox LQ~
from Henkel. Bronidox L~ has a solubility of about 0.46°ra in water When Branidax is used as the preservative in the present invention it is typically present at a level of from about 0.0005°f° to about 0.02°ro, preferably from about 0.001°~o to about 0.01°,a, by weight ofthe composition;
2-bromo-2-nitropropane-1,3-diol, available under the trade name Bronapof~
from lnolex can be used as the preservative in the present invention. $ranapol has a solubility of about 25°.'° in water. When Bronopol is used as the preservative in the present invention it is typically present at a Ievei affrom about 0.002°~e to about 0.1°,'A, preferably from about 0.005°r'o to about 0.05%, by weight of the composition;
1,1"-hexamethylene bis(S-(p-chlorophenyl)biguanide), camnranly known as chlarhexidine, and its salts, e.g., with acetic and glucazuc acids can be used as a preservative in the present invention. The digluconate salt is highiy water-soluble, about 70°rn in water, and the diacetate salt has a solubility of about 1.8°,~o in water.
When chlorohexidine is used as the preservative in the present invention it is typically present at a level of from about 0.0001°l° to about 0.04%, preferably from about 0.0005°,~o to about 0.01%, by weight of the composition.
1,1,1-Trichloro-2-methylpropan-2-al, commonly known as chlorobutanal, with water solubility of about 0.8°ln; a typical effective level of chlorabutanol is from about 0.1 °rb to about 0.~°.'n, by weight of the composition.

4,4'- (Trimethylenedioxy)his-(3-bromobenaamidine) diisethionate, or dibromopropamidine, with water solubility of about 50°ro; when dibromapropamidine is used as the preservative in the present invention it is typically present at a le~,~el of from about 0.0001% to about 0.05°.0, preferably from about 0.0005°/n to about 0.01°ra by weight ofthe composition.
hfixtures of the preferred halogenated compounds can also be used as the preservative in the present invention.

WO 9Gl05358 PCTlUS9510908G

(3) Cvclic Organic Nitra~en Compounds Preferred water-soluble preservatives for use in the present invention are cyclic organic nitrogen compounds. Some pan-limiting examples of cyclic organic nitrogen compounds suitable far use in the present invention are:
(a) Imidazolidinedione Compounds Preferred preservatives far use in the present invention are imidazalidione compounds. Some non-limiting examples of imidazolidinedione compounds suitable far use in the present invention are:
1,3-bis(hydraxymethyl)-S,S-dimethyl-2,4-imidazalidinedione, commonly known as dimethyloldimethylhydantoin, or DMDl~4 hydantain, available as, e.g., Glydant~ from Lonza. DMDbI hydantoin has a water solubility of more than ~0°ro in water, and is mainly effective on bacteria. When DMDMI hydantoin is used, it is preferable that it be used in combination with a broad spectrum presen~ative such as Kathon CG~, or formaldehyde. .A preferred mixture is about a 95:5 DhIDMI
hydantoin to 3-butyl-2-iodopropynylcarbamate mixture, available under the trade name Glydant Plus~ from Lonza. When Glydant Plush is used as the preservative in the present invention, it is typically present at a level offrom about 0.005% to about 0.2%;
N-[ 1,3-bis(hydroxymethyl)2,5-dioxo-4-imidazolidinylj-N,N'-bis(hydroxymethyl} urea, commonly known as diazolidinyl urea, available under the trade name Germall III from Sutton Laboratories; Inc. (Sutton) can be used as the preservative in the present invention. lVhen German IIQ is used as the preservative in the present invention, it is typically present at a level of from about 0.01°,~o to about 0.1°r°;
N,N"-methylenebis; N'-[1-(hydroxymtethyl}-2,5-dioxa-4-imidazolidinyl]ureaf, commonly known as imidazolidinyl urea, available, e.g., under the trade name AbiolC
from 3V-Sigma, Unicide U-13~ from Induchem, Germall l 15~ from (Sutton) can be used as the preservative in the present invention. When imidazolidinyl urea is used as the presen°ative, it is typically present at a level of from about 0.05° o to about 0.2°~0, by weight ofthe composition.
Mixtures of the preferred imidazolidinedione compounds can also be used as the presewative in the present invention.
(b) Polvmethoav Bicvclic Oxazolidine Another preferred water-soluble cyclic organic nitrogen preservative is polymethoxy bicyclic oxazolidine, having the general formula:

WO 9b105358 ~ ~ ~ ~ ~ PCT/US95IOhOgb Ha_.~JH
.
where n has a value of from about 0 to about 5. and is available under the trade name Nuasept~ C fTam Huts Arrrerica. When Nuosept~ C is used as the preservative, it is typically present at a level of from about 0.005°,'o to about 0.1°.'6, by weight of the composition.
Mixtures of the preferred cyclic organic nitrogen compounds can also be used as the preservative in the present invention.
(4) Low Molecular 'Vei2ht Aldehvdes (a). Formaldehyde .~, preferred preservative for use in the present invention is formaldehyde.
Formaldehyde is a broad spectrum preservative which is normally available as formalin which is a 37°rb aqueous solution of formaldehyde. Wtren formaldehyde is used as the preservative in the present invention, typical levels are from about 0.003°~'o to about 0.2°~6, preferably from about 0.008% to about 0.1%, more preferably from about 0.01°ro to about 0.05°r°, by weight ofttre composition.
(b) Glutaraldehvde A preferred preservative for use in the present invention is glutaraldehyde.
Glutaraldehyde is a water-soluble, broad spectrum preservative commonly available as a 25°~0 or a 50% solution in water. When glutaraldehyde is used as the preservative in the present invention it is typically present at a level of from about 0.005°,~o to about 0.1°ro, preferably from about 0.01°.'° to about 0.05°r'°, by weight of the composition.

(5) Ouaternarv Compounds Preferred preservatives for use in the present invention are cationic and~ar quaternary compounds. Such compounds include polyarninopropyl biguanidc, also known as polyhexamethylene biguanide having the general formula:
HC1~NHz-(CHZ)3-[-(CH2);-NH-C(~=NHrNH-C(=Nli.HCI~NH-(CH2)3-jx-fCFfxj~-Nri-CS'NtiFNf~i~CN

z~ 9~~40 Wp 96105358 PCTIUS95/0908f _15_ Polyaminopropyl bi;uanide is a water-soluble, broad spectrum preservative which is available as a 20° o aqueous solution available under the trade name Cosmocil C(2~ from ICI Americas, Inc., ar under the trade name I~fikrokill~ from Brooks, Inc.
I-(3-Chlarallyl) -3,5,7-triaza-1-azoniaadamantane chloride, available, e.~;., under the trade name Dowicil 200 from Dow Chemical, is an effective quaternary ammonium preservative; it is freely soluble in water; however, it has the tendency to discolor (yellow), therefore it is not highly preferred.
Mixtures of the preferred quaternary ammonium compounds can also be used as the preservative in the present invention.
When quaternary ammonium compounds are used as the preservative in the present invention, they are typically present at a level of from about 0.005°~o to about 0.2°,~0, preferably from about 0.01 % to about 0. l°ro, by weight of the composition.

(6). Dehvdroacetic Acid I S A preferred preservative for use in the present invention is dehydroacetic acid.
Dehydroacetic acid is a broad spectrum preservative preferably in the form of a sodium or a potassium salt so that it is water-soluble. This presen~ative acts more as a biostatic preservative than a biocidal preservative. When dehydroacetic acid is used as the preservative it is typically used at a level of from about 0.005°,r° to about 0.2%, preferably from about 0.008% to about 0.1%, more preferably from about 0.01%
to about 0.05%, by weight of the composition.

(7) Phenvl and Phenoxv Comuounds Some non-limiting examples of phenyl and phenoxy compounds suitable for use in the present invention are:
4,4'-diamidino-a,ra-diphenoxypropane diisethionate, commonly known as propamidine isethionate, with water solubility of about 16%; and 4,4'-diamidino-a,m-diphenoxyhexane diisethionate, commonly known as hexamidine isethionate.
Typical effective level of these salts is about 0.0002% to about 0.05%.
Other examples are benzyl alcohol, with a water solubility of about 4°r°; 2-phenylethanol, with a water solubility of about 2%; and 2-phenoxyethanol, with a water solubility of about 2.67%; typical effective level of these phenyl and phenoxy alcohol is from about 0.1°,/o to about 0.5°ro, by weight of the composition.

(8) Mixtures thereof The preservatives of the present invention can be used in mixtures in order to control a broad range of microorganisms.

