Patent Application
20150164764
The present application relates to the field of perfumery. In particular, the compositions can have improved intensity and/or longevity of the fragrance profile.
It has been a long tradition that highly skilled perfumers carefully select fragrance materials to blend into a composition with the goal of achieving an overall specific fragrance profile of strength and character. In so doing, they need to bear in mind differences in the individual character and volatility of the fragrance materials that are the components of the full fragrance. Conventional perfuming compositions have fragrance profile characterized by a high amount of the low volatile fragrance materials and lower amounts of the volatile fragrance materials. The low volatile fragrance materials are known as “base notes”, while the volatile fragrance materials can be further divided into high volatile fragrance materials, identified as “top or head notes”, and medium volatile fragrance materials, identified as “middle or heart notes”.
The top notes tend to smell citrusy, green, light, fresh, and comprise typically from about 0.1 wt % to 40 wt % relative to the total weight of the perfume formulation. Top notes tend to evaporate quickly due to their high volatility and are characterized by vapor pressure >0.1 Torr at 25° C. (Calculated using Advanced Chemistry Development (ACD/Labs) Software V11.02 (© 1994-2013 ACD/Labs)). Typically, perfumers use top notes to deliver the initial impression of the composition but do not rely on them to contribute much to its overall fragrance profile over time after application.
Middle or heart notes make up from about 0.1 wt % to about 40 wt % relative to the total weight of the perfume formulation. Generally, they become dominant to the untrained nose from several minutes after application and can last up to a few hours afterwards. Middle notes are associated with floral aromas (e.g., jasmin, rose), fruity, marine or spicy aromas and have an intermediate volatity in the vapor pressure range of 0.001 to 0.1 Torr at 25° C.
Base or bottom notes can exist at >30 wt % relative to the total weight of the perfume formulation. They are characterized as animalic, woody, sweet, amber or musky, not being very volatile and having a vapor pressure <0.001 Torr at 25° C. Typically, they are not perceived as dominant until several hours after the application of the perfume or during “dry-down”. Base notes are relied upon to improve the strength of the overall fragrance profile over time and replace the heart notes when these are declining, The consequence of using base notes at high levels is that they impart particular odour characters, such as for example, musky, woody, ambery, warm and sweet, which overpower and dominate the fragrance character over time. Some of these base notes have become such common materials (e.g., hedione, galaxolide, etc.) that many fragrance dry-downs appear repetitive, boring, non-memorable and un-interesting to consumers. However, if base notes are reduced or excluded then the fragrance strength weakens over time and does not last for a sufficient duration.
To date, due to the volatility of the fragrance materials, the possible types of fragrance profiles or characters have been somewhat limited. A common complaint by consumers is that middle notes tend to fade too quickly after application of the composition and that the character of the middle notes are undesirably altered by the presence of large amounts of the base notes during the period known as the “dry-down” phase.
Thus, it is desirable to have a composition which retains a significant portion of its initial fragrance character over time, hence, the floral, fruity or spicy characters of the ‘heart notes’ are perceived for many hours It is also desirable that the fragrance strength of the composition remains noticeable to the consumer over longer periods of time. It is further desirable to be able to create new to the world fragrance profiles wherein one, or several, well-recognized heart note characters, are maintained over time.
It is therefore a challenge to formulate a composition having improved longevity of the fragrance character, without having the fragrance character substantially altered over time by the presence of the base notes in the composition. One approach for addressing the challenge has been to formulate with higher proportions of perfume raw materials with a low volatility and which are therefore more substantive on the substrate. However, as discussed above, this restricts the type of fragrance profile that can be achieved over time.
Another approach, as disclosed in U.S. Pat. No. 4,264,478 (Amerchol Corp.), has been to use a non-odorous material, such as an alkoxylated methyl glucoside, as a modulator to extend the longevity of the perfume raw materials, which are normally too volatile to last for very long. However, U.S. Pat. No. '478 simply teaches the addition of the modulator to an existing fragrance composition with a traditional construction of high levels of base note materials. As such, the resultant overall effect on the fragrance profile of the composition would be to make the whole fragrance weaker because the impact of the modulator on the more volatile fragrance materials cannot be noticed due to the presence of excessive levels of the base notes in the composition.
Similarly, Moshel, et al., Perfumer & Flavorist, Vol. 7, pp. 41-47, 1982, teaches that alkoxylated methyl glucosides function as a “fixative” and bind to individual perfume raw materials for improving the longevity of a particular perfume raw material. Moshel, et al., shows that the fixative's ability to improve the longevity for any particular perfume raw material will depend on its boiling point. However, Moshel, et al., does not disclose or suggest how to formulate with the fixative for a full fragrance composition, which incorporates multiple perfume raw materials, so that the fragrance strength is maintained and the character of the middle notes is perceived as dominant after many hours.
As such the prior art teachings still have limitations, and do not adequately teach how to provide a composition wherein the prolonged fragrance profile has sufficient strength to be noticeable and remains distinctive in character over time. Therefore, there remains a need for a composition that is perceived by the consumer over long duration after application. There is also a need for a composition which exhibits enhanced intensity of the fragrance profile over time, so that the volatile fragrance materials remains significantly consistent from its initial impression to the end. It is desirable that the compositions are relevant to fragrances derived from volatile fragrance materials having a vapor pressure ≧0.001 Torr at 25° C.
In one example, a composition comprises: (i) a fragrance component present in an amount of about 0.04 wt % to about 30 wt %, relative to the total weight of the composition; and wherein: (a) the fragrance component comprises at least one low volatile fragrance material having a vapor pressure less than 0.001 Torr at 25° C.; and (b) the low volatile fragrance material is present in an amount of from about 0.1 wt % to about 30 wt %, relative to the total weight of the fragrance component; and (ii) at least one alkoxylated glucoside non-odorous fragrance modulator in an amount of about 0.1 wt % to about 20 wt %, relative to the total weight of the composition.
These and other features of the present invention will become apparent to one skilled in the art upon review of the following detailed description and the appended claims.
While the specification concludes with claims particularly pointing out and distinctly claiming the invention, it is believed that the invention will be better understood from the following description of the accompanying figures wherein:
As used herein, articles such as “a” and “an” when used in a claim, are understood to mean one or more of what is claimed or described.
As used herein, the terms “include”, “includes” and “including” are meant to be non-limiting.
