CA2196294C

CA2196294C - Fabric treating composition containing beta-cyclodextrin

Info

Publication number: CA2196294C
Application number: CA002196294A
Authority: CA
Inventors: David Pilosof; Jerome Paul Cappel; Philip Anthony Geis; Mark Lee Mccarty; Toan Trinh; Susan Schmaedecke Zwerdling
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1994-08-12
Filing date: 1995-07-26
Publication date: 2001-05-15
Anticipated expiration: 2015-07-26
Also published as: AU3148395A; JP3098040B2; ATE264696T1; EP0776220B1; JPH10503955A; US5534165A; CN1157574A; DE69532925D1; TW295608B; EP0776220A1; DE69532925T2; WO1996004939A1; CA2196294A1; ES2219663T3

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 % of solubilized, uncomplexed cyclodextrin, preferably, an effective amount of a solubilized, water-soluble antimicrobial preservative having a water-solubility of greater than about 0.3 %, preferably, from about 0 % to about 10 %, by weight of the composition, of solubilized, water-soluble metallic salt, aqueous carrier and wherein said composition is essentially free of any material that would soil or stain fabric and wherein said composition is essentially free of perfume and has a pH greater than about 3.

Description

W0 96/(14939 PCT/CTS951t19415 FABRIC TREATING COMPOSITION CONTAINING BETA-CYCLODEXTRIN
TECHNICAL FCELD
The present invention relates to a stable, preferably clear, aqueous odor-absorbing composition preferably not for use on human skin, comprising solubilized, uncomplexed cyclodextrin and optionally but, preferably, solubilized, water-soluble, antimicrobial preservative for said cyclodexttin solution and wherein said composition is essentially free of perfume. The odor-absorbing composition is designed to control odors caused by a broad spectrum of organic odoriferous materials, which may, or may not, contain reactive functional groups, and to remain shelf stable for a substantial period of time. Preferably, the aqueous odor-absorbing composition is for use on surfaces, especially fabrics, and more specifically, clothes, in order to restore andlor maintain freshness by reducing malodor without the need 1 i for washing or dry cleaning.
BACKGROUND OF THE INVENTION
The present invention relates to a stable, preferably clear, aqueous odor absorbing composition, preferably, not for use directly on human skin, as an odor freshening composition. Preferably, the composition is sprayed onto fabrics, particularly clothes, to restore their freshness by reducing malodor, without washing or dry cleaning. The composition is preferably not used directly on human skin because when the preferrable preservative is used it may cause skin irritation.
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 on fabrics, in particular clothes, has been accompiished by using perfumes, colognes, etc. However, preference for perfume is greatly varied and high levels are needed to ensure that the malodor is no longer noticeable.
Odor modification, in which the odor is changed, e.g., by chemical modification, has also been used. Current malodor modification methods known in the art are oxidative degradation, which uses oxidizing agents such as oxygen bleaches, chlorine, chlorinated materials such as sodium hy~pochlarite, chlorine dioxide, etc" and potassium permanganate to reduce malodor, and reductive 3S degradation which uses reducing agents such as sodium bisulfite 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 discolor colored fabrics.

Other methods of odor control involve actives that are targeted to react with malodors having specific chemical functional groups. Examples of such actives are;
biguanide polymers, which complex with organic compounds containing organically bound :~1 and/or S atoms, and fatty alcohol esters of methyl methacrylic acid which 5 react with thiols, amines, and aldehydes. Such actives are limited in scope because they only react with limited types of malodor. A more detailed description of these methods can be found in U.S. Pat. Nos. 2,544,093, 3,074,891, 4,818,524, and 4,946,672, -- -Other types of deodorizing compositions known in the art contain 10 antibacterial and antifungal agents which regulate the malodor producing microorganisms found on 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.
I 5 Fabric malodor is most commonly caused by environmental odors such as tobacco odor, cooking and/or food odors, or body odor. The unpleasant odors are mainly organic molecules which have differem structures and functional groups, such as amines, acids, alcohols, aldehydes, ketoses, phenoGcs, polycycGcs, indoles, aromatics, polyaromatics, ete. They can also be made up of sulfur-containing 20 functional groups, such as, thiol, mercaptan, sulfide and/or disulfide groups.
It is preferablo-to apply as 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 cls3rnical reaction material, an odor absorbing material can 25 eliminate a broad spectrum of odoriferous molecules and usually does not contribute as odor of its own. The commonly known solid odor absorbers such as activated charcoal and zeoiites can be harrt>ful to fabrics and therefore are not preferred as an odor controlling agent under these circumstances. Activated charcoal easily stains light colored fabrics and zeoGtes are sees as a light colored stain on dark colored 30 fabrics. --- Uncomplexed cyclodextrin 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 ate made up of varying numbers of glucose units.
See Effect of H~,oxypr~vl-B-cyclodextrin on the Antimicrobial Action of Preservatives, S. J. Lehner, B. W. Muller and J. K. Seydel. J. Pharm.
Pharmacol 1994, 46~p.188 and Interactions Between P-Hvdroxybenzoic acid Esters and Hvdroxvnropvl-B-Cvclodextrin and Their Antimicrobial Effect Against Candida Albicans, S. J. Lehner. B. W. Muller and J. K. Seydel. International Journal of 5 Pharmaceutics, 1993, 93, pp. 201-208. 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 cyclodextrin solutions for any significant length of time.
Contamination by certain microorganisms, can cause microbial growth resulting in an unsightly 10 and/or malodorous solution. Because microbial growth 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 cyclodexttin. ' IS
SUMMARY OF THE iZYVENTIOI~i In accordance with one embodiment of the invention, a statle, aqueous odor-absorbing composition comprises:
A. from about 0.1~ to about 5~ of solubilized, uncomplexed 20 cyclodextrin comprising up to 1.5~ by weight of beta-cyclodextrin; and B. preferably, an effective amount of a solubilized, water-soluble antimicrobial preservative having a water-solubility of greater than about 0.3%;
25 C. preferably, from about 0% to about 10%, by weight of the composition, of solubilized, water-soluble metallic salt; and D. aqueous carrier, and whereitr said composition is essentially free of any material that would soil or stain fabric; and wherein said composition is essentially free of perfume and has a pH of 30 . greater than about 3.
This composition is for use on inanimate surfaces.

-3a-In accordance with a further embodiment, a stable, aqueous odor absorbing composition, for use on inanimate surfaces, comprises:
from about 0.5o to about 5~, by weight of the composition, of a mixture of alpha-cyclodextrin and up to 1.85 by weight of beta-cyclodestrin;
g from about 0.0001% to about 0.01°f°, by weight of the composition of solubiliZed. water-soluble, antimicrobial preservative comprising a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4~
isothiazolin-3-one; and C- water, and wherein said composition is essentially free of any material that would soil or satin fabric_ and wherein said composition is essentially free of ar~y perfume and has ~a pEf of greater than about 4_ In accordance with a further embodiment, a clear, stable, aqueous odor absorbing composition, for use on inanimate surfaces, comprises:
from about 0.3% to about t.85%, by weight of the compositiocz, of beta-cyclodGxtrin;
ZO 13_ from about p.pppt°/'° to about 0.01% by weight of the compositior~ of tha composition of solubilized, water soluble antimicrobiai Preservative comprising a mixtyre of 5-chloro-2-methyl-4-;soth;azoGn-3-one and 2-methyl-4-isothiamlin-3-onr and C. water, and wherein said composition is essentially free of any material that would soil or satin fabric and wherein said composition is essentially free of any perfume and has a pFi of greater than about 4_ In accordance with a further embodiment, a clear, stable, aqueous . odor absorbing composition for use on inanimate surface - - ' . comprises:
A-. . from about 0.1% to about 5%, by weight of the composition, of a - mixture of hydroxypropyl beta-ryclodextrin and hydroxypropyl alpha-cyclodextrin;
tom about 0.0001% to about 4.01% by weight of the composition- of the composition of solubiLiied, water-soluble, antimicrobial preservative comprising a mixture of S-chloro-2-methyl-4--isothiazolin-3-one and 2-methyl-4-isothiazoGn-3-onc; and -3b-C. from about 0.3% to about 5%, by weight of the composition, of ZnCI-~, and D water; and wherein said composition is essentially free of any material that would soil or satin fabric: and wherein said composition is essentially free of any perfume and has a pH of from about 4 to about 5.5.

