Fragrance composition and method for reducing and / or eliminating habituation to an odour
A fragrance composition with trigeminal-stimulating and alerting materials prevents habituation by enhancing noticeability, addressing the issue of fragrance compositions becoming less noticeable over time.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- TAKASAGO INTERNATIONAL CORP
- Filing Date
- 2025-12-09
- Publication Date
- 2026-06-18
AI Technical Summary
Conventional fragrance compositions lead to habituation over time, reducing their noticeability, and existing solutions like increasing application frequency or switching fragrances can be overwhelming or offensive.
A fragrance composition combining trigeminal-stimulating compounds, alerting materials, and fragrance compounds, where the alerting materials include sulphur or nitrogen atoms or carboxylic acids, to enhance noticeability and prevent habituation.
The combination maintains fragrance noticeability over extended periods, reducing habituation effectively.
Smart Images

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Abstract
Description
[0001] FRAGRANCE COMPOSITION AND METHOD FOR REDUCING AND / OR ELIMINATING HABITUATION TO AN ODOUR
[0002] Field of the Invention
[0003] The present invention relates to fragrance compositions, e.g. for use in fragranced consumer products, as well as methods for reducing and / or eliminating consumer fragrance habituation, said fragrance compositions combining at least one trigeminal- stimulating compound, at least one alerting material, and at least one fragrance compound. The present invention also concerns consumer products, such as household products, laundry products, personal care and cosmetic products, fine fragrances, containing fragrance compositions according to the invention.
[0004] Background
[0005] Conventional perfuming compositions can provide desirable scents initially, but over time consumers can become habituated to the perfume raw materials that form the fragrance. This means that after a period of time of continual exposure, users can no longer detect the presence of the fragrance. The habituation problem can be found with any kind of perfume raw materials as long as they are present on the skin and in the air around the consumer for long periods and therefore have ample time to induce habituation. Fragrance compositions can thus become less noticeable due to a consumer's decrease in sensitivity following prolonged exposure to these fragrance compositions. To avoid habituation possible options are to replace or modulate the intensity of the fragrance source.
[0006] To combat the habituation effect and enable consumers to continually perceive an original fragrance, especially over extended periods, users tend to progressively employ larger quantities of the fragrance composition, for example by regularly reapplying the fragrance throughout the day. Device manufacturers have also searched for solutions such as repeatedly switching fragrances from one to another. However, these solutions have drawbacks, for example the use of a larger quantity of the fragrance composition may result in an initial scent that is overwhelming and potentially offensive to the consumers and those in their vicinity.
[0007] US 9,708,568 Al describes a fragrance composition comprising a fragrance oil that resists fragrance habituation, said fragrance oil comprising a low percentage of one or more perfume raw materials comprising a thiol moiety, a sulphide moiety, a thiazole moiety, an oxathiane moiety, an oxygen, sulphur and nitrogen, a pyrazine moiety, a nitrile moiety, an indole moiety, an oxime moiety, an amine moiety, an isothiocyanate, a diamine moiety, and mixtures thereof.
[0008] However, there is still a demand for enhanced fragrance compositions that offer enduring and appealing scents, capable of minimizing or eradicating the habituation effect experienced by consumers over long periods of time, without altering the consumers' regular habits.
[0009] Through mammals and humans' evolution, olfaction has been refined to produce chemosensory signal when detecting threats and source of danger (fire, diseases, poison, predators, etc.), that would mobilize all body resources to face this danger by "fight" or "flight". The fight or flight response is a survival mechanism allowing organisms to react quickly to a situation that is life-threatening. This response is controlled by the sympathetic nervous system, which is one part of the autonomic nervous system. As such, it is an uncontrolled phenomenon, and the sensory input can even be perceived at an unconscious level.
[0010] Without being bound by any theory, the Inventors have observed that it is possible to act at two levels with specific compounds to prevent habituation:
[0011] Alertness olfactory cues can give importance to the olfactory percept in terms of noticeability and, consequently, prevent habituation behaviour. This leads to the primary function of olfaction, which is to detect threats in order to avoid danger. In this way, certain compounds can trigger alertness behaviour (increase of noticeability and reduction of habituation).
[0012] Physicochemical properties of olfactory products can have an influence on the level of olfactory signal production by facilitating the activation, co-activation or inhibitory effect of olfactory receptors, etc.
[0013] The use of compounds associated with danger prevents the phenomenon of habituation, which is a behavioural response to the adaptation of sensory neurons to prolonged exposure to stimuli.
[0014] The Inventors have now shown that the addition of a trigeminal dimension to a fragrance comprising a compound that triggers alertness behaviour increases further the response to a continuous olfactory stimulus and prevents habituation. The Inventors have shown that the use of trigeminal compounds in combination with alerting materials results in a fragrance composition that reduces and / or eliminates habituation to prolonged exposure to this fragrance composition. Surprisingly, the Inventors have also discovered that the combination of the alerting materials and trigeminal-stimulating compounds of the invention enabled a long-lasting effect and noticeability to be maintained over a much longer period of time. of the invention
[0015] In one aspect, the present invention provides a fragrance composition comprising:
[0016] (a) at least one, and preferably at least two, trigeminal-stimulating compounds,
[0017] (b) at least one, and preferably at least two, alerting materials which comprise at least one sulphur atom or at least one nitrogen atom or at least one carboxylic acid or carboxylate moiety, and
[0018] (c) at least one fragrance compound other than said at least one trigeminal-stimulating compound (a) and other than said at least one alerting material (b), wherein the at least one alerting material (b) represents from 1x1010to 3x101%, preferably from lxlO-9to 2x101%, more preferably from lxlO-8to 2x101%, even more preferably from lxlO-7to 1x101%, and even more preferably from 1x1010to 1x101%, by weight of the total of the fragrance composition.
[0019] In another aspect, the present invention relates to the use of at least one trigeminal- stimulating compound (a) in combination with at least one alerting material (b), in a fragrance composition, for reducing and / or eliminating habituation to the odour of this fragrance composition.
[0020] In another aspect, the present invention relates to a method for reducing and / or eliminating habituation to a fragrance composition, comprising the step of adding at least one trigeminal-stimulating compound (a) in combination with at least one alerting material (b) which comprises at least one sulphur atom or at least one nitrogen atom or at least one carboxylic acid or carboxylate moiety, to the fragrance composition.
[0021] Figure 1 illustrates the perceived fragrance intensity following continuous exposure of a floral marine fragrance composition (reference) from an electric air diffuser, of the same fragrance composition with a trigeminal-stimulating compound (a) added (comparative), of the same fragrance composition with an alerting material (b) comprising at least one sulphur atom added (comparative), and of the same fragrance composition with a trigeminal-stimulating compound (a) and an alerting material (b) comprising at least one sulphur atom added (invention). Figure 2 illustrates the perceived fragrance intensity following continuous exposure of a floral marine fragrance composition (reference) from an electric air diffuser, of the same fragrance composition with a trigeminal-stimulating compound (a) added (comparative), of the same fragrance composition with an alerting material (b) comprising at least one carboxylic acid moiety added (comparative), and of the same fragrance composition with a trigeminal-stimulating compound (a) and an alerting material (b) comprising at least one carboxylic acid moiety added (invention).
[0022] Figure 3 illustrates the perceived fragrance intensity following continuous exposure of a linen fragrance composition (reference) from an automatic spray air diffuser, of the same fragrance composition with a trigeminal-stimulating compound (a) added (comparative), of the same fragrance composition with another alerting material (b) comprising at least one nitrogen atom added (comparative), and of the same fragrance composition with a trigeminal-stimulating compound (a) and an alerting material (b) comprising at least one nitrogen atom added (invention).
[0023] Figure 4 illustrates the perceived fragrance intensity following continuous exposure of a linen fragrance composition (reference) from an automatic spray air diffuser, of the same fragrance composition with a trigeminal-stimulating compound (a) added (comparative), of the same fragrance composition with another alerting material (b) comprising at least one sulphur atom added (comparative), and of the same fragrance composition added with a trigeminal-stimulating compound (a) and an alerting material (b) comprising at least one sulphur atom added (invention).
[0024] Detailed description of the invention
[0025] Unless otherwise stated, all percentages are weight percentages.
[0026] Unless otherwise indicated, all chemical terms have the meanings defined by the IUPAC Compendium of Chemical Terminology, 2ndEdition compiled by A. D. McNaught and A. Wilkinson, published by Blackwell Scientific Publications Oxford 1997, and IUPAC Nomenclature of Organic Chemistry, published by Blackwell Scientific Publications Oxford 1993 ISBN 0632034882.
[0027] Certain substances, notably perfumery molecules, may exist as distinct isomers (or as mixture of distinct isomers). Hereinafter, they may be identified also by means of their CAS number. In these cases, the CAS number of a single isomer is reported. However, and unless otherwise indicated, the reference shall be understood to cover all existing isomers and isomer mixtures. In the context of the invention, the term "habituation" refers to the long-term loss of perceived intensity and / or awareness and / or sensitivity of a user or tester to an odour. Habituation can be seen as a form of learning that can result from prolonged / repeated exposure to an odour.
[0028] In the context of the present invention, the various embodiments described in the various aspects of the invention can be combined.
[0029] In a first aspect, the present invention relates to a fragrance composition comprising:
[0030] (a) at least one, and preferably at least two, trigeminal-stimulating compounds,
[0031] (b) at least one, and preferably at least two, alerting materials which comprise at least one sulphur atom or at least one nitrogen atom or at least one carboxylic acid or carboxylate moiety, and
[0032] (c) at least one fragrance compound other than said at least one trigeminal-stimulating compound (a) and other than said at least one alerting material (b), wherein the at least one alerting material (b) represents from 1x1010to 3x101%, preferably from lxlO-9to 2x101%, more preferably from lxlO-8to 2x101%, even more preferably from lxlO-7to 1x101%, and even more preferably from 1x1010to 1x101%, by weight of the total of the fragrance composition.
[0033] In the sense of the invention, a trigeminal-stimulating compound (a) is a compound which generates a trigeminal perception. The trigeminal-stimulating compound (a) of the invention can induce a variety of different sensations by chemical activation of ion channels. In particular, the trigeminal-stimulating compounds (a) have been identified either because they have shown in vitro activity on at least one of the following Transient Receptor Potential (TRP) (not exclusive) receptors and / or because they have been shown to trigger a sensory perception associated with the trigeminal sensations (a perceived cooling, warming and / or tingling sensation):
[0034] - the TRPM8 gene (Transient Receptor Potential cation channel subfamily M (Melastatin) member 8), when the trigeminal-stimulating compound is a cooling compound (Y. Yin et al., Science 363, 945 (2019)),
[0035] - the TRPV1 gene (Transient Receptor Potential cation channel subfamily V member 1), when the trigeminal-stimulating compound is a warming compound (Turning up the Heat on Pain: TRPV1 Receptors in Pain and Inflammation, Editors: Annika B. Malmberg, Keith R. Bley), and - the TRPA1 gene (Transient Receptor Potential cation channel subfamily A member 1), when the trigeminal-stimulating compound is a tingling compound (T. Me Donald et al., Chemesthesis: Chemical Touch in Food and Eating, March 2016, Wiley-Blackwell).
[0036] The trigeminal-stimulating compound (a) can also be known as chemesthetic compound. In particular, the trigeminal-stimulating compound (a) of the invention is selected from cooling compounds, warming compounds, tingling compounds, and mixtures thereof, and preferably from cooling compounds or warming compounds, and mixtures thereof.
