GB2422780A - Deodorant compositions - Google Patents

Abstract

A deodorant composition comprises: <SL> <LI>(a) a perfume composition which comprises at least 30% by weight of one or more of the following perfume components: (Z)-3,4,5,6,6-pentamethylhept-3-en-2-one, mixtures of diethyl- and dimethyl- cyclohex-2-en-1-one, citronellol, 2-methyl-3-(4-(1-methylethyl)phenyl)propanal, 2-(methyloxy)-4-propyl-1-benzenol, diphenylmethane, tetrahydrolinalol, 4-(4-methyl-3-pentenyl)cyclohex-3-ene-1-carbaldehyde, 3 -(4-methyl-3-pentenyl)cyclohex-3-ene-1-carbaldehyde, 3-(1,3-benzodioxol-5-yl)-2-methylpropanal, a -ionone, b -ionone, tricyclo [5.2.1.0 2,6] dec-4-en-8-yl ethanoate, 4-(4-hydroxy-4-methylpentyl)cyclohex-3-enecarbaldehyde, 3-(4-hydroxy-4-methylpentyl)-cyclohex-3-enecarbaldehyde, methyl isoeugenol, 2-(1, 1-dimethylethyl)cyclohexyl ethanoate, 4-(1,1-dimethylethyl)cyclohexyl ethanoate, 4-methyl-2-(2-methylprop-1-enyl)tetrahydropyran; and <LI>(b) a transition metal chelator. </SL> The transition metal chelator is an iron (III) chelator, preferably an aminopolycarboxylic acid compound or salt thereof, which can be selected from one or more of ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid (CDTA), ethylenediaminedisuccinic acid (EDDS), diethylenetriaminepentaacetic acid (DTPA), triethylenetetraaminehexaacetic acid (TTHA), ethylenebis [2-(hydroxyphenyl) glycine] (EDDHA), and salts thereof. The perfume composition in combination with transition metal chelator conveniently provides an improved deodorant effect than may be obtained from the perfume composition alone. In particular, the addition of a transition metal chelator to a perfume composition may increase the activity of the perfume composition in terms of inhibiting corynebacteria present on the skin surface, which bacteria are capable of producing odoriferous compounds which contribute to body malodour.

Description

1 2422780 Title: Improvements in or relating to method of reducing or

preventing malodour

Field of the Invention

This invention relates to deodorant compositions, and to the use of a deodorant composition to deliver an improved deodorant effect. In particular, the invention relates to deodorant compositions for reducing or preventing body malodour, particularly but not exclusively, axillary malodour.

Background to the Invention

It is known that, at the point of secretion, sweat is odourless. Body malodour is the result of a variety of biotransformations of components of sweat by certain species of natural micro-organisms present on the surface of the skin. These transformations produce a number of odoriferous compounds such as short chain fatty acids (e.g. butyric acid, isobutyric acid, isovaleric acid), amongst others, which contribute to body malodour.

Products such as soaps, shower gels, body washes and laundry products are intended for use in combating body malodour. Other types of product routinely used to combat body malodour include antiperspirants, deodorants and perfumes.

Antiperspirants typically include a metal salt, such as an aluminium or zirconium salt, and work by blocking the sweat glands to thereby reduce perspiration.

Antimicrobial agents used in deodorants are designed to reduce the population, inhibit the growth or diminish the metabolic activities of micro-organisms living on the surface of the skin. Typical agents of this nature include ethanol and triclosan (2'4,4'- trichloro-2- hydroxydiphenyl ether) which are well known to exert antimicrobial effects. The use of common deodorant actives results in a non-selective antimicrobial action exerted upon most of the skin's natural microflora. This is an undesirable disadvantage of such deodorant formulations, since the natural microflora provides a protective barrier (colonisation resistance) against invasion by potentially pathogenic bacteria.

Perfumes may simply mask body malodour. However, perfume compositions have been disclosed which exhibit a deodorant action. For example, WO 00/01356 describes certain perfume components and compositions thereof, useful in reducing or preventing body malodour. The perfume components (or compositions comprising the perfume components) are described as inhibiting particular coryneform bacteria which are capable of catabolising fatty acids and are responsible for the production of short chain fatty acid malodour. In this way, the perfume components (or compositions thereof) in-use produce a deodorant effect.

A further approach that may be used to combat body malodour is to incorporate transition metal chelators in deodorant compositions. For example, US 4356190 discloses the use of an aminopolycarboxylic compound or water-soluble salt thereof, e.g. diethylenetriaminepentaacetic acid (DTPA), in a composition for inhibiting the formation of fatty acids by bacteria, e.g. corynebacteria, on the skin.

Transition metal chelators useful in compositions of the following documents are described as potentially functioning to inhibit the up-take of essential transition metal ion nutrients by micro-organisms, thereby minimising the growth of the micro-organism. The transition metal chelators preferably have an affinity for iron (III) and are thought to preferentially bind this metal to deprive a relevant micro-organism of the nutrient and significantly inhibit its growth. WO 01/52804 discloses an anti-microbial product comprising an antiperspirant active and an amount of transition metal chelator sufficient to enhance the deodorancy performance of the antiperspirant active; WO 01/52805 discloses antimicrobial compositions comprising a solution in an organic solvent of certain transition metal chelator salts; WO 02/30383 discloses a method of achieving an anti-microbial and deodorant benefit comprising the application to the human body or to an article wearable in close proximity thereto, of an anti-microbial product comprising a transition metal chelator and a certain phenolic or enolic compound; and WO 01/52652 discloses an anti-microbial aerosol composition comprising an alcohol carrier fluid, a specified iron (III) chelator and a solubility promotor selected from a specific group of materials.

It has now been surprisingly found that particular perfume compositions when combined with transition metal chelators demonstrate an improved deodorant action than may be obtained, for example, with the perfume compositions alone.

