WO2000049868A1

WO2000049868A1 - Selenium antimicrobial compositions

Info

Publication number: WO2000049868A1
Application number: PCT/US2000/004727
Authority: WO
Inventors: Eugene F. Rothgery; George Polson; Rahim Hani
Original assignee: Arch Chemicals, Inc.
Priority date: 1999-02-25
Filing date: 2000-02-24
Publication date: 2000-08-31
Also published as: AU3243700A

Abstract

Selected selenium compounds useful as antimicrobial agents in soaps, shampoos, skin care medicaments, hard surface cleaners and fabric care compositions.

Description

SELENIUM ANTIMICROBIAL COMPOSITIONS

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to selected selenium compounds as novel compositions-of-matter. Furthermore, the present invention relates to antimicrobial compositions useful in soaps, shampoos, skin care medicaments as well as hard surface cleaning compositions and fabric care compositions that contain selected selenium compounds. And still further, the present invention relates to antidandruff shampoo compositions that contain selected selenium compounds as antidandruff agents.

2. Brief Description of the Art

Zinc pyrithone and selenium disulfide are both well known antidandruff agents that have been used for decades in a variety of commercial shampoos.

In U.S. Patent No. 4,496,559 (Henderson et al.), certain 2-seleno-pyridine-N-oxide compounds were disclosed as useful as agricultural fungicides and bactericides. That patent did not disclose that these compounds were useful in personal care applications.

In U.S. Patent Nos. 5,424,435 (Hani et al.) and 5,675,013 (Hani et al.), certain l-hydroxy-6-substituted-2-pyridones and l-hydroxy-6-substituted-2-pyrithiones were disclosed as being useful as biocidal agents, particularly as antifungal agents in soaps, adhesives, coatings, elastomers, sealants, shampoos, skin care medicaments, cosmetics, paints and other polymer compositions. It has now been discovered that novel selenium analogs to these 2-pyridone and 2-pyrithione compounds are suitable in shampoos and skin care medicaments.

BRTEF SUMMARY OF THE INVENTION Accordingly, one aspect of the present invention is directed to antimicrobial compositions of formula (I):

wherein Y-R is hydrogen or Y is an oxygen, sulfur, selenium or an NR' moiety, wherein N is nitrogen and R and R' are independently selected from hydrogen, substituted or unsubstituted hydrocarbon radicals having one to twenty carbon atoms; and metal salts thereof, either alone or in combination with zinc pyrithione or ketoconazole or mixtures thereof.

Another aspect of the present invention is directed to an antimicrobial composition comprising (a) a functional product selected from the group consisting soaps, shampoo or skin care medicaments, and further comprising (b) an antimicrobially effective amount of (i) at least one compound selected from the group consisting of the formulae (I), (II), (III) and (IV):

wherein Y-R is hydrogen or Y is an oxygen, sulfur, selenium or an NR' moiety, wherein N is nitrogen and R and R' are independently selected from hydrogen, substituted or unsubstituted hydrocarbon radicals having 1 to 20 carbon atoms; and metal salts thereof;

wherein each R" is either hydrogen or an alkyl group; either alone or in combination with (ii) zinc pyrithione, ketoconazole or mixtures there. Still another aspect of the present invention is directed to an antidandruff shampoo that comprises (a) a shampoo base and (b) an effective antidandruff amount of (i) at least one compound selected from the group consisting of the formulae (I), (II), (III) and (IV) as defined above; either alone or in combination with (ii) zinc pyrithione, ketoconazole or mixtures thereof. In yet another aspect, the present invention is directed to a hard surface cleaning composition, comprising (a) a cleaning solution and (b) an antimicrobially effective amount of (i) at least one compound selected from the group consisting of the formulae (I), (II), (III) and (IV) as defined above, either alone or in combination with (ii) zinc pyrithione, ketoconazole or mixtures thereof. In yet another aspect, the present invention is directed to a fabric care composition, comprising (a) suitable carrier and (b) an antimicrobially effective amount of (i) at least one compound selected from the group consisting of the formulae (I), (II), (III) and (IV) as defined above, either alone or in combination with (ii) zinc pyrithione, ketoconazole or mixtures thereof. These and other aspects of the present invention will become apparent upon reading the following detailed description of this invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE PRESENT INVENTION Preferred hydrocarbon radicals for the R and R groups in the above formula (I) are aliphatic hydrocarbons having between 3 and 15 carbons, more preferably a straight chain hydrocarbon having between 5 and 10 carbons. The term "substituted hydrocarbon" is intended to include substituents such as halogen such as chloro, iodo, fluoro or bromo, alkoxy such as methoxy, ethoxy, propoxy or butoxy, nitro, thio, and amino combinations thereof, and the like. Illustrative hydrocarbon groups include n-octyl, 2,4,4-trimethylpentyl- 3,5,5-trimethylhexyl, combinations thereof, and the like. Compounds of Formula (I) wherein Y is oxygen may be made by a process which comprises the steps of:

(a) reacting 2,6-dichloropyridine N-oxide, a hydroxy compound containing between 1 and 20 carbon atoms (such as an alcohol such as n-octanol or a phenol compound such as 4-methylphenol, preferably selected from the group consisting of alkyl, arylalkyl and aryl compounds containing at least one hydroxyl group, and combinations thereof) and a base (such as sodium hydroxide or potassium hydroxide), optionally in the presence of water or an organic solvent, at an elevated temperature to produce a corresponding 2-chloro- 6-substrituted-pyridine N-oxide; and (b) reacting said 2-chloro-6-substituted-pyridine N-oxide with a selenium- containing base (such as sodium hydroselenide) to produce the corresponding 1- hydroxy-6-substituted-pyridine-2-selenium. Compounds of Formula (I) wherein Y is nitrogen may be made by a process which comprises the steps of: (a) reacting 2,6-dichloropyridine N-oxide, a primary or secondary amine containing between 1 and 20 carbon atoms (such as dimethanolamine or triethanolamine) and a base (such as sodium hydroxide or potassium hydroxide), optionally in the presence of water or an organic solvent, at an elevated temperature to produce a corresponding 2-chloro-6-substituted-pyridine N-oxide and (b) reacting said 2-chloro-6-substituted-pyridine N-oxide with a selenium- containing base to produce the corresponding l-hydroxy-6-substituted-pyridine- 2-selenium compound. Compounds of Formula (I) wherein Y is sulfur may be made by a process which comprises the following steps:

(a) reacting a 2,6-dichloropyridine N-oxide, a thiol compound having between 1 and 20 carbon atoms, (for example alkyl, arylalkyl and aryl thio compounds, and combinations thereof) and base (such as sodium hydroxide or potassium hydroxide) in an organic solvent at an elevated temperature to produce a corresponding 2-chloro-6-substituted-pyridine N-oxide; and

(b) reacting said 2-chloro-6-substituted-pyridine N-oxide with a selenium- containing base to produce the corresponding l-hydroxy-6-substituted-pyridine- 2-selenium compound.

Compounds of Formula (I) wherein Y is selenium may be made by a process similar to where Y is sulfur except that a selenium compound having between 1 and 20 carbon atoms or combinations thereof is used instead of thiol compound in step (a).

The above processes can be carried out sequentially or simultaneously in a single step. Surfactants and/or phase transfer catalysts are optionally employed to facilitate the step (a) reaction in any of these processes.

The reactions for making compounds of Formula (I) are suitably conducted at atmospheric pressure, although higher or lower pressures may be used if desired. Suitable reaction temperatures for steps (a) and (b) range between a temperature of about 25° C to about 150° C, preferably employing a reflux temperature of between about 70° C and about 90° C. Total reaction time for the process of this invention can vary over a wide range, but is advantageously between 30 minutes and 5 hours for step (a) and between 30 minutes and 5 hours for step (b).