WO )fil0$35$ ~ ~ ;~ ~ PCTIU5~35f0~Q13G
$acteriostatic effects can sometimes be obtained for aqueous compositions ny adjusting the composition pH to an acid pH, e.g., Less than about pH 4, preferably less than about pH 3, or a basic pl~I, e.g., greater than about 10. preferably greater than about 11. Low pH for microbial control is not a preferred approach in the present invention because the low pH can cause chemical degradation of the cycladextrins High pH for microbial control is also not preferred because at high pH's, e.g., greater than about 10, preferably greater than about I l, the cyclodextrins can be ionized and their ability to complex with organic materials is reduced. Therefore, aqueous compositions of the present invention should have a pH of from about ~ uy about 10, preferably from about =1 to about 8, more preferably from about ~.5 to about 6.
As stated above, it is preferable to use the preservative at an effective amount, as detined herein above. Optionally however, the preseruative can be used at a level which provides an antimicrobial effect on the treated fabrics. Even when the preservative is used in this capacity, it is preferable that an effective level of cyclodextrin molecules remain uncomplexed in the solution in order to provide the odor absorbing benefit.
(D) PEITFUME
The odor absorbing composition of the present invention can also optionally provide a "scent signal" in the form of a pleasant odor which signals the removal of malodor From fabrics. The scent signal is designed to provide a tlecting perfume scent, and is not designed to be overwhelming or to be used as an odor masking ingrediert. When perfume is added as a scent signal, it is added only at very law levels, e.g., from about 0% to about 0.5°/'°, preferably from about 0.003°.%o to about 0.3°/d, mare preferably from about 0.005% to about 0.2°!0, by weight of the composition.
Perfume can also be added as a more intense odor in product and on surf=aces.
When stranger levels of perfume are preferred, relatively higher levels of perfume can be added. It is essential, however, that the perfume bs added at a Level wherein even if all of the perfume in the composition were to complex with the cyclodextrin molecules, there will still be an effective level of uncamplexed cyclodextrin molecules present in the solution to provide adequate odor control. In order to reserve an ' effective amount of cyclodextrin molecules for odor control, peri-'ume is typicaEly°
present at a level wherein less than about 90% of the cyclodextrin complexes with the ' perfume, preferably less than about 50°ro of the cyclodextrin complexes with the perfume, mare preferably, less than about 30% of the cyclodextrin complexes with the perfume, and most preferably, less than about 10°.0 of the cycladextrin complexes with 2r97440 WO 96105358 PCTlU59510908G

the perfume. The cyclodextrin to perfume weight ratio should be greater than about $:l, preferably ~=reater than about 10:1, more preferably greater than about 20:1, even more preferably greater than 40:1 and most preferably greater than about 7U:1.
Any type of perfume can be incorporated into the composition of the present S invention. There are however, perfume characteristics which are preferred for use on fabrics in order to provide a fresh fabric impression and perfume characteristics which are preferred for household use.
Preferably, at least about 25°,~a, more preferably at least about SO°%, most preferably at least about 75°~0, by weight of the perfume is composed of fragrance l0 material selected from the group consisting of aromatic and aliphatic esters having molecular weights From about 130 to about 250; aliphatic and aromatic alcohols having molecular weights from about 90 to about 240; aliphatic ketones having molecular weights from about 1 S0 to about 260; aromatic ketones having molecular weights from about 1 SO to about 270; aromatic and aliphatic lactones having I 5 molecular weights from about 130 to about 290; aliphatic aldehydes having molecular weights from about 140 to about 200; aromatic aldehydes having molecular weights from about 90 to about 230; aliphatic and aromatic ethers having molecular weights from about ISO to about 270; and condensation products of aldehydes and amines having molecular weights from about I80 to about 320; and essentially free from 20 nitromusks and halogenated fragrance materials.
More preferably, at least about 25%, more preferably at least about SO%, most preferably at least about 7S°t°, by weight of the perfume is composed of fragrance material selected from the group consisting of:
I Common Name Chemical Chemical Name Approa.
Type ni.w.

adoxal ali haticaldehvdc2.6,10-trimetlrvl-9-undecen-1-al210 ailvl am'1 lvcolate ester allvl amyl lvcolate l82 allvl cvclohe~.3ne ester allvl-3-cvclohexvl l9l ro innate ro innate amvl acetate ester 3-methyl-I-butanol l3(1 acetate amyl salicvlate ester amyl salicvlate 208 anisic aldehvde aromatic 4-metho, benzaldehvde136 aldehvde aurantiol schiff'basecondensation product 305 of methyl anthranilate and hvdroxvcitronellal bacdanol aliphatic 2-ethyl-4-(2,2,3-trimethyl-3-208 alcohol evclo enten-I-vl)-2-butea-I-of benzaldehvde aromatic benzaldehvde 106 aldehvde W096/05358 ~ j' ~ PCTJG~595109086 bcnzo hemme aromatic benzn henone 18 ketone ~

benni acetate ester ~bennl acetate _ 15(1 beuwl sali~ late ester benzvl salicwlate 228 betadanutscone alipltrticketonet-I2,ti.6-trimethvl-1-cvclo-heeen-tr)-1-vl)_Z-buten-I-onr beCt ~armna hexanol alcohol 3-hexes-1-of !O1(i buecnxime aliphatirketone1,5-dimethy9-oximebicyclo[3,2.1Id7 octan-8-one cedrol alcohol octahydro-3,6,8,8-tetramett~yt-222 1H-3A.7-methartoazulen-C-of cetalox ether dodecahydro-3A,6,6,9A-236 tetramethvlna htho 2.1B -fiuan cis-3-hexenvi acetateester cis-3-hexenvl acetate142 cis-3-hexenvl salicvlateester beta, wma-hexeavl 22(1 salicvlate citronellol alrnhol 3,7dimethvl-ti-octcnoll5ti citronetivl nitrile nitrite eram~l nitrite 151 clove stem oil natural coumarin lactose coutnarin 146 cyclohexvi salicvlateester aclohexvl Bali lute 22(1 c;mal aromatic 2-methyl-3-(para iso I9t1 aldehyde propyl hen'I) ro ionaldeh de decvl aldehvde alt hatic decvl aldeh de I SG
aldehvde delta darnascone aliphatic l-('2.b.ti-trimethyl-3-cyclo-hexen-192 ketone 1- I -2-buten-I-ono dihvdromvrcenol alcohol 3-methvlene-7-meth Lib I octan-7-of dimeihyl benzyl carbinylester dimethyl benzyl carbinyl192 acetate acetate eUtvl vanillin aromatic ethyl vanillin ifi6 aldehvde ethyl-2-methvi butyrateewer ethyl-2-methyl butyrate13(1 ethylene brassylate macrocyclic ethylene tridecan-1,I3-dioate27(I
lactose enrai tot all hatic 1,8-e xv- a-menthane 4 oxide 13 eu enol alcohol 4-allvl-2-meilwxr _ henol Ifi4 exaltotide macroeyctic cyclopentadecanotide 24tJ
lactose tloraceGate ester dihydro-nor-cyclopentadiemll9ft acetate tlorhydral I aromatic 3-(3-isopropvlphenvll19(1 aldehvde butanal ~~ ~»~o innene ester dihydro-nor-cyrlopentadienyl20G
ro innate galaxolide ether 1,3.4,6,7.8-hexahydro-258 4,G,G,7,8,8-he.eamethylcyclopenta-gamma-2-benzo vmne gamma decalactone lactone 4-Id-hepty-4-hydroaybutanoic170 acid lactone ganuna dodecalactonclactone d-N-ocni-4-hvdroxv-butanoic198 acid lactone .