[0037] In some embodiments, the trigeminal-stimulating compound (a) is a cooling compound. The cooling compound may be selected from menthol, menthone, camphor, pulegone, pulegol, isopulegol (COOLACT® P), cineole, 2-isopropyl-N-2,3-trimethylbutyramide, N- ethyl-2-isopropyl-5-methylcyclohexane carboxamide, ethyl 3-(p-menthane-3-carboxamido) acetate, N-(4-methoxyphenyl)-p-menthanecarboxamide, N-ethyl-2,2- diisopropylbutanamide, N-cyclopropyl-5-methyl-2-isopropylcyclohexanecarboxamide, N- (l,l-dimethyl-2-hydroxyethyl)-2,2-diethylbutanamide, N-(4-cyanomethylphenyl)-p- menthanecarboxamide, N-(2-(pyridin-2-yl)ethyl)-3-p-menthanecarboxamide, N-(2- hydroxyethyl)-2-isopropyl-2,3-dimethylbutanamide, cyclopropanecarboxylic acid (2- isopropyl-5-methyl-cyclohexyl)-amide, N-[4-(2-amino-2-oxoethyl)phenyl]-p- menthanecarboxamide, menthyl pyrrolidone carboxylate, cubebol, icilin, 2-isopropyl-5- methylcyclohexyl 4-(dimethylamino)-4-oxobutanoate, N-benzo[l,3]dioxol-5-yl-3-p- menthanecarboxamide, N-benzooxazol-4-yl-3-p-menthanecarboxamide, N-4- ([l,2,4]triazol-l-yl)-phenyl-3-p-menthanecarboxamide, p-menthane carboxamide, N-4- (pyrazol-l-yl)-phenyl-3-p-menthanecarboxamide, N-(l-isopropyl-l,2-dimethylpropyl)-l,3- benzodioxole-5-carboxamide, N-(l-methyl-l-isopropylbutyl)benzamide, fenchyl-N,N- diemethylsuccinamide, fenchyl monosuccinate, ethyl fenchyl malonate, bornyl monosuccinate, isobornyl monosuccinate, menthyl 3-oxobutyrate, menthyl 3- oxopenta noate, 3-methoxypropane-l,2-diol, 3-methoxy-2-methylpropane-l,2-diol, p- menthane-3,8-diol (COOLACT® 38D), 2-1-methoxyethan-l-ol, 3-methoxypropan-l-ol, 4- methoxybutan-l-ol, methyl 3-hydroxybutyrate, 6-isopropyl-9-methyl-l,4-dioxaspiro-(4,5)- decane-2-methanol, 2-[(2-p-methoxy)ethoxy]ethanol, methyl succinate, methyl glutarate, dimethyl succinate, dimethyl glutarate, menthyl acetate, menthyl lactate, menthone glycerin ketal, mint oil, peppermint oil, peppermint cyclohexanone, spearmint oil, eucalyptus oil, l-(2-hydroxy-4-methylcyclohexyl)ethanone (COOLACT® HK), pennyroyal oil, armoise oil, cornmint oil, cinnamon oil, borneol, ringonol, sinensal, piperitone thymol, and mixtures thereof. In a preferred embodiment, the trigeminal-stimulating compound (a) is a cooling compound selected from menthol, menthone, camphor, pulegol, isopulegol (COOLACT® P), menthyl acetate, menthyl lactate, p-menthane-3,8-diol, mint oil, l-(2-hydroxy-4- methylcyclohexyl)ethanone (COOLACT® HK), spearmint oil, cinnamon oil, and mixtures thereof.
[0038] In another preferred embodiment, the trigeminal-stimulating compound (a) is a cooling compound selected from pulegol, isopulegol (COOLACT® P), menthyl acetate, menthyl lactate, p-menthane-3,8-diol, l-(2-hydroxy-4-methylcyclohexyl)ethanone (COOLACT® HK), and mixtures thereof.
[0039] In a particularly preferred embodiment, the trigeminal-stimulating compound (a) is isopulegol (COOLACT® P). Isopulegol is available either as a racemic mixture (CAS 7786- 67-6), or as the (-)-isomer (CAS 89-79-2). In one embodiment isopulegol is available as COOLACT® P, a product from Takasago. The isopulegol of the invention may have an optical isomer and chemical purity of greater than 90%, preferably greater than 95%, more preferably greater than 97.5%, and even more preferably greater than 99%. Isopulegol purity is determined by gas chromatography using the method described in US 5,773,410 by summing the area percent of impurity peaks and subtracting these from the total measured area which is taken to be 100%.
[0040] Menthol is available either as the racemate (CAS 89-78-1) or as the (-) isomer (CAS 2216- 51-5), the latter being the main form occurring in nature.
[0041] In some embodiments, the trigeminal-stimulating compound (a) is a warming compound. In a preferred embodiment, the warming compound is selected from vanillyl ethyl ether, vanillyl n-propyl ether, vanillyl isopropyl ether, vanillyl butyl ether, vanillin, vanillyl alcohol, ethyl vanillin, ethyl vanillyl alcohol, vanitrope, veraspice, ethyl maltol (veltol plus), 2- ethoxy-4-methylphenol, vanillin isobutyrate (Isobutavan®), cinnamaldehyde, N- acetylcysteine ethyl ester (NACET), guaiacol, phenyethyl alcohol, cyclohexanone, perilla aldehyde, gingerol, spice oils such as ginger oil, pepper oil, their extracts, and mixtures thereof, and preferably vanillyl ethyl ether, vanillyl n-propyl ether, vanillyl isopropyl ether, vanillyl butyl ether, vanitrope, veraspice, 2-ethoxy-4-methylphenol, vanillin isobutyrate (Isobutavan®), N-acetylcysteine ethyl ester (NACET), guaiacol, cyclohexanone, perilla aldehyde, gingerol, spice oils, their extracts, and mixtures thereof.
[0042] Such warming compounds are commercially available for example under the tradenames of Hotact® VEE from Takasago for vanillyl ethyl ether, or Hotact® VBE from Takasago for vanillyl butyl ether. In some embodiments, the trigeminal-stimulating compound (a) is a tingling compound. In a preferred embodiment, the tingling compound is selected from elemol, elemicin, elemi oil, lime oxide, citral, L-carvone, ocimene quintoxide, 2-isopropenyl-5-methyl-5- vinyltetrahydrofuran, jambu oleoresin, spilanthol, di hydromyrcene, perilla aldehyde, and mixtures thereof, preferably elemol, elemicin, ocimene quintoxide, 2-isopropenyl-5- methyl-5-vinyltetrahydrofuran, jambu, oleoresin, spilanthol, di hydromyrcene, perilla aldehyde, and mixtures thereof, and more preferably elemi oil, lime oxide, citral, L- carvone, and mixtures thereof.
[0043] Commercial lime oxide is a mixture of compounds obtained by acidic isomerisation of linalool, which contains ocimene quintoxide (citroxide) (CAS 7416-35-5). 2-isopropenyl-5- methyl-5-vinyltetrahydrofuran (CAS 13679-86-2) can also be obtained by acidic isomerization of linalool. In the sense of the invention, the word lime oxide encompasses all the stereoisomeric forms of ocimene quintoxide and 2-isopropenyl-5-methyl-5- vi nyltetra hyd rofura n .
[0044] In some embodiments, the at least one trigeminal-stimulating compound (a) represents from 0.01 to 5%, preferably from 0.02 to 2%, and more preferably from 0.05 to 1%, by weight of the total of the fragrance composition. In some embodiments, the at least one trigeminal-stimulating compound represents from 0.01 to less than 1%, preferably from 0.02 to less than 1%, and more preferably 0.05 to 0.9%, by weight of the total of the fragrance composition.
[0045] In the sense of the invention, an alerting material (b) is defined as a compound which comprises at least one sulphur atom and / or at least one nitrogen atom and / or at least one carboxylic acid or carboxylate moiety, typically associated with parosmia. Parosmia is a dysfunctional smell detection characterized by the inability of the brain to correctly identify an odour's "natural" smell. Instead, the natural odour is usually transformed into an unpleasant aroma, typically a "burned", "rotting", "fecal", or "chemical" smell. Such olfactory dysfunction was largely observed after the COVID-19 pandemic. It appears that there is a particular sensitivity (human response) to these substances (J K Parker et al., Communications Medicine, 2022, 2:58).
[0046] In some embodiments, the alerting material (b) is a compound comprising:
[0047] - at least one sulphur atom which is selected from a thiol moiety, a sulphide moiety, a disulphide moiety, a thiazole moiety, on oxathiane moiety, and / or
[0048] - at least one nitrogen atom which is selected from a pyrazine moiety including tri substituted pyrazine moieties and methoxy-pyrazine moieties, a nitrile moiety, an indole moiety, an oxime moiety, an amine moiety, an isothiocyanate, a diamine moiety, and / or
[0049] - at least one carboxylic acid or carboxylate moiety, and / or
[0050] - mixtures thereof.
[0051] In an embodiment, the alerting material (b) is a compound comprising at least one sulphur atom and / or at least one nitrogen atom and / or at least one carboxylic acid or carboxylate moiety, and / or mixture thereof, preferably a compound comprising at least one sulphur atom and / or at least one nitrogen atom, and / or mixture thereof, and more preferably a compound comprising at least one sulphur atom.
[0052] In a preferred embodiment, the alerting material (b) is a compound comprising at least one sulphur atom which is selected from a thiol moiety or a sulphide moiety.
[0053] The alerting material (b) may advantageously be a compound comprising at least one sulphur atom selected from 2-mercapto-3-methyl-l-butanol, 3-mercapto-3-methyl-l- butanol, 3-mercapto-3-methylbutyl formate, 3-mercapto-2-methyl-l-pentanol, 3- mercapto-2-methyl-l-propanol, 3-methyl-3-sulfanylhexanol, 3-methyl-3(2- methyldisulfanyl)-butan-l-ol, 3-mercapto-3-methyl-l-hexanol, 3-mercapto-2- methylpentanal, l-mercapto-3-pentanone, 2-mercapto-3-pentanone, 3-mercapto-3- pentanone, 3-methyl-3-mercaptobutyl acetate, 1-propanethiol, methanethiol, methional, p-mentha-8-thiol-3-one, 2-naphthalenethiol, 3-methyl-3-mercaptobutyl formate, 1- methoxyheptane-3-thiol, 4-methoxy-2-methylbutane-2-thiol, 1-propanethiol, thioglycolic acid, dithioglycolic acid, methyl-2-propenyl disulphide, 2,4-dithiapentane, dimethyl sulphide, dimethyl disulphide, dimethyl trisulphide, diallyl sulphide, diallyl trisulphide, allyl mercaptan, allicin, alliin, cysteine, 1-butylsulphanylbutane, 3-hydroxy-4,5-dimethylfuran- 2(5H)-one, and mixtures thereof.
[0054] The alerting material (b) may advantageously be a compound comprising at least one sulphur atom selected from 2-mercapto-3-methyl-l-butanol, 3-mercapto-3-methyl-l- butanol, 3-mercapto-3-methylbutyl formate, 3-mercapto-2-methyl-l-pentanol, 3- mercapto-2-methyl-l-propanol, 3-methyl-3-sulfanylhexanol, 3-methyl-3(2- methyldisulfanyl)-butan-l-ol, 3-mercapto-3-methyl-l-hexanol, 3-mercapto-2- methylpentanal, l-mercapto-3-pentanone, 2-mercapto-3-pentanone, 3-mercapto-3- pentanone, 3-methyl-3-mercaptobutyl acetate, 1-propanethiol, methanethiol, methional, 2-naphthalenethiol, 3-methyl-3-mercaptobutyl formate, l-methoxyheptane-3-thiol, 4- methoxy-2-methylbutane-2-thiol, 1-propanethiol, thioglycolic acid, dithioglycolic acid, methyl-2-propenyl disulphide, 2,4-dithiapentane, dimethyl sulphide, dimethyl disulphide, dimethyl trisulphide, diallyl sulphide, diallyl trisulphide, allyl mercaptan, allicin, alliin, cysteine, 1-butylsulphanylbutane, 3-hydroxy-4,5-dimethylfuran-2(5H)-one, and mixtures thereof.
[0055] In a preferred embodiment, the alerting material (b) is a compound comprising at least one sulphur atom selected from 3-mercapto-3-methyl-l-butanol, 3-mercapto-2-methyl-l- pentanol, dimethylsulfide, dimethyl disulphide, dimethyl trisulphide, diallyl sulphide, diallyl trisulphide, 3-hydroxy-4,5-dimethylfuran-2(5H)-one, and mixtures thereof.
[0056] In an embodiment, the alerting material (b) comprising at least one sulphur atom is 3- mercapto-3-methyl-l-butanol.
[0057] In an embodiment, the alerting material (b) comprising at least one sulphur atom is 3- mercapto-2-methyl-l-pentanol.
[0058] In an embodiment, the alerting material (b) comprising at least one sulphur atom is dimethylsulfide.
[0059] In an embodiment, the alerting material (b) comprising at least one sulphur atom is dimethyl disulphide.
[0060] In an embodiment, the alerting material (b) comprising at least one sulphur atom is dimethyl trisulphide.
[0061] In an embodiment, the alerting material (b) comprising at least one sulphur atom is diallyl sulphide.
[0062] In an embodiment, the alerting material (b) comprising at least one sulphur atom is diallyl trisulphide.
[0063] In an embodiment, the alerting material (b) comprising at least one sulphur atom is 3- hyd roxy-4, 5-d imethylfuran-2(5H)-one.
