Patent Application
20140178442
The present disclosure generally relates to compositions with fragrances, and specifically relates to compositions having a parent fragrance and microcapsules encapsulating a non-parent fragrance; and methods related thereto.
Some personal care products, such as antiperspirants and deodorants, are designed to provide the user with protection from wetness and/or malodor. Such products often include compositions with a parent fragrance dispersed throughout the composition. These compositions may also include a moisture triggered fragrance delivery technology, such as fragrance loaded beta-cyclodextrin or starch encapsulated accords, which can provide a burst of fragrance when triggered by a threshold level of moisture (e.g. sweat). However, a composition with a moisture triggered fragrance technology may not always receive enough moisture to be triggered. For example, a user may not sweat enough to trigger the release of a noticeable burst of fragrance, or an antiperspirant may reduce sweat to such a low level that the sweat does not trigger the release of a noticeable burst of fragrance. Thus, there may be a need for a fragrance delivery system that allows for the delivery of a parent fragrance and a non-parent fragrance such that a consumer can notice the bloom of both fragrances.
A composition or method comprising a parent fragrance that is dispersed throughout the composition; and a friction-triggered fragrance delivery technology comprising a plurality of microcapsules; wherein the microcapsules comprise a core material and a shell encapsulating the core material; wherein the core material comprises a first non-parent fragrance and the shell comprises a synthetic polymeric material.
An anhydrous composition or method comprising: from about 0.1% to about 30% by weight of the anhydrous composition, of one or more antiperspirant actives; from about 0.1% to about 35% by weight of the anhydrous composition, of one or more structurants; from about 10% to about 99% by weight of the anhydrous composition, of one or more anhydrous liquid carriers; a parent fragrance that is dispersed throughout the anhydrous composition; and a friction-triggered fragrance delivery technology comprising a plurality of microcapsules; wherein the microcapsules comprise a core material and a shell encapsulating the core material; wherein the core material comprises a first non-parent fragrance and the shell comprises a synthetic polymeric material.
A method of preventing habituation when using an anhydrous composition, the method comprising: preparing an anhydrous composition comprising a parent fragrance that is dispersed throughout the anhydrous composition; and a friction-triggered fragrance delivery technology comprising a plurality of microcapsules, wherein the microcapsules comprise a core material and a shell encapsulating the core material; wherein the core material comprises a first non-parent fragrance and the shell comprises a synthetic polymeric material.
The composition can be an anhydrous composition. The term “anhydrous” as used herein means that the antiperspirant stick composition of the present invention, and the essential or optional components thereof, are substantially free of added or free water. From a formulation standpoint, this means that the anhydrous antiperspirant stick compositions of the present invention contain less than about 1%, and more specifically zero percent, by mass of free or added water, other than the water of hydration typically associated with the particulate antiperspirant active and/or the spray dried microcapsules prior to formulation. “Substantially free of” means an amount of a material that is less than 1%, 0.5%, 0.25%, 0.1%, 0.05%, 0.01%, or 0.001% by weight of a composition. A parent fragrance may be a fragrance that is dispersed throughout the composition and is typically not encapsulated when added to the composition and/or article. Herein, a non-parent fragrance refers to a fragrance that differs from a parent fragrance included within the composition and/or article. Non-limiting examples of differences between a fragrance and a non-parent fragrance include differences in chemical make-up. Typically, a non-parent fragrance is encapsulated within a material before inclusion into a composition and/or article.
It has surprisingly been discovered that a friction-triggered fragrance technology can be added to a composition with a parent fragrance and a moisture-triggered fragrance technology. As a result, a bloom of fragrance can be delivered even when there is not enough moisture to trigger the release of the fragrance from the moisture-triggered fragrance technology. However, if the fragrance of the friction-triggered fragrance technology is the same as the parent fragrance, the release of the friction-triggered fragrance may not be noticeable to a user who has become habituated to the parent fragrance. Thus, the composition may include a parent fragrance and a microcapsule encapsulating a non-parent fragrance.
The composition herein can include microcapsules. The microcapsules can be any kind of microcapsule disclosed herein or known in the art. For example, the microcapsules can be made from synthetic polymeric materials or naturally-occurring polymers. Synthetic polymers can be derived from petroleum oil, and made by scientists and engineers. Non-limiting examples of synthetic polymers include nylon, polyethylenes, polyamides, polystyrenes, polyisoprenes, polycarbonates, polyesters, polyureas, polyurethanes, polyolefins, polysaccharides, epoxy resins, vinyl polymers, polyacrylates, and mixtures thereof. Natural polymers occur in nature and can often be extracted. They are often water-based. Non-limiting examples of naturally occurring polymers are silk, wool, gelatin, cellulose, proteins, an combinations thereof.
Also as an example, the microcapsules can be friable microcapsules. A friable microcapsule is configured to release its core material when its shell is ruptured. The rupture can be caused by forces applied to the shell during mechanical interactions. Some or all of the friable microcapsules can have various fracture strengths. For at least a first group of the provided microcapsules, each microcapsule can have an outer shell with a fracture strength of 0.2-10.0 mega Pascals, when measured according to the Fracture Strength Test Method, or any incremental value expressed in 0.1 mega Pascals in this range, or any range formed by any of these values for fracture strength. As an example, a microcapsule can have an shell with a fracture strength of 0.2-2.0 mega Pascals.