eeranioi alcohol 3,7-dimethvl-2,6-actadien-I-ofl5~

geranyI acemte ester ;, 7-dimethyl-2,ti-octadien-t-vlI96 acetate >eranvl nitrite ester 3,7-diemthvl-2.6-octadieneeutrileI49 helionat aromatic alpha-methyl-3,4, 192 aldehyde (methylenedioxy) hvdrocinnamaldehvde heliotro in aromatic heliotro in 150 aldehvde hexvl acetate ester he 'I acetate 144 hexvl cinnamic aldehvdearomatic al ha-n-hexvl cinnamic216 aldehvde aldehvde hexvl salicvlate ester he I salicvlate 222 hvdroxvambratt ali hatic 2-cvclododecvl- ro 226 alcohol anoi hvdromcitronellal all hatic h droxvcitronellal I72 aldetrdve ionone alpha aliphatic 4-(2,6,Ei-Irimethyl-1-192 ketone cvclohexenvl-I-t9)-3-buten-2-one ionone beta aliphatic 4-(2,6,6-trimethyl-1-cyclohexen-I92 ketone 1-vp-3-butene-2-tme ionone gamma methyl aliphatic 4-(2,6,6-trimethyl-2-cyclohexy206 ketone l-I-vl -3-methyl-3-buten-2-one iso E super aliphatic 7-acetyl-1,2,3,4,5,6,7,8-234 ketone octattydro-I ,1,6,7,tetramethy I
na hthalene iso eu euol ether 2-methoxv-4 1- ro IG4 envl? henol iso jasmone aliphatic 2-methyl-3-(2-pentenyl)-2-166 ketone cvclo nten-1-one koavone all hatic acetyl di-isoamvlene 182 aldeh 'de lauric aldehvde all hatic lauric aldehvde 184 aldehvde lavandin natural lavender natural 2~~~~40 W O 96105358 PCI'1U89510908ti lemon CY natural atajor component d-limonene d-liatonenelorange aikene i-methyl-4-iso-propenyl-I-I3E
tarpenes cvclohexene linalool ' alcohol 3-hydroxv-3,7-dinrethyi-l,fi-IS4 nctadiene linalyl acetate ester 3-hcdroy-3,7-dimethy9-1.6-19ti octadiene acetate Irg 201 ester 2,4-dihvdroxv-3,6-dimethr'11~)6 benzoic acid methyl ester lyral aliphatic 4-(4-hydroxy-.Z-methyl-pentyp2I0 aldehyde 3-cvlcohexene-1-carboea3dehvde majarnol aliphatic 2,2-dimethyl-3-(3-methylpttenyl)-l78 alcohol ro anol may'o1 alcohol 4-( 1-methylethy'I) 156 cyciohexane methanol methyl antltranilatearomatic methyl-2-aminobenzoatei51 amine methv'i beta na hthvlaromatic methvi beta hthyl l70 ketoae ketone ketonc methyl cedrv4one aii boric metitvt cedrenvl 246 ketone ketone methyl chavicol ester 1-metftyloey-4,2-propen-I48 I-vlbenzene mntiml dihvdro 'asmonatealt hatic methyl dihvdro 'asmonate22t:i ketone methyl aonvl acetaldehydea.li hatic methyl nortyl acetaldehyde184 aldehvde musktitdartone aromaticketone.I-acetyl-6-teributy4-I,Idimethyl24.1 indane nerol alcohol 2-cis-3,7-dimethy4-2,6-octadien-154 I-of nonatactone lactone 4-hvdroxvnonanoic I56 acid, lactone nortimbanol aliphatic I-(2,2,6-trimethyl-cyclohexyI)-3-226 alcohol hexanol orange CP natural major component d-limnnene P. T.bucinal aromaticaldehyde2-methyl-3(parateributylphenyl)204 ro ionaldehvde bvdroxv henyl butanonearomatic hvdro henvlhutanone I<i4 ketone atchouli natural henvl acetaldehyde aromatic I-oxo-2- henrlethane120 aldehvde phenyl acetaldehyde aromatic phenyl acetaldehyde 16E
dimethy9 aldehyde dimetityl aceial acetat z~ ~~~~.o WO 96/05358 PCT'JU595109086 Zl hem I ethyl acenue ester hem l ethyl acetate 64 henvl ethyl alcoholalcohol henvl etttvl alcohol I Z?

hettvl etltt7 heml ester 2- henvlethvl henvl 240 acetate acetate henvl hexanoU henoYanolalcohol :>-mcthVl-5- henvl 178 entartol poiysantoi aliphatic ,3-dimethyl-5-(2.2,3-tnmethyl-221 3 alcohol 3-cyclopenten-1-vll-4- enten-2-of renvl acetate ester 2-methvlbuten-2-ol-!-acetate128 rosy hen aromatic 2-methyl-5- hanvl 178 alcohol entanol sandahvood natural alpha-terpinene aliphatic I-methyl-3-iso- I36 alkatte ra v(cvclohe.aadiene-1.3 terpineol (t>Jpha alcohol para-menUr t-en-8-ol,154 terpineol and para-beta to ineol) menth-1-en-1-of to invl acetate ester arc-month-1-en-8-vl 196 acetate tetra hvdro lirtaloolalt htic 3,7-dimethvl-3-octanol158 alcohol tetraltvdronrvrcenolalt hatic 2,6-dimethvl-2-octanot158 alcohol tonalitUmusk plus aromatic 7-acetyl-1,1,3,4,4,6-hexamethyl258 ketone tetralin undecalactone lactone 4-N-hephl-4-hydroxybutanoic184 acid lactone undecavertol alcohol 4-methvi-3-decen-5-ofI70 undecvl aldehvde alt hatic undecanal 170 aldeh de undecvlenic aldehvdealt boric undecv4enic aldehvde 1ti8 aldehvde vanillin aromatic 4-hydroxy-3- 152 aldehyde metho. ~bomaldehvde verdox ester 2-tort-bu 'I cvclohexvll98 acetate vettener ester 4-tert-bu 1 cvclohe, 198 I acetate and mixturesthereof When high initial perfume odor impact on fabrics is desired, it is also preferable to select a perfume containing perfume ingredients which are not too hydrophobic.
The less hydrophobic perfume ingredients are more soluble in water, and are more available in the odor absorbing composition, The degree of hydrophobicity of a perfume ingredient can be correlated with its octanoUwater partitioning coeffrcient P.
The octanoUwater partitioning coef&cient of a perfume ingredient is the ratio between its equilibrium concentration in octanol and in water. A perfume ingredient with a greater partitioning coef;'tcient P is more hydrophobic. Conversely, a perfume ingredient with a smaller partitioning coefficient P is more hydrophilic. The preferred perfume ingredients of this invention have an octanoUwater partitioning coefficient P

_ ,>2 _ of about l ~=~Ou or smaller Since the partitiorune coefficients '~: the pe~;um:
m~redients normally have hi~.:h values. they are more conveniently ome,~, ;n the term of their lo;arnhm to the, base 1u. Io~P Thus the perfume Ingredients et this mennon have Io~P of about ?~ or smaller The IoeP of many perfume ingredients has been reported. for example. the Pomona9= database, available from Dayllight Cherrucal Information Systems. Inc (Daylight CIS). Irvine. California, contains many, along with citations to the oripnal literature However, the loge values are most conveniently calculated by the "CLOGP" program. also available from Daylight CIS This program also lists 10 erperimental IogP values when they are available in the Pomona9? database The "calculated IogP" (CIogP) is determined by the fragment approach of Hansch and Leo I cf , .~. Leo, in Comprehensive Medicinal Chemistry, Vol 4. C Hansch. P G
Sammens. 1. B. Taylor and C. A. Ramsden, Eds., p. ?95, Pergamon Press. 1990 >
.
The fragment approach is based on the chemical 1 ~ structure of each perfume ingredient, and takes into account the numbers and types of atoms, the atom connectivity, and chemical bonding. The CIogP values, which are the most reliable and widely used estimates for this physicochemical property, are used instead of the experimental loge values in the selection of perfume ingredients which are useful in the present invention.
'0 Non-limiting examples of perfume ingredients which have ClogP values of about 3 or smaller are benzaldehyde, benzyl acetate, cis-3-hexenyl acetate, coumarin, dihydromyrcenol, .dimethyl benryl carbinyl acetate, ethyl vanillin.
eucah~ptol, eugenol.
iso eugenol, floc acetate, geraniol, hydroxycitronetlal, koavone, linalool, methyl anthranilate, methyl beta naphthyl ketone, methyl dihydro jasmonate. nerol.
~S nonalactone, phenyl ethyl acetate, phenyl ethyl alcohol, alpha terpineol, beta terpineol.
vanillin, and mixtures thereof.
When hydrophilic _perfume is desired, at least about '_5% by weight of the perfume, more preferably about 50%, mast preferably about 75%, is composed of perfume ingredients having a ClogP of about 3 or smaller.
30 Cyclodextrin molecules are known for their ability to form complexes with perfume ingredients and have typically been taught as a perfume carrier. The prior art teaches the use of drier-added fabric softener sheets containing high levels of cyclodextrin/perfume complexes wherein the fabrics treated with this solid cyclodextrin complex release perfume when the fabrics are rewetted The art also 35 teaches that cyclodextrinlperfume complexes used in aqueous rinse-added fabric softener compositions must be protected with a hydrophobic wax coating so the cyclodextrin/perfume complexes will not decompose due to the presence of water W096105358 ~ ~ PCTIUS9510y086 See U.S. Pat. Nos. 5,10,564 Gardlik et al., issued April 7, (992; 5,234,610 Gardlik et al , issued August l0, 1993; 5,234,61 1 Trinh, et al., issued August 10, 199:1. It is therefore highly surprising and unexpected to find that fabrics treated with the aqueous compositions of the present invention, which contain low levels of uncomplexed cyclodextrin and even lower levels of perfume, also exhibit perfume release upon rewetting. 'this phenomenon creates a benefit in that fabrics treated with the composition of the present invention will thus remain fresh longer, via a perfume release, when said fabrics are rewetted, such as when the wearer perspires.
(E). CARRIER
Aqueous solutions are preferred for odor control. The dilute aqueous solution provides the maximum separation of cyclodextrin molecules on the fabric and thereby maximizes the chance that an odor molecule will interact with a cyclodextrin molecule.
The preferred carrier of the present invention is water. The water which is used can be distilled, deionized, or tap water. Water not only serves as the liquid carrier for the cycladextrins, but it also facilitates the complexation reaction between the cyclodextrin molecules and any malodorous molecules that are on the fabric when it is treated. It has recently been discovered that water has an unexpected odor controlling effect of its own. It has been discovered that the intensity of the odor generated by some golar, low molecular weight organic amines, acids, and mercaptans is reduced when the odor-contaminated fabrics are treated with an aqueous solution.
Not to be bound by theory, it is believed that water solubiiizes and depresses the vapor pressure of these polar, low molecular weight organic molecules, thus reducing their odor intensity.
(F) OTHER OPTIONAL INGREDIENTS
The composition of the present invention can optionally contain adjunct odor-controlling materials, chelating agents, antistatic agents, insect and moth repelling agents, colorants, especially bluing agents, antioxidants, and mixtures thereof in addition to the cyclodextrin molecules. Incorporating adjunct odor-controlling materials can enhance the capacity of the cyclodextrin to control odors as well as broaden the range of odor types and molecule sizes which can be controlled.
Such materials include, for example, metallic salts, water-soluble cationic and anionic polymers, zeolites, water-soluble bicarbonate salts, and mixtures thereof.