[0064] In another embodiment, the alerting material (b) is a compound comprising at least one nitrogen atom which is selected from a pyrazine moiety including tri substituted pyrazine moieties and methoxy-pyrazine moieties, a nitrile moiety, an indole moiety, an oxime moiety, an amine moiety, an isothiocyanate, a diamine moiety, preferably 2- methylpyrazine, 2,3-dimethylprazine, 2,5-dimethylpyrazine, 2-ethyl-3,5-dimethylpyrazine, 2,3-diethyl-5-methylpyrazine, 2,6-dimethylpyrazine, 2-ethyl-3-methoxypyrazine, 3- methoxy-2-isobutylpyrazine, acetonitrile, benzonitrile, 2-methylindole, 2-methyl-2- thiazoline, acetoxime, butyraldoxime, methylamine, ethylamine, phenethylamine, phenyl isothiocyanate, allyl isothiocyanate, ethylenediamine, 1,4-butanediamine, hexamethylenediamine, methylamine, ethylamine, trimethylamine, cadaverine, and mixtures thereof, and more preferably 2,3-diethyl-5-methylpyrazine, acetonitrile, benzonitrile, 2-methyl-2-thiazoline, acetoxime, butyraldoxime, methylamine, ethylamine, phenethylamine, phenyl isothiocyanate, allyl isothiocyanate, ethylenediamine, 1,4- butanediamine, hexamethylenediamine, methylamine, ethylamine, trimethylamine, cadaverine, and mixtures thereof.
[0065] In a preferred embodiment, the alerting material (b) is a compound comprising at least one nitrogen atom selected from 2,3-diethyl-5-methylpyrazine, 2-ethyl-3- methoxypyrazine, methylamine, ethylamine, trimethylamine, and mixtures thereof.
[0066] In an embodiment, the alerting material (b) comprising at least one nitrogen atom is 2,3- diethyl-5-methyl pyrazine.
[0067] In an embodiment, the alerting material (b) comprising at least one nitrogen atom is 2- ethyl-3-methoxypyrazine.
[0068] In an embodiment, the alerting material (b) comprising at least one nitrogen atom is methylamine.
[0069] In an embodiment, the alerting material (b) comprising at least one nitrogen atom is ethylamine.
[0070] In an embodiment, the alerting material (b) comprising at least one nitrogen atom is trimethylamine.
[0071] In another embodiment, the alerting material (b) is a compound comprising at least one carboxylic acid or carboxylate moiety, and advantageously a compound comprising at least one carboxylic acid selected from 3-methyl hexanoic acid, 4-ethyloctanoic acid, trans- 3-hexenoic acid, propionic acid, nonanoic acid, myristic acid, capric acid, 3-methyl-2- hexenoic acid, 3-hydroxy-3-methylhexanoic acid, 3-hexenoic acid, acetic acid, benzoic acid, butyric acid, caproic acid, citric acid, formic acid, lactic acid, oxalic acid, succinic acid, tartaric acid, valeric acid, isovaleric acid, malonic acid, and mixtures thereof.
[0072] In a preferred embodiment, the alerting material (b) comprising at least one carboxylic acid moiety is selected from butyric acid, caproic acid, isovaleric acid, and mixtures thereof.
[0073] In an embodiment, the alerting material (b) comprising at least one carboxylic acid moiety is butyric acid.
[0074] In an embodiment, the alerting material (b) comprising at least one carboxylic acid moiety is caproic acid.
[0075] In an embodiment, the alerting material (b) comprising at least one carboxylic acid moiety is isovaleric acid. In another preferred embodiment, the alerting material (b) is a compound selected from 3-mercapto-3-methyl-l-butanol, 3-mercapto-2-methyl-l-pentanol, dimethylsulfide, dimethyl disulphide, dimethyl trisulphide, diallyl sulphide, diallyl trisulphide, 3-hydroxy- 4,5-dimethylfuran-2(5H)-one, 2,3-diethyl-5-methylpyrazine, 2-ethyl-3-methoxypyrazine, methylamine, ethylamine, trimethylamine, butyric acid, caproic acid, isovaleric acid, and mixtures thereof.
[0076] In some embodiments, the at least one alerting material (b) represents from 1x1010to 3x101%, preferably from lxlO-9to 2x101%, more preferably lxlO-8to 2x101%, and even more preferably from lxlO-7to 1x101%, by weight of the total of the fragrance composition.
[0077] In some embodiments, the at least one alerting material (b) represents from 1x1010to 3x101%, preferably from lxlO-9to 2x101%, more preferably lxlO-8to 2x101%, even more preferably from lxlO-7to 1x101%, and even more preferably from 1x1010to 1x101%, by weight of the total of the fragrance composition.
[0078] The fragrance composition comprises, in addition to the at least one trigeminal- stimulating compound (a) and at least one alerting material (b) described above, at least one fragrance compound (c), and preferably at least two, such as at least five, or at least eight distinct fragrance compounds.
[0079] When the trigeminal-stimulating compound (a) can also fulfill the inherent function of fragrance compound, in this case the fragrance compound (c) is different from the trigeminal-stimulating compound (a). This means that the trigeminal-stimulating compound (a) cannot be counted as a fragrance compound (c).
[0080] When the alerting material (b) can also fulfill the inherent function of fragrance compound, in this case the fragrance compound (c) is different from the alerting material (b). This means that the alerting material (b) cannot be counted as a fragrance compound (c).
[0081] The at least one fragrance compound (c) can comprise highly complex mixtures of fragrance compounds, chosen to provide any desired odour. In the context of the present invention the term "fragrance" is intended to be synonymous with "perfume". The fragrance of the invention preferably excludes edible compounds. In other words, the fragrance of the invention is advantageously a non-edible compound, which means a compound non-intended for ingestion by humans or animals. Fragrance compounds typically used in the field of perfumery and suitable for the purposes of the present invention are described in the detailed IRFA Transparency List of "fragrance ingredients" available and maintained by IFRA on the website: https: / / ifrafragrance.org / priorities / ingredients / ifra-transparency-list. The term "fragrance compound" encompasses naturally occurring, as well as synthetic materials known for use in perfumes, as well as animal oils. A fragrance compound can also be any natural oil or extract used in a fragrance composition. Natural oils and extracts are described in The Essential Oils by E. Guenther published in 1949 by D. Van Nostrand Company, and may include extracts, pressings, collection of exudates, and distillates from any part of suitable plants: roots, rhizomes, bulbs, corms, stem, bark, heartwood, leaves, flowers, seeds and fruit. Examples of such extracts and distillates include citrus fruit oils such as orange, mandarin, grapefruit, lime or lemon oils, tree oils such as pine, or cedar wood, herb oils such as peppermint, thyme, lavender, basil, rosemary, clove or flower extracts such as rose, jasmine, muguet, or geranium oil.
[0082] Water solubility of fragrance compounds (c) can be related to a theoretically derived parameter ClogP. ClogP refers to the octanol / water partitioning coefficient (P) of fragrance compounds. The octanol / water partitioning coefficient of a fragrance compound is the ratio between its equilibrium concentrations in octanol and in water. The partitioning coefficients of fragrance compounds are more conveniently given in the form of their logarithm to the base 10, logP. The logP values of many fragrance compounds have been reported in the literature. The "calculated logP" (ClogP) is determined by the fragment approach of Hansch and Leo (A. J. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C.; Hansch, P. G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990). The fragment approach is based on the chemical structure of each fragrance compound and considers the numbers and types of atoms, the atom connectivity, and chemical bonding. The ClogP values, which are the most reliable and widely used estimates for this physicochemical property, are preferably used instead of the experimental logP values in the selection of fragrance compounds which are useful in the present invention. There are several alternative methods of calculating or estimating logP values which can show some variation in values. Even calculations within a given set of software may change over time as the algorithms are modified to give results which are closer to measured values. To remove any uncertainty the ClogP values reported herein are most conveniently calculated by the Daylight program version 4.94 available from Daylight Chemical Information Systems. The ClogP values are preferably used instead of the experimental logP values in the selection of fragrance compounds which are useful in the present invention. Guidance for determining the composition of natural oils or extracts can be found in the ESO 2000 database published by BACIS (Boelens Aroma Chemical Information Service, Groen van Prinsterlaan 21, 1272 GB Huizen, The Netherlands). In some embodiments, the fragrance compound (c) has a CLogP of at least 1.5. Advantageously, the fragrance compound (c) has a CLogP ranging from 1.5 to 6. In the context of the invention, the CLogP of the fragrance compound (c) corresponds to the weighted average of CLogP values of each of the fragrance compounds (c) constituting the "at least one fragrance compound (c)".
[0083] In some embodiments, each fragrance compound (c) has a molecular weight greater than 30 g.mol-1, preferably greater than 120 g.mol1and lower than 325 g.mol-1, preferably lower than 300 g.mol-1. In some embodiments each fragrance compound (c) has a boiling point in the range 80-400°C, such as in the range 100-350°C, when measured at 760 mm Hg.
[0084] In some embodiment, each fragrance compound (c) comprises fewer than three heteroatoms and a molecular weight ranging from 30 to 300 g.mol-1.
[0085] Non-limiting examples of fragrance compounds (c) suitable for use in the present invention include:
[0086] • Cs-Cis hydrocarbons, preferably delta-3-carene, alpha-pinene, beta-pinene, alphaterpinene, gamma-terpinene, p-cymene, bisabolene, camphene, caryophyllene, cedrene, farnesene, limonene, longifolene, myrcene, ocimene, valencene, (E,Z)-1,3,5- undecatriene;
[0087] • C2-C18 aliphatic alcohols, preferably hexanol, octanol, 3-octanol, 2,6-dimethylheptanol, 2-methylheptanol, 2-methyloctanol, (E)-3-hexenol, (E)- and (Z)-3-hexenol, l-octen-3- ol, mixtures of 3,4,5,6,6-pentamethyl-3 / 4-hepten-2-ol and 3,5,6,6-tetramethyl-4- methyleneheptan-2-ol, (E,Z)-2,6-nonadienol, 3,7-dimethyl-7-methoxyoctan-2-ol, 9- decenol, 10-undecenol, 4-methyl-3-decen-5-ol;
[0088] • C2-C18 aliphatic aldehydes and their acetals, preferably hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal, 2-methyloctanal, 2-methylnonanal, (E)-2-hexenal, (Z)-4-heptenal, 2,6-dimethyl-5-heptenal (Melonal®), 10-undecenal, (E)- 4-decenal, 2-dodecenal, 2,6,10-trimethyl-5,9-undecadienal, heptanal diethyl acetal, l,l-dimethoxy-2,2,5-trimethyl-4-hexene, citronellyl oxyacetaldehyde;
[0089] • C3-C18 aliphatic ketones and oximes thereof, preferably 2-heptanone, 2-octanone, 3- octanone, 2-nonanone, 5-methyl-3-heptanone, 5-methyl-3-heptanone oxime, 2, 4,4,7- tetramethyl-6-octen-3-one;