Some or all of the microcapsules can have various core to shell ratios. For at least a first group of the provided microcapsules, each microcapsule can have a shell, a core within the shell, and a core to shell ratio that is greater than or equal to: 70% to 30%, 75% to 25%, 80% to 20%, 85% to 15%, 90% to 10%, 95% to 5%.
Some or all of the microcapsules can have shells made from any material in any size, shape, and configuration known in the art. Some or all of the shells can include a polyacrylate material, such as a polyacrylate random copolymer. For example, the polyacrylate random copolymer can have a total polyacrylate mass, which includes ingredients selected from the group including: amine content of 0.2-2.0% of total polyacrylate mass; carboxylic acid of 0.6-6.0% of total polyacrylate mass; and a combination of amine content of 0.1-1.0% and carboxylic acid of 0.3-3.0% of total polyacrylate mass.
When a microcapsule's shell includes a polyacrylate material, and the shell has an overall mass, the polyacrylate material can form 5-100% of the overall mass, or any integer value for percentage in this range, or any range formed by any of these values for percentage. As examples, the polyacrylate material can form at least 5%, at least 10%, at least 25%, at least 33%, at least 50%, at least 70%, or at least 90% of the overall mass.
Some or all of the microcapsules can have various shell thicknesses. For at least a first group of the provided microcapsules, each microcapsule can have a shell with an overall thickness of 1-300 nanometers, or any integer value for nanometers in this range, or any range formed by any of these values for thickness. As an example, microcapsules can have a shell with an overall thickness of 2-200 nanometers.
The anhydrous composition can include microcapsules wherein, for at least a first group of the microcapsules, the microcapsules encapsulate one or more benefit agents. The benefit agent(s) can include one or more of chromogens, dyes, antibacterial agents, cooling sensates, warming sensates, perfumes, flavorants, sweeteners, oils, pigments, pharmaceuticals, moldicides, herbicides, fertilizers, phase change materials, adhesives, and any other kind of benefit agent known in the art, in any combination. In some examples, the fragrance encapsulated can have a ClogP of less than 4.5 or a ClogP of less than 4. In some examples, the microcapsule may be anionic, cationic, zwitterionic, or have a neutral charge. The benefit agents(s) can be in the form of solids and/or liquids. The benefit agent(s) can be any kind of fragrance(s) known in the art, in any combination.
In some examples, the microcapsule's shell comprises a reaction product of a first mixture in the presence of a second mixture comprising an emulsifier, the first mixture comprising a reaction product of i) an oil soluble or dispersible amine with ii) a multifunctional acrylate or methacrylate monomer or oligomer, an oil soluble acid and an initiator, the emulsifier comprising a water soluble or water dispersible acrylic acid alkyl acid copolymer, an alkali or alkali salt, and optionally a water phase initiator. In some examples, said amine is an aminoalkyl acrylate or aminoalkyl methacrylate.
In some examples, the microcapsules include a core material and a shell surrounding the core material, wherein the shell comprises: a plurality of amine monomers selected from the group consisting of aminoalkyl acrylates, alkyl aminoalkyl acrylates, dialkyl aminoalykl acrylates, aminoalkyl methacrylates, alkylamino aminoalkyl methacrylates, dialkyl aminoalykl methacrylates, tertiarybutyl ammethyl methacrylates, diethylaminoethyl methacrylates, dimethylaminoethyl methacrylates, dipropylaminoethyl methacrylates, and mixtures thereof; and a plurality of multifunctional monomers or multifunctional oligomers.
In some examples, the microcapsule may be spray-dried to form spray-dried microcapsules. Spray-dried microcapsules may be employed in anhydrous compositions. For example, a polyacrylate microcapsule encapsulating a fragrance may be spray-dried before inclusion in an anhydrous composition, the anhydrous composition including a parent fragrance. The cyclodextrin may also be spray-dried before inclusion in the anhydrous composition.
The composition can also contain one or more additional delivery systems for providing one or more benefit agents, in addition to the microcapsules. The additional delivery system(s) can differ in kind from the microcapsules. For example, wherein the microcapsules encapsulates a fragrance, the additional delivery system can be an additional fragrance delivery system, such as a moisture-triggered fragrance delivery system. Non-limiting examples of moisture-triggered fragrance delivery systems include cyclic oligosaccaride, starch (or other polysaccharide material), starch derivatives, and combinations thereof. Said polysaccharide material may or may not be modified. The compositions can also include a parent fragrance and one or more encapsulated fragrances that may or may not differ from the parent fragrance.
Some fragrances can be considered to be volatiles and other fragrances can be considered to be or non-volatiles, as described and defined herein. The term “non-volatile,” as used herein, unless otherwise specified, refers to those materials that are liquid under ambient conditions and which have a measurable vapor pressure at 25° C. These materials typically have a vapor pressure less than about 0.01 mmHg, and an average boiling point typically greater than about 250° C. The term “volatile,” as used herein, unless otherwise specified, refers to those materials that are liquid under ambient conditions and which have a measurable vapor pressure at 25° C. These materials typically have a vapor pressure greater than about 0.01 mmHg, more typically from about 0.02 mmHg to about 20 mmHg, and an average boiling point typically less than about 250° C., more typically less than about 235° C.