As used herein, the term “composition” includes a fine fragrance composition intended for application to a body surface, such as for example, skin or hair, i.e., to impart a pleasant odour thereto, or cover a malodour thereof. They are generally in the form of perfume concentrates, perfumes, eau de parfums, eau de toilettes, aftershaves, colognes, body splashes, or body sprays. The fine fragrance compositions may be ethanol based compositions. The term “composition” may also include a cosmetic composition, which comprises a fragrance material for the purposes of delivering a pleasant smell to drive consumer acceptance of the cosmetic composition. The term “composition” may also include cleaning compositions, such as fabric care composition or home care compositions, including air care compositions, for use on clothing or other substrates such as hard surfaces (e.g., dishes, floors, countertops). Additional non-limiting examples of “composition” may also include facial or body powder, foundation, body/facial oil, mousse, creams (e.g., cold creams), waxes, sunscreens and blocks, bath and shower gels, lip balms, self-tanning compositions, masks and patches.
As used herein, the term “consumer” means both the user of the composition and the observer nearby or around the user.
As used herein, the term “fragrance material” and “fragrance materials” relates to a perfume raw material, or a mixture of perfume raw materials, that are used to impart an overall pleasant odour or fragrance profile to a composition. “Fragrance materials” can encompass any suitable perfume raw materials for fragrance uses, including materials such as, for example, alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpene hydrocarbons, nitrogenous or sulfurous heterocyclic compounds and essential oils. However, naturally occurring plant and animal oils and exudates comprising complex mixtures of various chemical components are also know for use as “fragrance materials”. The individual perfume raw materials which comprise a known natural oil can be found by reference to Journals commonly used by those skilled in the art such as “Perfume and Flavourist” or “Journal of Essential Oil Research”, or listed in reference texts such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, N.J., USA and more recently re-published by Allured Publishing Corporation Illinois (1994). Additionally, some perfume raw materials are supplied by the fragrance houses (Firmenich, International Flavors & Fragrances, Givaudan, Symrise) as mixtures in the form of proprietary specialty accords. Non-limiting examples of the fragrance materials useful herein include pro-fragrances such as acetal pro-fragrances, ketal pro-fragrances, ester pro-fragrances, hydrolyzable inorganic-organic pro-fragrances, and mixtures thereof. The fragrance materials may be released from the pro-fragrances in a number of ways. For example, the fragrance may be released as a result of simple hydrolysis, or by a shift in an equilibrium reaction, or by a pH-change, or by enzymatic release.
As used herein, the term “fragrance profile” means the description of how the fragrance perceived by the human nose evolves over time from when it is first applied. It is a result of the combination of the top, middle and base notes, if present, of a fragrance. A fragrance profile is composed of 2 characteristics: ‘intensity’ and ‘character’. The ‘intensity’ relates to the perceived strength whilst ‘character’ refers to the odour impression or quality of the perfume, i.e., fruity, floral, woody, etc.
As used herein, the terms “perfume” and “fragrance” are used interchangeably to designate the component in the composition that is formed of fragrance materials, i.e., ingredients capable of imparting or modifying the odour of skin or hair or other substrate.
As used herein, the terms “modulator” and “fixative” are used interchangeably to designate an agent having the capacity to affect the fragrance profile by impacting the fragrance materials' evaporation rate. By incorporating the modulator, it is desired that the fragrance profile, like the volatile fragrance materials components, of the composition can be perceived by an observer or user thereof, over a longer period of time, as compared to the same perception in the absence of the modulator. In particular, alkoxylated glucoside, like PPG-20 Methyl Glucose Ether (Glucam™ P-20 available from Lubrizol (USA)), is a modulator of the perceived tenacity of the compositions, i.e., it is used to prolong the perceived intensity of the fragrance profile over time, as compared to the perception when PPG-20 Methyl Glucose Ether is not used in the composition. However, simply adding modulators to a traditionally constructed fragrance composition will not ensure an improved or enhanced fragrance profile over time. Instead, when the modulators are added in the presence of reduce levels of low volatile fragrance materials the intensity of the fragrance profile, like the volatile fragrance materials, can be perceived for longer periods as compared to control composition absent the modulators and low levels of low volatile fragrance materials.
As used herein, the term “co-modulator” means an agent that is added to the composition in addition to the modulators and has the similar function of impacting the evaporation rate and intensity of the fragrance materials, so as to improve or prolong the perception of the fragrance profile by the consumer. An example of a co-modulator is isocetyl alcohol (CERAPHYL® ICA; see PCT Publication No. WO2013/64412 (Firmenich)).
As used herein, the term “non-odorous” means an agent that does not impart an odour of its own when added into an exemplary composition. For example, a “non-odorous modulator” such as PPG-20 Methyl Glucose Ether does not impart a new odour that alters the character of the composition to which it is added.
As used herein, the term “vapor pressure” means the partial pressure in air at a defined temperature for a given chemical species. It defines a chemical species' desire to be in the gas phase rather than the liquid or solid state. The higher the vapour pressure the greater the proportion of the material that will, at equilibrium, be found in a closed headspace. It is also related to the rate of evaporation of a fragrance material which is defined in an open environment where material is leaving the system. The vapor pressure is determined according to the reference program Advanced Chemistry Development (ACD/Labs) Software Version 11.02, (© 1994-2013).
It is understood that the test methods that are disclosed in the Test Methods Section of the present application are to be used to determine the respective values of the parameters of as described and claimed herein.
All percentages are by weight of the total composition unless specifically stated otherwise. All ratios are weight ratios, unless specifically stated otherwise, and all measurements are made at 25° C., unless otherwise designated.
A composition can comprise a fragrance component present in an amount of from about 0.04 wt % to 30 wt %, relative to the total weight of the composition. The fragrance component may also be less than about 25 wt %, less than about 20 wt %, less than about 15 wt %, less than about 10 wt % or less than about 8 wt %, relative to the total weight of the composition. The fragrance component may be present in an amount of from about 0.04 wt %, 0.3 wt %, 1 wt %, 8 wt % or 10 wt %, to about 15 wt %, 20 wt %, 25 wt % or 30 wt %, relative to the total weight of the composition.
