CA1122520A - Surface treatment products - Google Patents

Abstract

- 62 - cR.185 ABSTRACT

A deodorant product comprises a deodorant composition and a carrier for the composition chosen from abrasive cleaners, bleaching agents, waxes, film-forming polymers or mixtures thereof, the deodorant composition having a deodorant value of from 0.50 to 3.5 as measured by the Deodorant Value Test.

Description

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- l - cR.185 ~UR~ACE TREA~ME~T~ PRODUCl'S

~ he invention relates to deodorant products suitable for application to surfaces other than human skin, in domestic, commercial, industrial and agricultural situations where malodour presents a problem.
ackground to the Invention It has long been realised that malodour, whether originating from the huma~ body or from ot'ner sources, particularly in the domestic, commercial, industrial and agricultural environments can constitute an unpleasant e~perience and that benefit could be obtained by preventing the development of malodours or -Dy masking or othe~Jise obliteratinO malodours ~./here they already exist.
As a means for solving this problem it is recognised that perfumes have been used as odour maskants since ancient . -, , .

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- 2 ~ cR.185 times and that perfumes have for this reason been incorporated into all manner of consumer products for use in the hu~an environment.
It is, however, recognised that the use of perfumes in this manner has its limitations, in that the duration of effectiveness can be relatively short-lived, or that offensive malodours are only partially mas~ed.
Summar~ of the Invention It has now been discovered that certain combinations of materials, some of which can be perfumer~ materials, and hereinafter referred to as "deodorant compositio~s"~ when incorporated into products for use in the human environment can provide a more effective means for preventing malodour development or for reducing the perception of malodours which are already present. Although the products of the invention may be fragrant, it is apparent that their effectiveness as deodorants is not solely due to odour masking, since in many instances there is no detectable residual fragrance of the composition remaining after its application or deployment. Accordingly, the use of deodorant compositions in such products represents a new operati~e principle.
In the course of attempts to characterise this new principle, many hundreds of materials have been screened and hundreds of formulations made by blending these materials have been examined.
Definition of the Invention In its widest aspect, the invention provides a deodorant product for application to surfaces other than human skin, which product comprises a deodorising amount of a deodorant composition and a carrier for the composition chosen from abrasive materials, bleaching agents, waxes, ~ilm-forming pol~mers, or mixtures thereof, the deodorant composition h~ving a deodorant value of from 0.50 to 3~5 as measured by the Deodorant Value ~est.

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_ 3 _ cR.185 ~ he invention also provides a process for preparing a deodorant product for application to surfaces other than human skin, which process comprises mixing a deodorant composition with a carrier for the composition chosen f~om abrasive materials, bleaching agents, waxes, film-forming polymers, or mixtures thereof, to provide a deodorant product, the deodorant composition havin~ a deodorant value of from 0.50 to 3.5 as measured by the Deodorant Value test.
~he invention furthermore provides a method for suppressing malodour which comprises deploying an effective amount of a deodorant product comprising a deodorant composition and a carrier for the composition as herein-defined, the deodorant composition having a deodorant value of from 0~50 to 3.5 as measured by the Deodorant Value test.
~he Deodorant Value ~est In this test the deodorant value of a deodorant composition is measured by assessing its effectiveness, when contained in a standard soap bar at a standard concentration, in reducing body malodour when the standard soap bar is used to wash the axillae (armpits) of a panel of human subjects.
~ he choice of a soap base is not critical to the performance of the test -out as illustrative of the conduct of the test in this respect the procedure followed in the preparation of the base is included in the description of the test.
~ tandard soap bars are prepared as follo~s, all amounts given being by weight.
As soap base there is used a neutral wet sodium soap containing 63% of total fatty matter of ~hich 82% is tallow fatty acid and 18% is coconut oil fatty acid. ~o a homo-geneous miYtur~ of 9000 parts of this soap base and 340 parts of free coconut oil fatty acid at 80C are added with mixing, 9.4 parts of a 20% aqueous solution of tetra-sodium etky~enediamine tetraacetate, 2.2 parts of a 60%

3~ aqueous solution of l-hydroxyethane-l,l-diphosphonic acid and 7.2 parts of butylated h~drox~ toluene (BH~) anti-oxidant dissolved in a little me~hylated spirits and tke :
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_ 4 _ cR.185 temperature of the mass is raised to 140C under super-atmospheric pressure. ~he mass is then sprayed at about 30 mm of mercury, to produce a dried soap composition which is collected and extruded at ~0C as noodles of about 12%
moisture content.
9,770 parts of the soap noodles thus obtained are mixed at ambient temperature with 150 parts of the deodorant composition to be tested, together with 30 parts of a titanium dioxide opacifier and 50 parts o~ a colourant 1~ suspension. ~he resulting mixture is milled and stamped into tablets. ~he deodorant composition to be tested is therefore present at the standard level of 1.5%.
Control soap bars are prepared in a similar manner except that the deodorant composition is omitted. In other respects, the control bar should only contain those additives conventionally present in personal washing products and for the purpose in the amount con~entionally used in the art. ~or example, it is permissible as indicated in the foregoing description to include anti-oxidants in the control bar, but these should be presentonly in the amount required to stabilise the soap base.
~he test is conducted as follows:
A team of 3 Caucasian female assessors of age within the range of from 20 to 40 years is selected for olfactory evaluation on the basis that each is able to r~ correctl~
the odour levels of the series of aqueous iso~aleric acid solutions listed in ~able 1 below, and each is able to detect the reduction in body odour following application to the axillae of human subjects of soap containing 2%
germicides, according to the procedure described in Whitehouse and Carter, Proc.~cientific ~ection of the Toilet Goods Association, 4$, 31, ~1967).
A panel of 50 hwman subjects for use in the test is assembled from Caucasian male subjects of age within the range of from 20 to 55 years. By screening, subjects are chosen who develop axilliary body malodour that is not , : ~

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- 5 - cR.185 unusually strong and who do not develop a stronger body malodour in one axilla compared with the other. Subjects who develop unusually strong bod~ malodour, for example due to a diet including curry or garlic, are not selected for the panel.
~ or two weeks before the start of a test, the panel subjects are assigned a non-deodorant soap bar exclusively for use when bathing, and are denied the use of a~y type of deodorant or antiperspirant. At the end of this period, the 50 subjects are randomly divided into two groups of 25. The control soap bars are then applied to the left axillae of the first group and the right axillae of the second, and the test soap bars are applied to the right axillae of the first group and the left axillae of the second.
The soap bars are applied by a technician using a standard technique in which a wet flannel is soaped with the soap bar for 15 seconds, the axilla is washed with the soaped fl~nnel for 30 seconds, then wiped with a water rinsed flannel and dried with a clean towel. Each subject then puts on a freshly laundered shirt, and 5 hours after application the odour intensity of each subject is assessed, the left axilla of each subject being assessed before the right. The application and assessment are carried out on each of four successive days.
The odour intensity is evaluated by all three assessors who, operating ~ithout knowledge of the soap bars used for each subject or the result of evaluation of their fellow-assessors, sniff each axilla and assign a score corresponding to the strength of the odour on a scale from 0 to 5, with 0 corresponding to no odour and 5 representing very strong odour. ~efore evaluation each subject stands with his arms against his side: he then raises one arm straight overhead, flattening the axilla vault and making it possible for the assessor's nose to be brought close to the sk n, the assessor makes an evaluaticn and the procedure is repeated with the other ~xilla.

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;2~) - 6 - cR.185 Standard aqueous solutions of isovaleric acid which correspond to each of the scores 1,2,3,4 and 5 are provided for reference to assist the assessors in the evaluation.
These are shown in ~able 1 below.
~able 1 Concentrations of aqueous solution of isovaleric Score Odour ~evel acid (ml~'l) .
O ~o odour O
1 Slight 0.013 2 Definite 0.053 3 Moderate 0.22

4 ~trong 0.87 Very strong 3.57 ~he scores recorded by each assessor for each soap bar are averaged and the average score of the test soap bars deducted from the average score of the control soap bars to give the deodorant value of the deodorant composition present in the test soap bars.
As a check that the selection of panel subJects is satisfactory for operation of the test, the avarage score with the control soap bars should be between 2.5 and 3.5.
Although the invention in its widest aspect provides deodorant products comprisin~ deodorant compositions having a deodorant value of from 0.50 to 3.5, preferred deodorant products are those comprising deodorant compositions ~hich have a deodorant value of at least 0.60, or 0.8, or 1.0, or 1.2, or 1.5, the higher the minim~m value, the more effective is the product as a deodorant product as recorded b~ the assessors in the deodorant value test.
1. ~he Deodorant Composition ~ he characterisation of the deodorant composition of the invention presents difficulties, since it c~nnot be defined solely in terms of materials of specified structure and combinations in specified proportions. Nev~rtheless, procedures have been discovered that enable the essential materials of the deodorant compositions to be identified by tests.