Summary of the Invention

Thus, in one aspect the present invention provides a deodorant composition comprising: (a) a perfume composition comprising at least 30% by weight of one or more of the following perfume components: (Z)-3,4,5,6, 6-pentamethylhept- 3-en-2-one mixtures of diethyl- and dimethylcyclohex-2-en-1-one, citronellol, 2-methyl-3-(4-(1methylethyl)phenyl)propanal, 2-(methyloxy)-4-propyl- 1 -benzenol, diphenylmethane, tetrahydrolinalol, 4-(4-methyl-3-pentenyl)cyclohex3...ene 1 -carbaldehyde, 3-(4-methyl-3- pentenyl)cyclohex-3-ene 1 -carbaldehyde, 3-( 1, 3-benzodioxol-5yl) 2methy1propana1 a- ionone, 3-ionone, tricyclo[5.2. 1.0 2,6Jdec-4-en-8-yl ethanoate, 4-(4- hydroxy-4methylpentyl)cyclohex.3enecarbaldehyde 3-(4-hydroxy-4-methylpentyl) cyclohex...3.

enecarbaldehyde, methyl isoeugenol, 2-( 1,1 -dimethylethyl)cyclohexyl ethanoate, 4-( 1,1 - dimethylethyl)cyclohexyl ethanoate, 4-methyl-2-(2-methylprop 1 -enyl) tetrahydropyran; and (b) a transition metal chelator.

The present invention is thus based on the appreciation that perfume compositions formulated according to the principles disclosed in WO 00/01356 when combined with a transition metal chelator, conveniently provide improved deodorant effect than may be obtained from the perfume compositions alone. In particular, the addition of a transition metal chelator to a perfume composition may increase the activity of the perfume composition in terms of inhibiting corynebacteria present on the skin surface, which bacteria are capable of producing odoriferous compounds which contribute to body malodour. It is therefore thought that a synergistic effect may occur between the perfume composition and transition metal chelator, which in combination may give a greater combined deodorant effect than would be expected by simply adding together the deodorant effect of each. Moreover, the deodorant effect of a composition of the invention is such that less perfume and/or chelator may be used in a composition than would otherwise be the case.

The composition may be optionally admixed with further excipients. Preferably, the composition is in the form of a deodorant product. For the purposes of the present invention a "deodorant product" is defined as including said perfume composition and transition metal chelator, to which are additionally admixed other excipients such as for example one or more suitably compatible carriers, structurants, emulsifiers, sensory modifiers, e.g. emollients, humectants, volatile and non-volatile oils, particulate solids etc. A deodorant product will include additional and optional ingredients appropriate to the product in question, as is known to those skilled in the art.

Suitable deodorant products include, but are not limited to, body deodorants and antiperspirants including rolls ons, sprays, creams, wipes, gel products, sticks; shampoos; soaps; shower gels; talcum powder; hand creams; skin conditioners; sunscreens; sun tan lotions; and hair conditioners.

The deodorant compositions defined herein may also be conveniently employed for deodorant purposes by incorporation into other products, e.g. laundry and household products such as rinse conditioners, household cleaners and detergent cleaners. The compositions can be incorporated into textiles themselves during their production using techniques known in the art, to provide deodorant protection.

The following perfume components are useful in the perfume compositions of the deodorant compositions defined herein: (Z)-3,4, 5,6,6-pentamethylhept-3-en-2-one (acetyl di iso amylene); mixture of diethyl- and dimethyl-cyclohex-2-en-1-one (also known as AZARBRE where AZARBRE is a trade mark of Quest International); citronellol; 2-methyl-3-(4-( 1 -methylethyl)phenyl)propanal (cyclamen aldehyde); 2-(methyloxy)-4-propyl- 1 -benzenol (dihydroeugenol); diphenylmethane; tetrahydrolinalol; 4-(4-methyl-3-pentenyl)cyclohex-3enelcarbaldehyde (also known as EMPETAAL where EMPETAAL is a trade mark of Quest International); 3-(4-methyl-3-pentenyl)cyclohex-3-ene.. I -carbaldehyde (also known as EMPETAAL where EMPETAAL is a trade mark of Quest International); 3-(l,3-benzodioxol-5-yl)-2-methylpropanal (also known as HELIONAL where HELlO NAL is a trade mark of International Flavours & Fragrances Inc.); aand -ionone and mixtures thereof (ionone); tricyclo[5.2. 1.0 2,6]dec-4en-8-yl ethanoate (also known as JASMACYCLENE where JASMACYCLENE is a trade mark of Quest International); 4-(4-hydroxy-4-methylpentyl)cyclohex3enecarbaldehyde (also known as LYRAL where LYRAL is a Trade Mark of International Flavours & Fragrances mc); 3-(4-hydroxy-4-methy1penty1)cyc1ohex-3enecarba1dehyde (also known as LYRAL where LYRAL is a Trade Mark of International Flavours & Fragrances Inc.); methyl isoeugenol; 2-( 1,1 -dimethylethyl)cyclohexyl ethanoate (also known as ORTHOLATE where ORTHOLATE is a trade mark of Quest International); 4-( 1,1 -dimethylethyl)cyclohexyl ethanoate (also known as ORTHOLATE where ORTHOLATE is a trade mark of Quest International); and 4-methyl-2-(2-methylprop- 1 -enyl)tetrahydropyran (Rose oxide).

The term "perfume component" is used herein to represent a material which is added to a perfume composition to contribute to the olfactive properties of the composition. A perfume component can be acceptably employed to provide odour contributions to the overall hedonic performance of products. Typically, a perfume component will be generally recognised as possessing odours in its own right, will be relatively volatile and often has a molecular weight within the range 100 to 300. Typical materials which are perfume components are described in "Perfume and Flavour Chemicals", Volumes I and II (Steffan Arctander, 1969).