Further, the fragrance component comprises at least one low volatile fragrance material having a vapor pressure <0.001 Torr at 25° C. For example, a composition comprises at least 5 low volatile fragrance materials. A composition comprises low, very low, or even negligible, levels of the low volatile fragrance materials than would traditionally be present in a fragrance composition. As such, compositions can comprise low levels of the volatile fragrance material present in an amount of from about 0.01 wt % to about 30 wt %, less than about 25%, less than about 20 wt %, less than about 12 wt %, less than about 10 wt %, less than about 8 wt %, less than about 5 wt %, less than about 2 wt %, less than about 1 wt %, or combinations thereof, relative to the total weight of the fragrance component. Alternatively, the low volatile fragrance material is present in an amount of from about 0.01 wt %, 1 wt %, 2 wt %, 5 wt %, 8 wt %, 10 wt %, 12 wt %, 15 wt %, 20 wt %, 25 wt % or 30 wt %, relative to the total weight of the fragrance component. If there is more than one low volatile fragrance materials, then the ranges provided hereinabove cover the total of all of the low volatile fragrance materials.
The composition further comprises at least one non-odorous fragrance modulator formed from an alkoxylated glucoside. The non-odorous fragrance modulator can be selected, for example, from the group consisting of methyl glucoside polyol, ethyl glucoside polyol, and propyl glucoside polyol. In one example, the alkoxylated glucoside is PPG-20 Methyl Glucose Ether (GLUCAM™ P-20 available from Lubrizol, USA). The alkoxylated glucoside is present in an amount of from about 0.1 wt % to about 20 wt %, from about 0.5 wt % to about 18 wt %, from about 2.5 wt % to about 15 wt %, or combinations thereof, relative to the total weight of the composition. The alkoxylated glucoside is present in an amount of from about 0.1 wt %, 0.5 wt % or 2.5 wt %, to about 15 wt %, 18 wt % or 20 wt %, relative to the total weight of the composition. If there is more than one non-odorous fragrance modulators, then the ranges provided hereinabove cover the total of all of the non-odorous fragrance modulators.
The non-odorous modulator can be a liquid at temperatures lower than 100° C., even at ambient temperature. In one example, non-odorous modulators are fully miscible with the PRMs to form a single phase liquid. However, if the PRMs are not entirely miscible, or are immiscible, then co-solvents (e.g., dipropylene glycol (DPG), triethyl citrate, or others as well known to those skilled in the art) can be added to aid in the solubility of the PRMs.
It has been surprisingly discovered that by reducing the levels of the low volatile fragrance materials (i.e., base notes) in a composition, the effect of the non-odorous modulator on the fragrance profile, particularly the portion of the fragrance profile which is derived from volatile fragrance materials (i.e., top and middle notes), can be improved. By “improved” it is meant that the fragrance character of the composition, particular the components contributed by the volatile fragrance materials, can be perceived by the consumer at later time points such as, for example, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, and possibly all the way up to 24 hrs after application as compared to controls, i.e., compositions containing normal or large levels of the low volatile fragrance materials and the non-odorous modulator or compositions containing reduced levels of low volatility fragrance materials and no non-odorous modulator.
Alternatively, by “improved” it can mean that the perception of the components contributed by the volatile fragrance materials, by the consumer, is markedly increased or enhanced as compared to the controls. “Increased” or “enhanced” perception of the fragrance profile means that the consumer perceives the fragrance profile of a composition as not changing from its initial impression or the changes are minimal from when the composition was first applied to when it dissipates.
Typically, it has been very difficult to formulate fragrance profile with an accord, particularly a floral accord characteristic of the middle notes, which can last for very long periods, especially throughout the life of the composition after its application, without giving way to the stronger odours of the base notes. Reducing levels of the low volatile fragrance materials (i.e., base notes) with the modulators will allow perfumers to increase the perception of the volatile perfume materials, particularly the middle notes, to create new characters and address a re-occurring consumer issue that particular fragrance profiles, particularly the floral aromas, do not last long enough.
Such a solution as presented herein provides enhanced longevity of the fragrance profile, particularly amongst those composition formulated from volatile fragrance materials having medium to high vapor pressure ranges (≧0.001 Torr at 25° C.), without having to rely on the presence or significant amounts of the low volatile fragrance materials, which has a tendency to overpower and alter the overall character of a fragrance. This provides the perfumer options to formulate accords having new fragrance profiles.
The fragrance component can further comprise one or more volatile fragrance materials having a vapor pressure ≧0.001 Torr at 25° C. The volatile fragrance material is present in an amount of from about 70 wt % to about 99.9 wt %, greater than about 80 wt %, or greater than 88 wt %, or combinations thereof, relative to the total weight of the fragrance component. In addition, the volatile fragrance material can be present in an amount of from about 70 wt %, 75 wt %, 80 wt %, 85 wt %, 88 wt %, to about 90 wt %, 92 wt %, 95 wt %, 98 wt % or 99.9 wt %, relative to the total weight of the fragrance component. The compositions can comprise at least 5, at least 10, at least 15 or at least 20, volatile fragrance materials. If there is more than one volatile fragrance materials, then the ranges provided hereinabove cover the total weight of all of the volatile fragrance materials.
Volatile fragrance materials can be divided into: (i) a high volatile fragrance material having a vapor pressure >0.1 Torr at 25° C. and (ii) a medium volatile fragrance material having a vapor pressure in the range of from 0.001 Torr at 25° C. to 0.1 Torr at 25° C. While the further classification of the volatile fragrance materials into high and medium volatile fragrance materials is provided to help illustrate the fragrance characters of the perfume raw materials and is useful for when it comes to formulating new fragrance profiles, it should not be construed as limiting on what qualifies as a volatile fragrance material.
The low volatile fragrance material can be selected, for example, from ingredients listed in Table 1 hereinafter.
A composition may further comprise one or more non-odorous fragrance co-modulators selected from the group consisting of:
(i) Isocetyl alcohol (CERAPHYL® ICA);
(ii) PPG-3 myristyl ether (like Tegosoft™ APM and/or Varonic® APM);
(iii) Neopentyl glycol diethylhexanoate (like Schercemol™ NGDO); and
(iv) a mixture thereof;
wherein the fragrance co-modulators are present in an amount of from about 0.05 wt % to about 10 wt %, from about 0.5 wt % to about 6 wt %, from about 0.05 wt % or 0.5 wt % to about 6 wt % or 10 wt %, or combinations thereof, relative to the total weight of the composition. If there is more than one non-odorous fragrance co-modulator, then the ranges provided hereinabove cover all of the non-odorous fragrance co-modulators.