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_ 7 _ cR.185 ~ he essential materials required for the formulation of deodorant compositions are those having a lipoxidase-inhibiting capacity of at least 50% or those having a Raoult variance ratio of at least 1.1, as determined b~
the following tests, which are designated the lipoxidase and morpholine tests respectivel~.
~he ~ipoxidase ~est Tn this test the capacit~ of a material to inhibit the oxidation of linoleic acid b~ lipoxidase (~Cl.13.1.13) to form a h~droperoxide is measured.
Aqueous 0.2M sodium borate solution (pH 9.0) is used as buffer solution.
A control substrate solution is prepared b~ dissolving linoleic acid (2.0 ml) in absolute ethanol (60 ml), dilutin~

~1~2~i2~
8 - cR.185 with distilled water to 100 ml and then adding borate buffer (100 ml) and absolute ethanol (300 ml)~
A test substrate solution is prepared in the same way as the control substrate solution except that for the absolute ethanol (300 ml) is substituted the same volume of a o.50/O by weight solution in ethanol of the material to be tested.
A solution of the enzyme lipoxidase in the borate buPfer and having an activity within the range of from 15,000 to 40,000 units per ml is prepared.
~ he activity of the lipoxidase in catal~sing the oxidation of linoleic acid is first assa~ed spec-tro hoto-metrically using the control. An automatic continuously recording spectrophotometer is used and -the increase in extinction at 234 nm (the peak of hydropero~ide~ is measured to follow the course of oxidation, the enzyme concentration used being such that it gives an increase in optical density ~ OD) at 234 n~ within the range of from 0.6 to 1.0 ~mits per minute. ~he following ingredients are placed in two 3 ml cuvettes:
Control ~ml) Blank ~ml) Control substrate solution ~ 0.10 0.10 Absolute ethanol 0.10 0.10 Borate buffer 2.75 ~.80 ~ipoxidase solution 0.05 ~ he lipoxidase solution is added to the control cuvette last and the reaction immediately Pollowed spectro-photometrically for about 3 minutes, with recording of the increase in optical density at 234 nm as a cur~e on a graph.
The capacity of a material to inhibit the oxidation is then measured using a test sample containing enzyme, substrate and a deodorant material. ~he following ingredients are placed in two 3 ml cuvettes.

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- 9 - cR.1~5 ~est Sample (ml) Blank (ml) ~est substrate solution 0.10 0.10 Absolute ethanol 0.10 0.10 ~orate buffer 2.75 ~.80

5 ~ipoxidase solution 0.05 ~ he lipoxidase solution is added to the test sample cuvette last and the course of the reaction immediatel~
followed as before.
~ he lipoxidase-inhibiting capacity of the material is then calculated from the formula 100 (Sl-~2)/~ here ~1 is the slope of the curve obtained with the control and S2 is the slope of the curve obtained with the test sample, and thus expressed as % inhibition. A material that gives at least 50% inhibition in the test is herea~ter re~erred to as having a lipoxidase-inhibiting capacity of at least 5oo~o.
~he Morpholine ~est In this test the capacity of a material to depress the partial vapour pressure of morpholine more than that required by Raoultls ~aw is measured. Substances that undergo chemical reaction with morpholine, for e~ample alden~des a are to be regarded as excluded from the test.
Into a sample bottle of capacity 20 ml is introduced morpholine (lg) the bottle fitted with a serum cap and then maintained at 37C for 30 minutes for equilibrium to be reached. ~he gas in the headspace of the bottle is analysed b~ piercing the serum cap with a capillary needle through which nitroge~ at ~7C is passed to increase the pressure in the bottle by a standard amount and then allowing the excess pressure to inject a sample from the headspace into gas chromatograph apparatus, which analyses it and provides a chromatographic trace curve with a peak due to morpholine, the area under which is proportional to the amount of morpholine in the sample.
~he procedure is repeated under exactly the same conditions using instead of morpholine alone, morpholine (Q.25g) and the material to be tested (lg); ~nd also - . ~ ~.- ~ : . :
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- 10 - cR.185 using the material ~lg) without the morpholine to check whether it gives an in~erfere~ce with the morpholine peak (which is wnusual).
~he procedure is repea-ted until reproducible results are obtained. ~he areas under the morpholine peaks are measured and any necessary correction due to interference by the material is made.
A suitable apparatus for carrying out the abo~e procedure is a Perkin-~lmer Automatic GC Multifract ~40 for Head Space Analysis. Further details of this method æe described by Eolb in "CZ-Chemie-lechnik", Vol 1, ~o 2, 87-91 (1972) and by Jentzsch et al in "Z.Anal.Chem."
236, 96-118 (1968).
~he measured areas representing the morpholine concentration are proportional to the partial vapour pressure of the morpholine in the bottle headspace. If A
is the area under the morpholine peak when only morpholine is tested and A' is the area due to morpholine when a material is present, the relative lowering of partial vapour pressure of morpholine by the material is given by 1 -A'/A.
According to Raoult's ~aw, if at a given temperature the partial vapour pressure of morpholine in equilibrium with air above liquid morpholine is p, the partial vapour pressure p' axerted by morpholine in a homogeneous li~uid mixture of morpholine and material at the same temperature is pM/(M+PC), where M and PC are the molar concentrations of morpholine and material. Hence, according to Raoult's ~aw the relative lowering of morpholine partial vapour pressure (p-p')/p, is given by l-M/(M+PC), which under the circumstances of ~he test is 87/(87+m/4), where m is the molecular weight of the perfume materiall .

cR.185 ~he extent to which the behaviour of the mixture departs from ~aoult's ~aw is given by the ratio l-A'/A
87/(87+m/4) ~he above ratio, which will be referred to as the Raoult variance ratio, is calculated from the test results.
Where a material is a mixture of compounds, a calculated or experimentally determined average molecular weight is used for m. A material that depresses the partial vapour pressure of morpholine by at least 10% more than that required by Raoult's Law is one in which the Raoult v æiance ratio is at least 1.1.
Q large number of materials which satisfy one or both tests is described later in this specification and these are hereafter referred to as "components" 7 in contrast to other materials which fail both tests which are referred to as "ingredients".
~ efore defining the more detailed aspects of the invention so far as it relates to deodorant compositions, it is necessary to clarify some of the terms that will be employed.
A composition is a blend of organic compounds. ~or the purposes of this specification it is necessary to identify the "components" in the composition. ~his is done by first describing the composition in terms of four catego~ies. ~hese categories are given belo~. ~xamples o~ components in each category are provided~
1) Single chemical compounds whether nat~al or synthetic, e.g. coumarin (natural or synthetic), iso-eugenol, benzyl salicylate. ~he majority of components are in this categor~.
2) ~nthetic reaction products (products of reaction), mixtures of isomers and possibly homologues, e.g.~-iso-meth~l ionone~

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_ 12 _ cR.185 3) ~atural oils, gums and resins, and their extracts, e.g. patchouli oil, geranium oil, clove leaf oil, benzoin resinoid.
4) ~ynthetic analogues of category 3. ~his categor~ includes materials that are not strict analogues of natural oils, gums and resins but are materials that result ~rom attempts to copy or improve upon materials of category 3, e.g. Bergamot AB 430, Geranium AB 76, Pomeransol ~3 314.
Components of Categories (3) and (4) although often uncharacterised chemically are available commercially.
Where a material is supplied or used conventionally for convenience as a mixture, e.g. p-t-Amylcyclohexanone diluted with diethyl phthalate, for the purposes of this specification two components are present, so that use of 5% of a blend of 1 part of this ketone and 9 parts of diethyl phthalate is represented as 0.5% of the ketone a~d 4.5% of diethyl phthalate.
It has been found advantageous in formulating the most effective deodorant composition for incorporation into the deodorant product of the invention to use components that, well as satisfying the lipoxidase or morpholine tests, satisfy further conditions. These conditions are: ;
i) there must be at least five components prese~t, ii) each of these components must be selected from at least four different chemical classes (to be de~ined belo~), iii) a component from each of classes 1,2 and 4 must be present, iv) at least 45%, preferably at least 50 and most preferably from 60 to 100%, b~ weight of the deodorant composition must Gomprise components~
v) a component is not considered to contribute to the efficacy of the deodorant composition if it is presen~ in the deodorant composition at a concentration o~ less than 0.5% b~ weight, and -' z~ ~
- 13 - cR.1$5 vi) a class is not considered to contribute to the efficacy of the deodorant composition if it is present in the deodorant composition at a concentration of less than 0.5% by weight.
~herefore, according to a preferred embodiment of the invention, there is provided a deodorant product as herein defined in which the deodorant composition consists essentially of from about 45 to 100% by weight of at least fi-~e components and from 0 to about 55% by weight of ingredients, each of the components being selected from components having a lipoxidase inhibiting capacity of at least 50% and components having a Raoult variance ratio of at least 1.1, the components and ingredients being so chosen that the deodorant value of the deodorant composition is within the rP~ge 0.50 to 3.5.
~ach component should be allocated to one of six classes. ~hese classes æe:
Class 1 - Phenolic substances;
2 - Essential oils, extracts, resins, "synthetic"
oils (denoted by "AB");
3 - Aldehydes and ketones;
4 - Polycyclic compounds;
5 - ~sters;

6 - Alcohols.
In attributing a component to a class, the following rules are to be observed. Where the component could be assigned to more than one class, the component is allocated to the class occurring first in the order given above: for example clove oil, ~hich is phenolic in ch æ acter, is placed in Class 1 although it otherwise might have been allocated to Class 2. Simil æ ly, 2-n-heptyl cyclopentanone which is a polycyclic ketone is attributed to Class 3 instead of Class 4.
The followin~ æ e examples of deodorant components that either have a lipoxidase inhibiting capacity (~IC) of at least 50% or have a Raoult variance ratio (RVR) of : - . . . ,.,...., -:
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- 14 - cR.185 at least 1.1. Their class, molecular weight (m), ~IC
and RVR as determined by the tests already described herein are also listed.
~he nomenclature adopted for the components listed below and for the ingredients which appear in the deodorant formulations of the Examples is, so far as is possible, that employed by Steffen Arctander in "Perfume and Flavour Chemicals (Aroma Chemicals)"
Volumes I and II (1969) and the "Perfume & Flavour Materials of ~atural Origin" (1960) by the same author~
Where a component or other ingredient is not described by Arctander, then either the chemical na~e is given or, where this is not known (such as is the case with perfumery house specialities), then the supplier9s identity can be established by reference to the appendix which appears at the end of the specification.