11 Metallic Salt Opoonallv. but hi~hlv preferred. the present invention can wclude metallm ;alt:
for added odor absorption and. or antimicrobial benefit for the cvclodextnn solu;~;.~n The metallic salts are selected from the croup consisting of copper salts.
tine salt: and rruxtures thereof Copper salts have some antimicrobial benefits Specifically. cupn;, ab~etate acts as a fungicide, copper acetate acts as a nvldew inhibitor. cupric chloride acts as a fungicide, copper lactate acts as a fungicide, and copper sulfate acts as a ~ernucide Copper salts also ,possess some malodor control abilities See C,' S Pat vo 10 3.l 7..817. Leupold, et al.. which discloses deodorizing compositions for treann~
disposable articles, comprising at least slightly water-soluble sale of acvacetone.
including copper salts and zinc salts .
The preferred zinc salts possess malodor control abilities. Zinc has been used 15 most often for its ability to ameliorate malodor, e.g., in mouth wash products. as disclosed in U.S. Pat. Nos. 4,325,939, issued Apr. 20, 1982 and 4,469,674, issued Sept. 4, 1983, to N. B. Shah, et al.
Highly-ionized and soluble zinc salts such as zinc chloride, provide the best source of zinc ions. Zinc borate functions as a fungistat and a mildew inhibitor, zinc caprylate 20 functions as a fungicide, zinc chloride provides antiseptic and deodorant benefits, zinc ricinoleate functions as a firngicide, zinc sulfate heptahydrate functions as a fungicide and zinc undecylenate functions as a fungistat.
Preferably the metallic salts are water-soluble zinc salts, copper salts or mixtures thereof, and more preferably zinc salts, especially ZnCl2. These salts are 25 preferably present in the present invention primarily to absorb amine and sulfur containing compounds that have molecular sizes too small to be effectively complexed with the cyclodextrin molecules. Low molecular weight sulfur-containing materials.
e.g., sulfide and mercaptans, are components of many types of malodors, e.g., food odors (garlic, onion), body/perspiration odor, breath odor, etc. Low molecular weight 30 amines are also components of many malodors, e.g., food odors, body odors, urine.
etc.
When metallic salts are added to the composition of the present invention they are typically present at a level of from about 0.1% to about 10%, preferably from about 0.2% to about 8%, more preferably from about 0.3% to about 5% by weight of 35 the composition. When zinc salts are used as the metallic salt, and a clear solution is desired, it is preferable that the pH of the solution is adjusted to less than about 7.

_ 2~~ _ more preferably less than grout h. most preferably. less than about ~. m order t,~ ~.e::
the solution clear (2) Water-Soluble Polymers Some water-soluble polymers. a a . water-soluble cationic polymer and water-soluble anionic polymers can be used in the composition of the present m enoon t.~
provide additional odor control benefits a. Cationic polymers. e.Q.. nolvamines Water-soluble cationic polymers, a g., those containing amino tuncuonalines.
10 amido functionalities, and mixtures thereof, are useful in the present invention to control certain acid-type odors.
b. .W ionic oolvmers, e.Q.. oolvacrvlic acid Water-soluble anionic polymers, e.g., polyacrylic acids and their water-soluble salts are useful in the present invention to control certain amine-type odors Preferred 1 ~ polvacrylic acids and their alkali metal salts have an average molecular weight of less than about 20,000, more preferably less than 5,000. Polymers containing sulfonic acid groups, phosphoric acid groups, phosphoric acid groups, and their water-soluble salts, and mixtures thereof, and mixtures with carboxylic acid and carboxylate groups, are also suitable.
20 Water-soluble polymers containing both cationic and anionic functionalities are also suitable. Examples of these polymers are given in U.S. Pat. 4,909,986, issued March 20, 1990 to N. Kobayashi and A. Kawazoe .
Another example of water-soluble polymers containing both cationic and anionic functionalities is a copolymer of dimethyldiallyl ammonium chloride and acrylic acid.
25 commercially available under the trade name Merquat 280~ from Calgon.
(3). Soluble Carbonate and/or Bicarbonate Salts Water-soluble alkali metal carbonate and/or bicarbonate salts, such as sodium bicarbonate, potassium bicarbonate, potassium carbonate, cesium carbonate, sodium 30 carbonate, and mixtures thereof can be added to the composition of the present invention in order to help to control certain acid-type odors. Preferred salts are sodium carbonate monohydrate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, and mixtures thereof. When these salts are added to the composition of the present invention, they are typically present at a level of from about 0.1% to about 35 5%, preferably from about 0.2% to about 3%, more preferably from about 0 3°~o to about 2%, by weight of the composition. When these salts are added to the composition of the present invention it is preferably that incompatible metal salts roc wo ~~ross~ rcrnrshsrovoss -2t;_ be present in the invention, Preferably, when these salts are used the composition should be essentially free of zinc and other incompatible metal ions, e.~., Ca, Fe, Eia, etc. which form water-insoluble salts.
(d). ChelatinE.r~aents Some amine acid chelating agents such as ethyienediaminetrtraacetic acid (EDTA) can optionally be added to the composition of the present invention m order to enhance the activity of the water-soluble, antimicrabial preservative.
~lrhcn a chelating agent is added to the composition of the present invention, it is typically It) present at a level nffrom about 0.01°!° to about 0.3°n, preferably from about 0.05°'o to about 0.2°~0. It is important that the composition of the present invention be essentially free of any added metal ions that can be chelated by any chelating agent that is added to the compositiaa of the present invention because such metal ions complex with, and deactivate, the chelating agents.
I
(5). Antistatic.gents The composition of the present invention can optionally contain an elective amount of antistatic agent to provide the treated clothes with in-wear static.
Preferred antistatic agents are those that are water soluble in at least elective amount, such that 20 the composition remains a dear solution. Examples of these antistatic agents are monoalkyl cationic quaternary ammonium compounds, e.g., mono(C I O-C 14 alky()trimethyl ammonium halide, such as monolauryl trimethyl ammonium chloride, hydroxycetyl hydraxyethyl dimethyl ammonium chloride, available under the trade name Dehyquart E~ from Henkel, and ethyl bis(polyetho;Ky ethanol) alkylammonium 25 ethylsulfate, available under the trade name Variquat 66~ from Witco Corp., polyethylene glycols, polymeric quaternary ammonium salts, such as polymers conforming to the general formula:
-1N(CH3)z-(CHI)3-NH-CO-Nl-I-(CH2)3-N(CH~)Z+-CH~CHZOCHZCHZI-x ~~' 2x(C'1°1 available under the trade name Mirapal A-I5~ from Rhone-Poulenc, and -[N(CI-I3),-(CHZ)~-NH-CO-(CH?)Q-CO-NH-(CHZ)3-N(CH~)2-(CHZCHZOCH2CH~j-k~ x[C1-], available under the trade name Mirapol AD-1~ from Rhone-Poulenc, quaternized polyethyleneinvnes, v'rnylpyrrolidone/methacrylamidopropyltrimethylarnmonium chloride copolymer, available under the trade name Gafquat H5-100 from GAF;