The non-odorous fragrance modulators are formed, for example, of at least 50 wt % of a non-odorous fragrance modulator, relative to the total weight of the non-odorous modulators and the non-odorous co-modulators present in the composition.
A composition may also comprise:
The composition may also comprise an entrapment material at a level such that the weight ratio of the entrapment material to the fragrance materials is in the range of from about 1:20 to about 20:1. The composition may comprise an entrapment material in the amount of from about 0.001 wt % to about 40 wt %, from about 0.1 wt % to about 25 wt %, from about 0.3 wt % to about 20 wt %, from about 0.5 wt % to about 10 wt %, or from about 0.75 wt % to about 5 wt %, relative to the total weight of the composition.
Suitable entrapment materials for use herein are selected from polymers; capsules, microcapsules and nanocapsules; liposomes, absorbents; cyclic oligosaccharides and mixtures thereof. Cyclic oligosaccharides can include PCT Publication Nos. WO2000/67721 (Procter & Gamble); and WO2000/67720 (Procter & Gamble); and U.S. Pat. No. 6,893,647 (Procter & Gamble)).
As used herein, the term “cyclic oligosaccharide” means a cyclic structure comprising six or more saccharide units. In one example, cyclic oligosaccharides have six, seven, or eight saccharide units. It is common in the art to abbreviate six, seven and eight membered cyclic oligosaccharides to α, β and γ respectively.
The cyclic oligosaccharide of the compositions may comprise any suitable saccharide or mixtures of saccharides. Examples of suitable saccharides include, but are not limited to, glucose, fructose, mannose, galactose, maltose and mixtures thereof. A cyclic oligosaccharide comprises glucose. The cyclic oligosaccharides for use herein can include α-cyclodextrins or β-cyclodextrins, or mixtures thereof.
The cyclic oligosaccharide, or mixture of cyclic oligosaccharides, for use herein may be substituted by any suitable substituent or mixture of substituents. Herein the use of the term “mixture of substituents” means that two or more different suitable substituents can be substituted onto one cyclic oligosaccharide. The derivatives of cyclodextrins consist mainly of molecules wherein some of the OH groups have been substituted. Suitable substituents include, but are not limited to, alkyl groups; hydroxyalkyl groups; dihydroxyalkyl groups; (hydroxyalkyl)alkylenyl bridging groups such as cyclodextrin glycerol ethers; aryl groups; maltosyl groups; allyl groups; benzyl groups; alkanoyl groups; cationic cyclodextrins such as those containing 2-hydroxy-3-(dimethylamino) propyl ether; quaternary ammonium groups; anionic cyclodextrins such as carboxyalkyl groups, sulphobutylether groups, sulphate groups, and succinylates; amphoteric cyclodextrins; and mixtures thereof.
The substituents may be saturated or unsaturated, straight or branched chain. Substituents can include, for example, saturated and straight chain alkyl groups, hydroxyalkyl groups and mixtures thereof. Alkyl and hydroxyalkyl substituents can be selected from C1-C8 alkyl or hydroxyalkyl groups or mixtures thereof, alkyl and hydroxyalkyl substituents can be selected from C1-C6 alkyl or hydroxyalkyl groups or mixtures thereof, alkyl and hydroxyalkyl substituents can be selected from C1-C4 alkyl or hydroxyalkyl groups, and mixtures thereof. Exemplary alkyl and hydroxyalkyl substituents include propyl, ethyl, methyl, for example hydroxypropyl and methyl.
Exemplary cyclic oligosaccharides are unsubstituted, or are substituted by only saturated straight chain alkyl, or hydroxyalkyl substituents. Therefore, examples of cyclic oligosaccharides for use herein are α-cyclodextrin, β-cyclodextrin, methyl-α-cyclodextrin, methyl-β-cyclodextrin, hydroxypropyl-α-cyclodextrin and hydroxypropyl-β-cyclodextrin. These are available from Wacker-Chemie GmbH Hanns-Seidel-Platz 4, Munchen, DE under the tradename Alpha W6 M and Beta W7 M respectively.
The cyclic oligosaccharides of the compositions can be soluble in water, ethanol, or both water and ethanol. As used herein, “soluble” means at least about 0.1 g of solute dissolves in 100 mL of solvent, at 25° C. and 1 atm of pressure. Cyclic oligosaccharides for use herein can have a solubility of at least about 1 g/100 mL, at 25° C. and 1 atm of pressure. In one example, cyclic oligosaccharides are only present at levels up to their solubility limits in a given composition at room temperature. A person skilled in the art will recognize that the levels of cyclic oligosaccharides will also be dependent on the components of the composition and their levels, for example the solvents used or the exact fragrance oils, or combination of fragrance oils, present in the composition.
The compositions disclosed herein may comprise from 0.001 wt % to 40%, from 0.1 wt % to 25 wt %, from 0.3 wt % to 20 wt %, from 0.5 wt % to 10 wt % or from 0.75 wt % to 5 wt %, relative to the total weight of the composition, of a cyclic oligosaccharide.
Fine fragrance compositions commonly contain high levels of ethanol or other alcohols (e.g., methanol, propanol, isopropanol, butanol, and mixtures thereof) commonly found in commercial fine fragrance products. Accordingly, ethanol may be present in the compositions, and more specifically, it can form from about 10 wt % to about 80 wt %, or even from about 25 wt % to about 75 wt % of the composition, relative to the total weight of the composition. Any acceptable quality of ethanol, compatible and safe for the specific intended use of the composition such as, for example, topical applications of fine fragrance or cosmetic compositions, and is convenient for use in the compositions herein.
The composition may comprise a non-volatile solvent or a mixture of non-volatile solvents. Non-limiting examples of non-volatile solvents include benzyl benzoate, diethyl phthalate, isopropyl myristate, propylene glycol, dipropylene glycol, triethyl citrate, and mixtures thereof. These solvents often are introduced to the product via the perfume oil as many perfume raw materials may be purchased as a dilution in one of these solvents. Where non-volatile solvents are present, introduced either with the perfume materials or separately, then for the purposes of calculating the proportion of fragrance component having a vapour pressure of <0.001 Torr at 25° C. the total fragrance components does not include non-volatile solvents. In addition if present with cyclic oligosaccharides, the non-volatile solvent may be included at a weight ratio of the non-volatile solvent to the cyclic oligosaccharide of less than 1:1, less than 1:2, less than 1:10, or less than 1:100.