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- 15 - cR.185 Class 1 - Phenolic Substances ~IC RVR m _ iso-Amyl salic~ylate 95 1.24 208 Benzyl salicylate 0 1.58 228 - 5 Carvacrol 32 1.43 150 Clove leaf oil 79 1.43 164 ~thyl vanillin 100 1.43 152 iso-Eugenol 100 1.48 164 IRG 201 100 1.21 196 10 Mousse de chene Yugo 98 1.29 182 Pimento lea~ oil 100 - 165 Th~me oil red 55 1.37 150 Class 2 - ~ssential oils, extracts, resins, "s~ynthetic"
_ _ oils, (denoted b~ "AB") 15 Benzoin Siam resinoid 87 Bergamot AB 37 58 97 175 Bergamot AB 430 58 97 175 Geranium AB 76 26 1029 154 Geranium oil 26 1.29 154 20 Opoponax resinoid 96 1.33 150 Patchouli oil 76 1.25 140 Petitgrain oil 34 1.27 175 Pomeransol AB 314 100 Class 3 - Alde~ydes and Eetones 25 6-Acet,yl-1,1,3,4,4,6-hexamethyl-tetr~ydronaphthalene 100 1.03 258 p-t-Am~l c~clohexanone 50 1.10 182 p-t-Butyl~-meth~l h,ydrocinnamic aldehyde 74 - 204 30 2-n-hept~ylc~yclopentanone 56 1.05 182 c~_iso-Methyl ionone 100 1.13 206 ~-Meth~yl naphth~yl ketone 100 0.96 170 .

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- 16 - cR.185 Class 4 - Pol~c~clic Compounds ~IC RVR m Coumarin 58 1.22 146 1,3,4,6,7,8-Hexah~dro-4,6,6,7,8,8-hexamet~yl cyclopenta-~-2-benzo- 100 - 240 3a-Methyl-dodecahydro-6 6,9a-trimethylnaphtho(2,1-b~furan 58 1.30 230 ~-~aphthyl meth~l ether 100 - 158 Class 5 - ~sters o-t-Butylc~clohex~l acetate 52 1.08 198 p-t-~ut~lcyclohexyl acetate 54 0.98 198 Diethyl phthalate 79 1.20 222 ~onanediol-1,3-diacetate 33 1.17 244 15 ~onanolide-1:4 92 0.87 156 i-~on~l acetate 50 0.83 186 i-~onyl formate 19 1.49 172 Class 6 - Alcohols Dimyrcetol 16 1.22 156 Phenylether alcohol 22 1.24 122 ~etrahydromuguol 24 1.23 158 It has been shown that for best results, a certain min;mum average concentration of components should be present. ~his minimum concentration is a f~mction of the number of classes present - the more cl~sses present, the lower the minim~lm concentration. ~he minim~lm average concentration in the various situations that can apply is shown in the ~able below:
~umber of classes Average concentration 30 represented in of com~onents deodorant com~osition min;mum not preferably not less than (%) less than_(%) ~5 55 6 4.5 5 .. ~ . . ~ , 2~;Z~
- 17 - cR.185 ~ lso, it is pre~erred that at least 1% of each of four classes is present in the deodorant composition, but individual components which are present at a concentration of less than 0.5% are eliminated from this calculation, as is the class into which the~ fall if there is present no component at a concentration of at least 0.5% which falls within that class.
~ ore specificall~, the inventiGn also provides a deodorant product as herein de~ined wherein the amount of deodorant components in the deodorant composition present in the classes 1,2 and 4 as herein de~ined is at least 1%, most preferably at least 3% 'D~ weight of the deodorant composition for each class, and the amount o~ components present in each of at least two other classes is at least 1% by weight of the composition, provided also that any component that is present in the deodorant composition at a concentration of less than a threshold ~alue of 0.5%
by weight is eliminated from the calculation of the amounts of components in each class.
Although at least four different classes o~
components should preferabl~ be represented in the deodorant composition, superior compositions can be obtained if more than ~our classes-are represented.
Accordingl~ five or six classes can be represented in the deodorant composition.
It has been shown by the preparation, examination and testing of man~ hundreds of deodorant compositions that the best results are obtained b~ keeping within the aforementioned rules when selecting t~pes and amounts of components and i~gredients. ~or example, deodorant compositions which contain less than the minimum concentration o~ components of 45% are unlikel~ to result in a deodorant composition having a deodorant value of at least 0.50. ~herefore, in preParing the best deodorant ~5 compositions of the in~ention, the ~ules for selection o~
components accor~;ng to their classification, the . ~ ., .
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- 18 - cR.185 representation of different classes, the amounts of each component present, bearing in mind the threshold value below which it is believed a component will not significantly contribute, are all important to observe if the best results are to be obtained.
It should be explained that components present in the deodorant product for purposes other than obtaining deodorant effects, for example an adjunct like the anti~
oxidant included for the stabilisation of the product, æe excluded from the operation of the preceding instructions to the extent that the component is required for that other purpose. The levels at which adjuncts are conventionally present is well-established for established materials and readily determinable for new materials so that the application of the above e~clusion presents no difficulty.
Deodorant compositions can be incorporated in deodorant products according to the invention, at a concentration of from about 0.1 to about 20%, preferably from 0.5 to 10% and most preferably from 1 to 5% by weight.
It is apparent that if less than 0.1% of a deodorant composition is employed, then use of the deodorant product is unlikely to provide a significant reduction in malodour intensity. If more than 20% of a deodorant composition is employed, then use of the deodorant product is ~ ely to further reduce malodour intensity beyond that observed at the 20% level.
2. ~he Carrier ~ he carrier for the deodorant composition can function as a diluent, dispersant, a substrate or other means for conve~ing and/or distributing the deodorant composition in the environment where a deodorising effect is required.
~ he carrier can also perform other functions such as cleansing, bleaching and polishing which characterise the function of the product other than that of acting as a deodorant.

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- 19 - cR.185 When the carrier comprises an abrasive material it is generally a water-insoluble particulate abrasive material in ~hich the particle size diameters are usuall~ from 1 to 250 microns, the material usually having a specific gravity of from 0.5 to 5, and a Mohs' hardness of 2 to 7.
Preferably, the diameter of the particles is from 10 to 150, most preferably from 20 to 100 microns. The specific gravit~J
of the material is preferably from 1 to 3.
~xamples of suitable abraslve materials include, but are not limited to, quartz, pumice, pumicite, titanium dioxide, silica sand, calcium carbonate, zirconium silicate, diatomaceous earth, whiting, felspar, alumina, corundum, volc~n;c ash, bentonite, magnesium oxide, magnesium carbonate, chalk, dolomite, shell, talc, calcite and mixtures thereof.
~he amount of abrasive material when present in the deodorant product will normally be that which is appropriate for the normal function of the product other than that of a deodorant. ~he deodorant product can therefore in general terms contain up to 99% by weight of abrasive material. If, for example, the product is dry abrasive cleaner, the amount of abrasive material present will preferabl~ be from 60 to 99% by weight of the product. If, however, the product is a liquid abrasive cleaner, then the amo~mt of abrasive material present will normall~ be from 1 to 60% by ~eight of the product.
When the carrier comprises a bleaching agent, the bleaching agent will normally be one ~hich is a hypochlorite or a hypobromite, or in the case of a dry product, a precursor thereof~ ~hose bleaching agents which yield a hypochlorite species in aqueous solution and are therefore suitable for use in liquid products include alkali earth metal hypochlorites, hypochlorite addition products, chloramines, chlorimines, c~loramides, and chlorimides.
Specific examples of compounds of this type include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, ....