For the purposes of the present invention, by perfume composition is meant a mixture of individual perfume components, and optionally one or more suitable diluents, which is used to impart a desired odour to the skin and/or product for which an agreeable odour is indispensable or desirable. Commonly used diluents are benzyl benzoate, diethyl phthalate, dipropylene glycol and isopropyl myristate. The concentration of perfume components referred to herein is relative to the total concentration of perfume components present in the composition, i.e. excludes any diluents.

To deliver high deodorant effects the perfume component(s) are typically present in a perfume composition in an amount of 30% by weight of the total weight of the perfume composition, preferably 40%, more preferably at least 45%, and most preferably at least 50%.

Additionally, or alternatively, a perfume composition useful herein preferably comprises at least 5, more preferably at least 7, and even more preferably at least 10 of the specified perfume components.

Thus, in another aspect, the present invention provides a deodorant composition comprising: (a) a perfume composition comprising at least 5 of the following perfume components; (Z)-3,4,5, 6, 6-pentamethylhept-3-en-2-one, mixtures of diethyl- and dimethylcyclohex-2-en- 1-one, citronellol, 2-methyl-3-(4-( 1 -methylethyl)phenyl) propanal, 2- (methyloxy)-4-propyl- 1 -benzenol, diphenylmethane, tetrahydrolinalol, 4- (4-methyl-3 - pentenyl)cyclohex-3-ene- 1 -carbaldehyde, 3-(4-methyl-3-pentenyl)cyclohex- 3-ene. 1- carbaldehyde, 3-( 1, 3-benzodioxol-5-yl)-2-methylpropanal, cx-ionone, - ionone, tricyclo[5.2.1.0 2,6]dec-4-en-8-yl ethanoate, 4-(4-hydroxy-4methylpentyl)cyclohex3.

enecarbaldehyde, 3-(4-hydroxy-4-methylpentyl)cyclohex.3enecarbaldehyde, methyl isoeugenol, 2-( 1,1 -dimethylethyl)cyclohexyl ethanoate, 4-( 1,1 dimethylethyl)cyclohexyl ethanoate, 4-methyl-2--(2-methylprop- 1 -enyl) tetrahydropyran; and (b) a transition metal chelator.

The perfume components useful in a perfume composition of a deodorant composition in accordance with the invention may be mixed with other perfume components to provide perfume compositions with desired deodorant and hedonistic properties.

Deodorant compositions in accordance with the present invention preferably comprise at least 0.05% to 10%, more preferably 0.1 % to 3.0%, of a perfume composition by weight of the deodorant composition.

Deodorant compositions in accordance with the present invention may include one or more transition metal chelators. As used herein, the term "chelator" refers to any compound capable of complexing a transition metal ion, when applied to the surface of a human body, generally the skin.

Transition metal chelators useful in compositions in accordance with the present invention preferably have an affinity for iron (III). That is, preferred transition metal chelators are iron (III) chelators. The affinity of a particular chelator for iron (III) is measured by the iron (III) binding constant for a compound which is the absolute stability constant for the iron (III) chelator complex.

Transition metal chelators can occur in acid form or as a salt thereof.

Transition metal chelators in their acid form preferably have at least two, more preferably at least four, and most preferably at least five ionisable acid groups, where the acid groups may be phosphonic, carboxylic or, possibly suiphonic, groups, or mixtures thereof.

Examples of transition metal chelators with phosphonic acid groups include diethylenetriaminepenta (methyiphosphonic) acid (DTPMP), ethanehydroxydiphosphonic acid (EHDP), ethylenediaminetetra(methylenephosphonjc acid) (EDTMP), and hexamethylenediaminetetra (methylenephosphonic acid) (HMDTMP).

Examples of transition metal chelators with carboxylic acid groups include polycarboxylic acids and in particular aminopolycarboxylic acid compounds including one or more of ethylenediaminetetraacetjc acid (ED TA), trans-i,2-diaminocyclohexane-N, N, N', N'- tetraacetic acid (CDTA), ethylenediaminedjsuccjnjc acid (EDDS), diethylenetriaminepentaacetjc acid (DTPA), triethylenetetraarninehexaacetjc acid (TTHA) and ethylenebis [2(hydroxyphenyl) glycine] (EDDHA).

Preferred transition metal chelators for use herein are aminopolycarboxylic acid compounds, preferably one or more of diethylenetriaminepentaacetjc acid (DTPA), triethylenetetraamjnehexaacetjc acid (TTHA), ethylenediaminetetraacetjc acid (EDTA) and trans-i,2-diaminecycjohexane-jy, N, N', N'-tetraacetic acid (CDTA). Particularly preferred for use herein is diethylenetriaminepentaacetic acid (DTPA).

The transition metal chelators may also be used in their salt form. For certain applications, preferred salts of the transition metal chelators include monovalent alkali metal salts, e.g. sodium and potassium salts.

For certain other applications, e.g. formulation of the deodorant compositions in alcohol- based products, salts with organic counter-ions are preferred such as protonated or quaternised amines. Salts formed using aliphatic amines are generally preferred to those formed from aromatic amines. A further preference is for protonated or quaternised amine cations possessing a C1- C10 terminal hydrocarbyl group, wherein a hydrocarbyl group is a radical comprising solely carbon and hydrogen atoms.

Preferred protonated or quaternised amine cations of the chelator salts are of formula R1R2R3R4N, wherein R1 is H or CH3; R2, R3, and R4 are each independently H or an aliphatic or aromatic substitutent containing 0 to 3 hydroxyl groups, optionally interrupted and/or substituted by functional groups such as ether, amine, ester, or amide; with the provisos that at least one of R2, R3, or R4 comprises a C1-C10 terminal hydrocarbyl group, optionally R2 and R3 together forming a ring as the terminal hydrocarbyl group, and that R2, R3, and R4 are not all CH2CH(OH) CH3 groups.