Water may be present in the composition, at a level of about 40 wt % or less, about 20 wt % or less, or about 10 wt % or less, relative to the total weight of the composition. Water may be present in an amount of from about 10 wt % or 20 wt %, to about 40 wt %, relative to the total weight of the composition. When the composition is a cosmetic composition the level of water should not be so high that the product becomes cloudy thus negatively impacting the product aesthetics, where clarity is desired. It is understood that the amount of water present in the composition may be from the water present in the ethanol used in the composition, as the case may be.
The compositions described herein may include a propellant. Some examples of propellants include compressed air, nitrogen, inert gases, carbon dioxide, and mixtures thereof. Propellants may also include gaseous hydrocarbons like propane, n-butane, isobutene, cyclopropane, and mixtures thereof. Halogenated hydrocarbons like 1,1-difluoroethane may also be used as propellants. Some non-limiting examples of propellants include 1,1,1,2,2-pentafluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,1,2,3,3,3-heptafluoropropane, trans-1,3,3,3-tetrafluoroprop-1-ene, dimethyl ether, dichlorodifluoromethane (propellant 12), 1,1-dichloro-1,1,2,2-tetrafluoroethane (propellant 114), 1-chloro-1,1-difluoro-2,2-trifluoroethane (propellant 115), 1-chloro-1,1-difluoroethylene (propellant 142B), 1,1-difluoroethane (propellant 152A), monochlorodifluoromethane, and mixtures thereof. Some other propellants suitable for use include, but are not limited to, A-46 (a mixture of isobutane, butane and propane), A-31 (isobutane), A-17 (n-butane), A-108 (propane), AP70 (a mixture of propane, isobutane and n-butane), AP40 (a mixture of propane, isobutene and n-butane), AP30 (a mixture of propane, isobutane and n-butane), and 152A (1,1diflouroethane). The propellant may have a concentration from about 15%, 25%, 30%, 32%, 34%, 35%, 36%, 38%, 40%, or 42%, to about 70%, 65%, 60%, 54%, 52%, 50%, 48%, 46%, 44%, or 42%, by weight of the total fill of materials stored within a container.
The compositions described herein may be free of, substantially free of, or may include an antiperspirant active (i.e., any substance, mixture, or other material having antiperspirant activity). Examples of antiperspirant actives include astringent metallic salts, like the inorganic and organic salts of aluminum, zirconium and zinc, as well as mixtures thereof. Such antiperspirant actives include, for example, the aluminum and zirconium salts, such as aluminum halides, aluminum hydroxyhalides, zirconyl oxyhalides, zirconyl hydroxyhalides, and mixtures thereof.
In yet another aspect, the composition consists essentially of the recited ingredients but may contain small amounts (not more than about 10 wt %, no more than 5 wt %, or no more than 2 wt % thereof, relative to the total weight of the composition) of other ingredients that do not impact the fragrance profile, particularly the evaporation rate and release of the fragrance materials. For example, a fine fragrance composition may comprise stabilizing or anti-oxidant agents, UV filters or quenchers, or colouring agents, commonly used in perfumery. There are a number of other examples of additional ingredients that are suitable for inclusion in the present compositions, particularly in compositions for cosmetic use. These include, but are not limited to, alcohol denaturants such as denatonium benzoate; UV stabilisers such as benzophenone-2; antioxidants such as tocopheryl acetate; preservatives such as phenoxyethanol, benzyl alcohol, methyl paraben, and propyl paraben; dyes; pH adjusting agents such as lactic acid, citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, and sodium carbonate; deodorants and anti-microbials such as farnesol and zinc phenolsulphonate; humectants such as glycerine; oils; skin conditioning agents such as allantoin; cooling agents such as trimethyl isopropyl butanamide and menthol; hair conditioning ingredients such as panthenol, panthetine, pantotheine, panthenyl ethyl ether, and combinations thereof; silicones; solvents such as hexylene glycol; hair-hold polymers such as those described in PCT Publication WO94/08557 (Procter & Gamble); salts in general, such as potassium acetate and sodium chloride and mixtures thereof.
The composition may be a mixture of fragrance materials possibly together with other ingredients such as, for example, perfume carriers. By the term “perfume carrier”, it is meant to include materials which are practically neutral from a perfumery point of view, i.e., which does not significantly alter the organoleptic properties of perfuming components. The perfume carrier may be compatible liquid or solid fillers, diluents, extenders and the like. The term “compatible”, as used herein, means that the components of the compositions are capable of being combined with the primary actives, and with each other, in a manner such that there is no interaction which would substantially reduce the efficacy of the composition under ordinary use situations. The type of carrier utilized depends on the type of product desired and may comprise, but are not limited to, solutions, aerosols, emulsions (including oil-in-water or water-in-oil), gels, and liposomes. In one example, the carrier is a liquid and will be a solvent such as, for example, dipropyleneglycol, diethyl phthalate, isopropyl myristate, benzyl benzoate, 2-(2-ethoxyethoxy)-1-ethanol, or ethyl citrate (triethyl citrate).
The compositions may take any form suitable for use, like for perfumery or cosmetic use. These include, but are not limited to, vapour sprays, aerosols, emulsions, lotions, liquids, creams, gels, sticks, ointments, pastes, mousses, powders, granular products, substrates, cosmetics (e.g. semi-solid or liquid makeup, including foundations) and the like. In one example, the compositions take the form of a vapour spray. Compositions can be further added as an ingredient to other compositions, like fine fragrance or cosmetic compositions, in which they are compatible. As such they can be used within solid composition or applied to substrates etc.
In one example, a composition comprises:
The composition can further comprise one or more non-odorous fragrance co-modulators, for example, selected from the group consisting of isocetyl alcohol (CERAPHYL® ICA), PPG-3 myristyl ether (like Tegosoft™ APM and/or Varonic® APM), neopentyl glycol diethylhexanoate (like Schercemol™ NGDO), and a mixture thereof, present in an amount of from about 0.5 wt % to about 10 wt %, relative to the total weight of the composition.
The compositions described herein can encompass any of the ingredients cited herein, in any embodiment wherein each such ingredient is independently present in any appropriate amount as defined herein. Many such compositions, than what is specifically set out herein, can be encompassed.