[0090] • C2-C18 aliphatic nitrile-containing compounds, preferably 2-nonenenitrile, 2- tridecenenenitrile, 2,12-tridecenene-nitrile, 3,7-dimethyl-2,6-octadienenitrile, 3,7- dimethyl-6-octenenitrile;
[0091] • C2-C18 aliphatic carboxylic acids and esters thereof, preferably (E)- and (Z)-3-hexenyl formate, ethyl acetoacetate, isoamyl acetate, hexyl acetate, 3,5,5-trimethylhexyl acetate, 3-methyl-2-butenyl acetate, (E)-2-hexenyl acetate, (E)- and (Z)-3-hexenyl acetate, octyl acetate, 3-octyl acetate, l-octen-3-yl acetate, linalyl acetate, ethyl butyrate, butyl butyrate, isoamyl butyrate, hexyl butyrate, (E)- and (Z)-3-hexenyl isobutyrate, hexyl crotonate, ethyl isovalerate, ethyl 2-methylpentanoate, ethyl hexanoate, allyl hexanoate, ethyl hepta noate, allyl hepta noate, ethyl octanoate, ethyl (E,Z)-2,4-decadienoate, methyl 2-octynoate, methyl 2-nonynoate, allyl-2- isoamyloxyacetate, methyl-3,7-dimethyl-2,6-octadienoate, allyl amyl glycolate;
[0092] • C -C18 acyclic terpene alcohols, preferably citronellol, geraniol, nerol, linalool, lavandulol, nerolidol, farnesol, tetrahydrolinalool, tetrahydrogeraniol, 2,6-dimethyl-7- octen-2-ol, 2,6-dimethyloctan-2-ol (di hydromyrcenol), 2-methyl-6-methylene-7-octen-
[0093] 2-ol, 2,6-dimethyl-5,7-octadien-2-ol, 2,6-dimethyl-3,5-octadien-2-ol, 3,7-dimethyl-4,6- octadien-3-ol, 3,7-dimethyl-l,5,7-octatrien-3-ol, 2,6-dimethyl-2,5,7-octatrien-l-ol;
[0094] • C -C18 acyclic terpene aldehydes and ketones, preferably geranial, neral, citronellal, 7- hydroxy-3,7-dimethyloctanal, 7-methoxy-3,7-dimethyloctanal, 2,6,10-trimethyl-9- undecenal, geranylacetone, and the dimethyl and diethyl acetals of geranial, neral, 7- hydroxy-3,7-dimethyloctanal;
[0095] • C4-C18 cyclic terpene alcohols, preferably alpha-terpineol, terpineol-4, menthan-8-ol, menthan-l-ol, menthan-7-ol, linalool oxide, nopol, cedrol, ambrinol, vetiverol, guaiol;
[0096] • C4-C18 cyclic terpene aldehydes and ketones, preferably fenchone, alpha-ionone, betaionone, alpha-n-methylionone, beta-n-methyl ionone, methylionone gamma, alphaisomethylionone, beta-isomethylionone, alpha-irone, alpha-damascone, beta- damascone, beta-damascenone, delta-damascone, gamma-damascone, l-(2,4,4- trimethyl-2-cyclohexen-l-yl)-2-buten-l-one, l,3,4,6,7,8a-hexahydro-l,l,5,5- tetramethyl-2H-2,4a-methanonaphthalen-8(5H)-one, nootkatone, dihydronootkatone, alpha-sinensal, beta-sinensal, methyl cedryl ketone;
[0097] • C4-C18 cyclic alcohols, preferably 4-tert-butylcyclohexanol, 3,3,5-trimethylcyclohexanol,
[0098] 3-isocamphylcyclohexanol, 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-l-ol, 2-isobutyl-
[0099] 4-methyltetrahydro-2H-pyran-4-ol;
[0100] • C4-C18 cycloaliphatic alcohols, preferably alpha-3, 3-trimethylcyclohexylmethanol, 2- methyl-4-(2,2,3-trimethyl-3-cyclopent-l-yl)butanol, 2-methyl-4-(2,2,3-trimethyl-3- cyclopent-l-yl)-2-buten-l-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-l-yl)-2-buten-l-ol (Bacdanol®), 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-l-yl)-pentan-2-ol, 3-methyl-5- (2,2,3-trimethyl-3-cyclopent-l-yl)-4-penten-2-ol, 3,3-dimethyl-5-(2,2,3-trimethyl-3- cyclopent-l-yl)-4-penten-2-ol, l-(2,2,6-trimethylcyclohexyl)pentan-3-ol, l-(2,2,6- trimethylcyclohexyl)hexan-3-ol;
[0101] • C -C18 cyclic and cycloaliphatic ethers, preferably cedryl methyl ether, cyclododecyl methyl ether, (ethoxymethoxy)cyclododecane, alpha-cedrene epoxide, 3a, 6, 6,9a- tetramethyl-dodecahydronaphtho[2,l-b]furan, 3a-ethyl-6,6,9a-trimethyldodecahydro- naphtho[2,l-b]furan, l,5,9-trimethyl-13-oxabicyclo[10.1.0]trideca-4,8-diene, rose oxide, 2-(2,4-dimethyl-3-cyclohexen-l-yl)-5-methyl-5-(l-methylpropyl)-l,3-dioxane;
[0102] • C -C18 cyclic ketones, preferably 4-tert-butylcyclohexanone, 2,2,5-trimethyl-5- pentylcyclopentanone, 2-heptylcyclopentanone, 2-pentylcyclopentanone, 2-hydroxy-3- methyl-2-cyclopenten-l-one, 3-methyl-cis-2-penten-l-yl-2-cyclopenten-l-one, 3- methyl-2-pentyl-2-cyclopenten-l-one, 3-methyl-4-cyclopentadecenone, 3-methyl-5- cyclopentadecenone,3-methylcyclopentadecanone, 4-(l-ethoxyvinyl)-3, 3,5,5- tetramethylcyclohexanone, 4-tert-pentylcyclohexanone, 5-cyclohexadecen-l-one, 6,7- dihydro-l,l,2,3,3-pentamethyl-4(5H)-indanone, 9-cycloheptadecen-l-one, cyclopentadecanone, cyclohexadecanone;
[0103] • C4-C18 cycloaliphatic aldehydes, preferably 2,4-dimethyl-3-cyclohexenecarbaldehyde
[0104] (Triplal®), 2-methyl-4-(2,2,6-trimethyl-cyclohexen-l-yl)-2-butenal, 4-(4-hydroxy-4- methylpentyl)-3-cyclohexenecarbaldehyde, 4-(4-methyl-3-penten-l-yl)-3- cyclohexenecarbaldehyde;
[0105] • C4-C18 cycloaliphatic ketones, preferably l-(3,3-dimethylcyclohexyl)-4-penten-l-one, 1- (5,5-dimethyl-l-cyclohexen-l-yl)-4-penten-l-one, 2,3,8,8-tetramethyl-l,2,3,4,5,6,7,8- octahydro-2-naphthalenyl methyl ketone, methyl-2,6,10-trimethyl-2,5,9- cyclododecatrienyl ketone, tert-butyl(2,4-dimethyl-3-cyclohexen-l-yl)ketone;
[0106] • esters of cyclic alcohols in C4-C18, preferably isobornyl acetate, 2-tert-butylcyclohexyl acetate (Verdox®), 4-tert-butyl-cyclohexyl acetate, 2-tert-pentylcyclohexyl acetate, 4- tert-pentylcyclohexyl acetate, decahydro-2-naphthyl acetate, 3-pentyltetrahydro-2H- pyran-4-yl acetate, decahydro-2, 5, 5, 8a-tetramethyl-2-naphthyl acetate, 4,7-methano- 3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl acetate, 4,7-methano-3a,4,5,6,7,7a-hexahydro- 5 or 6-indenyl propionate, 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl isobutyrate, 4,7-methanooctahydro-5 or 6-indenyl acetate;
[0107] • esters of cycloaliphatic carboxylic acids in C4-C18, preferably allyl 3- cyclohexyl propionate, allyl cyclohexyloxyacetate, methyl dihydrojasmonate (Hedione®), methyl jasmonate, methyl 2-hexyl-3-oxocyclopentanecarboxylate, ethyl 2-ethyl-6,6- dimethyl-2-cyclohexenecarboxylate, ethyl 2,3,6,6-tetramethyl-2- cyclohexenecarboxylate, ethyl 2-methyl-l,3-dioxolane-2-acetate;
[0108] • C -C18 aromatic hydrocarbons, preferably styrene and diphenylmethane;
[0109] • C -C18 araliphatic alcohols, preferably benzyl alcohol, 1-phenylethyl alcohol, 2- phenylethyl alcohol, 3-phenylpropanol, 2-phenylpropanol, 2-phenoxyethanol, 2,2- dimethyl-3-phenylpropanol, 2,2-dimethyl-3-(3-methylphenyl)propanol, l,l-dimethyl-2- phenylethyl alcohol, l,l-dimethyl-3-phenylpropanol, l-ethyl-l-methyl-3- phenylpropanol, 2-methyl-5-phenylpentanol, 3-methyl-5-phenylpentanol, 3-phenyl-2- propen-l-ol, 4-methoxybenzyl alcohol, l-(4-isopropylphenyl)ethanol;
[0110] • esters of araliphatic alcohols in C4-C18 and aliphatic carboxylic acids in C4-C18, preferably benzyl acetate, benzyl propionate, benzyl isobutyrate, benzyl isovalerate, 2- phenylethyl acetate, 2-phenylethyl propionate, 2-phenylethyl isobutyrate, 2-phenylethyl isovalerate, 1-phenylethyl acetate, o-trichloromethyl benzyl acetate, o,o- dimethylphenylethyl acetate, o,o-dimethylphenylethyl butyrate, cinnamyl acetate, 2- phenoxyethyl isobutyrate, 4-methoxybenzyl acetate;
[0111] • C2-C18 araliphatic ethers, preferably 2-phenylethyl methyl ether, 2-phenylethyl isoamyl ether, 2-phenylethyl 1-ethoxyethyl ether, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, hydratropaldehyde dimethyl acetal, phenylacetaldehyde glycerol acetal, 2,4,6-trimethyl-4-phenyl-l,3-dioxane, 4, 4a, 5,9b- tetrahydroindeno[l,2-d]-m-dioxin, 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[l,2-d]-m- dioxin;
[0112] • C4-C18 aromatic and araliphatic aldehydes, preferably benzaldehyde, phenylacetaldehyde, 3-phenylpropanal, hydratropaldehyde, 4-methylbenzaldehyde, 4- methylphenylacetaldehyde, 3-(4-ethylphenyl)-2,2-dimethylpropanal, 2-methyl-3-(4- isopropylphenyl)propanal, 2-methyl-3-(4-tert-butylphenyl)propanal, 3-(4-tert- butylphenyl)propanal, cinnamaldehyde, alpha-butylcinnamaldehyde, alpha- amylcinnamaldehyde, alpha-hexylcinnamaldehyde, 3-methyl-5-phenylpentanal, 4- methoxybenzaldehyde (anisic aldehyde), 4-hydroxy-3-methoxybenzaldehyde, 4- hydroxy-3-ethoxybenzaldehyde, 3,4-methylenedioxybenzaldehyde, 3,4- dimethoxybenzaldehyde, 2-methyl-3-(4-methoxyphenyl)propanal, 2-methyl-3-(4- methylenedioxyphenyl)propanal;
[0113] • C4-C18 aromatic and araliphatic ketones, preferably acetophenone, 4- methylacetophenone, 4-methoxyacetophenone, 4-tert-butyl-2,6- dimethylacetophenone, 4-phenyl-2-butanone, 4-(4-hydroxyphenyl)-2-butanone, l-(2- naphthalenyl)ethanone, benzophenone, l,l,2,3,3,6-hexamethyl-5-indanyl methyl ketone, 6-tert-butyl-l,l-dimethyl-4-indanyl methyl ketone, l-[2,3-dihydro-l, 1,2,6- tetramethyl-3-(l-methylethyl)-lH-5-indenyl]ethanone, 5',6',7',8'-tetrahydro-
[0114] 3',5',5',6',8',8'-hexamethyl-2-acetonaphthone;
[0115] • C -C18 aromatic and araliphatic carboxylic acids and esters thereof, preferably phenylacetic acid, methyl benzoate, ethyl benzoate, hexyl benzoate, benzyl benzoate, methyl phenylacetate, ethyl phenylacetate, geranyl phenylacetate, phenylethyl phenylacetate, methyl cinnamate, ethyl cinnamate, benzyl cinnamate, phenylethyl cinnamate, cinnamyl cinnamate, allyl phenoxyacetate, methyl salicylate, isoamyl salicylate, hexyl salicylate, cyclohexyl salicylate, cis-3-hexenyl salicylate, benzyl salicylate, phenylethyl salicylate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, ethyl 3- phenylglycidate, ethyl 3-methyl-3-phenylglycidate;
[0116] • nitrogen-containing aromatic compounds in C4-C18, preferably 2,4,6-trinitro-l,3- dimethyl-5-tert-butylbenzene, 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone, cinnamonitrile, 5-phenyl-3-methyl-2-pentenenitrile, 5-phenyl-3-methylpentanenitrile, methyl anthranilate, methyl N-methylanthranilate, Schiff bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert-butylphenyl)propanal, 2,4- dimethyl-3-cyclohexene-carbaldehyde, 6-isopropylquinoline, 6-isobutylquinoline, 6-sec- butylquinoline, indole, skatole, 2-methoxy-3-isopropylpyrazine, 2-isobutyl-3- methoxypyrazine;
[0117] • phenols, phenyl ethers and phenyl esters, preferably estragole, anethole, eugenol, eugenyl methyl ether, isoeugenol, isoeugenyl methyl ether, thymol, carvacrol, diphenyl ether, beta-naphthyl methyl ether, beta-naphthyl ethyl ether, beta-naphthyl isobutyl ether, 1,4-dimethoxybenzene, eugenyl acetate, 2-methoxy-4-methylphenol, 2-ethoxy- 5-(l-propenyl)phenol, p-cresyl phenylacetate;
[0118] • heterocyclic compounds in C4-C12, preferably 2,5-dimethyl-4-hydroxy-2H-furan-3-one, 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one, 3-hydroxy-2-methyl-4H-pyran-4-one, 2- ethyl-3-hydroxy-4H-pyran-4-one;
[0119] • lactones in C4-C18, preferably 1,4-octanolide, 3-methyl-l,4-octanolide, 1,4-nonanolide,
[0120] 1.4-decanolide, 8-decen-l, 4-olide, 1,4-undecanolide, 1,4-dodecanolide, 1,5-decanolide,
[0121] 1.5-dodecanolide, 1,15-pentadecanolide, cis- and trans-ll-pentadecen-1, 15-olide, cisand trans-12-pentadecen-l, 15-olide, 1,16-hexadecanolide, 9-hexadecen-l, 16-olide, 10- oxa-l,16-hexadecanolide, ll-oxa-l,16-hexadecanolide, 12-oxa-l,16-hexadecanolide, ethylene 1,12-dodecanedioate, ethylene 1,13-tridecanedioate, coumarin, 2,3- dihydrocoumarin, octahydrocoumarin.