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- 20 - cRo185 potassium dichloroisocyanurate, sodium dichloroisocyanurate, 1,3-dichloro-5,5-dimethyIhydantoin, and N-chlorosulphamide and mixtures thereof. A preferred agent is sodium hypo-chlorite.
~hose bleaching agents ~hich are suitable for use in powdered products and which are capable of libera-ting a hypohali~e when the powdered product is employed in contact with water, for example in the cleaning of household industrial surfaces, are exemplified by het~rocyclic N-bromo and ~-chloro imides such as trichlorocyanuric tri-bromocyanuric acid, dibromocyanuric acid and dichloro-cyanuric acid, and salts thereof with water-solubilising cations such as potassium and sodium. Other N-bromo and N-chloro imides may be used, such as N-brominated and ~-chlorinated succinimide, malonimide, phthalimide andnaphthalimide. Other suitable bleaching agents are the hydantoins, such as 1,3-dibromo- and 1,3-dichloro-5,5-dimethylhydantoin; N-monochloro-C,C-dlmethylhydantoin methylene-bis, (~-bromo-C,C-di-methylhydantoin); 1,3-dibromo- and 1,3-dichloro-5-isobutylhydantoin; 1,3-bromo- and 1,3-dichloro-5-methyl-5-eth~lhydantoin; 1,3-dibromo- and 1,3-dichloro-5,5-diisobutyl-hydantoin; and 1,3-dibromo- and 1,3-dichloro-5-methyl-5-amylhydantoin.
Other useful bleaching agents are tribromomelamine and trichloromelamine. Dry, particulate, water soluble anhydrous inorganic salts are likewise suitable, such as lithium hypochlorite and lithium hypobromite. ~he bleaching agents may, if desired, be provided in the form of a stab-e, solid complex or hydrate, such as sodium p-toluene-sulpho-brom~mine-trihydrate, sodium benzene-sulpho-chloramine-dihydrate or calcium hypobromite tetrahydrate calcium hy~ochlorite tetrahydrate. ~rominated and chlorinated tri-sodium phosphate formed by the reaction of the corresponding sodium hypohalite solution ~ith trisodium phosphate (and water as necessary) also are efficaceous materials~ Use may be made of bleaching agents capable of liberating hypo-~22~
_ 21 - cR.185 chlorite as well as hypobromite such as N-brominated, ~'-chlorinated heterocyclic imides, for example M-bromo, ~'-chlorocyanuric acids and sal-ts thereof, e.g. ~-monobromo-~, ~-dichloroc~anuric acid, ~-monobromo-~T-monochlorocya~uric acid, N-monobromo-N-monochlorocyanuric acid, sodium-~-monobromo-~-monochlorocyanurate, potassium-N-monobromo-~-monochlorocyanurate; and ~-brominated, ~-chlorinated hydantoins, e.g. ~-bromo-~-chloro-5,5-dimethyl-hydantoin and ~-bromo-~-chloro-5-ethyl-5-methyl hydantoin.
lhe amount of bleaching agent when present in the deodorant product will normally be that which is appropriate for the normal function of the product other than that of a deodorant. ~he deodorant product can therefore contain up to 50%, preferably from 0.1 to 25%, most preferably from 0.5 to 10%
15 by weight of the product of a bleaching agent, the chosen amount depending on the nature and function of the product.
When the carrier comprises a wax, the wax can be any natural, synthetic wax or waxy substance that can find utiliy in polishes.
~xamples of natural waxes are vegetable waxes such as carnauba wax, cauassu wax, candelilla waY, o~icuri wax, raffia wax, palm wax, esparto wax, sugar cane wax, and cotton wax; animal waxes such as beeswax, ghedda wax, chinese insect wax, shellac waæ, lanolin and walrat 25 (spermaceti); mineral waxes such as paraffin wax, micro-crystalline w~xes, ozokerite-ceresin, petroleum waxes, montan wax.
~xamples of synthetic waxes are fatty alcohols such as lanette wax; fatty acid esters of polyhydric alcohols 30 such as glyceryl distearate, glyceryl monostearate, ethylene glycol monostearate, dieth~lene glycol mono-ste æ ate; chlorinated products such as chlorinated naphthalane waxes, chlorinated par~ffin wa~es; synthetic B waxes containing nitrogen such as ~ra~ c~ (Glycol 35 Products Co), Armowax (Armour Co.); pseudoesber waxes ~ c~enOt~ ~r~12 ~

~ : ~
: ~ :

- 22 - cR.185 such as alkylamide w æes, ester-pseudoester waxes, aryl-amide waxes; silicone waxes; and polyethylene waxes, polypropylene glycol waxes and polyethylene gl~col waxes such as carbowaxes.
~he amount of wax when present in the deodorant product will normally be that which is appropriate Por the normal function of the product other than that of a deodorant. ~he deodorant product can therefore contain up to 99.9%, preferably from 1 to 80% by weight of the product of a wax, the chosen amount depending on the nature and function of the product.
When the carrier comprises a film forming polymer, it is usually one which has the property of forming a hard ?
glossy, durable film on a surface such as a floor which is likely to suffer wear and tear from passage thereover of people, animals, furniture and equipment. ~xamples of suitable polymers are those which can be formed from polymerisable ethylenically unsaturated monomers such as styrene? lower alkyl methacrylates in which the alk~l group contains from 1 to 12 carbon atoms, lower alkyl acrylates in which the alkyl group contains from 1 to 12 carbon atoms, acrylonitrile and/or methacrylonitrile. An example of a styrene polymer is polystyrene. Specific examples of alkyl methacrylates include methyl, ethyl, propyl, isopropyl, but~l, pentyl, hex~l, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, 2-ethyl he~l, and cyclohexyl methacr~lates.
Suitable alk~l acrylates include methyl, ethyl, propyl ? butyl, pentyl, hexyl, heptyl ? octyl, nonyl, decyl ? undecyl, dodecyl, 2-ethyl hexyl, and cyclohexyl acrylates, the polymer should contain no more than about 30% butyl or higher alkyl acr~lates, since these ac~ylates soften the polymer more than the short chain alXyl acrylates.
~ urther examples of film forming polymers include non-volatile silicone fluids and 'waxes' such as polyalkyl-siloxanes, for example polydimethylsiloxane; polyalkylaryl-siloxanes, for example polymethylphenylsiloxane; polyether-siloxane copolymers, for example dimethylpolyoxyalkylene .

2~) - 23 - cR.185 ether copolymer; and poly higher alkylpolysiloxanes, where the alkyl group has 3 or more carbon atoms.
Further examples of suitable film forming polymers include graft polymers of low molecular weight styrene-maleic anhydride resins with heterocyclic compounds such as-caprolactam, 2-pyrrolidone or N-meth~1-2-pyrrolidone, as well as the water-soluble alkali metal or ammonium salts of these graft polymers.
Yet further examples of film forming polymers include copolymers such as polystyrene~ ethyl acrylate-acrylic acid copolymers, styrene-acrylate copolymers, ethyl acrylate-methacrylate acid copolymers, rosin acrylate copolymers and organic polycarbo~lic acid copolymers.
Other suitable film forming pol~mers include resins such as zinc resinate, and white glyptal resin.
It is also possible to employ two or more film forming polymers in the deodorant product of the invention.
~ he amount of film forming polymer ~hen present in the deodorant product does not normally exceed 50% ~y weight of the product. Preferably, the amount of film forming polymer forms from 0.1 to 25%, most preferably from 0.5 to 15% by weight of the product.
It is to be understood that the foregoing carriers are merely illustrative of the carriers which are suitable for incorporation in the products of the invention.
In ge~eral terms it can be stated that the carrier will form from 0.1 to 99.9%, usually from 1 to 99% by weight of the product. ~he preferred amount of carrier to be employed will, as can be seen from the foregoing discussion, be dictated by the category of carrier employed and the physical nature of the end product.
3. Products of the Invention qhe deodorant product of the invention ca~ take many forms, depending upon whether it is intended for use in a ~5 domestic, commercial, industrial or agricultural env;ronment, ~here human contact is likely to occur and where malodours are according'y li~ely to be perceived.

~ ;

~2~
- 24 - cR.185 Products of the invention can then be classified according to their ultimate utili-t~, but it is to be understood that the invention is not limited solely to these examples.
According to the following classification, the compositions of the invention can take the form of solid products or liquid products which contain a deodorising amount of the deodorant composition.
Examples of products of the in~ention which are domestic, commercial, industrial or agricultural products for use other than for direct application to the human bod~
æe abrasive cleaners, bleach products, paints and polishes intended for application to surfaces in an environment ~here malodour can exist or develop.
It is to be understood that products of the invention will normally contain further ingredients in addition to the deodorant composition and the carrier, as herein defined, appropriate to their normal function, for example as cleaners or polishes, these further ingredients being those conventionally employed in such products.
Products of the invention`t~ill usuall~ be packed in a container suited to their ultimate use ~hen dispensing and deploying the product in order to prevent or reduce the development of malodour. ~he construction and design of the container will also usualI~ be dictated by the ph~sical form of the product.
Containers suita~le for containing and, when re~uired, dispensing powdered products such as pot~der abrasive cleaners ~;
can be cannisters of board, metal or plastics material, ~0 perforated at one end to allow the powdered product to be sifted onto a surface. ~imilarly~ containers for liquid products can be glass or plastic bottles or cannisters which can be uncapped or perforated ~hen required for use. ~iquid products can also be packed in cannisters fitted with a suitable p~p spray ~or dispensing b~ finger or hand pressure, or when the product comprises a propellant liquid or gas, ~ z~
- 25 - cR.185 pressurised dispensers such as aerosol devices are suitable containers.
Other containers for household, domestic, industrial or agricultural powdered or liquid products as are conventionally emplo~ed, can be used to contain and dispense products of the invention.
4. Process for pre~aring deodorant products ~ he invention also provides a process for preparing deodorant products as herein defined.
Deodorant products of the invention can acccrdingly be prepared 'Dy mixing or blending the deodorant composition with one or more carriers. Where a heat treatment is employed in preparing the deodorant products, it is pre~erable to add the deodorant composition to the carrier and other ingredients of the product towards the end of the process when loss of an~ volatile substances in the deodorant composition is minimised.
5. Method of suppressin~ malodour ~he invention also provides a method for suppressin~
malodour.
Products of the invention can accordingly be deplo~ed in an effective amo~mt in an environment where malodour exists or is likely to develop. ~or e~ample, products of the invention such as abrasive cleaners, bleaches and polishes can be applied to kitchen, bathroom and other surfaces including floors, sinks, baths or lavatory basins and bowls in order to clean, bleach or polish these surfaces, while at the same time providing a deodorising effect which can be long lasting.
~ Examples of products of the invention ..
~ he following products are illustrative of compositions of the invention which comprise a carrier, which can be a liquid or a solid carrier, onto or into which a deodorant co~position can be incorporated, included ~5 or deposited.
In the following examples, the proportion of ingredients are in parts by weightO

.. . ~: : .