The composition may be included in an article of manufacture comprising a spray dispenser. The spray dispenser may comprise a vessel for containing the composition to be dispensed. The spray dispenser may comprise an aerosolized composition (i.e. a composition comprising a propellant) within the vessel as well. Other non-limiting examples of spray dispensers include non-aerosol dispensers (e.g. vapor sprays), manually activated dispensers, pump-spray dispensers, or any other suitable spray dispenser available in the art.
The composition described herein is a useful perfuming composition, which can be advantageously used as consumer products intended to perfume any suitable substrate. As used herein, the term “substrate” means any surface to which the composition may be applied to without causing any undue adverse effect. For example, this can include a wide range of surfaces including human or animal skin or hair, paper (fragranced paper), air in a room (air freshner or aromatherapy composition), fabric, furnishings, dishes, hard surfaces and related materials. Substrates can include body surfaces such as, for example, hair and skin.
The composition may be used in a conventional manner for fragrancing a substrate. An effective amount of the composition, typically from about 1 μL to about 10,000 μL, from about 10 μL to about 1,000 μL, from about 25 μL to about 500 μL, or from about 50 μL to about 100 μL, is applied to the suitable substrate. For example, an effective amount of the composition can be from about 1 μL, 10 μL, 25 μL or 50 μL, to about 100 μL, 500 μL, 1,000 μL or 10,000 μL. The composition may be applied by hand or applied utilizing a delivery apparatus such as, for example, a vaporizer or atomizer. The composition can be allowed to dry after its application to the substrate. Application could be the result of one or more distinct applications of the composition or the continuous release of a composition via a vaporizer or other type of atomizer.
The composition can be a fine fragrance composition in the form of a perfume, an eau de toilette, an eau de parfum, a cologne, a body splash, or a body spray, for example. Therefore, a method of modifying or enhancing the odour properties of a body surface, like hair or skin, can comprise contacting or treating the body surface with a composition as described herein.
In another example, composition may be used as consumer products or articles selected from the group consisting of a fabric care product, an air care product, or a home care product. Therefore, a method of modifying or enhancing the odour properties of a substrate, like fabric, furnishings, dishes, hard surfaces and related materials, can comprise contacting or treating the substrate with a composition as described herein.
Another method can include a method of enhancing the fragrance profile of a composition, by improving, for example, the longevity of an aroma of the composition. The method comprises bringing into contact or mixing at least one non-odorous fragrance modulator with at least one low volatile fragrance material. The aroma can be derived from the volatile fragrance materials in the composition and characterized by a floral aroma. Non-limiting examples of floral aroma include lavender-type note, a rose-type note, a lily of the valley-type note, a muguet-type note, a jasmine-type note, a magnolia-type note, a cyclamen-type note, a hyacinth-type note, a lilac-type note, an orange blossom-type note, a cherry blossom-type note, a peony-type note, a lotus-type note, a linden blossom-type note, an osmanthus-type note, a lilac-type note, a heliotrope-type note, a violet-type note, an orris-type note, a tiare-type note and the like.
The fragrance profile or aroma of the composition can be detectable by a consumer at later time points such as, for example, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, and possibly all the way up to 24 hours after application of the composition to a substrate as compared to controls.
The “fragrance materials” have been classified by their vapour pressure, as determined according to the reference program Advanced Chemistry Development (ACD/Labs) Software Version 11.02, (1994-2013). For the purpose of clarity, when the fragrance materials refer to a single individual compound, its vapor pressure should be determined according to the reference program cited above. In the case that the fragrance materials are a natural oil, extract or absolute, which comprises a mixture of several compounds, the vapor pressure of the complete oil should be treated as a mixture of the individual perfume raw material components using the reference program cited above. The individual components and their level, in any given natural oil or extract, can be determined by direct injection of the oil into a GC-MS column for analysis as known by one skilled in the art. In the scenario that the fragrance materials are a proprietary specialty accord, so called ‘bases’, the vapor pressure, using the reference program cited above, should preferably be obtained from the supplier. However, it is understood by one skilled in the art that they can physically analyze the composition of a full fragrance oil available commercially to identity the fragrance raw materials and their levels using standard GC-MS techniques. This would be irrespective of whether they had been added to the fragrance oil as individual chemicals, as components of naturals or from proprietary bases. Although proprietary bases and and naturals are included in our examples, when analyzing a commercially available fragrance via GC-MS one could simply identify the components of the base or natural oil as part of the overall fragrance mixture and their levels, without being able to identify which proprietary base or natural oil the fragrance had come from.
The nature and type of fragrance materials in the compositions can be selected by the skilled person, on the basis of its general knowledge together with the teachings contained herein, with reference to the intended use or application of the composition and the desired fragrance profile effect. Examples of suitable fragrance materials are disclosed in U.S. Pat. No. 4,145,184, U.S. Pat. No. 4,209,417, U.S. Pat. No. 4,515,705, and U.S. Pat. No. 4,152,272, provided that the composition comprises low volatile fragrance materials at levels in an amount of from about 0.1 wt % to about 30 wt %, relative to the total weight of the fragrance component.
Examples of fragrance materials having a vapor pressure <0.001 Torr at 25° C. (according to the reference program Advanced Chemistry Development (ACD/Labs) Software Version 11.02, (© 1994-2013)) to form the at most about 30 wt % of the low volatile fragrance materials are listed in Table 1 hereinafter.
In one example, the composition can comprise low volatile fragrance materials comprising at most about 30 wt %, relative to the total weight of the fragrance component. Exemplary low volatile fragrance materials can be selected from the group consisting of the ingredients mentioned in Table 1. However, it is understood by one skilled in the art that other low volatile fragrance materials, not recited in Table 1, would also fall within the scope, so long as they have a vapor pressure <0.001 Torr at 25° C.
Compositions can further comprise one or more volatile fragrance materials having a vapor pressure ≧0.001 Torr at 25° C. (according to the reference program Advanced Chemistry Development (ACD/Labs) Software Version 11.02, (© 1994-2013)). Examples of volatile fragrance materials are listed in the Table 2 hereinafter.
Other volatile fragrance materials, not recited in Table 2, would also fall within the scope, so long as they have a vapor pressure of ≧0.001 Torr at 25° C.