tr~ethemum hvdrolwed ~olia~en ethosulfate. ava~labte un.!er the trade .name to,:at_P.;, E = from Vlavorool:. and mmures thereof It is preferred that a no ioam~n~. or low foaming. went ~s used. to aeon team formation during fabric treatment It is also preferred that polvethow laced a~_:nc suc as polyethylene glycol or ~'ariquat 66~% are not used when alpha-cvclodemnn is used The polyethoxylate groups have a strong affinity to, and readily complex with.
aipha-cvclodextnn which in turn depletes the uncomplexed cvclodextrin available for odor control V'hen an antistatic agent is used it is typically present at a level of from about l0 0 0~°° to about 10°,°, preferably from about 0 1°o to about ~°ro, more preferably from about 0.3°~o to about 3°'0, by weight of the composition.
('). Insect and/or 'Moth Reyelling Agent The composition of the present invention can optionally contain an effective I ~ amount of insect and/or moth repelling agents. Typical insect and moth repelling agents are pheromones. such as anti-aggregation pheromones, and other natural and~or synthetic ingredients. Preferred insect and moth repellent agents useful in the composition of the present invention are perfume ingredients, such as citronellol, citranellal, citral, linalool, cedar extract, geranium oil, sandalwood oil, 20 (diethyiphenoxy)ethanol, 1-dodecene, etc Other examples of insect and/or moth repellents useful in the composition of the present invention are disclosed in ~.S Pat.
Vos. 4,449,987, 4,693,890, 4,696,676, 4,933.371, 5,030,660, 5,196.200, and in "Semio Activity of Flavor and Fragrance Molecules on Various Insect Species".
B D
V4ookherjee et al., published in Bioactive Volatile Compounds from Plants.
.aSC
'_5 Symposium Series 525, R. Teranishi, R.G. Buttery, and H. Sugisawa, 1993, pp. 35-48.
When an insect and/or moth repeLent is used it is typically present at a level of from about 0.005% to about 3%, by weight of the composition.
30 (8) Solubilizing Aid The odor absorbing composition of the present invention can also optionally contain a solubilizing aid to solubilize any excess hydrophobic organic materials, a g..
perfume, insect repelling agent, antioxidant, ete., that are not readily soluble in the composition, to form a clear solution. A suitable solubilizing aid is surfactant, 5 preferably no-foaming or low-foaming surfactant. Suitable surfactants are nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants.
zwitterionic surfactants, and mixtures thereof. Suitable surfactants can be emulsiners V40 9(105358 PCTfUS9510908(i and~or detersive surfactants, Mixtures of emulsifiers and detersive surfactants are also preferred. When a surfactant containing one, ar more, aliphatic alkyl group is used, it is preferred that it contain relatively short alkyl chains of from about 5 to ab<aut 1~1 carbon atoms. Preferred nonionic surfactants are polyethylene glycol-polypropylene glycol block copolymers, such as Pluronic~ and Pluronia R~~ surfactants from 13ASF;
Tetronic~ and Tetroruc Rfi3~ surfactants from BASF, ethoxyiated branched aliphatic diols such as Surtynol~ surfactants from Air Products; ethoxylated alkyl phenc.Vs, such as Igepal~r~ surf~actanis from Rhone-Paulenc; ethaxylated aliphatic alcohols and carboxylic acids; polyethy~iene glycol diesters of fatty acids; fatty acid esters of ethoxylated sorbitans; and mixtures thereof Preferred anionic surfactants are dialky°1 sulfosuccinate, ailtylarylsulfonate, fatty alcohol sulfate, paraffin sulfonate, alkyl sarcosinate, alkyl isethionate salts having suitable canons, e.g., sodium, potassium, alkanol ammonium, etc., and mixtures thereof. Preferred amphoteric surfactants are the betaines. It is preferred that the surfactant have goad wetting properties, Also IS preferred are surfactants that have the hydrophilic groups situated between hydrophobic chains, such as Pluronic R~ surfactants, Surfynal surfactants, polyethylene glycol diesters of fatty acids, fatty acid esters of ethoxylated sorbitans, dialkyl sulfosuccinate, di(Cg-CIZ aIkyl)di(CI-C2 sikyi)ammaruum halides, and mixtures thereof or surfactants that have the hydrophobic chains situated laetween hydrophilic groups, such as Pluronic surfactants; and mixtures thereof llZiactures of these surfactants and other types of surfactants are also preferred to farm na-foanung ar low-foaming solubilizing agents. Polyalkylene glycol c;an be used as a defoaming agent in combination with the solubiIizing agents.
If solubi3izing agent is used in the present compositions, it is typically used at a level of from about 0.05% to about 1% by weight of the composition, more preferably from about 0.05°f° to about 0.3%.

(9). Additional Qdor Absorbers When the clarity of the solution is not needed, and the solution is not sprayed an fabrics, other optional odor absorbing materials, e.g., zeolites andlor activated carbon, can also be used.
(a). Zeolites A preferred class of zeolites is characterized as "intermediate"
silicate/aluminate zeolites. The intermediate zeofites are characterized by Si02/AIOfi molar ratios of less than about i0. Preferably the molar ratio of Si02fA102 ranges from about 2 to about 10. The intermediate zeolites have an advantage aver the "high" zeolites. The intermediate zeolites have a higher afr'tnity for amine-type odors, ?_19~~40 WO 96I053S8 PCT/US9510908Cr they are mare weight et3icient for odor absorption because they have a larger surface area, and they are more moisture tolerant and retain more of their odor absorbing capacity in water than the high zeolites .A wide variety of intermediate zeolites suitable far use herein are commercially available as Valfor~ CP301-68, Valfor~ 300-63, Valfor~ CP300-35, and Valfar~ CP300->6, available from PQ Corporation, and the CBV 100J series of zeolites from Conteka.
Zealite materials marketed under the trade name Abscents~ and Smeilrite~, available from The Union Carbide Corporation and UOP are also preferred. These materials are typically available as a white powder in the 3-5 micron particle size range. Such materials are preferred over the intermediate zeolites for control of sulfur-containing odors, e.g., thiols, mercaptans.
(b). Activated Carbon The carbon material suitable foe use in the present invention is the material well known in commercial practice as an absorbent for organic molecules and/or for alr purification purposes. Often, such carbon material is referred to as "activated" carbon ar "activated" charcoal. Such carbon is available from commercial sources under such trade names as; Calgon-Type CPG~; Type PCB; Type SGL~;
Type CALF; and Type OLD.
It is preferred that no, or essentially no, volatile low molecular weight monohydric alcohols such as ethanol and/or isopropanol are intentionally added to the composition of the present invention since these volatile organic compounds will contribute both to flammabilit)~ problems and environmental pollution problems. If small amounts of low molecular weight monohydric alcohols are present in the composition of the present invention due to the addition of these alcohols to such things as perfumes and as stabilizers far some preservatives, it is preferable that the level of monohydric alcohol be less than about 5°ro, preferably less than about 3°ro, more preferably less than about l°ro.
(I(i) Colorant Colorants and dyes, especially blueing agents, can be optionally added to the odor absorbing compositions for visual appeal and performance impression. When colorants are used, they are used at extremely low levels to avoid fabric staining, Preferred colorants for use in the present compositions are highly water-soluble dyes, e.g., Liquitint~ dyes available from Milliken Chemical Co. Nan-limiting examples of suitable dyes are, Liquitint Blue HP~, Liquitint Blue 65~, Liquitint Patent Blues, Liquitint Royal Biue~, Liquitint Experimental Yellow 8949-43~, Liquitint Green HMC~, Liquitint Yellow III, and mixtures thereof, preferably Liquitint Blue HP~, 2 ~ ~~~~.~
WO 9GI05358 ~"~'~JS'~~'tt'~Og~
_30_ Liquitint Blue 6iTt~, Liquitint Patent Blue~~, Liquitint Royal Blue ~, Liquitint Experimental Yellow 8949-X323:, and nuxtures thereof LI. ARTICLE OF MANUF~CTCtRE
The composition of the present invention can also be used in an article of manufacture comprising said composition plus a spray dispenser. When the commercial embadimenC of the article of manufacture is used, it is optional, but preferable, to include the preservative. Therefore, the most basic article of manufacture comprises uncomplexed cyciodextrin, a carrier, and a spray dispenser.
i0 SPRAY ULSPENSER
The article of manufacture herein comprises a spray dispenser. The cyclodextrin composition is placed into a spray dispenser in order to be distributed onto the fabric, Said spray dispenser is any of the manually activated means 'For producing a spray of liquid droplets as is known in the art, e.g. trigger-type, pump-type, non-aerosol selF pressurized, and aerosol-type spray means. The spray dispenser herein does not include those that will substarnially foam the clear, aqueous odor absorbing composition. It is preferred that at least about 80%, more preferably, at least about 90% of the droplets have a particle size of larger than about 30iam The spray dispenser can be an aerosol dispenser. Said aerosol dispenser comprises a container which can be constructed of any of tire conventional materials employed in fabricating aerosol containers. The dispenser must be capable of withstanding internal pressure in the range of from about 20 to about I1~~
pa.i.g., more preferably from about 20 to about 70 p.s.i.g. The one important requirement concerning the dispenser is that it be provided with a valve member which will permit the clear, aqueous odor absorbing composition cantaiired in the dispenser to be dispensed in the fwrm of a spray of very fine, or finely divided, particles or droplets.
The aerosol dispenser utilizes a pressurized sealed container from which the char, aqueous odor-absorbing composition is dispensed through a special actuatorivalve assembly under pressure. The aerosol dispenser is pressurized by incorporating therein a gaseous component generally known as a propellant. Common aerosol propellants, e.g., gaseous hydrocarbons such as isobutane, and mixed halogenated hydrocarbons, which ors not preferred. Halogenated hydrocarbon propellants such as chlarailuoro hydrocarbons have been alleged to contribute to environmental problems.
Hydrocarbon propellants can form complexes with the cyclodextrin molecules thereby reducing the availability of uncomplexed cyclodextrin molecules for odor absorption Preferred propellants are compressed air, nitrogen, inert gases, carbon dioxide, etc. ,A