WO 96!04939 PCTIUS9:4109425 _ø-DETAILED DE5~~i21PTIC)N OF THE L'V1'ENT10N
The present invention relates to a clear, aqueous odor-absorbing composition for use on inanimate surfaces, comprising A. from about 0.1°~o tn about 5°~rs ofsalubilized, uncampiexed cyclodextrin comprising an effective amount of beta-cycladextrin;
and B. preferably, an effective amount of a solubilized, water-soluble antimicrobial preservative having a water-soluhility of greater than about 0.3°ro;
l0 C', preferably, from about 0°.% to about 10°ib, by weight of the composition, of solubilized, water-soluble metallic salt; and D. aqueous carrier; and wherein said composition is essentially free of any material that would soil or stain fabric; and wherein said composition is essentially free of perfume and has a pI-1 of I 5 greater than about 3.
I. COhIPOSiTION' (A). CYCLODEXTRIN
As used herein, the term "cycladextrin" includes any of the known 20 cyclodextrins such as unsubstituted cyclodextrins containing from six to twelve glucose units, especially, alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin andior their derivatives and/or mixtures thereof so long as there is an effective amount of beta-cyclodextrin. The alpha-cyclodextrin consists of six glucose units, the beta-cyclodextrin consists of seven glucose units, and the gamma-cycladextrin 25 consists of eight glucose units arranged in a donut-shaped ring. The specific coupling and conformation of the glucose units give the cyclodextrins a rigid, conical molecular structure with a hollow interior of a specific volume. The "fining"
of the internal cavity is formed by hydrogen atoms and glycasidic bridging oxygen atoms;
therefore, this surface is fairly hydrophobic. The unique shape and physical-chemical 30 properties of the cavity enable the cyclodextrin molecules to absorb (form inclusion complexes with) organic molecules or parts of organic molecules which can fit into the cavity. tvfany odorous molecules can fit into the cavity including many malodorous molecules and perfume molecules. Therefore, cyclodextrins, and especially mixtures of cyclodextrins with different size cavities, can be used to 3S control odors caused by a broad spectrum of organic odoriferous materials, which may or may net contain reactive functional groups. The complexation between cyclodextrin and odorous molecules occurs rapidly in the presence of water.