- 26 - cR.185 ~couring powder for kitchen and household use Hard soap, powdered 70 ~odium metabisulphite 50 Sodium carbonate 80 ~risodium phosphate 50 Chalk 749 Deodorant composition Bath Cleaner ~risodium phosphate 250 ~oap, powdered 250 Chalk 499 Deodorant composition T,avatory Cleaner Sodium hydro~en sulphate 600 Al~um (powdered) 300 Salt 9~
Deodorant composition 2 Laundr~ Bleach Calcium hypochlorite 500 Monocalcium phosphate 498 Deodorant composition 2 Floor Polish Carnauba waY 150 Cumarone resin 60 Oleic acid 40 ~riethanol~mine 40 Borax 60 Water 245 Deodorant composition 5 .
.

- 27 - cR.185 Antiseptic Insecticidal ~loor and ~urniture Polish Terpentine 645 ~erpineol 50 Derris, powdered 30 Pyrethrum, powdered 30 30rn~yl acetate 20 ~or~yl chloride 20 Zinc resinate 5 Deodorant composition 5 Window Polish Diglycol stearate 150 Water 495 Magnesium carbonate 150 Chalk 100 White bole 100 Deodorant composition 5 ~urniture Polish 3eeswax 25 Diglycol stearate 10 Montan wax 25 Rosin 3 Ozokerite (60/62C) 17 Ammonia 70 Water 848 Deodorant composition 2 White Gloss Enamel Paint Stock ~ second pyroxylin 400 White glyptal resin (film-forming polymer) 180 Thinners 380 Plasticiser 70 Cellosolve 60 Pigment (white) 340 Deodorant composition 20 .

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- 28 - cR.185

7. Specific Examples of the Invention Illustrating Deodorant E~fectiveness ~he invention is illustrated by the ~ollowing examples, in which all parts and percentages are b~ weight.
In each of Examples l to 6 a deodorant composition was prepared b~ mixing the components and other ingredients listed in the relevant Deodorant Composition, which gives the amount of components in each class. ~est products containing the deodorant composition and control products containing no deodorant composition were prepared and tested in each instance.

~ : ' ,.

-' .:,' ~ : ' ' ~ '- :: ' ~Z2520 _ 29 - cR.185 Example 1 ~his ~xample illustrates the invention in terms of a polish suitable for application to floors to provide a hard, clear, shiny non-slip protective coating.
~he test polish contained the following ingredients:
% w/w Pol~ethylene wax (AC 629) (a) 2.4 Copol~mer (PR ~ B231) (b) 12.8 Resin (SR 88) (c) 0.8 10 ~ynperonic A7 (d) 0.9 2-amino-2-methyl propanol 0.18 Oleic acid 0.3 Tributox~l ethyl ~hosphate 0.6 PROx~l, AB paste (e) 0.03 ~C 128 (f) 0.006 Carbitol 1~6 Industrial methylated ,spirit 0.8 Ammonia 0.27 Deodorant Composition 1 0.2 20 Water to 100 (a) A wax manufactured by Allied Chemicals having a softening point of 101C, a specific gravity of 0.93 and an acid value of 14 to 17.
(b) Styrene acrylate copol~mer manufactured by Rohm & Haas.
(c) Rosin maleic anh~dride manufactured by Schenectady Chemicals Inc., and having a melting point of 150 to 160C, and an acid value of 185 to 200.
(d) A synthetic primary alcohol eth~lene oxide condensate (nonionic detergent) manufactured b~ ICI and having an HLB value of 12.2.
(e) A preservative manufactured by ICI.
(f) 1% solution of the potassium salt of ~-eth~
perfluoro octane sulphon~l glycine manufactured by 3M Company~ ' ~ denOf~s t~e ~a~ -2 ~ S ~
_ 30 _ cR.185 ~he formulation of the Deodorant Composition 1 is as follows:
Deodorant Composition 1 Gomponents Parts Class Total in class iso-Amyl salicylate 5.0 Benz~l salic~late 4.0 1 ) 10.25 ~RG 201 1.25 Bergamot AB 430 15.0 2 Ger~n;um AB 76 4.0 2 ) 20.7 10 Opoponax resinoid 1.7 2 1,3,4,6,7,8-Hexanydro-4,6,6,-7,8,8-hexamethylc~clopenta-~-2-benzop~ran 10.0 4 10.0 o-t-But~lc~clohex~l acetate O.5 5 ) 4 2 Dieth~l phthalate 3.75 5 ) 5 ~onanolide-1,4 0.2~ (5) Ingredients Amber AB 358 3.0 Benzyl alcohol 0~15 Cedar atlas oil 5.0 Citronellol 7.0 Citronella oil 16.1 Citronell~loxyacetaldeh~de O.5 ~e~yl aldone O.7 ~asmin AB 284 12.0 Oran~e oil sweet 8.0 10-Undecen~l-al 0.15 Vetyvert oil 2.0 100 .0 30 eliminated from calculation - below threshold value of 0.5%-,i .

- ' ' .

2~
- 31 cR.185 ~otal amount of components 45.2 ~umber of components present 9 Average amount of each component 5.0 ~umber of classes represented 4 The deodorant value of Deodorant Composition 1 was determihed b~ the Deodorant Value test as described hereinbefore and was ^alculated as the difference between the control and test soap bar series. ~he results were as follows:
10 De dorant value of Deodorant Composition 1 Control ~est soap bar soap bar `~verage scores 3.46 2.93 Deodorant value (difference) 0.53 A control polish was also prepared which was identical except that the Deodorant Composition 1 was omitted.
~he abilit~ of the test polish compared with that of the control polish to reduce malodour was assessed as follows:
Each polish was painted onto the outside of glass ~ials of surface area 25 cm and allowed to dr~ for 1 hour~ ~he amount of polish applied was such that the residual dried film on each vial weighed O.Olg. ~ polish coated ~ial was then placed in a series of air tight screw capped jars together with 5 ml of each of four different concentrations of a standard kitchen malodour prepared according to the table below. One hour later, each jar was uncapped and the odour within assessed according to a O to 5 hedonic scale b~ a panel of trained assessors.
~he standard kitchen malodour concentrate was prepared from the following ingredients:

o - 32 - cR.185 Kitchen malodour concentrate :
GSA-~SS P-D-00200a* % w/w diacet~l (2,3-butanedione) 3-85 Pyridine 3.85 5 diallyl sulphide (thio-allyl ether) 9.23 dimethyl sulphide 40.00 Heptaldeh~de 3.85 Paraldeh~de - 1.90 Propionic aci.d 36.92 10 Glacial acetic acid 0.40 General Services Administration ~ederal Suppl~
Service Interim ~ederal Specification ~he kitchen malodour concentrate was then diluted with odourless paraffin oil according to the following table to provide a basis for the odour scores recorded.
Concentration g kitchen odour .
per 1 paraffin oil Odour score 0.00~ 1 0.01 2 0.056 3 0.32 4 ~he particular dilutions of kitchen malodour chosen corresponded, so far as odour level was concerned, with the standard solutions 1 to 4 of iso~aleric acid referred to in the Deodorant Value ~est which were used for reference purposes by the panel of trained assessors in the evaluation of axilliary bod~ malodour as described in thàt ~est. ~he assessors were accordingl~ able to assess with remarkable consistency the malodour level in the screw topped jars emplo~ed in the malodour reduction tests described in Example 1 and the remaining Examples.
~he results which were anal~sed statisticall~ in each case and for Example 1 can be summarised as follows:

- 33 - cR.185 Malodour reduction value of polish Control polish Test polish A~erage scores 3.63 1.42 Malodour reduction value of 2~21 test polish lhis result indicated that the test polish possessed a substantial capacity for reducing malodour.
It should be understood that the 'Deodorant Value' of the deodorant co~position and the 'Malodour Reduction Value' of the corresponding product recorded in Example 1 cannot be compared numerically with each other, as the criteria involved in each test were different. ~he same consideration applies to the remaining Examples.