The reactions for compounds of Formula (I) are suitably carried out in the presence of a base and an organic solvent. Suitable bases include alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, alkaline earth metal hydroxides such as calcium or magnesium hydroxide, pyridine, triethylamine and other tertiary amine bases, potassium carbonate, "DABCO" amine catalyst (l,4-diazabicyclo(2.2.2)octane), "DBU" (1,8- diazabicyclo(5.4.0)undec-7-ene), "DBN" (l,5-diazabicyclo(4.3.0)non-5-ene, t- butyltetramethyl-guanidine, combinations thereof, and the like. Preferred bases for step (a) are anhydrous, granular or powdered sodium or potassium hydroxide, and preferred bases for step (b) are concentrated aqueous solutions of sodium hydro selenide having a concentration of base of between about 10% and about 90% by weight based upon the weight of the solution. Preferably, the base is employed in at least an amount equal to the number of moles for each reactant, and a molar excess of base relative to each reactant can be employed as desired. The reactions for making compounds of Formula (I) are suitably carried out in the presence of a solvent. Suitable organic solvents include, for example, ether, and acetone, methylene chloride, benzene, toluene, pyridine, tetrahydrofuran ("THF"), acetonitrile, dimethylsulfoxide ("DMSO"), dimethylformamide ("DMF"), and combinations thereof. Although the preferred solvent is acetonitrile, it is more preferred to run the reactions neat. As another alternative, a reactive solvent can be employed, if desired, for example by using an organic alcohol, e.g. isopropanol, or n-octanol, in an amount sufficient to provide the desired reactant and solvent characteristics.

The molar ratio of reactants for the processes of this invention can vary over a wide range, but is preferably between 10:1 and 1:10, more preferably between 2:1 and 1:2, most preferably about 1 :1.

Final shape of the compounds of formulae (I), (II), (III) or (IV) may be any desired shape for the desired antimicrobiocial application. For example, they may be either platelets, rods, needles, spheres and the like. The particle size may be from submicron to several microns in the largest dimension, for example, 0.05-30 microns. Particles distributions may be unimodal or multimodal within this range of 0.1 to 30 microns.

Compounds of formula (I) may be used as antimicrobial agents in paints, adhesives, coatings, elastomers, sealants, shampoo, skin care medicaments and metal-working fluids.

Suitable salts of the compounds of Formula (I) include amine salts, alkali metal salts and alkaline earth metal salts and the like. An amine salt such as monoethanol amine ("MEN') is preferred.

Compounds of formulae (II), (III), and (IV) may be made according to processes described in the above-noted U.S. Patent No. 4,496,559.

The antimicrobial compositions of the present invention are directed to shampoos and skin care medicaments that contain an antimicrobially effective amount of at least compound of formulae (I), (II), (III), or (IV), alone or combination with zinc pyrithione ketoconazole or both. By the term "antimicrobial effective amount" is meant an amount sufficient to impart to the compositions resistance against microbial attack by fungi and/or bacteria.

Preferred types of shampoos include antidandruff-type shampoos and hair tonics. For these particular antidandruff uses, an antidandruff effective amount of the active ingredients must be in the formulation. By the term "antidandruff effective amount" is meant an amount sufficient to treat a dandruff condition in humans.

Preferably the antimicrobial compounds are employed in the composition in a total amount of between 0.05 and about 10 weight percent, more preferably between about 0.1 and about 5 weight percent, based upon the total weight of the antimicrobial composition. If zinc pyrithione or ketoconazole or mixtures of the two are used in combination with one or more compounds of the Formulae (I), (II), (III) and (IV), the relative amount of zinc pyrithione or ketoconazole or both may be from about 1 % to about 99%, preferably about 10-90%, by weight of the total combination of antimicrobial ingredients.

Generally, the antimicrobial soaps, shampoos and skin care medicaments of the present invention may contain any base medium ingredient commonly used in soaps, shampoos or skin care medicaments that is compatible with the antimicrobial agents described above. By compatible, it is meant no adverse reaction or effect would occur by their combination. Illustrative base medium ingredients include glycerine, aloe, surfactants such as dodecyl-benzene-sulfate ("DDBS"), water and other ingredients such as listed in the Examples below. Likewise, the compositions of formulae (I), (II), (III) or (IV) may be useful additives in industrial fluids (e.g. metalworking fluids), paints, coatings, other personal care products (e.g. cosmetics), hard surface cleaners, fabric care compositions, swimming pool sanitizers, wood treatment products, plastic treatment products, medical products, or any other application where microorganism growth must be stopped or slowed. One other significant use application for these inventive selenium compositions may be in hard surface cleaning compositions. Generally, such hard surface cleaners may contain any cleaning solution commonly used in hard surface cleaners that are compatible with the antimicrobial agents of the present invention. By compatible, it is meant no adverse reaction or effect would occur by their combination. Illustrative cleaning solutions would include any commercially known powdered cleaner of the type used to clean kitchen counters, both tubs and the like with up to 10% by weight of the cleaner containing the antimicrobial agents of the present invention. Another significant use of the present antimicrobial agents is in fabric care compositions. Generally, such fabric care compositions may contain any carrier composition commonly used in fabric care compositions that are compatible with the antimicrobial agents of the present invention. By compatible, it is meant no adverse reaction or effect will occur by their combination. Illustrative carrier compositions would include solvent sand cleaners commonly used to remove stains from carpets, clothing and the like.