[0122] In some embodiments, the fragrance compounds (c) present in the fragrance do not contain ionizing functional groups, such as sulfonates, sulphates, phosphates or quaternary ammonium ions.
[0123] In some embodiments, the at least one fragrance compound (c) represents from 20 to 99.9%, preferably from 30 to 99.9%, and more preferably 40 to 99.9%, by weight of the total of the fragrance composition.
[0124] In some embodiments, in addition to the compounds (a), (b) and (c), the fragrance composition of the invention further comprises at least one support material. Support materials typically used in the field of perfumery and suitable for the purposes of the present invention are described in the detailed IRFA Transparency List of "functional ingredients" - such as antioxidants, preservatives, diluents, solvents or colorants - available and maintained by IFRA on the website: https: / / ifrafragrance.org / priorities / ingredients / ifra-transparency-list.
[0125] In some embodiments, the support material is preferably a solvent or a UV stabilizer, and more preferably a solvent. Suitable solvents are advantageously biodegradable, biosourced, and more advantageously of non-animal origin. Examples of suitable solvents include hydrocarbons such as those sold under the trade name Isopar®, ethers such as those sold under the Dowanol® trade name, dialkyl adipates, dialkyl succinates, dialkyl glutarates such as the dimethyl ester, which in a blend with other dimethyl esters is sold under the trade name Flexisolv®, citrate esters (such as triethyl citrate and acetyl tributyl citrate), soybean methyl ester (such as ME-S1885 sold by Peter Cremer NA), diethyl phthalate, diethylene glycol monoethyl ether, 3-methoxy-3-methyl-l-butanol, dipropylene glycol, isopropylidene glycerol (sold under the AUGEO® Clean Multi brand name), C1-C5 alkyl butyrate, and mixtures thereof. Preferred solvents are hydrocarbons, dipropylene glycol, C1-C5 alkyl butyrate, and mixtures thereof. Examples of UV stabilizers include butyl methoxy dibenzoyl methane, bis ethylhexyloxyphenolmethoxyphenyl triazine, those sold under the Uvinol® trade name such as Uvinul® D50 (bis(2,4-dihydroxyphenyl)- methanone), Uvinul® MC80 (ethylhexyl methoxycinnamate) and Uvinul® M40 (benzophenone-3), those sold under the Parsol® trade name, such as Parsol® MCX and Parsol® 1789 (butyl methoxydibenzoylmethane), and those sold under the Tinogard® trade name, such as Tinogard® TT (pentaerythrityl tetra di-t-butyl hyd roxy hyd roci n na m ate) .
[0126] The at least one support material may represent from 1 to 60% by weight, preferably 1 to 50% by weight, and more preferably 1 to 40% by weight, based on the total weight of the fragrance composition.
[0127] In some embodiments, the at least one trigeminal-stimulating compound (a), at least one alerting material (b), and at least one fragrance compounds (c), make up at least 20% by weight, such as at least 30% by weight, at least 40% by weight, based on the total weight of the fragrance composition, the remainder (if appropriate) being made up of support materials as defined above.
[0128] The fragrance composition of the invention can be encapsulated in a delivery system, which system can then be incorporated into e.g. laundry products with the view of eventually delivering a noticeable odour to the consumer. Non-limiting examples of delivery systems include starch capsules, silica capsules and core-shell capsules.
[0129] General descriptions and methods of preparation of microcapsules can be found in "MICROENCAPSULATION: Methods and Industrial Applications Edited by Benita and Simon (Marcel Dekker, Inc. 1996)". Microcapsules are also described in Kirk Othmer's Encyclopaedia of Chemical Technology 5thedition. Capsules can be formed by mechanical or chemical means. Mechanically formed capsules can be formed by means, such as spray chilling e.g. in US 2004 / 0106536, by compression of solids or by spray drying emulsions e.g. in US 6,200,949. Chemically formed capsules are produced by chemical reactions forming ionic or covalent bonds using techniques such as co-acervation, interfacial polymerisation, condensation reactions and free radical polymerisation. One particularly efficient and commercially important type of microcapsules is referred to as a wall or shell or core-shell microcapsule and comprises a generally spherical shell of water- and oilinsoluble materials, typically a network polymer material, within which fragrance or other hydrophobic material is contained. It can be understood that these various methods of encapsulation can be combined as can the different chemical reactions used to prepare capsule walls. Encapsulation may combine physical and chemical means of capsule preparation or combine more than one type of chemical reaction to prepare multi walled capsules or hybrid capsule walls. Capsules can also be obtained by co-acervation methods. More specific descriptions of such methods can be found in US 2,800,457; US 2,800,458, US 3,041,288 and WO 99 / 17871. Descriptions of interfacial polymerisation methods can be found in US 4,681,806; US 3,415,758; US 8,426,353; US 2008 / 020629 and EP-A-2 038 053. Examples of capsules formed by condensation reactions can be found in US 3,516,941; US 3,516,846; US 6,261,483; US 2004 / 087477; GB-A-2,073,132 and EP-A-1 393 706. Capsules formed by free radical polymerisation are described in US 6,849,591; US 6,951,836 and US 2010 / 002860.
[0130] In some embodiments, the fragrance composition of the invention is encapsulated in core-shell capsules, i.e. capsules having a core (comprising, such as consisting essentially of, the fragrance composition) surrounded by a shell which can be made from various materials.
[0131] In some embodiments, the shell of the microcapsules comprises a material selected from polyolefins such as polyethylenes, polyamides, polystyrenes, polyisoprenes, polycarbonates, polyesters, polyacrylates, polyurethanes, aminoplasts, polysaccharides such as alginate and / or chitosan, gelatine, shellac, epoxy resins, vinyl polymers, water insoluble inorganics, silicone, and mixtures thereof.
[0132] In some embodiments, the shell of the microcapsules comprises urea-formaldehyde, melamine formaldehyde or crosslinked melamine formaldehyde.
[0133] In some embodiments, the shell of the microcapsules comprises a polyacrylate. Nonlimiting examples of polyacrylate shells are disclosed e.g. in EP-A-2 620 211, EP-A- 2 832 440, EP-A-2 832 441 and EP-A-2 832 442, the content of which is incorporated by reference.
[0134] In some embodiments, the shell of the microcapsules comprises the reaction product of a Michael donor and a Michael acceptor, wherein the reaction is optionally carried out in the presence of solid colloidal particles and / or a catalyst. For example, the shell can comprise the reaction product of (i) an o,p-unsaturated carbonyl compound and a multifunctional amine, optionally in the presence of solid colloidal particles; or (ii) an o,p-unsaturated carbonyl compound and a multifunctional thiol compound, optionally in the presence of a catalyst.
[0135] In some embodiments, the shell of the microcapsules comprises the reaction product of a multifunctional isocyanate and a multifunctional thiol compound, optionally in the presence of solid colloidal particles and / or a catalyst.
[0136] In some embodiments, the shell of the microcapsules is as defined in WO 2019 / 121736, WO 2019 / 121738, WO 2020 / 020829, KR 20190023697, EP 3 871 764 Al, EP 3 871 765 Al, or else EP 3 871 766 Al.
[0137] In some embodiment, the shell of the microcapsules is biodegradable according to the requirements of the OECD Guideline for testing of chemicals 301 F: Manometric respirometry (adopted on 17 July 1992). The biodegradability test under the OECD 301 F method is based on the measurement of the oxygen consumed by bacteria to mineralize the test substance, i.e. the Biochemical Oxygen Demand (BOD). The BOD is deduced from the pressure variation measured in the test vial using an OxiTop® device. In another embodiment, the shell of the microcapsules is biodegradable and passes one or more of the tests specified in "Restriction on synthetic polymer microparticles (microplastics) - (EU) 2023 / 2055" such that it is not considered to be a microplastic.
[0138] In a second aspect, the invention relates to the use of at least one trigeminal-stimulating compound (a) in combination with at least one alerting material (b) which comprises at least one sulphur atom or at least one nitrogen atom or at least one carboxylic acid or carboxylate moiety, for reducing and / or eliminating habituation to an odour. In particular, the invention relates to the use of at least one trigeminal-stimulating compound (a) in combination with at least one alerting material (b) which comprises at least one sulphur atom or at least one nitrogen atom or at least one carboxylic acid or carboxylate moiety, in a fragrance composition, for reducing and / or eliminating habituation to the odour of this fragrance composition. The trigeminal-stimulating compound (a) and the alerting material (b) which comprises at least one sulphur atom or at least one nitrogen atom or at least one carboxylic acid or carboxylate moiety, implemented for this use are as defined above. In the use described above, the at least one alerting material is used in an amount from 1x1010to 3x101%, preferably from lxlO-9to 2x101%, more preferably from lxlO-8to 2x101%, even more preferably from lxlO-7to 1x101%, and even more preferably from 1x1010to 1x101%, by weight of the total of the fragrance composition.
[0139] In a third aspect, the invention relates to the use, in a fragrance composition comprising of at least one trigeminal-stimulating compound as defined above, of at least one alerting material as defined above, for reducing and / or eliminating habituation to the odour of this fragrance composition, in particular the odour associated to the at least one trigeminal- stimulating compound. In said aspect, the at least one alerting material is used in an amount from 1x1010to 3x101%, preferably from lxlO-9to 2x101%, more preferably from lxlO-8to 2x101%, even more preferably from lxlO-7to 1x101%, and even more preferably from 1x1010to 1x101%, by weight of the total of the fragrance composition.
[0140] A fourth aspect of the invention is directed to a method for reducing and / or eliminating habituation to the odour of a fragrance composition, comprising the step of adding at least one trigeminal-stimulating compound (a) in combination with at least one alerting material (b) which comprises at least one sulphur atom or at least one nitrogen atom or at least one carboxylic acid or carboxylate moiety, to the fragrance composition. The trigeminal-stimulating compound (a) and the alerting material (b) which comprises at least one sulphur atom or at least one nitrogen atom or at least one carboxylic acid or carboxylate moiety, implemented for the method of the invention are as defined above. In the method described above, the at least one alerting material is used in an amount from 1x1010to 3x101%, preferably from lxlO-9to 2x101%, more preferably from lxlO-8to 2x101%, even more preferably from lxlO-7to 1x101%, and even more preferably from 1x1010to 1x101%, by weight of the total of the fragrance composition.
[0141] Another aspect of the invention is concerned with a consumer product comprising a fragrance composition according to the invention or a fragrance product comprising a fragrance composition according to the invention. The product may be a non-edible consumer goods product such as a household product, a laundry product, a personal care product or a cosmetic product, or a fine fragrance. As used herein, a consumer product is intended to be used or consumed in the form in which it is sold, and not for further commercial manufacturing modification or resale.
[0142] Unless otherwise indicated, non-edible means non-intended for ingestion by humans or animals. This includes non-food products that may accidentally be swallowed during normal use. Notably, included within the definition of non-edible products are products for dental and oral care, such as toothpastes, mouth washes and lip balms which although not intended for ingestion may nevertheless accidentally enter the gastro-intestinal tract.
[0143] The formulations and ingredients of liquid household products, laundry products, personal care and cosmetic products, and fine fragrances, in which the fragrance composition of the invention may be used are well known to those skilled in the art, reference may be made to the following works:
[0144] - Formulating Detergents and Personal Care Products: A guide to Product Development, by L. Tan Tai Ho, ISBN 1-893997-10-3, published by the AOCS Press,
[0145] - A review of: "Liquid Detergents", K-Y. Li, Ed. Surfactant Science Series 67, Marcel Dekker, Inc (ISBN 0-8247-9391-9),
[0146] - Volume 67 of the Surfactant Science Series Liquid Detergents ISBN 0-8247-9391-9 (Marcel Dekker Inc),
[0147] - Volume 71 of the Surfactant Science Series Liquid Detergents ISBN 0-8247-9988-7 (Marcel Dekker Inc), and
[0148] - Harry's Cosmeticology, 8thEdition, 2000, published by CHS Press (ISBN 0820603724).