A composition or article can comprise a parent fragrance that is dispersed throughout the composition or article, wherein the parent fragrance is made from a parent plurality of fragrance components; and microcapsules, wherein for at least a first group of microcapsules (and optionally, also for a second group of microcapsules), the microcapsules encapsulate a non-parent fragrance; wherein a first Friction Sample Headspace Ratio Average of the non-parent fragranceto the parent fragrance, when calculated with the Headspace Analysis Test Method, is greater than or equal to 2.8, greater than or equal to 4.2, greater than or equal to 5.6, and/or less than 400.
A composition or article can comprise a parent fragrance that is dispersed throughout the composition or article, wherein the parent fragrance is made from a parent plurality of fragrance components; and microcapsules, wherein for at least a first group of the microcapsules (and optionally, also for a second group of microcapsules), each of the microcapsules encapsulates a first fragrance, which is made from a first plurality of fragrance components; wherein a first Friction Sample Headspace Ratio Maximum of the first plurality of fragrance components to the parent plurality of fragrance components, when calculated with the Headspace Analysis Test Method, is greater than or equal to 10, greater than or equal to 20, greater than or equal to 50, and/or less than 400.
A composition or article can comprise a parent fragrance that is dispersed throughout the composition or article, wherein the parent fragrance is made from a parent plurality of fragrance components; and microcapsules, wherein for at least a first group of the microcapsules (and optionally, also for a second group of microcapsules), each of the microcapsules encapsulates a first fragrance, which is made from a first plurality of fragrance components; wherein a first Moisture Sample Headspace Ratio Average of the first plurality of fragrance components to the parent plurality of fragrance components, when calculated with the Headspace Analysis Test Method, is greater than or equal to 6, greater than or equal to 9, greater than or equal to 12, and/or less than 400.
A composition or article can comprise a parent fragrance that is dispersed throughout the composition or article, wherein the parent fragrance is made from a parent plurality of fragrance components; and microcapsules, wherein for at least a first group of the microcapsules (and optionally, also for a second group of microcapsules), each of the microcapsules encapsulates a first fragrance, which is made from a first plurality of fragrance components; wherein a first Moisture Sample Headspace Ratio Maximum of the first plurality of fragrance components to the parent plurality of fragrance components, when calculated with the Headspace Analysis Test Method, is greater than or equal to 25, greater than or equal to 40, greater than or equal to 100, and/or less than 400.
The composition can be selected from the group including: a fluid fabric enhancer; a solid fabric enhancer; a fluid shampoo; a solid shampoo; a powder shampoo; a powder hair or skin refresher; a fluid skin care formulation; a solid skin care formulation; hair conditioner; body wash, body spray, bar soap, hand sanitizer, solid antiperspirant, fluid antiperspirant, solid deodorant, fluid deodorant, fluid detergent, solid detergent, fluid hard surface cleaner, solid hard surface cleaner; or a unit dose detergent comprising a detergent and a water soluble film encapsulating said detergent.
When the composition includes a first group of microcapsules and a second group of microcapsules, for at least the first group of the microcapsules, the microcapsules can be a first kind of microcapsule, configured with a first delivery technology, and for at least the second group of the microcapsules, each of the microcapsules is a second kind of microcapsule, configured with a second delivery technology that differs from the first delivery technology. Non-limited examples of delivery technologies include friction-triggered fragrance technologies (e.g. polyacrylate microcapsules) and moisture-triggered fragrance technologies (e.g. beta-cyclodextrin).
As a result, a composition can have a parent fragrance and a moisture-triggered fragrance delivery technology that provide bursts of fragrance when triggered by a threshold level of moisture, providing a noticeable fragrance when the fragrance of the moisture-triggered fragrance delivery technology differs from the parent fragrance; further, if the personal care product also has a composition with a friction-triggered fragrance technology, then the composition can provide additional bursts of fragrance when triggered by friction and can provide additional noticeable fragrance when the fragrance of the friction triggered fragrance delivery technology also differs from the parent fragrance.
The anhydrous composition can be any kind of composition disclosed herein or known in the art. For example, the anhydrous composition can be a composition such as a semi-solid deodorant, semi-solid antiperspirant, an invisible solid deodorant, an invisible solid antiperspirant, aerosol antiperspirant, fluid antiperspirant, body powder, and foot powder.
The compositions or articles described herein may include a moisture-triggered fragrance technology incorporating cyclic oligosaccharides. As used herein, the term “cyclic oligosaccharide” means a cyclic structure comprising six or more saccharide units. The cyclic oligosaccharides can have six, seven, or eight saccharide units or mixtures thereof. It is common in the art to refer to six, seven and eight membered cyclic oligosaccharides as α, β, and γ, respectively. The cyclic oligosaccharides that may be useful include those that are soluble in water, ethanol, or both water and ethanol. The cyclic oligosaccharides useful herein may have a solubility of at least about 0.1 g/100 ml, at 25° C. and 1 atm of pressure in either water, ethanol, or both water and ethanol. The compositions disclosed herein may comprise from about 0.001% to about 40%, from about 0.1% to about 25%, from about 0.3% to about 20%, from about 0.5% to about 10%, or from about 0.75% to about 5%, by weight of the composition, of a cyclic oligosaccharide. The compositions disclosed herein may comprise from 0.001% to 40%, from 0.1% to 25%, from 0.3% to 20%, from 0.5% to 10%, or from 0.75% to 5%, by weight of the composition, of a cyclic oligosaccharide.