The composition of the present invention are useful, in any of the variety of applications described herein, as disinfectants and preservatives, inn a liquid or spreadable form, alone or in combination with an inert carrier such as water, liquid hydrocarbons, ethanol, isopropanol and the like. They can be employed using conventional procedures to control bacteria and fungi in various substrates, and can be applied bacterial or fungal organism directly.

The compositions of this invention may also be applied to the substrate to be protected by any of the conventional methods, including dipping, spraying or brushing. The following examples further illustrate the present invention. All parts and percentages employed therein are by weight unless otherwise indicated.

EXAMPLE 1: Antidandruff Shampoo Formulation I

An antidandruff shampoo composition can be made using deagglomerated particles of zinc pyrithione and one or more compounds of Formulae (I), (II), (III), or (IV) in combination with the following ingredients: Component N:

Water 45.0%

Magnesium aluminum silicate 1.2%

Hydroxypropyl methylcellulose 1.0%

Component B: Zinc Pyrithione (25% aqueous dispersion) 0.5%

Compound(s) of Formulae (I), (II), (III) or (IV) 0.5%

Component C:

Cocamide DEA 1.2%

Component D: Triethanolamine lauryl sulfate, 40% 44.0%

Triethanolamine, 99% 4.0%

FD&C Blue No. 1 (0.2%) 1.6%

FD&C Yellow No. 5 (0.1 %) 0.6%

Fragrance q.s.

The antidandruff shampoo composition can be made as follows: Component A is prepared by heating water to 70° C and dissolving the other two ingredients with stirring (about 1500 rpm). Component B is then added, and stirring continued for 5 minutes. Stirring speed is reduced to -300 RPM. Component C is melted in a separate container, and is added then to the A/B mixture. The heat is removed and component D is added while the mixture cools. The term "q.s." refers to quantity sufficient. EXAMPLE 2: Antidandruff Shampoo Formulation II

Another antidandruff shampoo composition may be made using zinc pyrithione and one or more compounds of Formulae (I), (II), (III) or (IV) in combination with the following ingredients: Component A:

Deionized water 76.0%

Ammonium lauryl sulfate 15.0%

Cocamide DEA 2.0%

Component B: Di(hydrogenated) tallow phthalic acid amine 5.0%

Compound(s) of Formulae (I), (II), (III) or (IV) 1.0%

Component C:

Preservative q.s.

Component D: Citric Acid, 50% aq. Solution, or

Sodium hydroxide, 50% squeous solution q.s.

Component E:

Ammonium chloride q.s.

The antidandruff shampoo composition can be made by having components A and B each mixed well in separate containers. Component A is heated to 165-170°F and component B is added. The mixture is stirred for 30 minutes. The mixture is then cooled to 120°F, and component C is added. The pH of the resulting mixture is adjusted to 5.0-6.2 with component D, and the viscosity is adjusted with component E.

EXAMPLE 3 : Antidandruff Shampoo with Conditioner I

An antidandruff shampoo and conditioner composition is made using needle and rod forms of zinc pyrithione and one or more compounds of Formulae (I), (II), (III) and (IV) in combination with the following ingredients: Component A:

Deionized Water 72.0%

Ammonium lauryl sulfate 20.0%

Cocamide DEA 2.0%

Component B: Di(hydrogenated) tallow phthalic acid amide 4.0%

Zinc Pyrithione (25% aqueous dispersion) 0.75%

Compound(s) of Formulae (I), (II), (III) and (IV) 0.25%

Dimethicone, 12,000 cps .5%

Component C: Preservative q.s.

Component D:

Citric acid, 50% aqueous solution, or

Sodium hydroxide, 50% aqueous solution q.s.

Component E: Ammonium chloride q.s.