[0149] In an embodiment, the invention relates to a household product comprising a fragrance composition as defined above. The household product of the invention can be for example an air freshener dispenser device, a hand dishwashing product, a surface care product, a toilet care product. In an embodiment, the household product is an air freshener dispenser device for the delivery of a volatile material to the atmosphere or on inanimate surfaces (e.g. fabric surfaces as a fabric refresher). The air freshener dispenser device can be:
[0150] - a passive evaporative device selected from sprayers (such as automatic sprays, hand operated pressurised aerosol sprays or pump action sprays, as illustrated in US 2007 / 0122373), diffusers, gels, candles, waxes, wax melts, potpourri, impregnated papers, laminated cardboards, membranes using polyolefin synthetic substrates such as Teslin® as described in US 9,468,697, polyethylene membrane devices such as described in US 2005 / 0199742, fragrance gel or fragrance reserve in laminated sealed pouches such as described in IN3304MU2015, or
[0151] - an electrically powered air freshener dispenser device, preferably a piezo-electric device, or an electrically powered air freshener dispenser device comprising a heating element, as described in US 6,123,935.
[0152] According to another aspect, the household product of the invention can be cleaners for floors, solid work surfaces, tiled surfaces, crockery by hand or machine washing and mirrors and glass; and soft furnishing treatments such as liquid cleaners and refresher products such as odour treatment agents as exemplified by Febreze® (P&G). Household cleaners may be in the form of cream cleaners, isotropic liquid cleaners, spray cleaners, scent beads, liquid scent boosters and pre-moistened surface cleaning wipes (reference can be made for example to WO 91 / 08283, EP 0 743 280, WO 96 / 34938, WO 01 / 23510, WO 99 / 28428).
[0153] Spray cleaners may be dispensed from a trigger sprayer or aerosol sprayer, as are well known in the art. An aerosol sprayer dispenses the product using propellant pressure, while a trigger sprayer dispenses the product by pumping it under manual actuation. A suitable aerosol dispenser may have a dip tube or bag on valve, according to US 2015 / 0108163 and / or US 2011 / 0303766. A suitable trigger sprayer is found in US 8,322,631.
[0154] According to another aspect, the household product of the invention is a solid or liquid toilet rim block. The solid toilet rim blocks are intended to be located under the rim of a lavatory bowl or urinal such that, during a flushing cycle, water from the cistern flows over the block thereby dissolving a portion of the toilet rim block. The invention also relates to cageless rim blocks which adhere directly to the surface of the lavatory pan, and to solid toilet cistern blocks which are placed in the cistern and dissolve slowly in the water contained therein. It will be appreciated that the solubility characteristics of these two products are quite different, since one is constantly under water while the other has intermittent short-term contact with water. However, they both contain a surfactant, fillers, and a fragrance composition as defined according to the invention, and optionally bleaching agents, germicides and anti-limescale agents. Typical formulations are described in EP 0 462 643, GB 2 178 442, US 8,658,588 and US 4,874,536, which are incorporated herein by reference.
[0155] The liquid toilet rim blocks are devices that dispense liquid compositions directly into a lavatory bowl from under the rim of said bowl. Such liquid toilet rim blocks are usually attached by various means, such as hooks and the like, to the rim of the lavatory bowl. Every time a toilet equipped with a liquid toilet rim block is flushed, an amount of composition is dispensed into the lavatory bowl. Examples of liquid toilet rim blocks are given in WO 02 / 40792, EP 0 775 741 and WO 01 / 94520, which are incorporated herein by reference.
[0156] The household product of the invention can also be a cat litter, products for rubbish / garbage bins, products for rubbish / garbage dumps, or products for sewage treatment plants.
[0157] In some embodiments, the invention relates to a laundry product comprising a fragrance composition as defined above. In one aspect the laundry product is a laundry detergent (either powdered, pelleted, dissolvable sheet, tablet or liquid), a fabric softener, a fabric conditioner. Fabric softeners and conditioners specifically include both conventional diluted liquid active concentration softeners and concentrated liquid active concentration softeners, as well as fabric conditioners which may contain ingredients to protect colours or garment shape and appearance (reference can be made for example to US 6,335,315, US 5,674,832, US 5,759,990, US 5,877,145, US 5,574,179). Laundry detergents, particularly liquid laundry detergents, specifically include light duty liquid detergents and heavy duty liquid detergents which may be structured multi-phase liquids or isotropic liquids and which may be aqueous or non-aqueous liquids, and more specialised cleaners for woollen or dark garments; and fabric softeners and pre-, in- and post-wash treatments such as tumble drier sheets, ironing waters and wash additives, including scent boosters such as those branded Lenor Unstoppables™ from P&G, the Dr Beckman™ range of laundry additives from Dr. Beckman, and Vanish™ laundry additives from Reckitt Benckiser. These products may optionally contain bleaching agents or enzymes (reference can be made for example to US 5,929,022, US 5,916,862, US 5,731,278, US 5,470,507, US 5,466,802, US 5,460,752, US 5,458,810).
[0158] In some embodiments, the invention relates to personal care products and cosmetic products comprising a fragrance composition as defined above. Personal care and cosmetic products include products that can be applied to the skin, hair and nails, either as leave on or rinse off product. In the context of the invention, "rinse-off" means that the intended product use includes application to skin and / or hair followed by rinsing and / or wiping the product from the skin and / or hair within a few seconds to minutes of the application step. Personal care and cosmetic products include powders, creams, emulsions, lotions, gels and oils for the skin (face, hands, feet, etc.), tinted bases (liquids and pastes) and liquid impregnated tissues; products for applying and removing make-up from the face and eyes; hair care products including hair tints and bleaches; products for waving, straightening, setting and fixing hair; shaving products including creams, foams mousses and depilatory products; sun bathing products and products for tanning without the sun. Personal care products also include personal care underarm products such as deodorants and antiperspirant products, depilatory products, foot / shoe treatment products.
[0159] In some embodiments, a personal care or cosmetic product is selected from the group consisting of a shaving aid, a shampoo, a hair-conditioner product, a leave-on-skin-care product, a skin cleansing or washing product (such as a rinse-off skin cleansing or washing product), a moist tissue and a body spray.
[0160] Shaving aids specifically include foams, gels, creams and bars (reference can be made for example to US 7,069,658, US 6,944,952, US 6,594,904, US 6,182,365, US 6,185,822, US 6,298,558, US 5,113,585).
[0161] Shampoos and hair conditioners specifically include two-in-one shampoos, solid shampoos, dry shampoos, and shampoos especially formulated for dry or greasy hair or containing additives such as antidandruff agents. Hair conditioners may be rinse off or leave on hair conditioners also included are hair tonics, bleaches colorants, setting and styling products. Reference can be made for example to US 6,162,423, US 5,968,286, US 5,935,561, US 5,932,203, US 5,837,661, US 5,776,443, US 5,756,436, US 5,661,118, US 5,618,523.
[0162] Leave-on-skin-care products comprise skin washing products, moist tissues, body sprays, deodorants and antiperspirants. Skin washing products specifically include beauty and hygiene bar soaps, shower gels, liquid soaps, body washes, exfoliating gels and pastes (reference can be made for example to US 3,697,644, US 4,065,398, US 4,387,040).
[0163] Moist tissues (wipes) specifically include skin cleansing wipes, baby wipes, make-up removal wipes and skin refreshing wipes (reference can be made for example to US 4,775,582, WO 02 / 07701, WO 2007 / 069214, WO 95 / 16474).
[0164] Body sprays, deodorants and antiperspirants specifically include sticks, liquid roll-on applicators and pressurized sprays.
[0165] In another aspect, the personal care and cosmetic products further include absorbent articles, such as a sanitary product. Preferably said absorbent article comprises an absorbent core, and optionally a backsheet, topsheet, acquisition layer or outer wrapper, wherein the fragrance composition of the invention is disposed on the absorbent core or between one or more of the optional layers. The absorbent article can be contained in a polybag or paper carton. The absorbent article may further comprise a lotion.
[0166] In a preferred embodiment, the personal care products or cosmetic products are selected from shampoos, shower gels, conditioners, deodorants.
[0167] In some embodiments, the invention relates to a fine fragrance. In one aspect the fine fragrance is a water-based or an alcohol-based fine fragrance comprising a fragrance composition as defined above.
[0168] The invention will be better understood in the light of the following examples given by way of illustration only. In these examples the percentages expressed are percentages by weight unless otherwise mentioned.
[0169] EXAMPLES:
[0170] In the following examples and figures, the perceived habituation of different fragrance compositions was evaluated by panellists over a prolonged and continuous period of time. The fragrance intensities were rated over time at different time point leading to a time intensity curve. The curves show fragrances intensity at all evaluation time points. The difference between initial intensity and final intensity perceived by panellists after continuous exposure is expressed as a % of decrease and is related to the perceived habituation. Indeed, the lower the % of decrease is, the lower the habituation to the corresponding fragrance composition is, and the more stable the fragrance intensity is perceived. The time intensity curves were also analysed with a linear regression to obtain the speed of perceived fragrance intensity decay thanks to the slope of the linear regressions. The smaller the slope is, the lower the perceived habituation to the fragrance is.
[0171] Example 1: Sensory testing of electric air freshening compositions with a floral marine fragrance
[0172] Methodology of testing perceived habituation:
[0173] The following test was carried out in olfactory booths whose characteristics described below are typical of the characteristics used for olfactory testing. In booth A, was placed one electric air freshening unit filled with a floral marine fragrance which was the control fragrance composition (fragrance composition "1A"). In booth B, was placed another electric air freshening unit filled with a floral marine fragrance having a trigeminal- stimulating compound (a) (fragrance composition "IB")- In booth C, was placed another electric air freshening unit filled with a floral marine fragrance having an alerting material (b) (fragrance composition "1C"). In booth D, was placed another electric air freshening unit filled with a floral marine fragrance having a trigeminal-stimulating compound (a) and an alerting material (b) (fragrance composition "ID"). The compositions of the four fragrance compositions are summarised in Table 1 below.
[0174] All the electric units were powered up and allowed to equilibrate in the booths for 60 minutes prior to the test beginning. 12 females and 1 male panellists were asked to spend 60 minutes sitting in a booth once a day, on 2 separate days. The panellists visited the same booth for each 60 minutes session making then 2 repetitions. Maximum 3 panellists could enter simultaneously in the same booths for the duration of the assessment. Methods of measuring perceived intensity were employed, including the use of unstructured linear scale from 0 "no odour" to 10 "extremely strong odour". The test consists of continuously exposing a panellist during a prolonged time from 0 to 60 minutes. The panellists remained in the booth for the duration of the test and were asked to rate perceived fragrance intensity using sensory software every 15 minutes during 60 minutes.
[0175] Characteristics of smelling booths:
[0176] - Booth size: 13.2 m3,
[0177] - Conditions: 22°C + / - 2°C,
[0178] - Evaluation airflow: 2.3 m3 / h.
[0179] The results are shown in Table 2 below and in Figure 1. Table 1: Fragrance compositions (in % by weight)
[0180] Fragrance composition "IB" contains isopulegol as trigeminal stimulating compound (a). Fragrance composition "1C" contains 3-mercapto-3-methyl-l-butanol as alerting material (b). Fragrance composition "ID" contains isopulegol as trigeminal-stimulating compound (a) and 3-mercapto-3-methyl-l-butanol as alerting material (b).
[0181] The four air freshening electric units were filled with 20 mL of each of the above four fragrance compositions.
[0182] Table 2: Results of testing perceived habituation for fragrances compositions 1A, IB, 1C and ID
[0183] Table 3: Statistical analysis of pairwise comparison of the slopes of perceived fragrance intensity over time
[0184] As shown in Table 2 and Figure 1, the results demonstrated that the tested fragrance compositions were perceived with a similar intensity at 1stevaluation time point but the fragrance composition "ID" was perceived with a higher intensity between TO and T60 minutes, as well as observed with a reduced slope of perceived fragrance intensity over time compared to the control fragrance composition "1A". The decrease of the control fragrance composition "1A" intensity is much more important (52%) compared to the fragrance composition of the invention "ID" (14%). Additionally, the fragrance composition of the invention "ID" is observed and consistently rated at higher levels of intensity from T15 minutes to T60 minutes of continuous exposure compared to the fragrance composition "1C" (and obviously the two others). The rate of decay, as well as the loss of intensity, between the 1stevaluation until 60 minutes of exposure, is much reduced for the fragrance composition "ID" (14%) than fragrance composition "1C" (66%). This is accomplished without altering the character or initial intensity of the original fragrance composition "1A". A linear regression analysis of odour ratings over time was conducted to compare the slopes of fragrance composition "1A" and fragrance composition "ID" over time. The model revealed a significant difference in the effect of time on ratings depending on the fragrance composition, indicating that the slope of fragrance composition "ID" differs significantly from that of fragrance composition "1A", "IB" and "1C" (see Table 3). This demonstrates that fragrance composition "ID" decreases significantly less rapidly over time compared to fragrance composition "1A", "IB" and "1C". This shows that adding a trigeminal-stimulating compound (a) + an alerting material (b) to a fragrance compound (c) lead to a synergistic effect that helps to prevent habituation over time.