The cyclic oligosaccharide may comprise any suitablesaccharide or mixture of saccharides. Examples of suitable saccharides include, but are not limited to, glucose, fructose, mannose, galactose, maltose, and mixtures thereof. The cyclic oligosaccharide, or mixture of cyclic oligosaccharides, 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 may be substituted onto one cyclic oligosaccharide. Suitable examples of substituents include, but are not limited to, alkyl groups, hydroxyalkyl groups, dihydroxyalkyl groups, carboxyalkyl groups, aryl groups, maltosyl groups, allyl groups, benzyl groups, alkanoyl groups, and mixtures thereof. These substituents may be saturated or unsaturated, straight or branched chain. For example, the substituents may include saturated and straight chain alkyl groups, hydroxyalkyl groups, and mixtures thereof. The alkyl and hydroxyalkyl substituents, for example, may also be selected from C1-C8 alkyl or hydroxyalkyl groups, alkyl and hydroxyalkyl substituents from C1-C6alkyl or hydroxyalkyl groups, and alkyl and hydroxyalkyl substituents from C1-C4 alkyl or hydroxyalkyl groups. The alkyl and hydroxyalkyl substituents may be, for example, propyl, ethyl, methyl, and hydroxypropyl.
In addition to the substituents themselves, the cyclic oligosaccharides may have an average degree of substitution of at least 1.6, wherein the term “degree of substitution” means the average number of substituents per saccharide unit. For example, the cyclic oligosaccharides may have an average degree of substitution of less than about 2.8 or from about 1.7 to about 2.0. The average number of substituents may be determined using common Nuclear Magnetic Resonance techniques known in the art. Examples of cyclic oligosaccharides useful herein include cthe cyclodextrins such as methyl-α-cyclodextrins, methyl-β-cyclodextrins, hydroxypropyl-α-cyclodextrins, hydroxypropyl-β-cyclodextrins, and mixtures thereof. The cyclodextrins may be in the form of particles. The cyclodextiins may also be spray-dried and may also be spray-dried particles.
The compositions or articles may comprise fragrances. As used herein, “fragrance” is used to indicate any odoriferous material. Any fragrance that is cosmetically acceptable may be used in the composition. For example, the fragrance may be one that is a liquid at room temperature. Generally, the fragrance(s) may be present at a level from about 0.01% to about 40%, from about 0.1% to about 25%, from about 0.25% to about 20%, or from about 0.5% to about 15%, by weight of the composition.
A wide variety of chemicals are known as fragrances, including aldehydes, ketones, and esters. More commonly, naturally occurring plant and animal oils and exudates comprising complex mixtures of various chemical components are known for use as fragrances. Non-limiting examples of the fragrances 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 fragrances 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. The fragrances herein may be relatively simple in their chemical make-up, comprising a single chemical, or may comprise highly sophisticated complex mixtures of natural and synthetic chemical components, all chosen to provide any desired odor.
The fragrances may have a boiling point (BP) of about 500° C. or lower, about 400° C. or lower, or about 350° C. or lower. The BP of many fragrances are disclosed in Perfume and Flavor Chemicals (Aroma Chemicals), Steffen Arctander (1969). The ClogP value of the fragrances may be about 0.1 or greater, about 0.5 or greater, about 1.0 or greater, and about 1.2 or greater. As used herein, “ClogP” means the logarithm to the base 10 of the octanol/water partition coefficient. The ClogP can be readily calculated from a program called “CLOGP” which is available from Daylight Chemical Information Systems Inc., Irvine Calif., USA. Octanol/water partition coefficients are described in more detail in U.S. Pat. No. 5,578,563.
Suitable fragrances are also 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. Non-limiting examples of fragrances include animal fragrances such as musk oil, civet, castoreum, ambergris, plant fragrances such as nutmeg extract, cardomon extract, ginger extract, cinnamon extract, patchouli oil, geranium oil, orange oil, mandarin oil, orange flower extract, cedarwood, vetyver, lavandin, ylang extract, tuberose extract, sandalwood oil, bergamot oil, rosemary oil, spearmint oil, peppermint oil, lemon oil, lavender oil, citronella oil, chamomille oil, clove oil, sage oil, neroli oil, labdanum oil, eucalyptus oil, verbena oil, mimosa extract, narcissus extract, carrot seed extract, jasmine extract, olibanum extract, rose extract, and mixtures thereof.