Particularly preferred chelator-ainine salts are salts of 2-amino-2methyl-i-propanol, cyclohexylaniine, diisopropanolamine, or 2-amino-i butanol.

Partial salts of a chelator possessing more than one acidic group may also be employed, whereby such salts retain one or more non-ionised acid groups. Also suitable for use herein are salts where the cations are in part protonated or are quaternised amines and in part some other cation, for example an alkali metal cation, in particular a sodium ion.

Deodorant compositions in accordance with the present invention preferably comprise at least 0.01% to 10.0%, more preferably 0.05% to 5. 0%, of a transition metal chelator by weight of the deodorant composition.

A composition in accordance with the invention is capable of reducing or preventing body malodour by inhibiting those micro-organisms associated with the production of malodorous short chain fatty acids. In particular, a composition is capable of inactivating corynebacteria. Corynebacteria are known to be responsible for the production of malodorous short chain fatty acids on the skin. Such fatty acids are known to contribute to body malodour, particularly axillary malodour. The biotransformations effected by this micro-organism on the components of sweat to produce such odoriferous metabolites may occur via a number of possible, and typically, ill-defined metabolic pathways.

One possible pathway by which short chain fatty acids are produced is from the metabolism of long chain fatty acids such as pentadecanoic acid. Using this knowledge, corynebacteria were tested using the method described in Example I of WO 00/01356 to determine whether a particular Corynebacterium is capable of fatty acid catabolism.

Without wishing to be bound or limited by theory, we believe that the Corynebacterium genus can be subdivided into two groups according to ability to catabolise fatty acids. For brevity and simplicity, the subgroups have been designated "Corynebacteria A" and "Corynebacteria B". These designations are based on the appreciation that only particular coryneform bacteria are capable of fatty acid metabolism. Corynebacteria which are capable of catabolising fatty acids and thus contribute strongly to the formation of body malodour, particularly axillary malodour, fall within the subgroup Corynebacteria A, whilst corynebacteria which catabolise fatty acids much less so or not at all fall within the subgroup Corynebacteria B. We believe that it is possible to selectively inhibit the generation of odorous metabolites by Corynebacteria A, whilst leaving other bacteria much less affected or possibly not notably affected at all. Significant deodorant action can therefore result.

The perfume compositions useful herein preferably selectively inhibit Corynebacteria A resulting in a reduction in the production of malodorous short chain fatty acids. Also it is possible that compositions in accordance with the invention also selectively inhibit Corynebacteria A. One property that characterises the effectiveness of a compound or composition to inhibit the production of short chain fatty acids produced by corynebacteria present on the skin, is the minimum inhibitory concentration, or MIC, of the compound or composition. The MIC is the minimum amount of a compound or composition (e.g. in ppm) at which no bacterial growth is observed. Generally, the lower the MIC of a compound or composition for a bacterium, the more effective the compound will be at inhibiting bacterial growth.

At concentrations at or above the MIC, a compound or composition acts by directly killing existing viable bacteria or inhibiting the growth and reproduction of the bacteria (antimicrobial effect). At concentrations below the MIC, a compound or composition can interfere with metabolic process, e.g. by inactivating bacteria producing malodorous compounds, but typically does not inhibit the growth and reproduction of bacteria (sublethal or sub-MIC effect).

The inhibitory effect of a deodorant composition in accordance with the invention can be achieved antimicrobially or sub-lethally.

The antimicrobial effects of compounds or compositions are usually divided into two types; they can either inhibit bacterial growth (bacteriostatic action) or alternatively they can act by directly killing existing viable bacteria (bactericidal action).

The bacteriostatic action of a compound or composition "X" against a particulax bacterium, can be tested for in vitro by inoculating a standard, small number of bacteria into broths containing an appropriate range of concentrations of X. The broths are then incubated for a suitable time, and growth compared with a control containing no inhibitor.

The broth containing the lowest concentration of X which shows reduction of growth compared to the control broth, is defined as the minimum inhibitory concentration (MIC).

The determination of bactericidal action of a compound or composition "Y" is carried out by adding various concentrations of compound or composition Y to replicate broths containing relatively high, standard numbers of bacteria. After a certain period allowing any antibacterial activity to take place, a total viable count (TVC) is carried out in the following way; aliquots of the bacterial cultures are diluted (usually in 10-fold steps) and dispensed onto agar plates. The plates are incubated with the expectation that each viable cell should produce a visible colony. The numbers of colonies are multiplied to take account of the dilution, to establish the number of viable cells in the broths. Once again, the broths containing compound or composition Y are compared with an untreated control broth. The minimum concentration of compound or compositions Y which causes a reduction in the viable number of bacteria is the minimum bactericidal concentration (MBC). MBC can also be expressed in terms of the MBC required to produce a certain degree of killing (for example, a 3 log10 reduction in count, equivalent to a 99.9% kill).

Still further, the MBC can be expressed in kinetic terms - the time of exposure to an agent required for a given MBC effect.

A further possibility is that the process of inhibition could be sublethal (or sub-MIC), whereby a compound or composition interferes with the metabolic process, but typically does not inhibit bacterial growth.

Three modes of inactivating corynebacteria are possible. In the first mode, the compositions may act by direct (overt antimicrobial) killing of the bacteria, e.g. by more than 10-fold; in the second mode, they may act to inhibit bacterial metabolism such as fatty acid catabolism whilst maintaining a microbial cell viability of at least 70%; in the third mode, they may act to inhibit corynebacterja metabolism such as fatty acid catabolism at a concentration below the minimum inhibitory concentration (MIC), determined as described in Example 1 and 2 below, to give a sublethal effect. The third mode is preferred, since this provides body malodour counteraction benefits, whilst leaving the natural microflora of the skin undisturbed. Thus, preferably the bacterial production of odoriferous short chain fatty acid metabolites can be reduced or eliminated without significantly disturbing the skin's natural microflora. This may be achieved by inactivating the bacteria responsible for the production of odoriferous fatty acids, in particular corynebacteria A, at a concentration below the MIC.