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_ 34 - cR.185 Example 2 ~ his example illustrates the invention in terms o~ a bleach product suitable for application to sinks, baths and ceramic sanitary ware to provide a cleaning, bleaching and deodorising action.
'~he test bleach product contained the following ingredients:
% w/w Caustic soda (47/0) 1.15 10 ~auric acid 0.9 Sodium stearate 0.61 EMPIG~ 0~ (30%) (a) 5.48 S~S (40%? (b) 1.88 Sodium silicate (47%) (c) 0.11 15 UMB (d) 0.~3 ~odium hypochlorite 15% 40 Calcium chloride 0.16 Deodorant Composition 2 0.2 Water to 100 (a) lauryl dimethyl amine oxide (b) sodium toluene sulphonate (c) 2:1 SiO2:~a20 (d) ultramarine blue pigment ~he formulation of Deodorant Composition 2 was as ~ollows:

ot~ r.~1~ m~,~

~z`~
_ ~5 _ cR~185 Deodorant Composition 2 Gomponents Parts Class Total in class Carvacrol 3.5 1 ) 4.5 ~hyme oil red 1.0 ~ergamot A~ 37 20.0 2 Pomeransol AB 413 6.0 2 ) 30.0 Petitgrain oil 4.0 2 6-Acetyl-1,1,3,4,4,6-hexa-methyl-tetrahydro-naphthalene 3.0 3 ) 8.0 ~-Methyl naphthyl ketone 5.0 3 3a-Methyl-dodecahydro-6,6,9a-trimethyl naphtho-2(2,1-b) furan 0.25* (4) 15 ~-~aphthyl methyl ether 9.0 4 9.0 Ingredients Citronellyl acetate 5.0 Dipropylene glycol 4.75 Geranyl nitrile 1.5 20 Indole 1.0 ~emongrass oil 3.0 ~ime AB 402 10.0 ~avendin oil 4.0 l-Menthol 8.0 25 ~eroli AB 78 6.0 Orange oil sweet 5.0 100 .0 eliminated from calculation - below threshold value of 0.5%.

~2 S 2~
- 36 - cR.185 ~otal amount of components 51-5 ~umber of components present 8 Average amount of each component 6.4 ~umber of classes represented 4 ~he deodorant value of Deodorant Composition 2 was determined b~ the Deodorant Value ~est as described herein before with the following results:
Deodorant Value of Deodorant Composition 2 Control ~est soap bar soap bar Average scores 3 ~4 2.7 Deodoran~ value (difference) 0.61 A control bleach product was also prepared which was identical except that the Deodorant Composition 2 was omitted.
~ he abilit~ of the test bleach compared with that of the control bleach product to reduce malodour was assessed generall~ according to the method described in Example l, but with the following differences.
~he bleach was poured into a lO ml capacity glass vial and the following procedure was adopted:
(i) fill vial with bleach to maximum volume of 10 ml, (ii) immediately empt~ vial ~y inverting it and allowing to drain for 30 minutes, ~iii) almost fill with water and shake, (iv) empty vial again and drain, (v) wipe interior of vial with paper tissues and leave for 1 hour.
Glass vials which had been treated in this manner with either test or control bleach product were then placed in a series of screw top glass jars together with the graded series of standard kitchen malodours as described i~ Example l. Malodour reduction values were assessed as previousl~ described.

' , . ' . ' ' : : , : ., .
.: , -, . .' ' l~Z2~2~
_ ~7 _ cR.185 ~ he statisticall~ analysed results were as follows:
Malodour reduction value of bleach Control bleach ~est bleach Average score 2.54 1.25 5 Malodour reduction value of 1.29 test bleach ~ his result indicated that the test bleach ver~
effectivel~ reduced malodour.

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- 38 - cR.185 Example ~
~ his example illustrates the invention in terms of a strippable polish suitable for applicat-ion to furniture.
~ he test polish contained the following ingredients:
% w/w Wax emulsion (a) 75-6 AlXaline soluble resin solution (b) 16.0 ~ributoxyethyl phosphate (c) 0.4 ~evelling aid (d) 0.5 10 Anionic surfactant solution (e) 3.0 Deodorant Composition 3 0.2 Ammonia (to adjust to pH 10.4) Water to 100 (a) the wax emulsion had the following formulation:
~ % w/w B Montan Wax K~0 (Eoechst) 12 Diethyl amino-ethanol 2.24 Water to 100 (b) ~Y~R0~ 812, a 10% aqueous emulsion of a styrene-maleic anh~dride copolymer (Monsanto) (c) KP 1~0 (Albright & Wilson) (d) FC 128, a 1% solution of the potassium salt of ~-ethyl-~-perfluoro-octane sulphon~l glycine (3M Co.)~
(e) Æ RGI~0~ 7, a 27% aqueous solution of a sulphonated derivative of 3,9-dieth~1-6-trideconol (Union Carbide) The formulation of Deodorant Composition 3 was as follows:
~k ~en~ m"~(C

.
.

: . : .. -.
-. .
...... . .

_ ~9 _ cR.185 Deodorant Com~osition 3 Components Parts Class Total in class Mousse de chene Yugo 1.25 1 ) 11.25 Pimento leaf oil 10.0 5 Benzoin SiAm resinoid 5.0 2 3ergamot AB 430 15.0 2 ) 25.0 Geranium oil 5.0 2 p-t-Amylcyclohexanone 5.0 3 )17.0 oc-iso-Methyl ionone - 12.0 3 10 Coumarin 4.0 4 1,3,4,6,7,8-Hexahydro- )7.0 4,6,6,7,8,8-hexamethyl-cyclopenta-~-2-benzopyran3O0 4 Diethyl phthalate 4.35 5 4.35 15 In~redien~s Hercolyn D 12.25 ~avendin oil 10.0 Musk ambrette 3.0 Rosenta ~B 380 10~0 20 Rose-D-oxide 0.15 100 .0 ~otal amount of components 64.6 ~umber of components present 10 Average amo~mt of each component ~ 6.5 25 ~ber o~ classes represented 5 ~ d ~no~ trale ~n~rk `: : `: :
:

~'~2 ~ 3 Z ~
- 40 - cR.185 ~ he deodorant value of Deodorant Composition 3 was determined by the Deodorant Value test as described hereinbefore with the following results:
Deodorant Value of Deodorant Compos tion 3 Control ~est soap bar soa~ bar Average scores 3.04 2.47 Deodorant value (difference) 0.57 A control polish was also prepared which was identical except that the Deodorant Composition 3 was omitted.
~ he ability of the test polish compared with that of the control polish to reduce malodour was assessed generally as described in Example 1.
~ he statistically anal~sed results were as follows:
Malodour reduction value of polish Control ~olish ~est polish Average scores 3.46 1.96 Malodour reduction value of 1.50 test polish ~his result indicated that the test polish possessed a considerable ability to reduce malodour.

' 2 ~ Z~
- 41 - cR.185 Example 4 ~ his example illustrates the invention in terms of a bleach product suitable for application to.sinks, baths and cer~m;c sanitar~ ware to provide cleaning, bleaching and deodorising action.
~ he test bleach product contained the following ingredients:
% ~T/W
Sodium hypochlorite (15% solution) 66.6 10 Amine oxide (30%) (a) 2.5 ~auric acid 0.23 ~odium hydroxide 1.00 Deodorant Composition 4 0.1 Water to 100 (a) laur~l dimethylamine oxide ~he formulation of Deodorant Composition 4 was as follows:

.- - . .

.. ~ . . - . . : :
, . . . -~ .
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.

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_ ~2 _ cR.185 Deodorant Com~osition 4 Components Parts Class ~otal in class Ethyl vanillin 0.2* (1) iso-Eugenol 5.0 1 ) 6.25 ~RG 201 1.25 Bergamot AB ~30 8.0 2 ) 15.0 Patchouli oil 7 2 2-n-Heptylcyclopentanone 0.5 3 ) 5 5 c<-iso-Methyl ionone 5.0 ~ ) 10 ~-~aphthyl methylether 7.5 4 7.5 p-t-Butylcyclohex~l acetate 4.3 5 Die~hyl phthalate 8.25 5 i-~onyl formate 5.0 5 ~ 26.55 ~onanediol-1,3-diacetate 4.0 5 15 Phenylethyl phenyl acetate 5.0 5 ~etrahydro muguol 6.0 6 6.0 Ingredients Citronella oil 6.0 Green Herbal AB 502 15.0 20 Indole 1.5 Rosenta A3 380 6~0 Sandalone 4.0 ~-Undecalactone 0.5 100 .0 eliminated from calculation - below threshold value of 0.5%.

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- 43 - cR.185 Total amount of components 66.8 Number of components present 14 Average amount of each component 4.8 ~umber of classes represented 6 The deodorant value o~ Deodorant Composition 4 was determined b~ the Deodorant Value Test as described hereinbefore with the following results:
Deodorant Value of Deodorant Composition 4 Control Test soap bar soap bar Average scores 3.25 2.10 Deodorant value (difference) 1.15 A control bleach product was also prepared which was identical except that the deodorant composition was omitted.
The ability of the test bleach compared ~ith that o~
the control bleach product to reduce malodour was assessed generall~ according to the method described in Example 2.
The statisticall~ anal~sed results were as follows:
Malodour reduction value of bleach Control Test bleach bleach Average values 2.46 1.42 Malodour reduc-tion value of 1.04 test bleach This result indicated that the test bleach possessed a substantial abilit~ to reduce malodour.