Compositions can comprise at least one non-odorous alkoxylated glucoside modulator. The non-odorous alkoxylated glucoside modulator can be selected from the non-limiting group consisting of methyl glucoside polyol, ethyl glucoside polyol, and propyl glucoside polyol. The modulator can be a compound of formula (I):
wherein:
R1 is hydrogen, alkyl, alkenyl or alkynyl;
R2 is selected from hydrogen, alkyl, alkenyl, alkynyl, —[R6R7(R8)O]wR9, wherein w is from 1 to 10, or 2 to 9;
R3 is selected from hydrogen, alkyl, alkenyl, alkynyl, —[R6R7(R8)O]yR9, wherein y is from 1 to 10, or 2 to 9;
R4 is selected from hydrogen, alkyl, alkenyl, alkynyl, —[R6R7(R8)O]xR9, wherein x is from 1 to 10, or 2 to 9;
R5 is selected from hydrogen, alkyl, alkenyl, alkynyl, —R6OR9, —R6O[R6R7(R8)O]zR9, wherein z is from 1 to 10, or 2 to 9;
each R6 and R7 are independently selected from alkylene, alkenylene, or alkynylene; and each R8 and R9 is independently selected from hydrogen or alkyl,
In an embodiment of formula (I), wherein the sum of w, y, x and z is equal to 4 to 40, 8 to 36, 10 to 32, or 10 to 28.
In one example, the modulator is Undecyl Glucoside and is available under the tradename Simulsol® SL 11 W from SEPPIC, France.
In another example of formula (I), the modulator is a compound of formula (Ia):
In an embodiment of formula (Ia), wherein w+x+y+z is equal to 4 to 40, 8 to 36, 10 to 32, or 10 to 28, or combinations thereof. The modulator ican be, for example, a PPG-10 Methyl Glucose Ether available under the tradename Glucam™ P-10 or Ethoxylated Methyl Glucose Ether and is available under the tradename Glucam™ E-20, respectively, from Lubrizol (USA).
In another example, the modulator is a compound of formula (II):
wherein:
R10 is hydrogen, alkyl, alkenyl or alkynyl;
each R11 is independently selected from hydrogen, alkyl, alkenyl, alkynyl;
each R12 is independently selected from hydrogen, alkyl, alkenyl, or alkynyl;
each R13 is independently selected from hydrogen, alkyl, alkenyl, or alkynyl;
each R14 is selected from alkylene, alkenylene, or alkynylene; and
R15 is hydrogen, alkyl, alkenyl or alkynyl;
wherein t is 5 or less, for example 1, 2 or 3.
The modulator of formula (II) can be, for example, Caprylyl/Capryl Glucoside and is available under the tradename Plantacare® 810 UP from BASF, Ludwigshafen, Germany.
Without being limited by theory, it is believed that the alkoxylated glucoside acts as a modulator of the perceived intensity and/or longevity of the fragrance profile of the composition when low levels of the low volatile fragrance materials are used. For example, the modulators act to prolong the duration during which the fragrance profile can be perceived as compared to a control composition in the absence of the modulators. As another example, the modulators can improve the intensity of the fragrance profile such that it remains significantly the same from initial impression to the end as compared to a control composition.
While not wishing to be bound by theory, it is believed that the modulators associate to the fragrance materials and retard evaporation.
In another aspect, compositions can further comprise one or more non-odorous fragrance co-modulators. The fragrance co-modulators consist of substances capable of increasing the intensity and/or longevity of the fragrance profile, and therefore of the composition, as compared to control composition absent the co-modulators. For example, the non-odorous fragrance co-modulators are selected from the group consisting of:
However, any such commercial forms of PPG-3 myristyl ether and mixtures thereof, are appropriate for use as co-modulators in the compositions.
The composition comprises non-odorous fragrance co-modulators in an amount of, for example, from about 0.05 wt % to about 10 wt %, from about 0.5 wt % to about 6 wt %, or combinations thereof, relative to the total weight of the composition. In additional examples, non-odorous fragrance co-modulators can be present in an amount of from about 0.05 wt %, or 0.5 wt %, to about 6 wt %, or 10 wt %, relative to the total weight of the composition. The non-odorous fragrance co-modulator can exist, for example, as mixtures of PPG-3 myristyl ether together with CERAPHYL® ICA and Schercemol™ NGDO ester, wherein the PPG-3 myristyl ether is 50 wt % and the other two components thereof are present in equal wt % in the mixture, wherein the wt % is the total weight of all the co-modulators in the composition. In one example, mixtures of PPG-3 myristyl ether with CERAPHYL® ICA, in a 1:1 weight ratio, can be used (PCT Publication No. WO2013/064412 (Firmenich)).
Co-modulators can also be mixtures of Neopentyl Glycol Diethylhexanoate together with CERAPHYL® ICA, wherein the Neopentyl Glycol Diethylhexanoate is 50 wt % and CERAPHYL® ICA is 50 wt %. Similarly, compositions can contain at least 50 wt % of Schercemol™ NGDO ester together with Tegosoft™ APM also proved to be useful to prolong the perception of the fragrance profile from the substrate on which it has been applied, as compared to control compositions (PCT Publication No. WO2013/060691 (Firmenich)).
The addition of the co-modulators is intended to further improve the intensity and/or longevity of the fragrance profile of the composition above the improvement already provided for by the modulators. In one example, at least 50 wt % of the non-odorous fragrance modulator is PPG-20 Methyl Glucose Ether, with the remainder to 100 wt % possibly being one or more other modulators or co-modulators.
In yet another aspect, compositions can comprise one or more non-odorous fragrance co-modulators selected from the group consisting of:
and being essentially free of non-odorous modulators formed from an alkoxylated glucoside selected from the group consisting of methyl glucoside polyol, ethyl glucoside polyol and propyl glucoside polyol. As used herein, the term “essentially free” means that the composition is free of that ingredient or no ingredient is intended to be added to the composition.
In one example, a composition comprises:
In order to determine the vapor pressure for the fragrance materials, go to the website https://scifinder.cas.org/scifinder/view/scifinder/scifinderExplorejsf and follow these steps to acquire the vapor pressure.
1. Input the CAS registry number for the particular fragrance material.
2. Select the vapor pressure from the search results.
3. Record the vapor pressure (given in Torr at 25° C.).
SciFinder uses Advanced Chemistry Development (ACD/Labs) Software Version 11.02. (© 1994-2013). If the CAS number for the particular fragrance material is unknown or does not exist, you can utilize the ACD/Labs reference program to directly determine the vapor pressure.