Also included within the scope of the invention is a method, particularly a cosmetic method, for reducing or preventing body malodour by topically applying to human skin a composition in accordance with the present invention.

In an even further aspect, the present invention provides the use of a perfume composition comprising at least 30% by weight of one or more of the following perfume components: (Z)-3,4,5,ó,6pentamethylhept.3en2.on mixtures of diethyl- and dimethyl- cyclohex-2- en-i-one, citronellol, 2-methyl-3-(4-( 1 -methylethyl)phenyl)propanal 2- (methyloxy)-4- propyl. 1 -benzenol, diphenylmetliane, tetrahydrolinalol, 4-(4-methyl-3pentenyl)cyclohex3 ene- 1 -carbaldehyde, 3-(4-methyl-3-pentenyl)cyclohex3ene 1 -carbaldehyde, 3-( 1,3benzodioxol5yl)2methylpropanaJ x-ionone, -ionone, tricyclo[5.2.1.0 2, 6] dec-4-en-8- yl ethanoate, 3-(4-hydroxy-4methylpentyl)cyclohex3enecarbajdehyde methyl isoeugenol, 2-(1, 1dimethylethyl)cyclohexyl ethanoate, 4-(1, l-dimethylethyl)cyclohexyl ethanoate, 4-methyl- 2-(2-methylprop- l-enyl)tetrahydropyran; and a transition metal chelator, in the manufacture of a composition for reducing or preventing body malodour.

The present invention also provides the use of a perfume composition comprising at least 5 of the following perfume components: (Z)-3,4,S,6,6pentamethylhept3en.2one mixtures of diethyl- and dimethylcyclohex-2-en-1-one, citronellol, 2-methyl-3-(4- (1methylethyl)phenyl)propanal 2-(methyloxy)-4-propyl 1 -benzenol, diphenylmethane, tetrahydrolinalol 4-(4-methyl-3-pentenyl)cyclohex3ene 1 -carbaldehyde, 3- (4-methyl-3- pentenyl)cyclohex3ene 1 -carbaldehyde, 3 -(1, 3-benzodioxol-5-yl) 2methylpropanal a- ionone, 3-ionone, tricyclo[5.2. 1.0 2,6]dec-4-en-8-yl ethanoate, 4-(4- hydroxy-4methylpentyl)cyclohex3eflecarbaldehyde 3-(4-hydroxy-4-methylpentyl) cyclohex3 enecarbaldehyde, methyl isoeugenol, 2-( 1,1 -dimethylethyl)cyclohexyl ethanoate, 4-( 1,1 - dimethylethyl)cyclohexyl ethanoate, 4-methyl-2-(2-methylprop 1 -enyl) tetrahydropyran; and a transition metal chelator, in the manufacture of a composition for reducing or preventing body malodour.

The invention is illustrated by the following examples.

Example 1

The minimum inhibitory concentration of a perfume composition useful in a deodorant composition in accordance with the invention, was determined by the following method.

A culture of the test strain - Coiynebacterjum xerosis NCTC 7243 (National Collection of Type Cultures, Public Health Laboratory Service, Central Public Health Laboratory, 61 Colindale Avenue, London, NW9 5HT) was grown in lOOml of tryptone soya broth (TSB) (Oxoid, Basingstoke, UK) for 16-24 hours, in a shaken flask at 37 C. The culture was then diluted in sterile 0.1 % TSB (Oxoid, Basingstoke, UK) to give a concentration of bacteria of approximately 106 colony forming units (cfu) per ml.

Perfume samples were in sterile TSB to give stock solutions with final concentrations of 40,000 ppm. Each row of a standard, 96-well plastic microtitre plate (labelled A-H) was allocated to one sample, thus eight samples per plate. Row H contained only TSB for use as a bacterial control to indicate the degree of turbidity resulting from bacterial growth in the absence of any test material. Aseptically, 200p.l of the initial dilution of perfume/perfume component was transferred to the l and 7th well of the appropriate row.

All other test wells were filled with i00j.ti of sterile TSB using an 8channel micro-pipette.

The contents of each of the wells in column 1 were mixed by sucking samples up and down in pipette tips, before 100tl was transferred to column 2. The same sterile pipette tips were used to transfer lOO.tl of each well in column 7, into the appropriate well in column 8. This set of eight tips was then discarded into disinfectant solution. Using eight fresh, sterile tips the process was repeated by transferring 1 0Od from column 2 into column 3 (and 8 into 9). The process was continued until all wells in columns 6 and 12 contained 200jil. After mixing, lOOp.l was discarded from wells in columns 6 and 12 to waste. Finally, lOOp.! of prediluted bacterial culture (approx. 106 cfu/ml) was added, thus giving 200pI final volume in each well.

A blank plate was prepared for each set of eight samples in exactly the same way, except that lOOp! of sterile 0.1 % TSB was added instead of bacterial culture. This plate was used as the control plate against which the test plate(s) could be read. Test and control plates were sealed using autoclave tape and incubated for 18-30 hours at 37 C.

A microtitre plate reader (Model MRX, Dynatech Laboratories) was preset togently agitate the plates and to mix the contents. The absorbance at 540nm (hereinafter referred to for brevity and simplicity as "A540") was used as a measure of turbidity resulting from bacterial growth. The control, un-inoculated plate for each set of samples was read first, and the plate reader then programmed to use the control readings to blank all other plate readings for the inoculated plates for the same set of test materials (i.e. removing turbidity due to perfume and possible colour changes during incubation). Thus, the corrected readings generated were absorbances resulting from turbidity from bacterial growth. The MIC was taken as the concentration of perfume required to inhibit growth so that the change in absorbance during the incubation period was <0.2 A540.