219629:
_S_ However, the extent of the complex formation also depends on the polarity of the absorbed molecules. In an aqueous solution, strongly hydrophilic molecules (those which are highly water-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 r1s the water is being removed however, e.g., the fabric is being dried off, some lore molecular weight organic amines and acids have more affinity 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 cycladextrin remains uncomplexed}
while in solution, in order to allow the cyclodextrin to absowb various odor molecules when the solution is applied to a surface. The availability of salubilized, uncomplexed cyclodextrin is essential for effective and efficient odor control performance.
The individual cycladextrins can also be linked together, e.g., using multifunctional agents to form oligomers, polymers, etc. Examples of such materials are available commercially from Amaizo and from Aldrich Chemical Company {beta-cyclodextrin~epichlorohydrin copolymers).
Examples of highly water soluble cyclodextrins are, alpha-cyclodextrin and its derivatives thereof, gamma-cycladextrin and its derivatives thereof, derivitised beta-cyclodextrin, and mixtures thereof Mixtures of beta-cyclodextrin and highly water-soluble cyclodextrins are also preferred.
Highly water-soluble cyclodextrins are those having a water-solubility of at least about l Og in 100m1 of water at room temperature, preferably at least about 20g in 100 ml of water, more preferably at least about 25g in 100m1 of water at room temperature. Highly water-soluble cyclodextrin derivatives include, e.g., those with short chain alkyl groups such as methyiated cyclodextrins, and ethylated cyclodextrins, wherein R is a methyl or an ethyl group; those with hydroxyl substituted groups, such as hydroxypropyl cyclodextrins and hydroxyethyl cyclodextrins, wherein R is a CH2-CH(OH)-CH3 or a CH2CH2-OH groups;
branched cyclodextrins such as maltose-bonded cyclodextrins; cationic cyclodextrins such as those containing 2-hydroxy-3(dimethylamino)propyl ether, w°herein R is CH2-CH(OH}-CH2-N(CH3}2; quaternary ammonium, e.g., 2-hydroxy-3-(trirnethylammonia)propyl ether chloride groups, wherein R is CH2-CH(OH}-CH2-N(CH3)3C1; anionic cyclodextrins such as carboxymethyl cyclodextrins, cyclodextrin 3 S sulfates, and cyclodextrin succinylates; amphoteric cyclodextrins such as caiboxymethyl/quaternary 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 Cyclodextrin Symposium Abstracts. April 1994, p. 491, and mixtures thereof. Other cyclodextrin derivatives are disclosed in U. S.
Pat. Nos: 3,426,011. Parmerter et al., issued Feb. 4, 1969; 3,453,257, 3,453.258, 3,453,259, and 3,453,260, all in the names of Parmerter et al., and all issued July l, 1969; 3,459,731, Crramera et al., issued Aug_ 5, 1969; 3,553,191, Parmerter et al., issued Jan. 5, 1971; 3,565,887, Parmerter et al., issued Feb. 23, 197I;
4,535,152, Szejtli et al., issued Aug. l3. 1985; 4,616,008, Hirai et al., issued Oct. 7, 1986;
4,638,058, Brandt et al., issued Jan. 20, 1987; 4,746,734, Tsuchiyama et al., issued May 24, 1988; and 4,678,598, Ogino et al., issued Jul. 7, 1987, Examples of preferred water-soluble cyclodextrin derivatives suitable for use herein are hydroxypropyl alpha-cyclodextrin, methyiated alpha-cyclodextrir~
methylated beta-cyclodextrin, hydroxyethyl beta-cyclodcxtrin, and hydroxypropyl beta-cyclodextrin. Hydroxyalkyl cyclodextrin derivatives preferably have a degree of substitution of from about 1 to about 14, more preferably from about 1.5 to about 7, wherein the total number of OR groups per cyciodextrin is defined as the degree of substitution. Methylated cyclodextrin derivatives typically have a degree of substitution of from about 1 to about 18, preferably firom about 3 to about 16. A
known methylated beta-cyclodextrirt is heptakis-2,6-di-O-methyl-~i-cyclodextrin, commonly known as DIMEB, 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 bet~cyclodextrin having a degree of substitution of about 12.6. The preferred cyclodextrins are available, e.g., from American Maize-Products Company and Wackec Chemicals (USA), Inc.
It is also preferable to use a mixture of eyclodextrins. Such mixtures absorb odors more broadly by complexing with a wider range of odoriferous molecules.
Preferably ai least a portion of the cyclodexuins are alpha-cyclodextrins, beta-cyclodeactrins, ganuna-cyclodextrins, and/or their derivatives. More preferably a mixture of alpha-cyclodeacuins, beta-cyclodexvins, and/or their derivatives, even more preferably a mixture of hydroxypropyl alpha-cyclodextrin and hydroxypropyl beta-cyclodextrin and/or a mixture of methylated alpha-cyclodextrin and methylated beta-cyclodextrin.
Normal or non-derivitised beta-cyclodextrin which has a low water solubility can be used up to a level of about 1.85%, which is its water solubility at room temperature. In order to obtain the preferably clear solution of the present invention _7_ it is essential that the composition be essentially free of perfume. Not to be limited by theon~, it is believed that some beta-cyclodextrin andlor beta-cycladextrin/pertume complexes solidify andlor 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 tOcm.
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 cycladextrin so that a visible stain does not appear on the fabric at normal usage levels. Typical levels of cyclodextrin are from about 0.1% to about 5%, preferably from about 0.2% to about 4°i°, more preferably from about 0.3%
to about 3°,%, most preferably from about 0.5% to about 2%. Compositions with higher concentrations~
can leave unacceptable visible stains an fabrics as the solution evaporates off of the fabric. This is especially a problem on thin, colored, synthetic fabrics. In order to avoid ar minimize the occurrence of fabric staining, it is preferable that the fabric be treated at a level of less than about 5 mg of cyclodextrin per mg of fabric, more preferably less than about 2 mg of cyclodextrin per mg of fabric.
Concentrated compositions can also be used in order to provide a less expensive product. When a concentration is used, i.e., when the level of cyclodextrin used is from about 3°,i° to about 5%, it is preferable to dilute the composition before treating fabrics in order to avoid staining. Preferably the cyclodextrin is diluted with about 50°io to about 2000%, mare preferably with about 60% to about 1000°J°, most preferably with about 75°I° to about S00% by weight of the composition of water.
(B). OPTIONAL ANTIMICROBIAI. PRESERVATIVE
Optionally, but preferably, the composition of the present invention can contain solubilized, water-soluble, antimicrobial preservative because cyclodextrin 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 compositions. This problem, that certain organisms grow extremely well an cyclodextrin, has not been previously disclosed. This drawback can lead to the problem of storage stability of cycladextrin solutions for any significant length of time. Contamination by certain microorganisms with subsequent microbial growth can result in an unsightly and/or malodorous solution. Because microbial growrth in cyclodextrin solutions is highly objectionable when it occurs, it is preferable to WO 961U4939 . PLTJ(T59il09425 include a water-soluble, antimicrobial presen:ative, which is effective far inhibiting ancfor regulating microbial growth in order to increase storage stability of the preferably clear, aqueous odor-absorbing solution contaitung water-soluble cvclodextrin.
Typical microorganisms that can be found in cyclodextrin supplies and wfiase growth are found in the presence of cyclodextrin in aqueous cyclodextrin solutions include bacteria, e.g., Bacillus thurin, iensis (cereus group) and bacillus s~haericus;
and fungi, e.g., As~gillus ustus. Bacillus snhaericus is one of the most numerous menrbers of Bacillus species in soils. Aspereillus ustus is common in grains and flours which are raw materials to produce cyclodextrins. Microorganisms such as Escherichia toll and Pseudomonas aeruginasa 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., one 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 w7th a broad spectrum preservative or other limited spectrum preservatives with complimentary activity. A
mixture of broad spectrum preservatives can also be used.
Antimicrobial preservatives useful in the present inuentian include biocidal compounds, i.e., substances that kill microorganisms, or biostatic compounds, i.e., substances that inhibit andlar regulate the growth of microorganisms.
Preferred antimicrobial preservatives are those that are water-soluble and are effectiv°e 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 cyelodextrins ineffective as odor controlling actives. Water-salable preservatives useful in the present invention are those that have a solubility in water of at least about 0.3 g per I00 ml of water, i.e., greater than about 0.3°io at room temperature, preferably greater than about U.5°ro at room temperature. These types of preservatives have a lower affinity to the cycladextrin cavity, at least in the aqueous phase, and era therefore more available to pro4°ide antinticmbial activity. Preservatives with a water-solubility of less than about 0.3°rb and a molecular structure that readily fits into the cyclodextrin cavity, have a greater tendency to form inclusion complexes with the cyclodextrin molecules, thus rendering the preservative less effective to control microbes in the cyclodextrin solution. Therefore, many well known preservatives such as short chain alkyl esters of p-hydraxybenzoic acid, commonly known as parabens; N-{4-chiaraphenyl)-N'-(3,4-dichloropheityl) urea, also known as 3,4,4'-trichlorocarbanilide or triclocarban;

WO 96JOd939 .. PCTIIT895tQ9425 _.

2,4,4'-trichlora-2'-hydroxy dipheny°l ether, commonly knowm as triclosan are not preferred in the present invention since they are relatively ineffective when used in conjunction with cyclodextrin.
The water-soluble antimicrobial presen°ative in the present invention is included at an effective amount. The term "effective amount" as herein defined means a level suffcient to prevent spoilage, or prevent growth of inadvertently added microorganisms, for a specific period of time. In other words, the presen~ative 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 life of the composition. Preferred levels of preservative are from about 0.0001% to about 0.5%, more preferably from about 0.0002% to about 0.2°0, most preferably from about 0.0003°io to about 0. I%, by weight of the composition.
In order to reserve most of the cyclodextrins for odor contra(, the IS cyclodextrin to presen~ative mole ratio should be greater than about 5:1, preferably greater than about 10:1, more preferably greater than about 50:1, even mare preferably greater than about 100:1.
The preservative can be an organic material, which will not cause damage to fabric appearance, e.g., discoloration, coloration, bleaching. Preferred water-soluble preservatives include organic sulfur compounds, halogenated compounds, cyclic organic nitrogen compounds, low molecular weight aldehydes, quaternary ammonium compounds, dehydroacetic acid, phenyl and phenoxy compounds, and mixtures thereof The following are non-limiting examples of preferred water-soluble preservatives for use in the present invention.
(1) Oreanic Sulfur 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:
(a) 3-Isothiazolone Compounds A preferred preservative is an antimicrobial, organic preservative containing 3-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 18 carbon atoms, an unsubstituted or substituted cycloalkyl group having from about a 3 5 to about a 6 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;
R 1 is hydrogen, halogen, or a (C 1-C4) alkyl group; and R2 is hydrogen, halogen, or a (C1-C4) alkyl group.
10 Preferably, when Y is methyl or ethyl, R1 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. Examples of said 15 compounds are: 5-chloro-2-methyl-4-isothiazolin-3-one; 2-n-butyl-3-isothiazolone;
2-benzyl-3-isothiazolone; 2-pherryl-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 mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazotin-3-one, more ZO preferably a mixture of about 77% 5-chloro-2-methyl-4-isothiazolin-3-one and aboun 23% 2-methyl-4-isothiaaolin-3-one, a broad spectrum preservative available as a 1.5% aqueous solution under the tradename ICathon~ CG by Rohm and Haas Company.
When Kathon~ is used as the preservative in the present invention it is 25 present at a level 'of from about 0.0001 % to about 0.01 %, preferably from about 0.0002% to about 0.005%, 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 30 Another preferred organic sulfur preservative is sodium pyrithione, with water solubility of about 50%. When sodium pyrithione 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% to about 0.005%, more preferably from about 0.0003% to about 0.003%, by weight of the composition.