more complete description cf commercially available aerosol-spray dispe-:<e,-;
s~~~~:
m ~ S Pat \os _.-~;6.'-=. Steb~nns. issued .-April 3. l9ca. and :.an:~.__~.
E~aut~wr, et ai . issued .W Qust l %, l 4" I , Preferably the spray dispenser can be a self pressurized non-aerosol ;,ontamer having a convoluted liner and an elastomeric sleeve Said self-pressurized dispenser comprises a liner.%sleeve assembly containing a thin, fle~cible radial!
etpandable convoluted plastic liner of from about 0 010 to about U 0.0 inch thick, inside an essentially cylindrical elastomeric sleeve The liner/sleeve is capable of holding a f 0 substantial quantity of odor-absorbing fluid product and of causing said product to be dispensed .~ more complete description of self pressurized spray dispensers can be found in C,'.S. Pat. Los. x.111.97(" w'iner, issued Vlav I'_, 199., and ~.=3=.1.6.
Wirier, issued AuQ. 3. 1993 .~rtother type of aerosol spray dispenser is one wherein a bamer separates 15 the odor absorbing composition from the propellant (preferably compressed air or nitrogen), as disclosed in U.S I'at. No. 4,260,110, issued April ?. 1981, Such a dispenser is available from EP Spray Systems. East Hanover. New Jersey.
'More preferably, the spray dispenser is a non-aerosol, manually activated.
20 pump-spray dispenser. Said pump-spray dispenser comprises a container and a pump mechanism which securely screws or snaps onto the container The container comprises a vessel for containing the aqueous odor-absorbing composition to be dispensed.
The pump mechanism comprises a pump chamber of substantially fixed 25 volume, having an opening at the inner end thereof. Within the pump chamber is located a pump stem having a piston on the end thereof disposed for reciprocal motion in the pump chamber. The pump stem has a passageway there through with a dispensing outlet at the outer end of the passageway and an axial inlet port located inwardly thereof.
30 The container and the pump mechanism can be constructed of any conventional material employed in fabricating pump-spray dispensers, including, but not limited to polyethylene; polypropylene; polyethyleneterephthalate; blends of polyethylene, vinyl acetate, and rubber elastomer. A preferred container is made of clear, e.g..
polyethylene terephthalate. Other materials can include stainless steel. A
more 3 5 complete disclosure of commercialhy available dispensing devices appears in: U S Pat Nos.: 4,895,279, Schultz, issued January 23, 1990; 4,735,347, Schult2 et al., issued April ~ 1 ~73S. and ~.~-~. Abu. Carter. issued June =;, I ~S I -Most preterablv. the spray dispenser is a manually actuated tvs__er-;pra~.
dispenser Said trieeer-spray dispenser comprises a container and a tneLer both W
which can be constructed of any of the conventional material employed m ;abricaon~;
trigger-spray dispensers. including, but not limited to polyethylene.
polypropylene.
polvacetal. polvcarbonate, polvethvleneterephthalate. polwinvl chloride.
polystyrene. blends of polyethylene, vinyl acetate, and rubber elastomer Other materials can include stainless steel and glass. .~ preferred container is made of clear.

10 a g. polyethylene terephthalate The trigger-spray dispenser does not incorporate a propellant aas into the odor-absorbing composition. and preferably it does not include those that will foam the odor-absorbing composition The trigger-spray dispenser herein is typically one which acts upon a discrete amount of the odor-absorbine composition itself, typically by means of a piston or a collapsing bellows that displaces l ~ the composition through a nozzle to create a spray of thin liquid Said trigger-spray dispenser typically comprises a pump chamber having either a piston or bellows which is movable through a limited stroke response to the trigger for varying the volume of said pump chamber This pump chamber or bellows chamber collects and holds the product for dispensing. The trigger spray dispenser typically has an outlet check valve 20 for blocking communication and flow of fluid through the nozzle and is responsive to the pressure inside the chamber. For the piston type trigger sprayers, as the trigger is compressed, it acts on the fluid in the chamber and the spring, increasing the pressure on the fluid. For the bellows spray dispenser, as the bellows is compressed.
the pressure increases on the fluid. The increase in fluid pressure in either trigger spray 25 dispenser acts to open the top outlet check valve. The top valve allows the product to be forced through the swirl chamber and out the nozzle to form a discharge pattern An adjustable nozzle cap can be used to vary the pattern of the fluid dispensed.
For the piston spray dispenser, as the trigger is released, the spring acts on the piston to return it to its original position. For the bellows spray dispenser.
the bellows 30 acts as the spring to return to its original position. This action causes a vacuum in the chamber. The responding fluid acts to close the outlet valve while opening the inlet valve drawing product up to the chamber froth the reservoir.
A more complete disclosure of commercially available dispensing devices appears in U.S. Pat. Nos. 4.082.223, Nozawa, issued Apr. 4, 1978; 4.161.
'_'88.
35 McKinney, issued 3u1. 17, 1985; 4,434,917, Saito et al., issued Mat. 6.
1984; and 4,819,835, Tasaki, issued Apr. 11, 1989: 5,303.867, Peterson, issued Apr 19.
1994.

W O 96105358 PCT~S95/0908G
219T4~p _ 3 ; _ ~ broad array of trigger sprayers or finger pump sprayers are suitable far use with the compositions of this invention These are readily available from suppliers such as Calmar, Inc" City of Industry, California; CSI (Continental Sprayers, Inc.j. St.
Peters, Missouri; Berry Plastics Corp., Evansville, Indiana-a distributor of Gualac~
sprayers; or Seaquest Dispensing, Cary, Illinois.
The preferred trigger sprayers are the blue inserted GualaCa7 sprayer.
available from Berry Plastics Carp., or the Calmar TS800-IAA sprayers, available from Calmar Inc., because of the tine uniform spray characteristics, spray volume, and pattern size.
Any suitable battle or container can be used with the trigger sprayer, the preferred bottle is a 17 fl-oz. bottle (about 500 ml) of good ergonomics similar in shape to the Cinch battle. It can be made of any materials such as high density polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyethylene terephthalate, glass, or any other material that forms bottles. Preferably, it is made of high density polyethylene or clear polyethyUene terephthalate.
For smaller four fl-oz. size (about I 18 ml), a finger pump can be used with canister ar cylindrical bottle. The preferred pump for this application is the cylindrical Euromist III from Seaquest Dispensing.
LII. IViETHOD OF USE
The cyclodextrin solution herein can be used by distributing, e.g., by placing the aqueous solution into a dispensing means, preferably a spray dispenser and spraying an effective amount onto the desired surface or article. r1n effective amount as defined herein means an amount sufftcient to absorb odor to the paint that it is not discernible by the human sense of smell yet not so much as to saturate or create a pool of liquid on said article or surface and so that when dry there is no visual deposit readily discernible. Distribution can be achieved by using a spray device, a roller, a pad, etc.
Preferably, the present invention does not encompass distributing the cyclodextrin solution on to shiny surfaces including, e.g., chrome, glass, smooth vinyl, leather, shiny plastic, shiny wood, etc. It is preferable not to distribute the cyclodextrin solution onto shiny surfaces because spotting and filming can mare readily occur on the surfaces. Furthermore, the cycladextrin solution is not far use on human skin, especially when an antimicrobial preservative is present in the composition because skin irritation can occur.
The present invention encompasses the method of spraying an etFective amount of cyclodextrin solution unto household surfaces. Preferably said household surfaces W O 96ttI5358 PCTlUS951t19ii86 .,4 are selected from the group consisting of countertops. cabinets, walls, floors.
bathroom surfaces and kitchen surfaces.
The present invention encompasses the method of spraying a mist of an effective amount of cyclodextrin solution onto fabric andlor fabric articles.
Freferabiy, said fabric andJor fabric articles include, but are not limited to, clothes, curtains, drapes, upholstered furniture, carpeting, bed linens, bath linens, tablecloths, sleeping bags, tents, car interior, etc.
The present invention encompasses the method of spraying a mist of an effective amount of cyclodextrin solution onto and into shoes wherein said shoes are not sprayed to saturation.
The present invention encompasses the method of spraying a mist of an effective amount of cyclodextrin solution onto shower curtains.
The present invention relates to the method of spraying a mist of an effective amount of cyclodextrin solution onto and/or into garbage cans and,~or recycling bins.
The present invention relates to the method of spraying a mist of an effective amount of cyclodextrin solution into the air to absorb malodor.
The present invention relates to the method of spraying a mist of an effective amount of cyclodextrin solution into and/or onto major household appliances including but not limited to: refrigerators, freezers, washing machines, automatic dn~ers, ovens, 2t7 microwave ovens, dishwashers etc., to absorb malodor.
T'he present invention relates to the method of spraying a mist of an effective amount of cyclodextrin solution onto cat litter, pet bedding and pet houses to absorb malodor.
The present invention relates to the method of spraying a mist of an effective amount of cycfodextiin solution onto household pets to absorb malodor.
.411 percentages, ratios, and parts herein" in the Specification, Examples, and Claims are by weight and are approximations unless otherwise stated.
The following are non-limiting examples of the instant composition. Perfume compositions that are used herein are as follows:

A B C

Perfume Ingredients 4lrt.:o:0 4i~t..o 3,7-Dimethyl-G-octenol 10 - 5 Benzyl salicyIate S 20 5 Benzyl acetate lp 1> 5 Benzophenone .i S -Octahydro-3,6,8,8-tetramethyl-IH-3A,7-methanoazulen-6-al 2 WO 96l~5358 PCTlUS95/0908d 3-Methylene-7-methyl octan-7-of 10 _ Dihydro-nor-cyclopentadieny) acetate 5 _ 5 I,_,,4,6,7,8-Hexahydro-4,(i,6,7,8,8-heaamethvl-lU - -cyclopenta -gamma-2-benzopyrane Phenyl ethyl alcohol 1> 1U Zt3 3-Hydroxy-3,7-dimethyl-1,6-octadiene acetate4 _ 5 3-Hydroxy-3,7-dimethyl-1,6-octadiene 6 15 5 Methyi dihydro jasmonate 3 10 5 2-Methyl-3(para tent butylphenyl) propionaldehdyeIU 15 2U

Phenyl ethyl acetate ~ 5 1 4-Hydroxy-3-methoxybenzaldehyde _ _ 1 para-Menth-1-en-8-ol, para-menth-I-en-1-of5 - 8 Anisic aldehyde _ -Coumarin _ _ j 2-Methyl-3-(para iso propyfphenyl)propionaldehyde- - 3 Total 100 100 100 _D _E

Periiime Material Wt.% Wt."io Amyl salicylate 8 Benzyi acetate g 8 Benzyl Salicylate _ Citronellol 7 27 Dihydromyrcenol ~

Eugenol 4 Flor acetate g Galaxolide I -Geraniol 5 Hexyl cinnamic aldehyde ~ -Hydroxycitronellal ~ -Lilial Linalool I2 13 Linalyl acetate 5 -Lyral 3 -Methyl dihydrojasmonate 3 _ Nerol 2 _ W O g6f05358 PCTlUS95f09t18fi Phenaxy ethyl propionate - 3 Phenvlethvl acetate S 17 Phenylethyl alcohol 8 l7 alpha-Terpineal 5 1:

alpha-Terpinene S - E

Tetrahydromyrcenol 2 -Tatal 100 IOCI

Perfume E is composed of , of ingredients CIagI' of about 70fo, by weight haying a about 3 or smaller.

The failawing are non-limiting examples ofthe instant composition.

c Exammple Example 2 II

Ingredients Wt io .W,~,~.~o Methylated heta-cycladexttin1.0 0.5 alpha-Cyclodextrin - 0.5 Ethylene Dlycol 0.1 0.1 Perfume .4 0.01 0.01 Kathon CG 0.001 0.0008 Distilled Water Balance Balance Examples I and Li The ingredients of ExamplesII are mixeddissolved into clear I and and solutions.

Example Example IV
III

In ~ nts W't lolo ~t%

Hydroxyethyl alpha-cyciodextrin0.27 -Hydroxyethyl beta-cyciodextrin0.73 1.0 Ethylene glycol 0.07 0.1 Perfume A 0.01 0.01 Kathon CG 0.001 -Bronopol - 0.02 Distilled Water Balance Balance ~19~440 WO 94105358 PCT'IUS9510908d Example III
The ingredients of Example IIl are mixed and dissolved into a clear solution.
Hydroxyethyl alpha-cyclodextrin and hydroxy~ethyl beta-cy~clodextrin are obtained as a mixture from the hydraxyethylation reaction of a mixture of alpha-cyclodextrin and beta-cyclodextrin. Ethylene glycol is a minor by-product of the same reaction.
Example 1V
The ingredients of Example IV are mixed and dissolved in a vessel into a clear solution.
i0 Example V Example ~'I
Ingredients Wt.~,o ~~t gn alpha-Cyclodextrin 0, 5 _ HydroxypropyI-beta-cyclodextrin0.5 1.0 Propylene glycol 0.1 0.1 Perfume B 0.01 0.01 Kathon CG 0.0005 Sodium Pyrithione - 0.001 Distilled water Balance Balance Examples l' and VI
The ingredients of Examples V and VI are mixed and dissolved into clear solutions.
The hydroxypropyl-beta-cyclodextrin has a degree of substitution of about S.0 Example VII Example VIII

Ingredients Wt,~io w ,goo Alpha-cyclodextrin 0.5 -Hydroxypropyi-alpha-cyclodextrin- 0.27 Hydroxypropyl-beta-cyclodextrin0.5 0.73 Propylene glycol 0.01 0.06 Perfume B - 0.01 Kathon CG O.OOI 0.0008 Distilled water Balance Balance VS'O 9bl05358 PCTILtS95l0908G

Example 1'II
T'he ingredients of Example l:'II are mixed and dissolved in a vessel iota a clear solution. The hydro~cy:prapyl-beta-cyclodextrin has a degree of substitution of about 5.4.
Example VIII
The ingredients of Example VIII are mixed and dissolved into a clear solution.
Hydrc>xypropyl alpha-cyclodextrin and hydraxyprapyl beta-cyclode~ctrin are obtained as a mixture with an average degree of substitution of about 4.9, from the hydraxypropylatian reaction of a mixture of alpha-cycladextrin and beta-cyclodexirin.
Propylene glycol is a minor by-product (about 6%) of the same reaction.
ExamQle IX Example 'i Ln~redients Wt.ii ' 1~'t.,o Alpha-cycladextrin 0.5 -Hydroxypropyl-alpha-cyclodextrin- 1.0 Hydroxypropyi-beta-cyclodextrinL0 2.5 gamma-Cyclodextrin 0.5 I .0 Propylene glycol 0.15 0.15 Perfume C 0.02 0.05 Kathan CG ' 0.001 Giutaraldehyde - 0.01 Ethanol - 2.0 Distilled water Balance Balance I S Examples IX and X
The ingredients ofExamples IX and X are mixed and dissolved into clear solutions.
x m I XI Example XLI

Innredients Wt...% W ,~o Alpha-cyclodextrin 0.5 -Methylated beta-cyciodextrin0.5 -Hydroxypropyl alpha-cyclodextrin- 0.27 Flydroxypropyl beta-cyclodextrin- 0.73 Zinc chloride 1.0 1.0 Perfume D 0.01 0.007 i X197440 WO 96!05358 PCTIfiS95109086 -39_ Kathon C,'G 0.0008 0.0008 Propylene glycol 0.1 0.06 HCI (a) (a) Distilled water Balance Balance ta) To adjust solution pH to about 4.8 Example ?CI
About 5 parts of alpha-cyclodextrin and about 5 parts of"methylated beta-cyclodextrin are added with mixing in a vessel containing about 980 parts of distilled water. When the cyclodextrins are totally dissolved into a clear solution, about 10 parts of zinc chloride is added with mixing. Zinc chloride is dissolved into a milky white solution The solution is adjusted to about pH 4.8 with a very small amount of hydrochloric acid, upon which the solution becomes clear again. About 0.1 part of perfume is added and mixed until the solution is clear. Then about 0.67 part of a nominally 1.5°,~0 aqueous solution of Kathon CG is added with mixing until the solution becomes water clear.
Example XII

I S The composition of Example XII is prepared similarly to that of Exatttple XI.

Exam Ip a Example XIV
~CIII

Ingredients Wt.~/u Wt.%

Alpha-cyclodextrin p,5 Hydroxypropyl alpha-cyclodextrin - 0.27 Hydroxypropyl beta-cyclodextrin 0.5 0.73 Propylene glycol 0.1 0.06 Zinc chloride I.0 I.0 Perfume E 0.1 0.05 Glydant Plus 0.01 _ Kathon CG _ O,pOpg HC1 (a) (a) Distilled water Balance Balance ' (a) To adjust solution pH to about ~.8 Examples 3CIII and XIV
The Compositions of Examples XfII and XIV are prepared similarly to that of Example XI.