Example 2

The deodorant effect of a composition in accordance with the invention was determined using the following in vitro assay.

The assay determines the ability of a composition to inhibit fatty acid producing Corynebacteria A and models in vitro the process of fatty acid catabolism by axillary bacteria which occurs in vivo. The Corynebacterium A used in the assay was Coiynebacterium sp. NCIMB 41019 (National Collections of Industrial, Food and Marine Bacteria, 23 St Machar Drive, Aberdeen, AB24 3RY, Scotland, UK) (also known as Coiynebacterium G42).

The compositions tested in the assay were as follows: 1. Perfume A described in the table bridging pages 10 & 11 of WO 00/0 1356 + DTPA; and 2. Perfume B described in the table bridging pages 10 & 11 of WO 00/01356 + DTPA.

For comparison, Perfumes A and B were tested on their own (i.e. without DTPA) and a further perfume, Perfume C of the following composition was also included in the assay, which does not satisfy the requirements of a perfume composition useful herein: %w/w ALDEHYDE ClO (DECANAL) 50% DEP 0. 5 ALDEHYDE Cli (UNDECYLENIC) 50% DEP 0.7 ALDEHYDE C12 (DODECANAL) 50% DEP 0.4 ALDEHYDE MNA 50% DEP 0.4 AMYL CINNAMIC ALDEHYDE 2 BENZYL SALICYLATE (Q) 2 COUMARIN 2 CYCLOPENTADECANOLIDE 0.7 DIPROPYLENE GLYCOL 16 ETHYL VANILLIN 10% DPG 6.6 ETHYLENE BRASSYLATE 4.3 EUMULGIN L 1.2 HEXYL CINNAMIC ALDEHYDE 5 H YDROXYCITRONELLAL 0.45 ISO AMBOIS SUPER CI (Q) 1 LEMON WASHED BULKED 6 LILIAL(G) 2.5 LINALOL 11 LINALYL ACETATE 2 LYRAL 2. 35 METHYL DIHYDRO JASMONATE SUPER (Q) I METHYL IONONE ALPHA ISO 10 MOSS OAKMOSS 1 ORANGE BRAZIL PURE 2.6 PHENYL ETHYL ALCOHOL 8.5 TETRAHYDROLINALOL 0.5 YLANGYLANG 0.2 SILVANONE SUPRA CI (Q) 1 TERPINEOL ALPHA 0.5 CITRONELLOL 2.5 PETITGRAIN TERPENELESS (Q) 2 ISO PROPYL MY1USTATE 2 GERANIOL 0.6 ROSE ACETONE 0.5 Total Quantity 100 Assay Method (i) Coiynebacterium sp. NCIMB 41019 was grown in 250 ml of Tween- supplemented Tryptone Soya Broth (TSBT) containing Tryptone Soya Broth 30. Og/1, Yeast Extract 10.Ogil, and Tween 80 l.Og/l, at 37 C for 24 hours.

(ii) To 25 ml universal bottles, was added 5m1 of a semi-synthetic medium supplemented with fatty acid substrate (pentadecanoic acid), the semisynthetic medium consisting of KH2PO4 1.6 g/l; (NH4)2 HPO4 5.Og/l; Na2SO4 0.38 g/l; Yeast Nitrogen Base (Difco) 3.35 gil; Yeast Extract 0.5 gil, Tween 80 0.2 g/l; Triton X-100 (where Triton X-100 is a Trade Mark of Sigma catalogue number X-100) 0.2 g/l; MgC12.6H20 0.5g/l and Pentadecanoic acid 2.Og/l. Flasks were then supplemented with Perfumes A, B or C or a composition in accordance with the invention containing DTPA (lOOppm or 500ppm) and Perfume A, B or C at a range of concentrations below their minimum inhibitory concentration (determined according to Example 1 above) according to the following matrix, to give stock solutions/emulsions: Perfume A (500ppm) + DTPA (lOOppm) Perfume B (500ppm) + DTPA (lOOppm) Perfume C (500ppm) + DTPA (lOOppm) Perfume A (l000ppm) + DTPA Perfume B (l000ppm) + DTPA (lOOppm) Perfume C (l000ppm) + DTPA (lOOppm) (lOOppm) Perfume B (2500ppm) + DTPA (lOOppm) Perfume C (2500ppm) + DTPA (lOOppm) Perfume A (2500ppm) + DTPA (lOOppm) Perfume A (500ppm) + DTPA (500ppm) Perfume B (500ppm) + DTPA (500ppm) Perfume C (500ppm) + DTPA (500ppm) Perfume A (l000ppm) + DTPA Perfume B (l000ppm) + DTPA (500ppm) Perfume C (l000ppm) + DTPA (SOOppm) (500ppm) Perfume B (2500ppm) + DTPA (500ppm) Perfume C (2500ppm) + DTPA (500ppm) Perfume A (2500ppm) + DTPA (500ppm) Perfume A (500ppm) Perfume B (500ppm) Perfume C (500ppm) Perfume A (l000ppm) Perfume B (l000ppm) Perfume C (l000ppm) Perfume A (2500ppm) Perfume B (2500ppm) Perfume C (2500ppm) Emulsions were formed by ultra-homogenisation of the contents by whirlimixingfor about 1 minute.

(iii) Each bottle was then inoculated with fresh bacterial biomass, prepared as described in (i) above, to give starting optical densities (A5) of 1.0 to 2.0.

(iv)Two further, control bottles were prepared, one containing the semisynthetic medium only and one containing the semi-synthetic medium and bacteria to give an optical density as described in (iii) above. Following inoculation, bottles were incubated aerobically at 37 C with agitation (160 rpm) and analysed after 48 hours for culture viability and fatty acid levels. The viability and fatty acid levels of bottles containing a test composition/perfume were compared with the contents of the control bottles.