2I9~29~
~W 0 461Od939 P4TIUS95I09d25 Mixtures of the preferred organic sulfur compounds can also be used as the preservative in the present invention.
(2) Halo~enated Compounds S Preferred presen~atives for use in the present invention are halogenated compounds. Some non-limiting examples of halogenated compounds suitable for use in the present invention are:
S-bromo-S-nitro-1,3-dioxane, available under the trade name Bronidox L~
from Henkel. Bronidox L~ has a solubility of about 0.46% in water. When Bronidox is used as the preservative in the present invention it is present at a level of from about O.OOOS% to about 0.02°io, preferably from about 0.001% to about 0.01%, by weight of the composition;
2-bromo-2-nitropropane-1,3-diol, available under the trade name Bronopol from Inolex can be used as the preservative in the present invention. Branopol has x 1S solubility of about 25% in water. When Bronopol is used as the preservative in the present invention it is present at a level of from about 0.002% to about 0.1%, preferably from about O.OOS% to about O.OS%, by weight of the composition;
1,1'-hexamethylene bis(S-(p-chlorophenyl)biguanide), commonly known as chlorhexidine, and its salts, e.g., with acetic and digluconic acids can be used as a preservative in the present invention. The digluconate salt is highly water-soluble, about 70% in water, and the diacetate salt has a solubility of about 1.8% in water.
When chlorohexidine is used as the preservative in the present invention it is present at a level of from about 0.0001% to about 0.04%, preferably from about O.OOOS%
to about 0.01%, by weight of the composition.
1,1,1-Trichloro-2-methylpropan-2-ol, commonly known as chlorobutanol, u~th water solubility of about 0.8°,%; typical effective level of chlorobutanol is from about 0. I % to about 0.5%, by weight of the composition.

4,4'- (Trimethylenedioxy)bis-(3-bromobenzamidine) diisethionate, or dibromopropamidine, with water solubility of about SO%; when dibromopropamidine is used as the preservative in the present invention it is present at a level of from about 0.0001°io to abaut O.OS%, preferably from about 0.0005% to about 0.01% by weight of the composition.
Mixtures of the preferred halogenated compounds can also be used as the preservative in the present invention.
(3} Cvclic Organic Nitrogen Compounds WU 9GJ(ia939 . ,, ;.
rcrrcrs9sro9ai~

Preferred water-soluble preservatives for use in the present invention are cyclic organic nitrogen compounds Soma non-Limiting examples of cyclic organic nitrogen compounds suitable for use in the present invention are:
(a) I_midazoiidinedione Camoounds Preferred preservatives for use in the present invention are imidazalidiane compounds. Same non-Limiting examples of imidazalidinedione compounds suitable for use in the present invention are:
1,3-bisfhydroxymethyl)-5,5-dimethyl-2,~-imidazolidinedione, commonly known as dimethyloldimethylhydantoin, ar D~1~IDM hydantoin., available as, e.g., Glydant~ from Lama. D14~M hydantoin has a water solubility of more than 50°-0 in water, and is mainly effective on bacteria. W hen DMDM hydantoin is used, it is preferable that it be used in combination with a broad spectrum preservative such as Kathon CG~, ar formaldehyde. A preferred mixture is about a 95:5 DntDM
hydantoin to 3-butyl-2-iodopropynylcarbamate mixture, available under the trade i 5 name Giydant Plus~ from Lonza. When Glydant Plush is used as the preservative in the present invention, it is present at a level offrom about 0.005% to about O.Z°io;
N-[ 1,3-bis(hydroxytnethyl)2,5-dioxo-4-imidazoIidinyi]-N,N'-bis(hydraxymethyl) urea, commonly known as diazolidinyI urea, available under the trade name Geimall III from Sutton Laboratories, Inc. (Sutton) can be used as the preservative in the present invention. When Germall III is used as the preservative in the present invention, it is present at a level offrom about 0.01% to about 0.1°ra;
N,N"-methylenebis{N'-[I-(hydroxyrtnethyi)-2,5-dioxo-4-imidazalidinyl]urea}, commonly known as imidazolidinyl urea, available, e.g., under the trade name flbial ~ from 3 V-Sigma, Unicide U-13~ from Induchem, Germall i 15~' from (Suttori) can be used as the preservative in the present invention. When imidazolidinyl urea is used as the preservative, it is present at a level of from about 0.05°,io to about 0.2~,a., by weight of the composition.
Mixtures of the preferred imidazolidinedione compounds can also be used as the preservative in the present invention.
(b) Polvmethoav Bicvclic Oxazolidine Another preferred water-soluble cyclic organic nitrogen preservative is polymethoxy bicyclic oxazolidine, having the general formula:
Hz)~H
O~N~O

-Ip-where n has a value of from about 0 to about 5, and is available under the trade name Nuosept~ C from Huls .~nerica. When NuoseptC~,.'' C is used as the preservative, it is present at a level of from about O.OOS°,% to about 0.1°ro, by weight of the composition.
Mixtures of the preferred cpcEic organic nitrogen compounds can also be used as the preservative in the present invention.

CA 02196294 2000-06-05 ' (4). Low i<lolecullr Weight Aldehvdes (a). Formaldehyde A preferred preservative for use in the present invention is formaldehyde.
Formaldehyde is a broad spectrum preservative which is normally available as S formalin which is a 37% aqueous solution of formaldehyde. When formaldehyde is used as the preservative in the present invention, typical levels are from about 0.003% 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.
10 (b). Glu dehvde A preferred preservative for use in the present invention is glutaraldehyde.
Glutaraldehyde is a water-soluble, broad spectrum preservative commonly available as a 25% 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-.
15 0.005% to about 0.1%, preferably from about 0.01% to about 0.05%, by weight of the composition.

(5). Quaternary Compounds Preferred preservatives for use in the present invention are cationic and/or 20 quaternary compounds. Such compounds include polyaminopropyl biguanide, also known as polyhexamethylene biguanide having the general formula:
HCI~NHZ-(CH2~-1~CH2~-NH-C(=NH~NH.~(=NH~HCyNH~CH2y3-~-(CHZ)3-NHS(=NH~Mi.CN
25 Polyaminopropyl biguanide is a water-soluble, broad spectrum preservative which is available as a 20% aqueous solution available under the trade name Cosmocil CQ~ from ICI Americas, Inc., or under the trade name l~fikrokill~
from Brooks, Inc.
1-(3-Chlorallyl) -3,5,7-triaza-1-azoniaadamantane chloride, available, e.g., TM
30 _ 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.
35 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%
to about 0.2%, preferably from about 0.01% to about 0.1%, by weight of the composition.

WO 96!04939 PCTlU595109425

(6). behvdroacetic Acid A preferred preservative for use in the present invention is dehydroacetic S 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 preservative acts more as a biostatic preservative than a biocidal preservative. When dehydroacteic acid is used as the preservative it is typically used at a level of from about 0.005% to about 0.2°~0, preferably from about 0.008°Ja to about 0.1°.6, more preferably from about 0.01°ro to l U about 0.05%, by weight of the composition.

(7) Phenyl and Pheuoxy Comuounds Some non-limiting examples of phenyl and phenoxy compounds suitable for use in the present invention are:
15 4,4'-diamidino-a,w-diphenoxypropane diisethionate, cormnonly known as propamidine isethionate, with water solubility of about l6%; and 4,4'-diamidino-a,w-diphenoxyhexane diisethianate, 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°,%; 2 20 phenylethanol, with a water solubility of about Z%; and 2-phenoxyethanol, with a water solubility of about 2.67%; typical effective levels of these phenyl and phenoxy alcohois are from about 0.1% to about 0.5%, by weight of the composition.