2 S ~ ~

- 44 - cR.185 Example 5 ~ his example illustrates the invention in terms o~
a thickened liquid abrasive product suitable for cleaning sinks, baths and ceramic sanitary ware to provide both a cleaning and a deodorising action.
~ he test liquid abrasive product contained the following ingredients:
% w/w C10 to C13 alkyl benzene sulphonate (D03S 102) 1.9 10 Potassium soap of distilled groundnut oil 0.6 Coconut diethanolamide 2.2 Sodium tripolyphosphate 5 Calcite 5 Deodorant Composition 5 0.3 15 Water to 100 ~ he formulation of Deodorant Composition 5 was as follows:

~ , ;26) - 45 - cR.185 , Deodorant Composition 5 Components Parts Class ~otal in class 3enzyl salicylate 15.0 1 )21.0 Mousse de chene Yugo 6.0 Bergamot AB 430 15.0 2 15.0 6-Acetyl-1,3,3,4,4,6-hexa-methyltetrahydro-naphthalene 2.5 3 ~5 p-t-Amylcyclohexanone 0.06* (3) 10 3a-Methyl-dodecah~dro-6,6,9a-trimethyl-naphtho-2~2,1 )0,75 4 0,75 ~iethyl phthalate 8.04 5 8.04 ~onanolide-1,4 0.2* (5) Dimyrcetol 16.0 6 16.0 I~gredients Cinnamic alcohol 5.0 Dimethyl benzyl carbinyl acetate 2.5 20 Dipropylene glycol 14.25 Geraniol 5.0 iso-Butyl phenyl acetate 5.0 Methyl salicylate 0.5 Pelargene 4.0 25 ~richloromethyl phen~l carbinyl acetate 0.2 100 .0 eliminated from calculation - below threshold value of o.5%.

- . ~ -.

.. : , - . , ~: , _ 46 - cR.185 ~otal amount of components 63.29 Number of components present 7 Average amount of each component 9.0 Number of classes represented 6 The deodorant value of Deodorant Composition 5 was determined b~ the Deodorant Value Test as described hereinbefore with the following results:
3eodorant Value of Deodorant Composition 5 Control lest soap bar soap bar Average scores 3.30 2.70 Deodorant value (difference) 0.60 A control liquid abrasive cleaner product was also prepared which was identical except that the Deodorant Composition 5 was omitted.
~he ability of the test liquid abrasi~e cleaner compared with that of the control liquid abrasive cleaner to reduce malodour was assessed generally according to the method described in E~ample 2.
~he statistically anal~sed results were as follows:
Malodour reduction value of liquid abrasive cleaner Control ~est cleaner cleaner ~verage scores 3.14 2.25 25 Malodour reduction value of 0.89 test cleaner ~ he results indicated that the test liquid abrasive cleaner was capable of reducing malodour to a significant extent.

.:
. : .. ..
: , -, ~

2 ~ % ~
- 47 - cR.185 Example 6 ~ his example illustrates the invention in terms of a liquid abrasive floor cleaner product.
~ he test cleaner product contained the following ingredients:
% w/w Clo to Cl~ alk~1 benzene sulphonate (DOB~ 102) 3.
Potassium soap 1.1 Coconut diethanolamide . 4.0 lO Sodium tripolyphosphate 9.0 Calcite lG.0 Deodorant Gomposition 6 0.
Water to lO0 ~ he formulation of Deodorant Composition 6 was as follows:

.. . .

, .

2~
_ 48 _ cR.185 Deodorant Composition 6 Com~onents Parts Class ~otal in class Clove lea~ oil 10.0 1 ) 11.25 ~RG 201 1.25 5 Petitgrain oil 10.0 2 10.0 p-t-~utyl~Y-meth~l hydro cinn~mic aldehyde 15.0 ~ 15.0 3a-Met~yl-dodecahydro-6,6 9a-trimethylnaphtho-2(2,1-b~
furan 0.5 4 0-5 o-t-Butylcyclohexyl acetate2.0 5 Diethyl phthalate 9.25 5 ) 21.25 i-No~yl acetate 10.0 5 Phenyl ethyl alcohol 10.0 6 10.0 In~redients Benzyl propionate 4.0 ~ergamot oil 15.0 Dimethyl benzyl carbinyl acetate 5.0 20 iso-Butyl benzoate 5.0 ~eroli oil 3.0 100.0 ~otal amount o~ components 68.0 ~umber of components present 9 25 Average amount o~ each component 7.6 ~umber o~ classes represented 6 , -` .

~Z~Z~

- 49 - cR~185 ~ he deodorant value of the Deodorant Composition 5 was determined by the Deodorant Value Test as described hereinbefore with the following results:
Deodorant Value of Deodorant Composition 6 Control ~est soap bar soaP bar Average scores ~.25 2.33 Deodorant value (differences) 0.92 A control liquid abrasive floor cleaner product was also prepared without the Deodorant Composition 6.
~ he abilit~ of the test liquid abrasive cleaner compared with that of the control liquid abrasive cleaner to reduce malodour was assessed generall~ according to the method described in Example 2.
~he statistically anal~sed results were as follows:
Malodour reduction value of liquid abrasive floor cleaner Control ~est floor floor cleaner cleaner Average scores 2.89 2.00 Malodour reduction value of 0.89 test liquid floor cleaner ~ he results indicated that the test liauid abrasive cleaner was Gapable of reducing malodour to a significa~t extent.

; ~ :

Z~
- 50 - cR.185 Example ~
This example illustrates the invention in terms of a powder abrasive surface cleaning product.
~ he test powder abrasive product contained the 5 following ingredients:
/a W/W
C to Cl6 alkyl benzene sulphonate flake 10 (DOBS 055) (85% AD) 3.0 ~risodium orthophosphate 3.0 10 Deodorant Composition 5 0.3 ~elspar to 100 A control powder abrasive product was also prepared without the Deodorant Composition 5.
The ability of the test powder abrasive product compared with that of the control powder abrasive product to reduce malodour was assessed in the following manner:
0.5g powder was applied to a damp tissue and rubbed onto the outer surface of a glass vial (surface æea 25 cm~) and allowed to dry for 30 minutes. The outer surface of the vial was then wiped clean with a fresh damp tissue and the vial was allowed to stand at room temperature for a further 30 minutes. qhe vial was then placed in a screw top jar together with standard malodour as generally described in Example 1, sufficient ~i~ls being so prepared to provide replicates for both test and control abrasive powders and for each of the four malodour concentrations. One hour later, each jar was uncapped and the odour within assessed according to a hedonic scale b~ a panel of trained assessors.
~he statistically anal~sed results were as follows:
Malodour reduction value of powder abrasi~e surface cleanin~ product Control ~est powder powder cleaner cleaner Average scores 3.04 1.08 Malodour reduction value ol 1.96 test powder cleaner - ~he results indicate that the test powder abrasive cleaner product was very effecti~e in reducing malodour~

: ' " , .: . ,- : ~
~ ~ .
. . . :

- 51 - - cR.185 xample 8 ~ his example illustrates the invention in terms of a window polishing product.
~ he test polishing product contained the following 5 ingredients:
% '~T/W
Phase A
~ilicone Fluid D C 200/50cs (a) 1.0 B ~MUL~OGEN M~ 12 (b) 1~5 10 SFF~T~SO~ T (c) 12 Phase B
Deionised water to 100 Phase C
Isoprop~l alcohol 20 15 Deodorant Composition 2 0.4 (a) A siloxane manufactured by Dow Corning (b) Oleyl polyglycolether manufactured by ~arbwerke Hoechst AG
(c) A high boiling aliphatic hydrocarbon solvent manufactured by Shell Chemicals ~imited.
~he poloshing product was prepared as follows:
Phase A was warmed to 70 to 75C and added to phase B
at the same temperature with rapid stirring~ Phase C warmed to 45C then added to the mixed phases A&B and cooled with slow stirring. A loose emulsion was obtained ~hich needed stirring or shaking thoroughly before use.
A control polishing product was also prepared without Deodorant Composition 2.
~ he ability of the test polishing product compared with 3 that o~ the control polishing product to reduce malodour was assessed generally according to the method described in Example 2.
- ~he statistically analysed res~ts were as follows:

~e~ ~r~ ~a~

~Z~i2~
- 52 - cR.185 Malodour reduction value of window polishing product Control Test polishing polishing product product 5 Average scores 3 9 2.75 Malodour reduction value of 0.34 test polishing product (difference) The results indicated that the test window polishin~
product possessed a marked ability to reduce malodour.

~' , ` ~ :

.- . - . . . - :
.' ~. ' ' 2~) _ 5~ ~ cR.185 Example 9 ~his example illustrates the invention in terms of an aerosol furniture polish.
~he test aerosol furniture polish contained the 5 following ingredients:
% W/W
Phase A
MO~AN Wax (a) 2~0 Hoechst W æ ESS (b) 2~0 10 ~MnLSOG~ OG (c) 1.5 Phase B
Silicone ~luid ~111/300(d) ~.0 ~HEL~SO~ ~ (e) 40.0 Phase C
15 Deionised water to 100 Preservative ` q.s.
Phase D
Deodorant Composition 3 0.3 Aerosol ~ill 20 Concentrate 82.0 Hydrocarbon propellant (f) 18.0 (a) HO~SCES~ ~A~, an ester was manufactured by Farbwerke Xoechst AG.
(b) An ester wax based on MO~ W~Y
(c) Digl~ceryl sesquioleate manufactured by ~arbwerke ~oechst AG.
(d) A linear dimethyl polysiloxane (300cs) at 25C manufactured by ICI.
(e) A high boiling, high flash aliphatic hydrocarbon ~isoparaffins) solvent manufactured by Shell Chemicals.
(f) A blend of n-butane, n-propane and iso-butane havi~g a pressure of 40 psig (2.812 kg/sq cm).