Culture viability was determined by a total viable count (TVC) on TSAT plates (consisting of Tryptone Soya Broth 30.0 g/l; Yeast Extract 10.0 g/l; Tween 80 1.Og/l, Agar 20.0 g/l) following serial dilution in phosphate buffered saline.

Fatty acid levels in the bottles were determined by capillary gas chromatography (GC) analysis. An internal standard (1.0 mg/ml lauric acid) was added to each universal bottle and the culture medium was acidified (pH -2) by the addition of hydrochloric acid.

Liquid-liquid extraction was then carried out using 2 vol (1 OmI) ethyl acetate and organic and aqueous phases were resolved by centrifugation (2000 rpm for 3 minutes). 2.0 ml of each organic (upper) phase was then transferred to a sampling tube prior to analysis on a Perkin Elmer 8000 (Series 2) GC fitted with a 15m x 0.32 mm (internal diameter) FFA (nitroterephthalic acid modified PEG/siloxane copolymer) fused silica capillary column (film thickness 0.25mm) (Quadrex). This colunm was attached to the split splitless injector and flame ionisation detector (FID) of the GC; injector and detector temperatures were each 300 C. Carrier gas for the column was helium (6.Opsi), while hydrogen (17 psi) and air (23 psi) were supplied to the FID. The temperature programme for fatty acid analysis was 80 C (2 mm); 80-250 C (20 C/mm); 250 C (5mm). Sample size for injection was 0.5 -1.0l. Fatty acid levels in the bottles were quantified by comparison of peak areas with known levels of both internal (lauric acid) and external (pentadecanoic acid) standards.

DTPA was also tested on its own according to the procedure described above at final concentrations in each bottle of lOOppm and 500ppm, but showed no inhibitory effect at either concentration. No differences in results were observed for Perfumes A and B tested with DTPA present at 100 or SOOppm and therefore, for simplicity, the data was combined.

The results for the compositions/perfumes tested in the assay are presented in the table below: Composition/Perfume Inhibition of Corynebacterium sp.

Volatile Fatty Acid Metabolism at 3 concentrations 500 ppm 1000 ppm 2500 ppm PerfumeA - - + PerfumeB - - ++ PerfumeC - - - Perfume A + DTPA - + + + Perfume B + DTPA - + + + Perfume C + DTPA - - + + + = >70% inhibition; + = 50-69% inhibition; - no inhibition.

It can be seen from the above that as expected Perfumes A and B of WO 00/0 1356 on their own are capable of inhibiting the production of volatile fatty acids by Corynebacterium sp., at a concentration of 2500ppm. Perfume B in particular clearly sub-lethally inhibits fatty acid catabolism, where sub-lethal inhibition of fatty acid catabolism is defined as significant inhibition of pentadecanoic acid utilisation (at least 70% inhibition) without concomitant reductions in cell viability.

The addition of DTPA to Perfumes A and B increased their activity, so that for example, evidence of good inhibition of fatty acid catabolism could be seen at a lower concentration i.e. l000ppm, at which no activity was shown by the perfumes alone. The combination of DTPA and Perfume A also gave increased activity at 2500ppm, with the resulting composition showing sub-lethal inactivation of fatty acid catabolism.

It will be seen that Perfume C was found to be inactive with regard to inhibiting fatty acid metabolism in Corynebacterium sp. NCIMB 41019 and the addition of DTPA gave little improvement in activity.

Example 3

The following are typical formulations of deodorant products in accordance with the invention, which comprise a perfume composition and a transition metal chelator. In each case, the perfume is perfume A or Perfume B. Aerosol Ingredient Content % by weight Ethanol B up to 100 Propylene glycol as required Perfume 2.5 Dimethyl ether 2.0 DTPA as free acid 0.5 2-Amino-2-methylpropanol (AMP) 0.37 Water 23 Roll On Ingredient Content % by weight Ethanol 60 Kiucel MF* 0.65 Cremophor RH41O** 0.5 Perfume 1 Na3 DTPA 0.5 Water 37.35 *Klucel MF is a Trade Mark and is hydroxypropyl cellulose, a thickening agent, supplied by Hercules **Cremophor RH410 is a registered Trade Mark of BASF Aktiengesellschaft and is a nonionic solubiliser and emulsifying agent

Claims (11)