(8) Mixtures thereof The preservatives ofthe present invention can be used in mixtures in order to 25 control a broad range of microorganisms.
Bacteriostatic effects can sometimes be obtained for aqueous compositions by adjusting the composition pH to an acid pH, e.g., less than about pH 4, preferably less than about pH 3, or a basic pH, e.g., greater than about 10, preferably greater than about l 1. Low pH far microbial control is not a preferred approach in the 30 present invention because the low pH can cause chemical degradation of the cyclodextrins. 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 1, 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 35 about 3 to about 10, preferably from about 4 to about 8, more preferably from about 4.5 to about 7.

~~ .':'';

9 -l6-.4s stated above, it is preferable to use the preservative at art effective amount, as defined hereinabove. Optionally however, the presen~at'tve can be used at a level wtrich 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 prov°ide the odor ahsorbing benefat.
(C). 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 of the cyclodextrins, but it also facilitates the complexation reaction between the cyclodextrin molecules and the malodorous molecules. 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 paler, 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 solubilizes and depresses the vapor pressure of these polar, low molecular weight organic molecules, thus reducing their odor intensity.
(Dj OPTIt)>'~AL INGREDIENTS
The composition of the present invention can optionally contain adjunct odor-controlling materials, chelating agents, solubilizing aids, antifoaming agents, defoaming agents, antistatic agents, insect and moth repelling agents, colorants, especially blueing agents, antioxidants, and mixtures thereof 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, water-soluble bicarbonate salts, zeolites, activated carbon, and mixtures thereof.
(I) Metallie~~lt Optionally, but highly preferred, the present invention can include metallic salts for added odor absorption and/or antimicrobial benefit for the cyclodextrin solution. The metallic salts are selected from the group consisting of copper salts.
zinc salts. and mixtures thereof.
Copper salts have some antimicrobial benefits. Specifically, cupric abietate acts as a fungicide, copper acetate acts as a mildew inhibitor, cupric chloride acts as a fungicide, copper lactate acts as a fungicide, and copper sulfate acts as a germicide.
Copper salts also possess some malodor control abilities. See U. S. Pat. No.
3.172,817, Leupold, et al., which discloses deodorizing compositions for treating disposable articles, comprising at least slightly water-soluble salts of acylacetone, including copper salts and zinc salts.
Zinc salts possess malodor control abilities. Zinc has been used 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 functions as a fungicide, zinc chloride provides antiseptic and deodorant benefits, zinc ricinoleate functions as a fungicide, nine sulfate heptahydrate functions as a fungicide and zinc undecylenate functions as a fungistai.
Preferably the metallic salts are water-soluble zinc salts, copper salts or mixtures thereol~ and more preferably the metallic sak is ZnCl2. These salts are 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., sul5de and mercaptans, are components of many types of malodors, e.g., food odors (garlic, onion), body/perspiration odor, breath odor, etc.
Low molecular weight 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 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, more preferably less than about 6, most preferably less than about 5 in order to keep the solution clear.
(2) Water-Soluble PolY,mers WO 961U4939 ~ ~ ~ ~ ~ ~ ~ ' ~ 1 ~ :, . PCTlLTS95/I19425~
_Ig_ Some mater-soluble polymers, e.g., water-soluble cationic polymer and water-soluble anionic p<riymers can be used in the composition of the present invention to provide additional odor control benefits.

a. Cationic oolvmers, e.e., oolvamines Water-soluble cationic polymers, e.g., those containing amino functionalities.
amido functionalities, and mixtures thereof. such as polyacrylamides, are useful in the present invention to control certain acid-type odors.
5 b. Anionic oolvmers, e.c., 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 polyacrylic acids and their alkali metal salts have an average molecular weight of less than about 20,000, more preferably less than 5,000. Polymers

10 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.
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, 15 issued March 20, 1990 to N. Kobayashi and A. Kawazoe.
Another example of water-soluble polymers containing both cationic and anionic funetionalities is a copolymer of dimethyldiallyl ammonium chloride and acrylic acid, commercially available under the trade name Merquat 280~ from Calgon.

(3), Low Molecular Weight Polvols Low molecular weight polyols with relatively high boiling points, as compared to water, such as ethylene glycol, propylene glycol and/or glycerol are preferred optional ingredients for improving odor control performance of the 25 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 cyclodextrin inclus__ion complexes as the fabric dries.
It is believed that the polyols' ability to remain on the fabric for a longer 30 , p~~od of time than water, as the fabric dries allows them to form ternary complexes -~ with the cyclodextrin and some 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 sizes. Preferably the glycol used is ethylene glycol, and/or propylene glycol. Cyctodextrins prepared by processes that result in a level of such polyols are highly desirable, since they can be used without removal of the polyols.

~39~~~
~4'hen glycols are added to the composition of the present invention the preferred weight ratio of low molecular weight polyol to cycladextrin is Ei~om about 1 1.000 to about 20:100, mare preferably From about 3v 1,000 to about 15:100, even more preferably from about 5:1,000 to about 10:100, and most preferably from about I :100 to about 7:100.
(4). Soluble Carbonate and Bicarbonate Salts Water-soluble alkali metal carbonate and bicarbonate salts, such as sodium bicarbonate, potassium bicarbonate, potassium carbonate, cesium carbonate, sodium IO 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 monahydrate; 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°o to I5 about S°.'o, preferably from about 0.2% to about 3°ro, more preferably from about 0.3°~6 to about 2"'r°, by weight of the composition. When these salts are added to the composition ofthe present invention it is preferably that incompatible metal salts not 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.g., Ca, Fe, Ba, 20 etc.
(5). Chelatine Agents Some arruno acid chelating agents such as ethylene diamitte tetraacetiC acid (EDTA) can optionally be added to the composition of the present invention in order 25 to enhance the activity of the water-soluble, antitrricrobiai preservative.
When a chelating agent is added to the composition of the present invention, it is typically present at a level of from about 0.01% to about 0.3°ro, preferably from about 0.05°ro to about 0.2°f°. It is important that the composition of the present invention be essentially free of any metal ions that can be chelated by any chelating agent that is 30 added to the composition of the present invention because such metal ions complex with, and deactivate, the chelating agents.
(6). Antistatic Agents The composition of the present invention can optionally contain an effective 35 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 effective amount, such that the composition remains a clear solution. Examples of these 2l-antistatic agents are monoalkyl cationic quaternary ammonium compounds, e.~., mono((.' 10-C l,I alkyl)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(polyethoxy ethanol) alkylammonium 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:
-[N(CH3)?-(CHZ)3-NH-CO-NH-(CHZ)~-N(CH3:12+-CHZCHaOCHZCH2Jx y+ 2x[CI-J
available under the trade name Mirapol A-15~ from Rhone-Poulenc, and -[N(CH;)~-(CH~)~-NH-CO-(CHZ)~-CO-NH-(CHZ)3-N(CH~)z-(CH~CHyOCHZCH2Ix+ x[CI-l, available under the trade name Mlirapol AD-1~ from Rhdne-Poulenc, quaternized polyethyleneimines, vinylpyrrolidone/methacrylamidopropyltrimethylammonium chloride copolymer, available under the trade name Gafquat HS-i00~ from GAF;
triethonium hydrolyzed collagen ethosulfate, available under the trade name Quat-Pro 1?~ From Maybrook; and nuxtures thereof.
It is preferred that a no foaming or low foaming agent is used, to avoid foam formation during fabric treatment. It is also preferred that polyethoxylated agents such as polyethylene glycol or Variquat 66~ are not used when alpha-cyclodextrin is used. The polyethoxylate groups have a strong atlinity to and readily complex with 2> alpha-cyclodextrin which in turn deplete the uncomplexed cyctodextrin available for odor control.
When an antistatic agent is used it is typically present at a level of from about 0.05% to about 10°io, preferably fram about 0.1% to about 5°io, more preferably from about 0.3°,'° to about 3%, by weight of the composition.
(7j. Insect and/or l~loth Reoelline A2ent The composition of the present invention can optionally contain an effective amount of insect andlor moth repelling agents. Typical insect and moth repelling agents are pheromones, such as anti-aggregation pheromones, and other natural andlar synthetic ingredients. Preferred insect and moth repellent agents useful in the composition of the present invention are perfume ingredients, such as citronellol, -r citranellal, citral, linaiool, cedar extract, geranium oil, sandalwood oil.
'_' (diethylphenoxy)ethanol, etc. When an insect and/or moth repellent is used it is typically present at a level of from about 0.005% to about 3%.
by weight of the composition.
5 citranellal. citral, linalool, cedar extract, geranium oil, sandalwood oil.
?
(diethylphenoxy)ethanol, etc. Other examples of insect and/or moth repellents useful in the composition of the present invention are disclosed in U.S. Pat. Nos.
4,449,987.
-1,69;.890, 4.696,676, 4,933,371. 5,196,200, and in "Semio Activity of Flavor and Fragrance Molecules on Various Insect Species". B.D. Mookherjee et al., published 10 in Bioactive Volatile Compounds from Plants, ASC Symposium Series 525, R.
Teranishi, R.G. Buttery, and H. Sugisawa, 1993, pp. 35-48.
When an insect and/or moth repellent is used it is typically present at a level of from about 0.005% to about 3%, by weight of the composition.