In order to show the effect of the modulators/co-modulators and low volatile fragrance materials on the perception of fragrance profile in a composition, test compositions are made, as described in the Example section, and given to panelists to evaluate.
At the testing facility, 50 μL samples of the compositions or the controls are applied to glass slides and placed on a hot plate at 32° C. to represent skin temperature for varying durations. The panelists are asked to evaluate the perceived fragrance profile (intensity and/or character) from each pair of samples, i.e., that of the test composition vs. the corresponding control, at time 0 and later time points (1, 2, 3 4 and 6 hours post application) as the fragrance profile evolves. Their assessments are recorded. Panelists are selected from individuals who are either trained to evaluate fragrances according to the scales below or who have experience of fragrance evaluation in the industry.
(a) Fragrance Intensity:
The panelists are asked to give a score on a scale of 1 to 5 for perceived fragrance intensity according to the odour intensity scale set out in Table 3 herein below.
(b) Fragrance Character:
The panelists are asked to assess the fragrance character in one of 2 ways:
The results of the panelists are averaged and then analysed using Analysis of Variance methods. The model treats the subject as a random effect and looks at the impact of product, time and the interaction between product and time. From the analysis the least square means for the product and time interaction are obtained. These means (as well as their confidence intervals) are then plotted to enable comparisons between products at each time point. It should be noted that the confidence levels plotted are intended as a guide, and not as a statistical comparison, as they do not take into account that multiple testing has been performed. As well as a graphical assessment, statistical comparisons between the two products at each of the time points are performed with a Sidak correction for multiple comparisons. The p-values for the product differences were obtained, with p-values <0.05 indicating a statistical difference between the two products at 5% significance (or 95% confidence).
The following examples are provided for further illustration and are not to be construed as limiting, as many variations are possible without departing from its spirit or scope.
Examples 1a to 5 are non-limiting examples of formulations of fragrance materials intended to form a fragrance component of a composition. The exemplary formulations of the fragrance materials span the range from “simple accords” (<10 fragrance materials) to “complex fragrances” (>30 fragrance materials). Typically, full bodied fragrance compositions do not comprise less than about 30 fragrance materials. Examples 1b and 6 are examples of a comparative formulation of fragrance materials intended to form a fragrance component. The following fragrance formulations are made by mixing the listed ingredients in the listed proportions (wt %) at room temperature, wherein the wt % is relative to the total weight of the fragrance component.
1 Supplied at 50% in IPM.
2 Supplied at 50% in DiPG.
3 Proprietary bases that contain a mixture of perfume raw materials, judged to be of high volatility for the purposes of calculating % of low volatility PRMs.
4 Natural oils or extracts that contain a mixture of perfume raw materials, judged to be of high volatility for the purposes of calculating % of low volatility PRMs.
5 Proprietary bases that contain a mixture of perfume raw materials, judged to be of low volatility for the purposes of calculating % of low volatility PRMs.
6 Natural oils or extracts that contain a mixture of perfume raw materials, judged to be of low volatility for the purposes of calculating % of low volatility PRMs.
Compositions A, C, E, G, and L are examples of fine fragrance compositions, made with Fragrances I to V, respectively. They are prepared by admixture of the components described in Tables 11a, in the proportions indicated. In parallel, control Compositions B, D, F, H, and M, are prepared by replacing the non-odorous fragrance modulator, Glucam™ P-20, by the same amount of demineralized water. Additionally, Compositions I and N are examples of a fine fragrance composition comprising excessive levels of low volatile fragrance materials, and Compositions J and O are their corresponding controls, minus the non-odorous fragrance modulator, Glucam™ P-20. Composition K is an example of a fine fragrance composition with both modulator and co-modulator.
1Wt % is relative to the total weight of the composition.
Compositions AA, BB, CC, DD, EE, FF, HH, II, and JJ are examples of fine fragrance compositions, made with Fragrances I, II and V the non-odorous fragrance modulators: Glucam™ P-10, Glucam™ E-10, and Glucam™ E-20, respectively. They are prepared by admixture of the components in Table 11b, in the proportions indicated. In parallel, Compositions GG and KK, are prepared by incorporating a non-odorous fragrance modulator and a co-modulator (Glucam™ P-10 and Isocetyl alcohol CERAPHYL ICA) or two non-odorous fragrance modulators (Glucam™ P-10, Glucam™ P-20), respectively.
1Wt % is relative to the total weight of the composition.
Compositions b and d are examples of compositions made with single perfume raw materials and the non-odorous modulators Simulsol SL 11W™ and Plantacare® 810 UP, respectively. They are prepared by admixture of the components in Table 11c, in the proportions indicated. In parallel, control Compositions a and c are prepared without a non-odorous modulator as a control.
1 Wt % is relative to the total weight of the composition.
2 Added as a 55 wt % active solution in water.
3 Added as a 62 wt % active solution in water.
Compositions P and Q are examples of body spray compositions. They are prepared by admixture of the components described in Table 12, in the proportions indicated.
1 wt % relative to the total weight of the composition.
2 Can be any Fragrances I, II, or V.
Composition R is an example of body lotion composition. It is prepared by admixture of the components described in Table 13, in the proportions indicated.
1 wt % relative to the total weight of the composition.
2 Can be any Fragrances I, II, or V.
Compositions disclosed in Table 11a are applied to glass slides in accordance with the protocol described in the Method Section and a panel of 9 expert panelists evaluated the perceived fragrance profile at initial time 0, then at various time points typically 1 hour, 2 hours, 3 hours, 4 hours and 6 hours post application.
(a) Compositions A vs. B:
(b) Compositions C vs. D:
(c) Compositions N and O
(d) Compositions I and J
Compositions disclosed in Table 11c are applied to glass slides in accordance with the protocol described in the Method Section and a panel of 8 expert panelists evaluated the perceived fragrance profile at initial time 0, then at various time points typically 1 hour, 3 hours, 5 hours and 6 hours post application.
(e) Compositions a vs. b:
(f) Compositions c vs. d:
It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical.
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm.”
Every document cited herein, including any cross referenced or related patent or application and any patent application or patent to which this application claims priority or benefit thereof, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
| Number | Date | Country | |
|---|---|---|---|
| 61915514 | Dec 2013 | US | |
| 62009923 | Jun 2014 | US |