This antidandruff shampoo and conditioner composition can be made by first mixing components A and B in separate containers. Component A is heated to 165-170°F and component B is added. The mixture is stirred for 30 minutes. The mixture is then cooled to 120°F, and component C is added. The pH of the resulting mixture is adjusted to 5.0-6.2 with component D, and the viscosity is adjusted with component E. EXAMPLE 4: Antidandruff Shampoo with Conditioner II

Another antidandruff shampoo and conditioner composition was made using needle and rod forms of zinc pyrithione and one or more compounds of Formulae (I), (II), (III) or

(IV) in combination with the following ingredients: Component N:

Deionized water 24.75%

Guar hydroxypropyl trimσnium chloride 0.30%

Magnesium Aluminum Silicate 0.70%

Zinc Pyrithione (25%> aqueous dispersion) 0.25% Compound(s) of Formulae (I), (II), (III) or (IV) 0.75%

Component B:

Sodium laureth sulfate 30.0%

Ammonium xylene sulfonate, 40% aq. 2.0%

Component C: Tricetylammonium chloride .50%

Cetyl alcohol ΝF .40%

Stearyl alcohol .40%

Glycol distearate 2.00%

Component D: Cocamide MEA 1.70%

Ammonium lauryl sulfate 36.00%

Component E:

Preservative .05%

Fragrance and dye q.s. Component F:

Citric acid, 25% aqueous solution q.s. The antidandruff shampoo and conditioner composition can be made as follows: Component A is prepared by heating water to 50%C and dispersing the guar hydroxypropyl trimonium chloride and the magnesium aluminum silicate with rapid agitation. The zinc pyrithione dispersion and compound of Formulae (I), (II), (III) or (IV) are added to this combination with stirring. The pH of component A is adjusted to 4.5-5.0 with component F. Both components of B are slowly added to component A, mixing well. The pH of the mixture is adjusted to 5.7-6.3 is heated to 70-75°C and blended with component C, mixing well. Both components of D are added to the hot mixture, and stirred well. The pH of the mixture is adjusted to 5.7-6.3 with component F. The mixture is cooled to 40-45°C, and component E is added with stirring. If desired, the viscosity of the product can be increased by adding 0.05-1 % sodium chloride.

EXAMPLE 5: "Extra Body" Antidandruff Shampoo

An "extra body" antidandruff shampoo and conditioner composition can be made using needle and rod forms of zinc pyrithione in combination with the following ingredients: Component A:

Deionized Water 65.6%

Zinc Pyrithione (25% aqueous dispersion) 0.75%

Compound(s) of Formulae (I), (II), (III) or (IV) 0.25%

Component B: Methyl Paraben 0.30%

Propyl Paraben 0.10%

Propylene Glycol 0.50%

Sodium Chloride 0.50%

Component C: Triethanolamine lauryl sulfate 20.0%

Cocamide MEA 4.0%

Ethylene glycol distearate 7.0%

Component D:

Cocodimonium hydrolyzed animal protein 1.00%) Component E:

FD&C Blue No. 1 q.s.

Component F:

Citric Acid, 50% aqueous solution q.s.

The antidandruff shampoo and conditioner composition can be made as follows: Component A is heated to 70°C. The ingredients of component B are added with good stirring until dissolved. The ingredients of component C are added to the mixture sequentially, and heated with mixing to 75°C. The mixture is cooled with stirring to 40°C, and components D and E are added with stirring. The pH of the final composition is adjusted to 4.7 with component F. EXAMPLE 6:

An antidandruff shampoo formulation of EXAMPLE 1 can be made using one or more compounds of formulae (I), (II), (III) or (IV) in combination with both zinc pyrithione (0.25% by weight of the formulation) and ketoconazole (0.25% by weight of formulation) in stead of zinc pyrithione alone.

EXAMPLE 7:

An antidandruff shampoo formulation of EXAMPLE 1 can be made using one or more compounds of formulae (I), (III), (III), or (IV) in combination with ketoconazole (0.5% by weight of the formulation) instead of zinc pyrithione.