Other examples of suitable fragrances include, but are not limited to, chemical substances such as acetophenone, adoxal, aldehyde C-12, aldehyde C-14, aldehyde C-18, allyl caprylate, ambroxan, amyl acetate, dimethylindane derivatives, α-amylcinnamic aldehyde, anethole, anisaldehyde, benzaldehyde, benzyl acetate, benzyl alcohol and ester derivatives, benzyl propionate, benzyl salicylate, borneol, butyl acetate, camphor, carbitol, cinnamaldehyde, cinnamyl acetate, cinnamyl alcohol, cis-3-hexanol and ester derivatives, cis-3-hexenyl methyl carbonate, citral, citronnellol and ester derivatives, cumin aldehyde, cyclamen aldehyde, cyclo galbanate, damascones, decalactone, decanol, estragole, dihydromyrcenol, dimethyl benzyl carbinol, 6,8-dimethyl-2-nonanol, dimethyl benzyl carbinyl butyrate, ethyl acetate, ethyl isobutyrate, ethyl butyrate, ethyl propionate, ethyl caprylate, ethyl cinnamate, ethyl hexanoate, ethyl valerate, ethyl vanillin, eugenol, exaltolide, fenchone, fruity esters such as ethyl 2-methyl butyrate, galaxolide, geraniol and ester derivatives, helional, 2-heptonone, hexenol, α-hexylcinnamic aldehyde, hydroxycitrolnellal, indole, isoamyl acetate, isoeugenol acetate, ionones, isoeugenol, isoamyl iso-valerate, iso E super, limonene, linalool, lilial, linalyl acetate, lyral, majantol, mayol, melonal, menthol, p-methylacetophenone, methyl anthranilate, methyl cedrylone, methyl dihydrojasmonate, methyl eugenol, methyl ionone, methyl-α-naphthyl ketone, methylphenylcarbinyl acetate, mugetanol, γ-nonalactone, octanal, phenyl ethyl acetate, phenyl-acetaldehyde dimethyl acetate, phenoxyethyl isobutyrate, phenyl ethyl alcohol, pinenes, sandalore, santalol, stemone, thymol, terpenes, triplal, triethyl citrate, 3,3,5-trimethylcyclohexanol, γ-undecalactone, undecenal, vanillin, veloutone, verdox, and mixtures thereof.
The non-limiting list of adjunct ingredients illustrated hereinafter are suitable for use in compositions and/or articles and may be desirably incorporated, for example to assist or enhance performance, for treatment of the substrate to be cleaned, or to modify the aesthetics of the composition as is the case with perfumes, colorants, dyes or the like. It is understood that such adjuncts are in addition to the components that are supplied via the microcapsules. The precise nature of these adjunct ingredients, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the operation for which it is to be used. Suitable adjunct materials include, but are not limited to, polymers, for example cationic polymers, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfume and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments, antiperspirant actives, skin care actives (e.g. niacinamide), glycerin, and mixtures thereof. In some examples, the adjunct may be a carrier like water. It is also envisioned that more than one type of adjunct ingredient may be included in the composition.
The compositions described herein may be packaged with any container known in the art or with any dispenser suitable for delivering the composition to a substrate. The composition may be applied to any substance where moisture and/or friction is available to trigger the release of the fragrance. When the composition is applied to the human body, the composition may be applied to any area of the skin or may be applied to any area of the body. The compositions may be used as consumer products (i.e. products intended to be sold to consumers without further modification or processing). Moreover, the microcapsules may be applied to any article, such as a fabric or any absorbent material including, but not limited to, feminine hygiene products, diapers, and adult incontinence products. The composition may also be incorporated into an article.
The compositions and articles described herein may also be used to overcome the habituation experienced by some consumers to a parent fragrance in an article and/or composition. For example, some consumers are known to suffer from habituation to the fragrance expressed by a composition and/or article such that the fragrance becomes less noticeable over time. One method of overcoming habituation in a composition and/or article is to incorporate a non-parent fragrance and a parent fragrance wherein the fragrances are expressed at different times or in an oscillating fashion. However, this is not easily done in practice as simply mixing the parent fragrance and non-parent fragrance together may result in a bloom that is a combination of both types of fragrances such that some consumers may still experience habituation to the combination. Additionally, many encapsulation technologies that allow for a triggered- or delayed-release of a non-parent fragrance result in some level of mixing of the parent and non-parent fragrances.
In this regard, some encapsulation technologies may not effectively prevent diffusion of the encapsulated, non-parent fragrance into the composition and/or the diffusion of the parent fragrance into the core of the encapsulation material such that there is a mixing of the parent fragrance and the non-parent fragrance. Although such technologies may provide a triggered- or delayed-release of a fragrance, these technologies may not be able to overcome the habituation as a result of the mixing of the parent and non-parent fragrances that occurs before the consumer uses the product.
Thus, the technologies described herein may overcome habituation in a composition and/or article by delaying the release of the non-parent fragrance so that the parent fragrance and the non-parent fragrance(s) bloom at different times and such that the non-parent and parent fragrance do not mix in the composition and/or article to a significant degree before usage. The technologies described herein can also be used to combat habituation without the need for a moisture-triggering event. For example, friction alone may be a sufficient triggering event that is used to express the non-parent fragrance. Additionally, the technologies described herein may also be used to combat habituation by utilizing multiple different classes of triggering events, such as moisture-triggering events and friction-triggered events.
Anhydrous compositions, like solid antiperspirant compositions, may require microcapsules with less than 20% water, preferably with less than 5% water. Free water in such anhydrous compositions can lead to the crystallization of the antiperspirant actives which may affect the performance of the composition when used. Spray-drying a slurry of microcapsules before inclusion into a solid antiperspirant composition is one way of reducing the amount of water associated with the microcapsules. Other ways of reducing the moisture content of the microcapsules are known, such as drying the microcapsules in an oven.