.
-- . `~ ~ ' 2~
- 54 - cR.185 ~he aerosol furniture polish was prepared as follows:
Phase A was melted by heating it at 90C. Phase ~ was heated to 80C and added to Phase A. Phase C was heated to 80C and added to -the mixture of phases A&B with rapid stirring. ~he mixture was cooled rapidl~ with stirring to 20C. Phase D was finall~ added with further stirring to provide the concentrate which was filled into aerosol cans together with the propellant mixture.
A control aerosol furniture polish was also prepared without the addition of phase C (Deodorant Composition 3).
~ he abilit~ of the test aerosol furniture polish compared with that of the control furniture polish to reduce malodour was assessed in the following manner:
Smooth pieces of boxwood of surface area of 50 cm2 were each spra~ed for 1 second at a distance of 5 cm with either the test or control furniture polish and left to dr~
at room temperature for 10 minutes. ~ach boxwood piece was wiped with a clean cloth to remove surplus polish and then buffed lightl~ to obtain a shine.
~he boxwood pieces were left at room temperature for a total of one hour after the initial spra~ing with polish and ~hen each was placed in a series of screw top aars each containing 5 ml of one of-the four concentrations of standard kitchen malodour. ~he jars were sealed and left for one hour and then the malodour in each àar was assessed according to the hedonic scale as previousl~ described in Example 1.
~ he statistically analysed results were as follows:
~alodour reduction value of aerosol furniture polish Control ~olish est ~olish Average scores 2.15 1.50 Malodour reduction value 0.65 of aerosol furniture polish (difference) ~he results indicate that the test aerosol furniture polish was effective in reducing m~lodour~

.

.

f~
_ 55 _ cR.185 APPE~DIX
~ he following glossary provides further information, including the suppliers' names, which ~Jill aid identification of some of the aforementioned deodorant 5 components and ingredients.

Dim~rcetol - Dim~rcetol (I~F) Hercol~n D - ~etrah~dro abietate +
dihydro abietate (HP) LRG 201 - Oakmoss speciality (RB) 10 Pelargene - Pelargene (PP~) Rose-D-Oxide - Rose oxide synthetic (PP~) Sandalone - Sandalone (PP~) Perfume Houses HP - Hercules Powder Co.
IF~ - International Flavour Fragrances Inc.
RB - Roure Bertrand PP~ - Proprietary Perfumes ~td.

All materials which are classified b~ a name and number, such as those having the 'AB' notation, are obtainable from Proprietary Perfumes ~imited.

-....

Claims (21)

- 56 - cR.185 CAN*

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

1. A deodorant product suitable for application to surfaces other than human skin which product comprises:
(i) a deodorising amount of a deodorant composition comprising essential materials having a lipoxidase-inhibiting capacity of at least 50%, or a Raoult variance ratio of at least 1.1, the deodorant composition having a deodorant value of from 0.50 to 3.5 as measured by the Deodorant Value Test; and (ii) a carrier for the deodorant composition chosen from abrasive materials, bleaching agents, waxes, film-forming polymers, or mixtures thereof.

2. A deodorant product according to claim 1, in which the deodorant composition has a deodorant value of from 1.00 to 3.5 as measured by the Deodorant Value Test.

3. A deodorant product according to claim 1, in which the deodorant composition has a deodorant value of from 1.50 to 3.5 as measured by the Deodorant Value Test.

4. A deodorant product according to claim 1, in which the deodorant composition comprises from 45 to 100% by weight of deodorant active components, said components having a lipoxidase-inhibiting capacity of at least 50% or a Raoult variance ratio of at least 1.1, said components being classified into six classes consisting of:
Class 1 : phenolic substances Class 2 : essential oils, extracts, resins and synthetic oils Class 3 : aldehydes and ketones Class 4 : polycyclic compounds Class 5 : esters Class 6 : alcohols _ 57 - cR.185 CAN

provided that where a component can be classified into more than one class, it is placed in the lower or lowest numbered class;
said components being so selected that (a) the deodorant composition contains at least five components of which at least one must be selected from each of Class 1, Class 2 and Class 4;
(b) the deodorant composition contains components from at least 4 of the 6 classes; and (c) any component present in the deodorant composition at a concentration of less than 0.5% by weight of said composition is eliminated from the requirements of (a) and (b).

5. A deodorant product according to claim 4, in which the amount of deodorant components present in said class comprising phenolic substances and said class comprising essential oils, extracts, resins and synthetic oils and said class comprising polycyclic compounds, is at least 1% by weight of the deodorant composition for each of said classes, and the amount of deodorant components present in said further class chosen from the remaining three classes is at least 1% by weight of the deodorant composition.

6. A deodorant product according to claim 4 in which the average concentration of all such components present is at least 5% by weight where four of said classes is represented, or at least 4.5% by weight where five or six said classes is represented.

7. A deodorant product according to claim 4,5 or 6, in which the amount of deodorant components present in said class comprising phenolic substances and said class comprising essential oils, extracts, resins and synthetic - 58 - cR.185 CAN

oils and said class comprising polycyclic compounds, is at least 3% by weight of the deodorant composition for each of said classes and the amount of deodorant components present in said further class chosen from the remaining three classes is at least 3% by weight of the deodorant composition.

8. A deodorant product according to claim 4,5 or 6, in which at least five of the classes are represented.

9. A deodorant product according to claim 4, 5 or 6, in which all six classes are represented.

10. A deodorant product according to claim 4,5 or 6, in which the deodorant components are chosen from:
Class 1 - Phenolic substances iso-Amyl salicylate Benzyl salicylate Carvacrol Clove leaf oil Ethyl vanillin iso-Eugenol Mousse de chene Yugo Pimento leaf oil Thyme oil red Class 2- Essential oils, extracts, resins, "synthetic"
oils (denoted by 'AB' Benzoin Siam resinoid Bergamot AB 37 Bergamot AB 430 Geranium AB 76 Geranium oil Opoponax resinoid Patchouli oil Petitgrain oil Pomeransol AB 314 - 59 - cR.185 CAN

Class 3 - Aldehydes and ketones 6-Acetyl-1,1,3,4,4,6-hexamethyltetrahydro-naphthalene p-t-Amyl cyclohexanone p-t-Butyl-.alpha.-methyl hydrocinnamic aldehyde 2-n-Heptyl cyclopentanone .alpha.-iso-Methyl inonone .alpha.-Methyl naphthyl ketone Class 4- Polycyclic compounds Coumarin 1,3,4,6,7,8-Hexahydro-4,6,6,7,8,9-hexamethyl cyclopenta-?-2-benzopyran 3a-Methyl-dodecahydro-6,6,9a-trimethynapththo-(2,1-b)furan .beta.-Naphtyl methyl ether Class 5 - Esters o-t-Butylcyclohexyl acetate p-t-Butylcyclohexyl acetate Dietyl phthalate Nonanediol-1,3-diacetate Nonanolide-1:4 i-Nonyl acetate i-Nonyl formate Class 6 - Alcohols Dimyrcetol Phenylethyl alcohol Tetrahydromuguol

11. A deodorant product according to claim 1, in which the carrier is an abrasive material chosen from quartz, pumice, pumicite, titanium dioxide, silica sand, calcuim carbonate, zirconium silicate, diatomaceous earth, whiting, felspar, alumina, corundum, volcanic ash, bentonite, magnesium oxide, magnesium carbonate, chalk, dolomite, shell, talc, calcite or mixtures thereof.

- 60 - cR.185 CAN

12. A deodorant product according to claim 1, in which the carrier is a bleaching agent chosen from hypochlorites, hypobromites or precursors thereof or mixtures thereof.

13. A deodorant product according to claim 1, in which the carrier is a wax chosen from natural waxes, synthetic waxes, waxy substances or mixtures thereof.

14. A deodorant product according to claim 1, in which the carrier is a film forming polymer chosen from polymers formed from polymerisable ethylenically unsaturated monomers chosen from styrene, C1 to C12 alkyl methacrylates, C1 to C12 alkyl acrylates, C1 to C12 acrylonitrile, C1 to C12 methacrylonitrile; non-volatile silicone fluids and 'waxes';
graft polymers of styrene-maleic anhydride resins with heterocyclic compounds chosen from .epsilon.-caprolactam, 2-pyrrolidone and N-methyl-2-pyrrolidone and the water soluble alkali metal or ammonium salts of these graft polymers; copolymers chosen from ethylacrylate-acrylic acid copolymers, styrene-acrylate copolymers, ethyl acrylate-methacrylic acid copolymers, rosin acrylate copolymers, organic polycarboxylic acid copolymers or mixtures thereof.

15. A deodorant pradoct according to claim 1,11 or 12, which is a liquid abrasive cleaner.

16. A deodorant product according to claim 1,11 or 12, which is a scouring powder.

17. A deodorant product according to claim 1,11 or 12, which is a liquid bleach product.

- 61 - cR.185 CAN*

18. A deodorant product according to claim 1,13 or 14, which is a polish.

19. A deodorant product according to claim 1,13 or 14, which is a floor cleaner and polish.

20. A process for preparing a deodorant product as defined in claim 1, which comprises blending a deodorant composition with a carrier for the deodorant composition chosen from abrasive materials, bleaching agents, waxes, film forming polymers or mixtures thereof, the deodorant composition comprising essential materials having a lipoxidase-inhibiting capacity of at least 50%, or a Raoult variance ratio of at least 1.1, the deodorant composition having a deodorant value of from 0.50 to 3.5 as measured by the Deodorant Value Test.

21. A method for suppressing malodour which comprises deploying an effective amount of the deodorant product as defined in claim 1.