1. C309.OOIQ

   A deodorant composition comprising: (a) a perfume composition comprising at least 30% by weight of one or more of the following perfume components: (Z)-3,4,5,6, 6-pentamethylhept- 3 -en-2-one, mixtures of diethyl- and dimethyl- cyclohex-2-en-1-one, citronellol, 2- methyl-3-(4- (1 -methylethyl)phenyl)propanal, 2-(methyloxy)-4-propyl- 1 -benzenol, diphenylmethane, tetrahydrolinalol, 4-(4-methyl-3-pentenyl)cyclohex-3-ene1- carbaldehyde, 3-(4-methyl-3-pentenyl)cyclohex-3-ene- 1 -carbaldehyde, 3-( 1,3- benzodioxol-5-yl)-2-methylpropanal, a-ionone, j3-ionone, tricyclo[5.2. 1. 0 2,6]dec- 4-en-8-yl ethanoate, 4-(4-hydroxy-4-methylpentyl)cyclohex-3- enecarbaldehyde, 3(4-hydroxy-4-methylpentyl)-cyclohex3enecarbaldehyde methyl isoeugenol, 2(1, 1-dimethylethyl)cyclohexyl ethanoate, 4-(1, 1-dimethylethyl) cyclohexyl ethanoate, 4-methyl-2-(2-methylprop- 1 -enyl)tetrahydropyran; and (b) a transition metal chelator.
2. 2. A deodorant composition according to claim 1, wherein the deodorant composition comprises a perfume composition comprising at least 30% by weight of at least 5 of specified perfume components and a transition metal chelator.
3. 3. A deodorant composition comprising: (a) a perfume composition comprising at least 5 of the following perfume components: (Z)-3,4,5,6,6-pentamethylhept-3-en-2-one, mixtures of diethyl- and dimethyl- cyclohex-2-en- 1-one, citronellol, 2-methyl-3 -(4-( 1methylethyl)phenyl)propanal, 2-(methyloxy)-4-propyl- 1 -benzenol, diphenylmethane, tetrahydrolinalol, 4-(4-methyl-3-pentenyl)cyclohex-3-ene1- carbaldehyde, 3-(4-methyl-3-pentenyl)cyclohex-3-ene- 1 -carbaldehyde, 3 - (1,3- benzodioxol-5-yl)-2-methylpropanal, a-ionone, 13-ionone, tricyclo [5.2.1. 0 2,6] dec- 4-en-8-yl ethanoate, 4-(4-hydroxy-4-methylpentyl)cyclohex3enecarbaldehyde, 3(4-hydroxy-4-methylpentyl)-cyclohex3enecarbaldehyde, methyl isoeugenol, 2(1, 1-dimethylethyl)cyclohexyl ethanoate, 4-(1, 1-dimethylethyl) cyclohexyl ethanoate, 4-methyl-2-(2-methylprop 1 -enyl)tetrahydropyran; and (b) a transition metal chelator.
4. 4. A deodorant composition according to any one of claims 1 to 3, wherein the transition metal chelator is an iron (III) chelator.
5. 5. A deodorant composition according to any one of the preceding claims, wherein the transition metal chelator is an aminopolycarboxylic acid compound or salt thereof.
6. 6. A deodorant composition according to claim 5, wherein the aminopolycarboxylic acid compound is selected from one or more of ethylenediaminetetraacetic acid (EDTA), trans-i,2-diaminocyclohexane-N, N, N, N'-tetraacetic acid (CDTA), ethylenediaminedisuccjnjc acid (EDDS), diethylenetriaminepentaacetjc acid (DTPA), triethylenetetraaminehexaacetjc acid (TTHA), ethylenebis [2- (hydroxyphenyl) glycine] (EDDHA), and salts thereof.
7. 7. A deodorant composition according to any one of the preceding claims, wherein the transition metal chelator is selected from one or more of diethylenetriaminepentaacetjc acid (DTPA), triethylenetetraaminehexaacetjc acid (TTHA), ethylenediaminetetraacetjc acid (EDTA), trans-i, 2diaminecyclohexane- N, N, N', N'-tetraacetjc acid (CDTA), and salts thereof.
8. 8. A deodorant composition according to any one of the preceding claims, wherein the transition metal chelator is diethylenetriaminepentaacetic acid (DTPA), or salts thereof.
9. 9. A method, particularly a cosmetic method, for reducing or preventing body malodour by topically applying to human skin a composition in accordance with any one of the preceding claims.
10. 10. Use of a perfume composition comprising at least 30% by weight of one or more of the following perfume components: (Z)-3,4,5,6,6pentamethylhept-3-en-2-one, mixtures of diethyl- and dimethylcyclohex-2-en-1-one, citronellol, 2- methyl-3-(4- (1 -methylethyl)phenyl) propanal, 2-(methyloxy)-4-propyl- 1 -benzenol, diphenylmethane, tetrahydrolinalol, 4-(4-methyl-3-pentenyl)cyclohex3 -ene- 1- carbaldehyde, 3-(4-methyl-3-peritenyl)cyclohex3ene 1 -carbaldehyde, 3-( 1, 3 benzodioxol-5-yl)-2methylpropanal a-ionone, -ionone, tricyclo[5.2.1.0 2, 6]dec- 4-en-8-yl ethanoate, 4-(4-hydroxy4methylpentyl)cyc1ohex3enecarba1dehyd 3(4-hydroxy4methy1pentyl)cyclohex3eflecba1dehyde methyl isoeugenol, 2- (1,1 -dimethylethyl)cyclohexyl ethanoate, 4-(1, 1 -dimethylethyl) cyclohexyl ethanoate, 4-methyl-2-(2-methylprop- 1 -enyl)tetrahydropyran; and a transition metal chelator, in the manufacture of a composition for reducing or preventing body malodour.
11. 11. Use of a perfume composition comprising at least 5 of the following perfume Components: (Z)-3,4,5,6,6-pentamethylhept.3en2one mixtures of diethyl- and dimethyl- cyclohex-2-en- 1-one, citronellol, 2-methyl-3-(4-( 1 -methylethyl)phenyl) propanal, 2-(methyloxy)-4-propyl- 1 -benzenol, diphenylmethane, tetrahydrolinalol, 4-(4-methyl-3-pentenyl)cyclohex3ene 1 -carbaldehyde, 3-(4-methyl-3- pentenyl)cyclohex-3-ene- 1 -carbaldehyde, 3-( 1, 3-benzodioxol-5-yl)-2- methylpropanal, a-ionone, 3-ionone, tricyclo[5.2. 1.0 2,6]dec-4-en-8-yl ethanoate, 4-(4-hydroxy-4methylpentyl)cyclohex3 -enecarbaldehyde, 3-(4-hydroxy-4methylpentyl)cyclohex3enecarba1dehyde methyl isoeugenol, 2-(1, 1dimethylethyl)cyclohexyl ethanoate, 4-( 1,1 -dimethylethyl)cyclohexyl ethanoate, 4- methyl-2-(2-methylprop- 1 -enyl)tetrahydropyran; and a transition metal chelator, in the manufacture of a composition for reducing or preventing body malodour.