Additionally, for at least some friable microcapsules, such microcapsules may be more flexible in environments containing high levels of water. For example, for at least some microcapsules, said microcapsules may not release their core material (e.g. a fragrance) when friction or other mechanical forces are applied in a hyper-hydrated state. By spray-drying said microcapsules before inclusion into the anhydrous composition, said microcapsules may be more likely to rupture and release their core materials.
Solid antiperspirant compositions may include an antiperspirant active suitable for application to human skin. The concentration of the antiperspirant active in the composition should be sufficient to provide the desired enhanced wetness protection. For example, the active may be present in an amount of from about 0.1%, about 0.5%, about 1%, about 5%, or about 10%; to about 60%, about 35%, about 30%, about 25% or about 20%, by weight of the composition. These weight percentages are calculated on an anhydrous metal salt basis exclusive of water and any complexing agents such as glycine, glycine salts, or other complexing agents.
An antiperspirant active can include any compound, composition, or other material having antiperspirant activity. Such actives may include astringent metallic salts, especially inorganic and organic salts of aluminum, zirconium and zinc, as well as mixtures thereof. For example, the antiperspirant actives may include zirconium-containing salts or materials, such as zirconyl oxyhalides, zirconyl hydroxyhalides, and mixtures thereof; and/or aluminum-containing salts such as, for example, aluminum halides, aluminum chlorohydrate, aluminum hydroxyhalides, and mixtures thereof.
1. Aluminum Salts
Aluminum salts useful herein can include those that conform to the formula:
Al2(OH)aClb.xH2O
wherein a is from about 2 to about 5; the sum of a and b is about 6; x is from about 1 to about 6; where a, b, and x may have non-integer values. For example, aluminum chlorohydroxides referred to as “5/6 basic chlorohydroxide,” wherein a is about 5 and “2/3 basic chlorohydroxide”, wherein a=4 may be used.
2. Zirconium Salts
Zirconium salts useful herein can include those which conform to the formula:
ZrO(OH)2-aCla.xH2O
wherein a is from about 1.5 to about 1.87; x is from about 1 to about 7; and wherein a and x may both have non-integer values. Useful are zirconium salt complexes that additionally contain aluminum and glycine, commonly known as “ZAG complexes”. These complexes can contain aluminum chlorohydroxide and zirconyl hydroxy chloride conforming to the above-described formulas. Examples of two such complexes include aluminum zirconium trichlorohydrex and aluminum zirconium tetrachlorohydrex.
Antiperspirant compositions can also include a structurant to help provide the composition with the desired viscosity, rheology, texture and/or product hardness, or to otherwise help suspend any dispersed solids or liquids within the composition. The term “structurant” may include any material known or otherwise effective in providing suspending, gelling, viscosifying, solidifying, or thickening properties to the composition or which otherwise provide structure to the final product form. These structurants may include, for example, gelling agents, polymeric or nonpolymeric agents, inorganic thickening agents, or viscosifying agents. The thickening agents may include, for example, organic solids, silicone solids, crystalline or other gellants, inorganic particulates such as clays or silicas, or combinations thereof.
The concentration and type of the structurant selected for use in the antiperspirant composition will vary depending upon the desired product form, viscosity, and hardness. The structurant suitable for use herein, may have a concentration range from about 0.1%, about 2%, about 3%, about 5%; or about 10%; to about 35%, about 20%, about 10%, or about 8%, by weight of the composition. Soft solids will often contain a lower amount of structurant than solid compositions. For example, a soft solid may contain from about 1.0% to about 9%, by weight of the composition, while a solid composition may contain from about 15% to about 25%, by weight of the composition, of structurant. This is not a hard and fast rule, however, as a soft solid product with a higher structurant value can be formed by, for example, shearing the product as it is dispensed from a package.
Non-limiting examples of suitable gelling agents include fatty acid gellants, salts of fatty acids, hydroxyl acids, hydroxyl acid gellants, esters and amides of fatty acid or hydroxyl fatty acid gellants, cholesterolic materials, dibenzylidene alditols, lanolinolic materials, fatty alcohols, triglycerides, sucrose esters such as SEFA behenate, inorganic materials such as clays or silicas, other amide or polyamide gellants, and mixtures thereof.
Suitable gelling agents include fatty acid gellants such as fatty acid and hydroxyl or alpha hydroxyl fatty acids, having from about 10 to about 40 carbon atoms, and ester and amides of such gelling agents. Non-limiting examples of such gelling agents include, but are not limited to, 12-hydroxystearic acid, 12-hydroxylauric acid, 16-hydroxyhexadecanoic acid, behenic acid, eurcic acid, stearic acid, caprylic acid, lauric acid, isostearic acid, and combinations thereof. Preferred gelling agents are 12-hydroxystearic acid, esters of 12-hydroxystearic acid, amides of 12-hydroxystearic acid and combinations thereof.