(8) Solubilizins Aid The odor absorbing composition of the present invention can also optionally contain a solubilizing aid to solubilize any excess hydrophobic organic materials, e.g., perfume, insect repelling agent, antioxidant, ete., that are not readily soluble in the 20 composition, to form a clear solution. A suitable solubilizing aid is surfactant, preferably no-foaming or low foaming surfactant. Suitable surfactants are nonionic surfactants, anionic surfactatns, cationic surfactants, amphoteric surfactants, zwitterionic surfactants. and mixtures thereof. Suitable surfactants can be emulsisers and/or detersive surfactanu. Mixtures of emulsifiers and detersive surfactants are 25 also preferred. When a surfactant containing one, or more, aliphatic alkyl group is used, it is preferred that it contain relatively short alkyl chains of from about 5 to about 14 carbon atoms. Preferred nonionic surfactants are polyethylene glycol-polypropylene glycol block copolymers, such as Pluronic~ and Pluronic R~
surfactants from BASF; Tetronic~ and Tetronic R~ surfactants from BASF.
30 ethoxylated branched aliphatic diols such as Surfynol~ surfactants from Air -- Products; ethoxylated alkyl phenols, such as Igepal~ surfactanu from Rhone Poulenc; ethoxylated aliphatic alcohols and carboxylic acids; polyethylene glycol diesters of fatty acids; fatty acid esters of ethoxylated sorbitans; and mixtures thereof.
Preferred anionic surfactants are dialkyl sulfosuccinate, alkylarylsulfonate, 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 good wetting properties. Also preferred are surfactants that have the hydrophilic groups situated between hydrophobic chains, such as Pluronic R~
surfactants, Surfjmol surfactants, polyethylene glycol diesters of fatty acids, fatty acid esters of ethoxylated sorbitans, dialkyl sulfosuccinate, di(Cg-C 12 alkyl)di(C