Other conventional ingredients may be used in the above shampoo formulations containing the antimicrobial agents. For example, other deposition agents may be used instead of the guar hydroxypropyl trimonium chloride in Example 4. Such deposition agents are generally cationic surfactant polymers materials and help deposit particulate active ingredients (e.g. the above-noted selenium compounds and zinc pyrithione, which are solid particulatεs but not ketoconazole which is soluble). The level of such cationic surfactant/polyer is preferably from 0.01% to 10%, more preferable from 0.05% to 5%, more preferably 0.1% to 2% by weight of the shampoo formulations. Preferably the cationic charge density of the deposition aid, which is defined as the reciprocal of the molecular weight of a monomeric unit of the polymer containing 1 charge, is at least 0.1 meq/g, preferably above 0.8 or higher. The cationic charge density should not exceed 4 meq/g, it is preferably less than 3 and more preferably less than 2 meq/g. The charge density can be measured using conductimetric analysis and should be within the above limits at the desired pH of use, which will in general be from about 3 to 9 and preferably between 4 and 8.

Preferred disposition aids are cationic derivatives of guar gum and cationic polyacrylamides.

Suitable cationic derivatives of guar gum are JAGUAR C13S, which has a low degree of substitution of the cationic groups and high viscosity. JAGUAR C15, having a moderate degree of substitution and a low viscosity, JAGUAR C17 (high degree of substitution, high viscosity), JAGUAR C16, which hs a hydroxypropylated cationic guar derivative containing a low level of substitutent groups as well as cationic quaternary ammonium groups, and JAGUAR 162 which is a high transparency, medium viscosity guar having a low degree of substitution.

Other examples of cationic surfactants include quaternary ammonium hydroxides, e.g. tetramethylammonium hydroxide, alkyltrimethylammonium hydroxides wherein the alkyl group has from about 8 to 22 carbon atoms, for example octyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, cetyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, stearyldi-methylbenzylammonium hydroxide, dioctadecyldimethylammonium hydroxide, tallow trimethylammonium hydroxide, cocotrimethylammonium hydroxide, and the corresponding salts thereof, e.g., chlorides as well as cetylpyridinium hydroxide or salts thereof, e.g., chloride.

Although the invention has been shown and described with respect to illustrative embodiments thereof, it should be appreciated that the foregoing and various other changes, omissions and additions in the form and detail thereof may be made without departing from the spirit and scope of the invention as delineated in the claims.

Claims

WHAT IS CLAIMED IS:

An antimicrobial composition of Formula (I):

wherein Y-R is hydrogen or Y is an oxygen, sulfur, selenium or an NR' moiety, wherein N is nitrogen and R and R¹ are independently selected from hydrogen, substituted or unsubstituted hydrocarbon radicals having one to twenty carbon atoms; and metal salts thereof, alone or in combination with zinc pyrithione.

2. An antimicrobial composition comprising (a) a functional product selected from the group consisting of soaps, shampoo skin care medicaments hard surface cleaners and fabric care compositions, and further comprising (a) an antimicrobially effective amount of (i) at least one compound selected from the group consisting of the Formulae (I), (II), (III) and (IV):

Zn (HI)

wherein each R" is either hydrogen or an alkyl group; either alone or in combination with (ii) zinc pyrithione, ketoconazole or mixtures thereof.

3. An antidandruff shampoo comprising (a) a shampoo base and (b) an effective antidandruff amount of (i) at least one compound selected from the group consisting of the Formulae (I), (II), (III) and (IV):

wherein each R" is either hydrogen or an alkyl group; either alone or in combination with (ii) zinc pyrithione or ketoconazole or combinations thereof.

4. An antimicrobial soap, shampoo or skin care medicament comprising (a) a functional product selected from the group consisting of soap, shampoo or skin care medicament, and further comprising (b) an antimicrobially effective amount of (i) at least one compound selected from the group consisting of the formulae (I), (II), (III) and (IV) as defined in claim 2, either alone or in combination with (ii) zinc pyrithione, ketoconazole or mixtures thereof.

5. An antimicrobial hard surface cleaning composition comprising (a) a cleaning solution and (b) an antimicrobial effective amount of (i) at least one compound selected from the group consisting of the formulae (I), (II), (III) and (IV) as defined in claim 2, either alone or in combination with (ii) zinc pyrithione, ketoconazole or mixtures thereof.

6. An antimicrobial fabric care composition comprising (a) a suitable carrier and (b) an antimicrobially effective amount of (i) at least one compound selected from the group consisting of the formulae (I), (II), (III) and (IV) as defined in claim 2, either alone or in combination with (ii) zinc pyrithione, ketoconazole or mixtures thereof.