Other suitable gelling agents include amide gellants such as di-substituted or branched monoamide gellants, monsubstituted or branched diamide gellants, triamide gellants, and combinations thereof, including n-acyl amino acid derivatives such as n-acyl amino acid amides, n-acyl amino acid esters prepared from glutamic acid, lysine, glutamine, aspartic acid, and combinations thereof.
Still other examples of suitable gelling agents include fatty alcohols having at least about 8 carbon atoms, at least about 12 carbon atoms but no more than about 40 carbon atoms, no more than about 30 carbon atoms, or no more than about 18 carbon atoms. For example, fatty alcohols include but are not limited to cetyl alcohol, myristyl alcohol, stearyl alcohol and combinations thereof.
Non-limiting examples of suitable tryiglyceride gellants include tristearin, hydrogenated vegetable oil, trihydroxysterin (Thixcin® R, available from Rheox, Inc.), rape seed oil, castor wax, fish oils, tripalmitin, Syncrowax® HRC and Syncrowax® HGL-C (Syncrowax® available from Croda, Inc.).
Other suitable structurants include waxes or wax-like materials having a melt point of above 65° C., more typically from about 65° C. to about 130° C., examples of which include, but are not limited to, waxes such as beeswax, carnauba, bayberry, candelilla, montan, ozokerite, ceresin, hydrogenated castor oil (castor wax), synthetic waxes and microcrystalline waxes. Castor wax is preferred within this group. The synthetic wax may be, for example, a polyethylene, a polymethylene, or a combination thereof. Some suitable polymethylenes may have a melting point from about 65° C. to about 75° C. Examples of suitable polyethylenes include those with a melting point from about 60° C. to about 95° C.
Further structurants for use in the solid antiperspirant compositions of the present invention may include inorganic particulate thickening agents such as clays and colloidal pyrogenic silica pigments. For example, colloidal pyrogenic silica pigments such as Cab-O-Sil®, a submicroscopic particulated pyrogenic silica may be used. Other known or otherwise effective inorganic particulate thickening agents that are commonly used in the art can also be used in the solid antiperspirant compositions of the present invention. Concentrations of particulate thickening agents may range, for example, from about 0.1%, about 1%, or about 5%; to about 35%, about 15%, about 10% or about 8%, by weight of the composition.
Suitable clay structurants include montmorillonite clays, examples of which include bentonites, hectorites, and colloidal magnesium aluminum silicates. These and other suitable clays may be hydrophobically treated, and when so treated will generally be used in combination with a clay activator. Non-limiting examples of suitable clay activators include propylene carbonate, ethanol, and combinations thereof. When clay activators are present, the amount of clay activator will typically range from about 40%, about 25%, or about 15%; to about 75%, about 60%, or about 50%, by weight of the clay.
Solid antiperspirant compositions may further include anhydrous liquid carriers. These are present, for example, at concentrations ranging from about 10%, about 15%, about 20%, about 25%; to about 99%, about 70%, about 60%, or about 50%, by weight of the composition. Such concentrations will vary depending upon variables such as product form, desired product hardness, and selection of other ingredients in the composition. The anhydrous carrier may be any anhydrous carrier known for use in personal care applications or otherwise suitable for topical application to the skin. For example, anhydrous carriers may include, but are not limited to volatile and nonvolatile fluids.
An antiperspirant composition may further include a volatile fluid such as a volatile silicone carrier. Volatile fluids are present, for example, at concentrations ranging from about 20% or from about 30%; to about 80%, or no about 60%, by weight of the composition. The volatile silicone of the solvent may be cyclic, linear, and/or branched chain silicone. “Volatile silicone”, as used herein, refers to those silicone materials that have measurable vapor pressure under ambient conditions.
The volatile silicone may be a cyclic silicone. The cyclic silicone may have from about 3 silicone atoms, or from about 5 silicone atoms; to about 7 silicone atoms, or about 6 silicone atoms. For example, volatile silicones may be used which conform to the formula:
wherein n is from about 3, or from about 5; to about 7, or about 6. These volatile cyclic silicones generally have a viscosity of less than about 10 centistokes at 25° C. Suitable volatile silicones for use herein include, but are not limited to, Cyclomethicone D5 (commercially available from G. E. Silicones); Dow Corning 344, and Dow Corning 345 (commercially available from Dow Corning Corp.); and GE 7207, GE 7158 and Silicone Fluids SF-1202 and SF-1173 (available from General Electric Co.). SWS-03314, SWS-03400, F-222, F-223, F-250, F-251 (available from SWS Silicones Corp.); Volatile Silicones 7158, 7207, 7349 (available from Union Carbide); Masil SF-V (available from Mazer) and combinations thereof.
An antiperspirant composition may further comprise a non-volatile fluid. These non-volatile fluids may be either non-volatile organic fluids or non-volatile silicone fluids. The non-volatile organic fluid can be present, for example, at concentrations ranging from about 1%, from about 2%; to about 20%, or about 15%, by weight of the composition.
Non-limiting examples of nonvolatile organic fluids include, but are not limited to, mineral oil, PPG-14 butyl ether, isopropyl myristate, petrolatum, butyl stearate, cetyl octanoate, butyl myristate, myristyl myristate, C12-15 alkylbenzoate (e.g., Finsolv™), dipropylene glycol dibenzoate, PPG-15 stearyl ether benzoate and blends thereof (e.g. Finsolv TPP), neopentyl glycol diheptanoate (e.g. Lexfeel 7 supplied by Inolex), octyldodecanol, isostearyl isostearate, octododecyl benzoate, isostearyl lactate, isostearyl palmitate, isononyl/isononoate, isoeicosane, octyldodecyl neopentanate, hydrogenated polyisobutane, and isobutyl stearate.