[0185] The fragrance composition of the invention thus allows a higher perceived intensity after a continuous and prolonged exposure to a fragrance. The fragrance composition of the invention showed long-lasting noticeability since the intensity scores are sustained over 60 minutes of fragrance exposure.
[0186] Example 2: Sensory testing of electric air freshening compositions with a marine fragrance
[0187] Table 4: Fragrance compositions (in % by weight)
[0188] The following test was run in olfactory booths with the characteristics described above which are typically of the characteristics used for olfactory testing. In booth A, was placed one electric air freshening unit filled with a marine fragrance which was the control fragrance composition (fragrance composition "2A"). In booth B, was placed another electric air freshening unit filled with a marine fragrance having isopulegol as trigeminal- stimulating compound (a) (fragrance composition "2B"). In booth C, was placed another electric air freshening unit filled with a marine fragrance having butyric acid as alerting material (b) (fragrance composition "2C"). In booth D, was placed another electric air freshening unit filled with a marine fragrance having isopulegol as trigeminal-stimulating compound (a) and butyric acid as alerting material (b) (fragrance composition "2D").
[0189] All the electric units were powered up and allowed to equilibrate in the booths for 60 minutes prior to the test beginning. 11 females and 1 male panellists were asked to spend 60 minutes sitting in a booth once a day, on 2 separate days. The panellists visited the same booth for each 60 minutes session making thus 2 repetitions. Maximum 3 panellists could enter simultaneously in the same booths for the duration of the assessment. Methods of measuring perceived intensity were employed, including the use of unstructured linear scale from 0 "no odour" to 10 "extremely strong odour". The test consists of continuously exposing a panellist during a prolonged time from 0 minute to 60 minutes. The panellists remained in the booth for the duration of the test and were asked to rate perceived fragrance intensity using sensory software every 15 minutes during 60 minutes. The results are shown in Table 5 below and in Figure 2. Table 5: Results of testing perceived habituation for fragrance compositions 2A, 2B, 2C and 2D
[0190] Table 6: Statistical analysis of pairwise comparison of the slopes of perceived fragrance intensity over time
[0191] As shown in Table 5 and Figure 2, the results demonstrated that the tested fragrance compositions were perceived with a similar intensity at 1stevaluation time point but the fragrance composition "2D" showed a slower rate of intensity decay compared to the control fragrance composition "2A" between TO and T60 minutes. The decrease of the control fragrance composition "2A" intensity is much more important (52%) compared to the fragrance composition "2D" (35%). Moreover, the fragrance composition "2B" is observed with a slower rate of intensity decay compared to the control fragrance composition "2A". The rate of decay is reduced (44% vs 52%). The fragrance composition "2C" is observed as well with a slower rate of intensity decay compared to the control fragrance composition "2A" (38% vs 52%). More importantly, the fragrance composition "2D" is observed with the slowest rate of intensity decay compared to the fragrance compositions "2A", "2B" and "2C". This is accomplished without altering the character or initial intensity of the original fragrance composition "2A". A linear regression analysis of odour ratings over time was conducted to compare the slopes of fragrance composition "2A" and fragrance composition "2D" over time. The model revealed a significant difference in the effect of time on ratings depending on the fragrance composition, indicating that the slope of fragrance composition "2D" differs significantly from that of fragrance composition "2A" and "2B" (see Table 6). This confirms that fragrance composition "2D" decreases significantly less rapidly over time compared to fragrance composition "2A" and "2B". This shows that adding a trigeminal-stimulating compound (a) + an alerting material (b) to a fragrance compound (c) leads to a synergistic effect that helps to prevent habituation over time.
[0192] Example 3: Sensory testing of automatic spray air freshening compositions with a linen fragrance Table 7: Fragrance compositions (in % by weight)
[0193] The following test was run in olfactory booths with the characteristics described above which are typically of the characteristics used for olfactory testing. In booth A, was placed one automatic spray air freshening unit filled with a linen fragrance which was the control fragrance composition (fragrance composition "3A"). In booth B, was placed another automatic spray air freshening unit filled with a marine fragrance having citral as trigeminal-stimulating compound (a) (fragrance composition "3B"). In booth C, another automatic spray air freshening unit filled with a marine fragrance having trimethylamine as alerting material (b). In booth D, was placed another automatic spray air freshening unit filled with a linen fragrance having a trigeminal-stimulating compound (a) and an alerting material (b) (fragrance composition "3D").
[0194] All the automatic spray units were powered up and allowed to equilibrate in the booths for 54 minutes in medium setting prior to the test beginning (on spray every 18 minutes). 4 females and 1 male panellists were asked to spend 18 minutes sitting in a booth once a day, on 2 separate days. The panellists visited the same booth for each session making thus 2 repetitions. Maximum 3 panellists could enter simultaneously in the same booths for the duration of the assessment. Methods of measuring perceived intensity were employed, including the use of unstructured linear scale from 0 "no odour" to 10 "extremely strong odour". The test consists of continuously exposing a panellist during a prolonged time from 0 minute to 18 minutes. The panellists remained in the booth for the duration of the test and were asked to rate perceived fragrance intensity using sensory software every 3 minutes during 18 minutes. The results are shown in Table 8 below and in Figure 3.
[0195] Table 8: Results of testing perceived habituation for fragrance compositions 3A, 3B, 3C and 3D
[0196] Table 9: Statistical analysis of pairwise comparison of slopes of perceived fragrance intensity over time As shown in Table 8 and Figure 3, the results demonstrated that the tested fragrance compositions were perceived with a similar intensity at 1stevaluation time point but fragrance composition "3D" was perceived with a higher intensity between TO and T18 minutes. The rate of perceived fragrance intensity decay, as well as the % of loss between the beginning to the end of exposure, are much reduced for the fragrance composition "3D" (33%) compared to the fragrance composition "3A" (73%). Moreover, the fragrance composition "3B" was observed with a slower rate of intensity decay compared to the control fragrance composition "3A" (53% vs 73%). The fragrance composition "3C" was observed as well with a slower rate of intensity decay compared to the control fragrance composition "3A" (68% vs 73%). More importantly, the fragrance composition "3D" was observed with the slowest rate of intensity decay compared to the fragrance composition "3A", "3B" and "3C". The fragrance composition of the invention "3D" was also observed and consistently rated at higher levels of intensity from TO minutes to T18 minutes of continuous exposure compared to the others. This is all accomplished without altering the character or initial intensity of the original fragrance composition "3A". A linear regression analysis of odour ratings over time was conducted to compare the slopes of fragrance composition "3A" and fragrance composition "3D" over time. The model revealed a significant difference in the effect of time on ratings depending on the fragrance composition, indicating that the slope of fragrance composition "3D" differs significantly from that of fragrance composition "3A" and "3B" (see Table 9). This confirms that fragrance composition "3D" decreases significantly less rapidly over time compared to fragrance composition "3A" and "3B". This shows that adding a trigeminal-stimulating compound (a) + an alerting material (b) to a fragrance compound (c) leads to a synergistic effect that helps to prevent habituation over time.
[0197] Example 4: Sensory testing of automatic spray air freshening compositions with a linen fragrance (effect of an alerting material comprising at least one sulphur atom)
[0198] Table 10: Fragrance compositions (in % by weight)
[0199] The following test was run in olfactory booths with the characteristics described above which are typically of the characteristics used for olfactory testing. In booth A, was placed one automatic spray air freshening unit filled with a linen fragrance which was the control fragrance composition (fragrance composition "4A"). In booth B, was placed automatic spray air freshening unit filled with a linen fragrance having a trigeminal-stimulating compound (a) (fragrance composition "4B"). In booth C, another automatic spray air freshening unit filled with a linen fragrance having an alerting material (b) (fragrance composition "4C"). In booth D, was placed another automatic spray air freshening unit filled with a linen fragrance having a trigeminal-stimulating compound (a) and an alerting material (b) (fragrance composition "4D").
[0200] All the automatic spray units were powered up and allowed to equilibrate in the booths for 54 minutes in medium setting prior to the test began (one spray every 18 minutes). 3 females and 1 male panellists were asked to spend 18 minutes sitting in a booth once a day, on 2 separate days. The panellists visited the same booth for each session making thus 2 repetitions. Maximum 3 panellists could enter simultaneously in the same booths for the duration of the assessment. Methods of measuring perceived intensity were employed, including the use of unstructured linear scale from 0 "no odour" to 10 "extremely strong odour". The test consists of continuously exposing a panellist during a prolonged time from 0 minute to 18 minutes. The panellists remained in the booth for the duration of the test and were asked to rate perceived fragrance intensity using sensory software every 3 minutes during 18 minutes. The results are shown in Table 11 below and in Figure 4. Table 11: Results of testing perceived habituation for fragrance compositions 4A, 4B, 4C and 4D
[0201] Table 12: Statistical analysis of pairwise comparison of the slope of perceived fragrance intensity over time
[0202] As shown in Table 11 and Figure 4, the results demonstrated that the tested fragrance compositions were perceived with a similar intensity at 1stevaluation time point but fragrance composition "4D" was perceived with a higher intensity between TO and T18 minutes. The rate of the perceived fragrance intensity decay, as well as the % of loss between the beginning to the end of exposure, are much reduced for the fragrance composition "4D" (27%) compared to the fragrance composition "4A" (73%). More importantly, the fragrance composition "4D" was also observed with the slowest rate of intensity decay compared to the fragrance composition "4A", "4B" and "4C". The fragrance of the invention "4D" was also observed and consistently rated at higher levels of intensity from TO minutes to T18 minutes of continuous exposure compared to the others. This is all accomplished without altering the character or initial intensity of the original fragrance composition "4A". A linear regression analysis of odour ratings over time was conducted to compare the slopes of fragrance composition "4A" and fragrance composition "4D" over time. The model revealed a significant difference in the effect of time on ratings depending on the fragrance composition, indicating that the slope of fragrance composition "4D" differs significantly from that of fragrance composition "4A", "4B" and "4C" (see Table 12). This confirms that fragrance composition "4D" decreases significantly less rapidly over time compared to fragrance composition "4A", "4B" and "4C". This shows that adding a trigeminal-stimulating compound (a) + an alerting material (b) to a fragrance compound (c) leads to a synergistic effect that helps to prevent habituation over time.
[0203] Example 5: Sensory testing of electric air freshening compositions with a marine fragrance
[0204] Table 13: Fragrance compositions (in % by weight)
[0205] Fragrance composition "5A", containing five trigeminal-stimulating compounds, one alerting material with a sulfur atom, one alerting material with a nitrogen atom, was found to exhibit an unexpectedly stable fragrance strength over an extended period of time.
Claims
CLAIMS1. A fragrance composition comprising:(a) at least one, and preferably at least two, trigeminal-stimulating compounds,(b) at least one, and preferably at least two, alerting materials which comprises at least one sulphur atom or at least one nitrogen atom or at least one carboxylic acid or carboxylate moiety, and(c) at least one fragrance compound other than said at least one trigeminal- stimulating compound (a) and other than said at least one alerting material (b), wherein the at least one alerting material (b) represents from 1x1010to 3x101%, preferably from lxlO-9to 2x101%, more preferably from lxlO-8to 2x101%, even more preferably from lxlO-7to 1x101%, and even more preferably from 1x1010to 1x101%, by weight of the total of the fragrance composition.
2. A fragrance composition according to claim 1, wherein the alerting material (b) is a compound comprising: at least one sulphur atom which is selected from a thiol moiety, a sulphide moiety, a disulphide moiety, a thiazole moiety, on oxathiane moiety, and / or at least one nitrogen atom which is selected from a pyrazine moiety (including tri substituted pyrazine moieties and methoxy-pyrazine moieties), a nitrile moiety, an indole moiety, an oxime moiety, an amine moiety, an isothiocyanate, a diamine moiety, and / or at least one carboxylic acid or carboxylate moiety, and / or mixtures thereof, and preferably at least one sulphur atom which is selected from a thiol moiety or a sulphide moiety.