PCT/US95l0942.R
?3 -alkyljammanium halides, and mixtures thereof; or surfactants that have the hydrophobic chains situated between hydrophilic groups, such as Pluronic surfactants; and mixtures thereof It~ixtures of these surfactants and other types of surtactants are also preferred to form no-foaming or law-foaming solubilizing agents-S Palyalkylene glycol can be used as a defoaming agent in combination with the solubilizing agents If solubilizing agent is used in the present compositions, it is typically used at a level of from about 0.05°,o to about l% by weight of the composition, more preferably from about 0.05°ro to about 0.3%.
l0 (9). Additional Odor Absorbers When the clarity ofthe solution is not needed, and the solution is not sprayed on fabrics, other optional odor absorbing materials, e.g., zeolites and activated carbon, can also be used.
15 (a). Zeolites A preferred class of zeolites is characterized as "intermediate"
siticateialuminate zeoGtes. The intermediate zeolites are characterized by Si02iA102 molar ratios of less than about 10. Preferably the molar ratio of Si02/A102 ranges from about 2 to about 10. The intermediate zeolites have an advantage over the 20 "high" zeolites. The intermediate zeolites have a higher affinity for amine-type odors, they are more weight eiTtcient 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 zeoGtes. A wide variety of intermediate zeolites suitable for use herein are commercially available as Valfor~ CF301-b8, Valfor~
25 300-63, Valfor~ CP300-35, and Valfor~ CP300-56, available from PQ
Corporation, and the CBVI00~ series ofzeolites from Conteka.
Zeolite materials marketed under the trade name Abscents~ and Smellrite~, available from The Union Carbide Corporation and UOF are also preferred. These materials are typically available as a white powder in the 3-5 micron particle size 30 range. Such materials are preferred over the intermediate zealites for control of sulfur-containing odors, e.g., thiols, mercaptans.
(b). Activated Carbon The carbon material suitable for use in the present invention is the material well known in commercial practice as an absorbent for organic molecules 35 andlor for air purification purposes. Often, such carbon material is referred to as "activated" carbon or "activated" charcoal. Such carbon is available from wo saro~s39 ~ ~ ~ ~ ~ g ~ _ r ~ .: i rcTicrsv~tt~aas r _ 2,~ _ commercial sources under such trade names as; Calgon-Type CPG~; Type PCBtft;;
Type SGL~fk~; Type C.4.L~t:; and Type OLD.
It is preferred that na, or essentially no, volatile law molecular weight monalaydric aloahols such as ethanol and/or isoprapanol are intantianally added to .5 the composition of the present invention since these volatile organic compounds will contribute both to flammability problems and environmental pallurian problems.
If small amounts of low molecular weight monohydric alcohols are present in the composition ofi the present invention due to thn addition of these alcahols to such things as perfumes and as stabilizers for same preservatives, it is preferable that the level of monohydric alcohol be less than about 5°io, preferably less than about 3n o, more preferably less than about 1°ro.
IID, Colorant Colorants and dyes, especially blueing agents, can be optionally added to the I S odor absorbing compositions for visual appeal and performance impression.
When colorants are used, they are used at extremely law levels to avoid fabric staining.
Preferred colorants for use in the present compositions are highly water-soluble dyes, e.g., Liquitint~ dyes available from 1'.~Iilliken Chemical Co. Non-limiting examples of suitable dyes are, Liquitint Blue HP~, Liquitint Blue 65~, Liquitint Patent Blues, Liquitint Royal Blues, Liquitint Experimental Yellow 89~I9-43~, Liquitint Green HMC~, Liquitint Yellow II~, and mixtures thereof, preferably Liquitint Blue IB'~i:, Liquitint Blue 65~, Liquitint Patent BlueQ~, Liquitint .Royal Blues, Liquitint Experimental Yellow 8919-43~, and mixtures thereof II. ARTICLE OF" MANUFACTURE
The composition of the present invention can also be used in an artiste of manufacture comprising said composition plus a spray dispenser. When the commercial embodiment of the article of manufacture is used, it is optional, but preferable, to include the preservative. Therefore, the most basic article of ~0 manufacture comprises uncomplexed cyciodextrin, a carrier, and a spray dispenser.
SPRr~Y DISPfNSER
The article of manufacture herein comprises a spray dispenser. The cyclodextrin composition is placed into a spray dispenser in order to be distributed 3S 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 _ 7j _ dispenser herein does not include those that will substantially 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 site of larger than about 30~tm The spray dispenser can be an aerosol dispenser. Said aerosol dispenser comprises a container which can be constructed of any of the conventional materials employed in fabricating aerosol containers. The dispenser must be capable of withstanding internal pressure in the range of from about ZO to about 110 p.s.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 contained in the dispenser to be dispensed in the form of a spray of very fine, or finely divided, particles or droplets.
The aerosol dispenser utilizes a pressurized sealed container from which the clear, aqueous odor-absorbing composition is dispensed through a special actuator/valve 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, are not preferred Halogenated hydrocarbon propellants such as chlorofluoro hydrocarbons have been alleged to contribute to em~ironmental 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 of commercially available aerosol-spray dispensers appears in U.S. Pat. Nos.: 3,436,772, Stebbins, issued April 8, 1969; and 3,600,325, Kaufrnan et al., issued August 17, 1971.
Preferably the spray dispenser can be a self press<rrizad npn-aerosol container having a convohrted liner and an elastomeric sleeve. Said self pressurized dispenser comprises a liner/sleeve assembly containing a thin, flexible radiaUy expandable convoluted plastic liner of from about 0.010 to about 0.020 inch thick inside an essentially cylindrical elastomeric sleeve. The liner~sleeve is capable of holding a substantial quantity of odor absorbing fluid product and of causing said product to be dispensed. A more complete description of self pressurized spray dispensers can be found in U.S. Pat. Nos. 5,111,971, Winer, issued May 12, 1992, and 5,232,126, Winer, issued Aug. 3, 1993:
Another type of aerosol spray dispenser is one wherein a barrier separates the odor absorbing composition from the propellant (preferably compressed air or nitrogen). Such a dispenser is available from EP Spray Systems.
East Hanover. New Jersey.
\~Iore preferably. the spray dispenser is a non-aerosol, manually activated, 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 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.
The contains and the pump mechanism can be constructed of any conventional material employed in fabricating pump-spray dispensers, including, but not limited to: polyethylene; polypropylene; polyethylenetsephthalate; blends of polyethylene, vinyl acetate, and rubbs dastoms. A preferred container is made of clear. e.g., polyethylene tsephthalate. Other materials can include stainless steel. A
more complete disclosure of commscially available dispensing devices appears in:
U. S. Pat. Nos.: 4,895,279, Schultz, issued January 23, 1990; 4,735,347, Schultz et al.. issued April 5, 1988; and 4,274,560, Carts, issued June 23, 1981.
Most preferably, the spray dispenss is a manually activated trigger-spray dispenser. Said triggs-spray dispense comprises a contains and a triggs both of which can be constructed of arty of the conventional material employed in fabricating trigger-spray disprnsers~, including, but not limited to: polyethylene;
polypropylene;
polyacetal; polycarbonate; polyethylenetsephthalate; polyvinyl chloride;
polystyrene; blends of polyethylene, vinyl acetate; and nrbbs elastomer. Other materials can include stainless sled and glass. A preferred contains is made of clear, . e.g. polyethylene tsephthalate. The triggs-spray dispenser does not incorporate a propellant gas into the odor-absorbing composition, and preferably it does not include those that will foam the odor-absorbing composition. The trigger-spray dispense herein is typically one which acts upon a discrete amount of the odor-absorbing composition itself; typically by means of a piston or a collapsing bellows that displaces the composition through a nozzle to create a spray of thin liquid. Said 3 5 trigger-spray dispenser typically comprises a pump chambs 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 for blocking communication and flow of fluid through the nozzle and is responsive to the pressure inside the chamber. For the piston type trigger 5 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 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 l0 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 acts as the spring to return to its original position: This action causes a I 5 vacuum in the chamber. The responding fluid acts to close the outlet valve while opening the inlet valve drawing product up to the chamber from the reservoir.
A more complete dixlosure of commercially available dispensing devices appears in U.S. Pat. Nos. 4,082,223, Nozawa, issued Apr. 4, 1978; 4,161, 288, McKinney, issued Jul. 17, 1985; 4.434,917, Saito et al., issued Mar. 6, 1984;
and 20 4,819,835, Tasaki, issued Apr. 11, 1989; 5,303,867, Peterson, issued Apr.
19, 1994.
A broad array.of trigger sprayers or finger pump sprayers are suitable for use with the compositions of this invention. These are readily available from suppliers such as Calmer, Inc., City of Industry. California; CSI (Continental Sprayers, Inc.), St. Peters, Missouri; Berry Plastics Corp.. Evansvill~ Indiana - a distributor of 25 Guala~ sprayers; or Seaquest Dispensing, Cary, Illinois.
The preferred trigger sprayers are the blue inserted Guala~ sprayer, available from Berry Plastics Corp., or the Calmer TS800-IA sprayers, available from Calmer Inc., because of the fine uniform spray characteristics, spray volume, and pattern size.
Any suitable bottle or container can be used with the trigger sprayer, the preferred 30 . bottle is a 17 fl-oz. bottle (about 500 ml) of good ergonomics similar in shape to the Cinch~ bottle. 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 polyethylene terephthalate.

1V0 96IO.t939 : , PCT1US9510942.5 _~g_ For smaller four il-oz. size (about 1.18 ml), a finger pump can be used with canister or c.'y:lindrical bottle. The preferred pump for this application is tfae cylindrical Euromist 1f9 from Seaquest Dispensing.
LII. METAOI? 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 eflFective amount onto the desired surface or article. An effective amount as defined herein means an amount sufficient to absorb odor to the point that it is not lU 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 cyc(odextrin 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 more readily occur on the surfaces. Furthermore, the cyciodextrin solution is not for use on human skirt, especially when an antimicrobial preservative is present in the ?CI composition because skin irritation can occur.
The present invention encompasses the method of spraying an effective amount ofcyclodextiitt solution onto household surfaces. Preferably said household surfaces 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 and/or fabric articles.
Preferably, said fabric and,~or fabric articles include, but are not limited ta, 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 ofan 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 cyclodexrtrin solution orto shower curtains 3S The present invention relates to the method of spraying a mist of an effective amount of cyciodextrin solution onto andlar into garbage cans andlor recycling bins.

W0 96!04939 PGTlUS95/09425 2~96~~~
_2c)_ 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 afcyclodextrin solution into and!or onto major household appliances includihg but not limited to: refrigerators, fPeezers, washing machines, automatic drv_, ers, ovens, microwave ovens, dishwashers etc., to absorb malodor The 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 cyclodextrin solution onto household pets to absorb malodor.
Ail 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:
The following are non-limiting examples of the instant composition Example I Example II

Inssedients Wt,,~p Wt.oi beta-Cyclodextrin 1.0 0.5 alpha-Cyclodextrin - O.S

Kathon CG 0.001 0.0008 Distilled Water Balance Balance Examples I and II
The ingredients of Examples I and II are mixed and dissolved into clear solutions.
Example III Example IV

Ingredients Wt.ii Wt.%

Methylated alpha-cycladextrin0.27 -Alethylated beta-cyclodextrin0.73 1.0 Kathon CG 0.001 -Bronopol - 0.02 Distilled Water Balance Balance Example III

WO ~Gltld939 ~ ~ PCTNS95/09425 s The in~,redients of Example III are mixed and dissolved into a clear solution.
Methylated alpha-cyclodextrin and methylated beta-cyclodextrin are obtained as a mixture from the methylation reaction of a mixture of alpha-cyclodextrin and beta-cvclndextrin.