WQ 96105358 PC1'25957494ilG
_~p_ ~ampl The composition of Example VIII is sprayed onto cioihing using a blue inserted Guala~ tri~s~er sprayer, available From Berry Plastics Corp and allowed to evaporate offofLhe clothing.
Example X~rI
The composition of Example III is sprayed onto a kitchen cotmtertop usin~t blue inserted Guala~ trigger sprayer, available from Berry Plastics Corp., and wiped otl'c~~th a paper tolvel.
Example ~'II
The composition of Example XIII is sprayed onto clothes using a cylindrical Euromist II~a pump sprayer available from Seaquest Dispensing, and allowed to evaporate off of the clothing.
IS

Claims (31)

WHAT IS CLAIMED IS:

1. An aqueous odor absorbing composition, comprising:

A. from about 0.1% to about 5%, by weight of the composition, of solubilized, water-soluble, uncomplexed cyclodextrin;

B. from about 0.01 % to about 1 %, by weight of the composition of low molecular weight polyol selected from the group consisting of propylene glycol, ethylene glycol, glycerol, and mixtures thereof;

C. aqueous carrier; and D. additional ingredient selected from the group consisting of:

(a) from about 0.0001% to about 0.5%, by weight of the composition of solubilized, water-soluble, antimicrobial preservative having a water-solubility of greater than about 0.3%;

(b) perfume at a level of from about 0.003% to about 0.3%, by weight of the composition;

(c) metallic salt selected from the group consisting of water-soluble zinc salts, water-soluble copper salts, and mixtures thereof; and (d) mixtures of (a), (b), and (c), D. being optional when the cyclodextrin is selected from the group consisting of:

(a) methylate-alpha-cyclodextrin (b) methylated-beta-cyclodextrin;
(c) hydroxypropyl beta-cyclodextrin; (d) hydroxypropyl alpha-cyclodextrin; and (e) mixtures thereof, wherein said composition is free of any material that would soil or stain fabric.

2. The composition of claims 1 wherein said cyclodextrin derivatives are selected from the group consisting of methyl substituted cyclodextrins, ethyl substituted cyclodextrins, hydroxyl alkyl substituted cyclodextrins, branched cyclodextrins, cationic cyclodextrins, quaternary ammonium cyclodextrins, anionic cyclodextrins, amphoteric cyclodextrins, cyclodextrins wherein at least one glucopyranose unit has as 3-6-anhydro-cyclomalto structure, and mixtures thereof.

3. The composition of claim 1 wherein said cyclodextrin is selected from the group consisting of alpha-cyclodextrin, methylated alpha-cyclodextrin, methylated beta-cyclodextrin, hydroxyethyl alpha-cyclodextrin, hydroxyethyl beta-cyclodextrin, hydroxypropyl alpha-cyclodextrin, hydroxypropyl beta-cyclodextrin, and mixtures thereof.

4. The composition of claim 1 wherein said cyclodextrin is methylated beta-cyclodextrin.

5. The composition of claim 1 wherein said cyclodextrin is a mixture of methylated-alpha-cyclodextrin and methylated-beta-cyclodextrin.

6. The composition of claim 1 wherein said cydodextrin is hydroxypropyl beta-cyclodextrin.

7. The composition of claim 1 wherein said cyclodextrin is a mixture or hydroxypropyl alpha-cyclodextrin and hydroxypropyl beta-cyclodextrin.

8. The composition of claim 1 wherein said polyol is propylene glycol.

9. The composition of claim 1 wherein said polyol is ethylene glycol.

10. The composition of claim 1 wherein said polyol is present at a level of from about 0.02% to about 0.5%, by weight of the composition.

11. The composition of claim 1 wherein said polyol is present at a level of from about 0.03% to about 0.3%; by weight of the composition.

12. The composition of claim 1 comprising solubilized, water-soluble, antimicrobial preservative having a water-solubility of greater than about 0.3%.

13. The composition of claim 12 wherein said cyclodextrin is present at a level of from about 0.2% to about 4% by weight of the composition.

14. The composition of claim 12 wherein said cyclodextrin is present at a level of from about 0.3% to about 3%, by weight of the composition and said preservative is present at a level of from about 0.0002% to about 0.2%, by weight of the composition.

15. The composition of claims 12 wherein said cyclodextrin is present at a level of from about 0.5% to about 2%, by weight of the composition and said preservative is present at a level of from about 0.0003% to about 0.10%, by weight of the composition.

16. The composition of claim 12 wherein said preservative is selected from the group consisting of organic sulfur compounds, halogenated compounds, cyclic organic nitrogen compounds, low molecular weight aldehydes, quaternary compounds, phenyl and phenoxy compounds, and mixtures thereof.

17. The composition of claim 12 wherein said preservative is an organic sulfur compound selected from the group consisting of 5-chloro-2-methyl-4-isothiazolin-3-one; 2-n-butyl-3-isothiazolone; 2-benzyl-3-isothiazolone; 2-phenyl-3-isothiazolone, 2-methyl-4,5-dichloroisothiazolone; 2-methyl-4-isothiazolin-3-one;
5-chloro-2-methyl-3-isothiazolone; and mixtures thereof.

18. The composition of claim 12 wherein said preservative is a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one present at a level of from about 0.0001 % to about 0.01 % by weight of the composition.

19. The composition of claim 12 wherein said preservative is a halogenated compound selected from the group consisting of 5-bromo-5-nitro-1,3-dioxane; 2-bromo-2-nitropropane-1,3-diol; 1,1'-hexamethylene bis(5-(p-chlorophenyl) biguanide); and mixtures thereof.

20. The composition of claims 12 wherein said preservative is 2-bromo-2-nitropropane-1,3-diol present at a level of from about 0.002% to about 0.1%, by weight of the composition.

21. The composition of claim. 12 wherein said preservative is a cyclic organic nitrogen compound selected from the group consisting of imidazolidinedione compounds, polymethoxy bicyclic oxazolidine, and mixtures thereof.

22. The composition of claim 1 comprising perfume.

23. The composition of claim 22 wherein said perfume is present at a level of from about 0.005% to about 0.2%, by weight of the composition.

24. The composition of claim 1 wherein the additional ingredient is a metallic salt selected from the group consisting of water-soluble zinc salts, water-soluble copper salts, and mixtures thereof.

25. The composition of claim 24 wherein said metallic salts is selected from the group consisting of ZnCl2, CuCl2, and mixtures thereof.

26. The composition of claim 24 wherein said metallic salt is ZnCl2 present at a level of from about 0.1 % to about 10%, by weight of the composition.

27. A stable, aqueous odor absorbing composition, for use on inanimate surfaces, comprising:

A. from about 0.5% to about 5%, by weight of the composition, of a mixture of methylated-beta-cyclodextrin and alpha-cyclodextrin;

B. from about 0.02% to about 0.5%, by weight of the composition of propylene glycol;

C. from about 0.0001% to about 0.01 %, by weight of the composition, of a water-soluble, antimicrobial preservative comprising a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one;

D. from about 0.003% to about 0.3%, by weight of the composition, of perfume; and E. water; and wherein said composition is free of any material that would soil or stain fabric.

28. A stable, aqueous odor absorbing composition, for use on inanimate surfaces, comprising:

A. from about 0.5% to about 2%, by weight of the composition, of a mixture of methylated-alpha-cyclodextrin and methylated-beta-cyclodextrin;

B. from about 0.03% to about 0.3%, by weight of the composition, of propylene glycol;

C. from about 0.0001% to about 0.01%, by weight of the composition of a water-soluble, antimicrobial preservative comprising a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one;

D. from about 0.1% to about 10%, by weight of the composition, of ZnCl2;

E. from about 0.005% to about 0.2%, by weight of the composition, of perfume; and F. water; and wherein said composition is free of any material that would soil or stain fabric and has a pH of from about 4 to about 5.5.

29. A stable, aqueous odor absorbing composition, for use on inanimate surfaces, comprising:

A. from about 0.5% to about 2%, by weight of the composition, a mixture of hydroxyethyl alpha-cyclodextrin and hydroxy ethyl beta-cyclodextrin;

B. from about 0.03% to about 0.3%, by weight of the composition, of ethylene glycol;
C. from about 0.0004% to about 0.002%, by weight of the composition, of a water-soluble, antimicrobial preservative comprising a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one;
D. from about 0.005% to about 0.2%, by weight of the composition of perfume; and E. water; and wherein said composition is free of any material that would soil or stain fabric and has a pH of greater than about 3.

30. A stable, aqueous odor absorbing composition, for use on inanimate surfaces, comprising:
A. from about 0.5% to about 2%, by weight of the composition, of a mixture of alpha-cyclodextrin and hydroxypropyl-beta-cyclodextrin;
B. from about 0.03% to about 0.3%, by weight of the composition, of propylene glycol; and C. from about 0.0001% to about 0.01%, by weight of the composition of a water-soluble, antimicrobial preservative comprising a mixture of S-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one;
D. water; and wherein said composition is free of any material that would soil or stain fabric and has a pH of greater than about 3.

31. A method of controlling odor on inanimate surfaces, the method comprising the step of spraying an effective amount of the composition of claim 1 onto fabric using a trigger-spray device wherein said trigger-spray device comprises a bottle made from clear polyethyleneterephthalate.