3. A fragrance composition according to claim 1 or claim 2, wherein the alerting material (b) is a compound comprising at least one sulphur atom selected from 2- mercapto-3-methyl-l-butanol, 3-mercapto-3-methyl-l-butanol, 3-mercapto-3-methylbutyl formate, 3-mercapto-2-methyl-l-pentanol, 3-mercapto-2-methyl-l-propanol, 3-methyl-3- sulfanylhexanol, 3-methyl-3(2-methyldisulfanyl)-butan-l-ol, 3-mercapto-3-methyl-l- hexanol, 3-mercapto-2-methylpentanal, l-mercapto-3-pentanone, 2-mercapto-3- pentanone, 3-mercapto-3-pentanone, 3-methyl-3-mercaptobutyl acetate, 1-propanethiol,methanethiol, methional, p-mentha-8-thiol-3-one, 2-naphthalenethiol, 3-methyl-3- mercaptobutyl formate, l-methoxyheptane-3-thiol, 4-methoxy-2-methylbutane-2-thiol, 1- propanethiol, thioglycolic acid, dithioglycolic acid, methyl-2-propenyl disulphide, 2,4- dithiapentane, dimethyl sulphide, dimethyl disulphide, dimethyl trisulphide, diallyl sulphide, diallyl trisulphide, allyl mercaptan, allicin, alliin, cysteine, 1- butylsulphanylbutane, 3-hydroxy-4,5-dimethylfuran-2(5H)-one, and mixtures thereof, and preferably 3-mercapto-3-methyl-l-butanol, 3-mercapto-2-methyl-l-pentanol, dimethylsulfide, dimethyl disulphide, dimethyl trisulphide, diallyl sulphide, diallyl trisulphide, 3-hydroxy-4,5-dimethylfuran-2(5H)-one, and mixtures thereof.
4. A fragrance composition according to claim 1 or claim 2, wherein the alerting material (b) is a compound comprising at least one nitrogen atom selected from 2- methylpyrazine, 2,3-dimethylprazine, 2,5-dimethylpyrazine, 2-ethyl-3,5-dimethylpyrazine, 2,3-diethyl-5-methylpyrazine, 2,6-dimethylpyrazine, 2-ethyl-3-methoxypyrazine, 3- methoxy-2-isobutylpyrazine, acetonitrile, benzonitrile, 2-methylindole, 2-methyl-2- thiazoline, acetoxime, butyraldoxime, methylamine, ethylamine, phenethylamine, phenyl isothiocyanate, allyl isothiocyanate, ethylenediamine, 1,4-butanediamine, hexamethylenediamine, methylamine, ethylamine, trimethylamine, cadaverine, and mixtures thereof, preferably 2,3-diethyl-5-methylpyrazine, acetonitrile, benzonitrile, 2- methyl-2-thiazoline, acetoxime, butyraldoxime, methylamine, ethylamine, phenethylamine, phenyl isothiocyanate, allyl isothiocyanate, ethylenediamine, 1,4- butanediamine, hexamethylenediamine, methylamine, ethylamine, trimethylamine, cadaverine, and mixtures thereof, and more preferably 2,3-diethyl-5-methylpyrazine, 2- ethyl-3-methoxypyrazine, methylamine, ethylamine, trimethylamine, and mixtures thereof.
5. A fragrance composition according to claim 1 or claim 2, wherein the alerting material (b) is a compound comprising at least one carboxylic acid moiety selected from 3-methylhexanoic acid, 4-ethyloctanoic acid, trans-3 -hexenoic acid, propionic acid, nonanoic acid, myristic acid, capric acid, 3-methyl-2-hexenoic acid, 3-hydroxy-3- methylhexanoic acid, 3-hexenoic acid, acetic acid, benzoic acid, butyric acid, caproic acid, citric acid, formic acid, lactic acid, oxalic acid, succinic acid, tartaric acid, valeric acid, isovaleric acid, malonic acid, and mixtures thereof, and preferably butyric acid, caproic acid, isovaleric acid, and mixtures thereof.
6. A fragrance composition according to any of claims 1 to 5, wherein the alerting material (b) is a compound selected from 3-mercapto-3-methyl-l-butanol, 3-mercapto-2- methyl-l-pentanol, dimethylsulfide, dimethyl disulphide, dimethyl trisulphide, diallyl sulphide, diallyl trisulphide, 3-hydroxy-4,5-dimethylfuran-2(5H)-one, 2,3-diethyl-5- methylpyrazine, 2-ethyl-3-methoxypyrazine, methylamine, ethylamine, trimethylamine, butyric acid, caproic acid, isovaleric acid, and mixtures thereof.
7. A fragrance composition according to any of claims 1 to 6, wherein the at least one trigeminal-stimulating compound (a) is selected from cooling compounds, warming compounds, tingling compounds, and mixtures thereof, and preferably cooling compounds and mixtures thereof.
8. A fragrance composition according to claim 7, wherein the cooling compounds are selected from menthol, menthone, camphor, pulegone, pulegol, isopulegol, cineole, 2- isopropyl-N-2,3-trimethylbutyramide, N-ethyl-2-isopropyl-5-methylcyclohexane carboxamide, ethyl 3-(p-menthane-3-carboxamido) acetate, N-(4-methoxyphenyl)-p- menthanecarboxamide, N-ethyl-2,2-diisopropylbutanamide, N-cyclopropyl-5-methyl-2- isopropylcyclohexanecarboxamide, N-(l,l-dimethyl-2-hydroxyethyl)-2,2- diethylbutanamide, N-(4-cyanomethylphenyl)-p-menthanecarboxamide, N-(2-(pyridin-2- yl)ethyl)-3-p-menthanecarboxamide, N-(2-hydroxyethyl)-2-isopropyl-2,3- dimethylbutanamide, cyclopropanecarboxylic acid (2-isopropyl-5-methyl-cyclohexyl)- amide, N-[4-(2-amino-2-oxoethyl)phenyl]-p-menthanecarboxamide, menthyl pyrrolidone carboxylate, cubebol, icilin, 2-isopropyl-5-methylcyclohexyl 4-(dimethylamino)-4- oxobutanoate, N-benzo[l,3]dioxol-5-yl-3-p-menthanecarboxamide, N-benzooxazol-4-yl-3- p-menthanecarboxamide, N-4-([l,2,4]triazol-l-yl)-phenyl-3-p-menthanecarboxamide, p- menthane carboxamide, N-4-(pyrazol-l-yl)-phenyl-3-p-menthanecarboxamide, N-(l- isopropyl-l,2-dimethylpropyl)-l,3-benzodioxole-5-carboxamide, N-(l-methyl-l- isopropylbutyl)benzamide, fenchyl-N,N-dimethylsuccinamide, fenchyl monosuccinate, ethyl fenchyl malonate, bornyl monosuccinate, isobornyl monosuccinate, menthyl 3- oxobutyrate, menthyl 3-oxopentanoate, 3-methoxypropane-l,2-diol, 3-methoxy-2- methylpropane-l,2-diol, p-methane-3,8-diol, 2-1-methoxyethan-l-ol, 3-methoxypropan-l- ol, 4-methoxybutan-l-ol, methyl 3-hydroxybutyrate, 6-isopropyl-9-methyl-l,4-dioxaspiro- (4,5)-decane-2-methanol, 2-[(2-p-methoxy)ethoxy]ethanol, methyl succinate, methyl glutarate, dimethyl succinate, dimethyl glutarate, menthyl acetate, menthyl lactate,menthone glycerin ketal, mint oil, peppermint oil, peppermint cyclohexanone, spearmint oil, eucalyptus oil, l-(2-hydroxy-4-methylcyclohexyl)ethanone, pennyroyal oil, armoise oil, cornmint oil, cinnamon oil, borneol, ringonol, sinensal, piperitone thymol, and mixtures thereof, preferably menthol, menthone, camphor, pulegol, isopulegol, menthyl acetate, menthyl lactate, p-menthane-3,8-diol, mint oil, l-(2-hydroxy-4- methylcyclohexyl)ethanone_. spearmint oil, cinnamon oil, and mixtures thereof, more preferably pulegol, isopulegol, menthyl acetate, menthyl lactate, p-menthane-3,8-diol, 1- (2-hydroxy-4-methylcyclohexyl)ethanone, and mixtures thereof, and even more preferably isopulegol.
9. A fragrance composition according to any of claims 1 to 7, wherein the warming compounds are selected from vanillyl ethyl ether, vanillyl n-propyl ether, vanillyl isopropyl ether, vanillyl butyl ether, vanillin, vanillyl alcohol, ethyl vanillin, ethyl vanillyl alcohol, vanitrope, veraspice, ethyl maltol (veltol plus), 2-ethoxy-4-methylphenol, vanillin isobutyrate (Isobutavan®), cinnamaldehyde, N-acetylcysteine ethyl ester (NACET), guaiacol, phenyethyl alcohol, cyclohexanone, perilla aldehyde, gingerol, spice oils such as ginger oil, pepper oil, their extracts, and mixtures thereof, and preferably vanillyl ethyl ether, vanillyl n-propyl ether, vanillyl isopropyl ether, vanillyl butyl ether, vanitrope, veraspice, 2-ethoxy-4-methylphenol, vanillin isobutyrate (Isobutavan®), N-acetylcysteine ethyl ester (NACET), guaiacol, cyclohexanone, perilla aldehyde, gingerol, spice oils, their extracts, and mixtures thereof.
10. A fragrance composition according to any of claims 1 to 7, wherein the tingling compounds are selected from elemol, elemicin, elemi oil, lime oxide, citral, L-carvone, ocimene quintoxide, 2-isopropenyl-5-methyl-5-vinyltetrahydrofuran, jambu oleoresin, spilanthol, di hydromyrcene, perilla aldehyde, and mixtures thereof, preferably elemol, elemicin, ocimene quintoxide, 2-isopropenyl-5-methyl-5-vinyltetrahydrofuran, jambu, oleoresin, spilanthol, di hydromyrcene, perilla aldehyde, and mixtures thereof, and more preferably elemi oil, lime oxide, citral, L-carvone, and mixtures thereof.
11. A fragrance composition according to any of claims 1 to 10, wherein the fragrance compound (c) comprises fewer than three heteroatoms and a molecular weight ranging from 30 to 300 g.mol'1.
12. A fragrance composition according to any of claims 1 to 11, comprising at least two distinct fragrance compounds (c), and preferably at least five distinct fragrance compounds (c), the fragrance compounds (c) advantageously has a CLogP of at least 1.5, and more advantageously has a CLogP ranging from 1.5 to 6.
13. A fragrance composition according to any of claims 1 to 12, wherein the at least one trigeminal-stimulating compound (a) represents from 0.01 to 5%, preferably from 0.02 to 2%, more preferably from 0.05 to 1%, more preferably from 0.01 to less than 1%, more preferably from 0.02 to less than 1%, and even more preferably from 0.05 to 0.9%, by weight of the total of the fragrance composition.
14. A fragrance composition according to any of claims 1 to 13, wherein the at least one alerting material (b) represents from lxlO-8to 3x101%, and more preferably from lxlO-7to 3x101%, by weight of the total of the fragrance composition.
15. A fragrance composition according to any of claims 1 to 14, wherein the at least one fragrance compound (c) represents from 60 to 99.9%, preferably from 70 to 99.9%, and more preferably 80 to 99.9%, by weight of the total of the fragrance composition.
16. A fragrance composition according to any of claims 1 to 15, wherein the fragrance composition further comprises at least one support material, preferably at least one solvent or UV stabilizer, and more preferably at least one solvent selected from hydrocarbons, ethers, dialkyl adipates, dialkyl succinates, dialkyl glutarates, citrate esters, soybean methyl ester, diethyl phthalate, diethylene glycol monoethyl ether, 3-methoxy-3- methyl-l-butanol, dipropylene glycol, isopropylidene glycerol, C1-C5 alkyl butyrate, and mixtures thereof, and preferably hydrocarbons, dipropylene glycol, C1-C5 alkyl butyrate, and mixtures thereof.
17. Use of at least one trigeminal-stimulating compound (a) in combination with at least one alerting material (b) which comprises at least one sulphur atom or at least one nitrogen atom or at least one carboxylic acid or carboxylate moiety, in a fragrance composition, for reducing and / or eliminating habituation to this fragrance composition.
18. A method for reducing and / or eliminating habituation to the odour of a fragrance composition, comprising the step of adding at least one trigeminal-stimulating compound (a) in combination with at least one alerting material (b) which comprises at least one sulphur atom or at least one nitrogen atom or at least one carboxylic acid or carboxylate moiety, to the fragrance composition.
19. A consumer product comprising a fragrance composition according to any of claims 1 to 16 or a fragrance product comprising a quantity, preferably from 0.2 to 100% by weight, of a fragrance composition according to any of claims 1 to 15.
20. A consumer product according to claim 19, which is a household product, a laundry product, a personal care product, a cosmetic product, or a fine fragrance.
21. A consumer product according to claim 20, which is a household product selected from air freshener dispenser devices, hand dishwashing products, surface care products, toilet care products.
22. A consumer product according to claim 20, which is a laundry product selected from laundry detergents, fabric softeners, fabric conditioners.
23. A consumer product according to claim 20, which is a personal care or cosmetic product selected from shampoos, shower gels, conditioners, deodorants.
24. A consumer product according to claim 20, which is a water-based or alcohol- based fine fragrance.