W09GI04939 21g629,~ PCTIUS95/09425 - --i 1 -Example IV
The inr~redients of Example IV are mixed and dissolved in a vessel into a clear solution.
Example V Example VI

Ingredients Wt.~b ~4't.%

alpha-Cyclodextrin 0.5 -Hydroxypropyl-beta-cycladextrin0.5 1,0 Kathon CG 0.0005 0.001 Distilled water Balance Balance , Exam~rles V 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 5.0 Example b'II Example VIII

Ingredients Wt.io Wt~

Alpha-cycladextrin 0.5 Hydraxypropyl-alpha-cyclodextrin- 0.27 Hydroxypropyl-beta-cyelodextrin0.5 0.73 Propylene glycol 0.01 O.Ob Kathon CG 0.001 0.0008 Distilled water Balance Balance Example VII
The ingredients of Example VIT are mixed and dissolved in a vessel into a clear solution. The hydroxygropyl-beta-cyclodextrin has a degree of substitution of about 5.4.
IS
Example VIII
The in~.redients of Example VII1 are mixed and dissolved into a clear solution.
Hydraxypropyl alpha-cyclodextrin and hydroxypropyl beta-cyclodextrin are obtained as a mixture with an average degree of substitution of about 4.9, from the hydroxypropylation reaction of a mixture of alpha-cyclodextrin and beta-cyclodextrin. Propylene glycol is a minor by-product (about 6%) of the same reaction.

wo 9s~oavav rc rnrsssro~a3s ~~s~~~. i Example IXIX Example X

Ingredients WI,~o lft.uu alpha-Cycladextrin O.s -Leta-t:ycladextrin 1.0 Hydroxypropyl-alpha-cyclodextrin- 1.0 Hydroxypropyl-beta-cycladextrin- 2.5 gamma-Cyclodextrin 0.5 1.0 Kathon CG 0.001 0.001 Distilled water Balance Balance Examl les LX and X
The in<rredients of Examples IX and X are mixed and dissolved into clear solutions Example XI Ex~ple XII

Ingredients Wt.% ~'t.,i alpha-Cyclodextrin 0.5 -Methylated beta-cycladaxtrin0.5 -Hydroxypropyl alpha-eyclodextrin- 0.27 Hydroxypropyl beta-cycladextrin- 0.73 Zinc chloride 1.0 1.0 Kathan CG 0,0008 0.0008 Propylene glycol - 0.06 HCI (aj (aj Distilled water Balance Balance {a) Tp adjust solurion pH to about 4.g Example XI
P.bout S parts of alpha-c5~clodextrin and about 5 parts of methylated beta cyclodextrin are added wdth mixing in a vessel containing about 980 parts of distilled water. Vdhen 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. Then about 0.67 part of a nominally 1.5% aqueous solution of Kathon CG is added witEt mixing until the solution becomes water clear.

W 0 9610.939 PCTlITS9S/t1942i 2~9629~ -;~_ 1 Examolc XII
The composition of Example III is prepared similarly to that of Example YI.
Example X1II Example XIV

Ingredients W t.% Wt.,o beta-t:'yclodextrin O.g Hydroxypropyl beta-cyciodextrin - 1.0 Zinc chloride 1.0 ZnSO,~7H20 - 2.2 Kathon CG 0.0008 0.0008 Propylene glycol - 0.05 HCI (a) la) Distilled water Balance Balance ta) To adjust solution pH to about 4.8 Examples XIII and ~' The composition of Examples XIII and ?QV are prepared similarly to that of Example hZ.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A stable, aqueous odor absorbing composition, comprising:
A. from about 0.1% to about 5% of solubilized, uncomplexed cyclodextrin comprising up to 1.5% by weight of beta-cyclodextrin; and B. aqueous carrier; and wherein said composition is essentially free of any material that would soil or stain fabric; and wherein said composition is essentially free of perfume and has a pH of greater than about 3.

2. The composition of Claim l additionally comprising cyclodextrin selected from the croup consisting of alpha-, beta-, and gamma-cyclodextrin, and their derivatives, and mixtures thereof.

3. The composition of Claim 2 wherein said cyclodextrin is a mixture of alpha-cyclodextrin and beta-cyclodextrin or their derivatives thereof.

4. The composition of Claim 1 additionally comprising solubilized, water-soluble, antimicrobial preservative having a water-solubility of greater than about 0.3% at room temperature.

5. The composition of Claim 4 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.

6. The composition of Claim 5 wherein said preservative is an organic sulfur compound selected from the group consisting of 5-chloro-Z-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.

7. The composition of Claim 6 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.

8. The composition of Claim 5 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.

9. The composition of Claim 8 wherein said preserevative 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.

10. The composition of Claim 5 wherein said preservative is a cyclic organic nitrogen compound selected from the group consisting of imidazolidinedione compounds, polymethoxy bicyclic oxazolidine, and mixtures thereof.

11. The composition of Claim 1 wherein said cyclodextrin is present at a level of From about 0.2% to about 4%, by weight of the composition and said preservative is present at a level of from about 0.0001% to about 0.5%, by weight of the composition.

12. The composition of Claim 11 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.

11. The composition of Claim 12 wherein said cyclodextrin is present at a 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 0.1%, by weight of the composition.

14. The composition of Claim 1 additionally comprising a metallic salt selected from the group consisting of water-soluble zinc salts, water-soluble copper salts, and mixtures thereof

15. The composition of Claim 14 wherein said metallic salt is selected from the group consisting of ZnCl2, CuCl2, and mixtures thereof.

16. The composition of Claim 15 wherein said metallic salt is ZnCl2 present at a level of from about 0.1% to about 10%, by weight of the composition.

17 A clear, 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 alpha-cyclodextrin and up to 1.85% by weight of beta-cyclodestrin;
B from about 0.0001% to about 0.01%, by weight of the composition of solubilized. water-soluble, antimicrobial preservative comprising a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one; and C. water; and wherein said composition is essentially free of any material that would soil or satin fabric: and wherein said composition is essentially free of any perfume and has a pH of greater than about 4.

18. A clear, stable, aqueous odor absorbing composition, for use on inanimate surfaces, comprising:
A. from about 0.3% to about 1.85%, by weight of the composition, of beta-cyclodextrin;
B. from about 0.0001% to about 0.01%, by weight of the composition, of the composition of solubilized, water-soluble, antimicrobial preservative comprising a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one; and C. water, and wherein said composition is essentially free of any material that would soil or satin fabric; and wherein said composition is essentially free of any perfume and has a pH of greater than about 4.

19. A clear, 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 a mixture of hydroxypropyl beta-cyclodextrin and hydroxypropyl alpha-cyclodextrin;
B. from about 0.0001% to about 0.01%, by weight of the composition, of the composition of solubilized, water-soluble, antimicrobial preservative comprising a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one; and from about 0.3% to about 5%, by weight of the composition, of ZnCl2, and water; and wherein said composition is essentially free of any material that would soil or satin fabric; and wherein said composition is essentially free of any perfume and has a pH of from about 4 to about 5.5.

20. The method of treating fabric comprising spraying an effective amount of the composition of Claim 1 onto fabric with a trigger-spray device having a bottle comprising clear polyekhyleneterephthalate.