An antiperspirant composition may further include a non-volatile silicone fluid. The non-volatile silicone fluid may be a liquid at or below human skin temperature, or otherwise in liquid form within the anhydrous antiperspirant composition during or shortly after topical application. The concentration of the non-volatile silicone may be from about 1%, from about 2%; to about 15%, about 10%, by weight of the composition. Nonvolatile silicone fluids of the present invention may include those which conform to the formula:
wherein n is greater than or equal to 1. These linear silicone materials may generally have viscosity values of from about 5 centistokes, from about 10 centistokes; to about 100,000 centistokes, about 500 centistokes, about 200 centistokes, or about 50 centistokes, as measured under ambient conditions.
Specific non limiting examples of suitable nonvolatile silicone fluids include Dow Corning 200, hexamethyldisiloxane, Dow Corning 225, Dow Corning 1732, Dow Corning 5732, Dow Corning 5750 (available from Dow Corning Corp.); and SF-96, SF-1066 and SF18(350) Silicone Fluids (available from G.E. Silicones).
Low surface tension non-volatile solvent may be also be used. Such solvents may be selected from the group consisting of dimethicones, dimethicone copolyols, phenyl trimethicones, alkyl dimethicones, alkyl methicones, and mixtures thereof. Low surface tension non-volatile solvents are also described in U.S. Pat. No. 6,835,373 (Kolodzik et al.).
An antiperspirant composition may include a malodor reducing agent. Malodor reducing agents include components other than the antiperspirant active within the composition that act to eliminate the effect that body odor has on fragrance display. These agents may combine with the offensive body odor so that they are not detectable including, but not limited to, suppressing evaporation of malodor from the body, absorbing sweat or malodor, masking the malodor or microbiological activity on odor causing organisms. The concentration of the malodor reducing agent within the composition is sufficient to provide such chemical or biological means for reducing or eliminating body odor. Although the concentration will vary depending on the agent used, generally, the malodor reducing agent may be included within the composition from about 0.05%, about 0.5%, or about 1%; to about 15%, about 10%, or about 6%, by weight of the composition.
Malodor reducing agents may include, but are not limited to, pantothenic acid and its derivatives, petrolatum, menthyl acetate, uncomplexed cyclodextrins and derivatives thereof, talc, silica and mixtures thereof.
For example, if panthenyl triacetate is used, the concentration of the malodor reducing agent may be from about 0.1% or about 0.25%; to about 3.0%, or about 2.0%, by weight of the composition. Another example of a malodor reducing agent is petrolatum which may be included from about 0.10%, or about 0.5%; to about 15%, or about 10%, by weight of the composition. A combination may also be used as the malodor reducing agent including, but not limited to, panthenyl triacetate and petrolatum at levels from about 0.1%, or 0.5%; to about 3.0%, or about 10%, by weight of the composition. Menthyl acetate, a derivative of menthol that does not have a cooling effect, may be included from about 0.05%, or 0.01%; to about 2.0%, or about 1.0%, by weight of the composition. The malodor reducing agent may be in the form of a liquid or a semi-solid such that it does not contribute to product residue.
The following, in Table 1A, is data related to a first Comparative Example of an antiperspirant product known in the prior art, wherein the product includes a composition known to have a parent fragrance, no friction-triggered fragrance delivery technology, and no moisture triggered fragrance delivery technology. The first Comparative Example was subjected to the Headspace Analysis Test Method, which generated the four chromatograms in
As shown in Table 1A, and as calculated according to the Headspace Analysis Test Method described herein for the first Comparative Example: the Friction Sample Headspace Ratio Average is 1.2, and the Friction Sample Headspace Ratio Maximum is 5.3. These relatively small ratio values accurately indicate the absence of a friction-triggered perfume delivery technology in the product of the first Comparative Example.
As shown in Table 1A, and as calculated according to the Headspace Analysis Test Method described herein for the first Comparative Example: the Moisture Sample Headspace Ratio Average is 2.2, and the Moisture Sample Headspace Ratio Maximum is 12.3. These relatively small ratio values accurately indicate the absence of a moisture-triggered perfume delivery technology in the product of the first Comparative Example.
The following, in Table 2A, is data related to a second Comparative Example of a deodorant/antiperspirant product known in the prior art, wherein the product includes a composition known to have a parent fragrance and a moisture-triggered fragrance delivery technology (beta-cyclodextrin) for a fragrance that differs from the parent fragrance. The second Comparative Example was subjected to the Headspace Analysis Test Method, which generated the four chromatograms in
As shown in Table 2A, and as calculated according to the Headspace Analysis Test Method described herein for the second Comparative Example: the Friction Sample Headspace Ratio Average is 1.1, and the Friction Sample Headspace Ratio Maximum is 5.0. These somewhat larger ratio values accurately indicate the absence of a friction-triggered perfume delivery technology in the product of the second Comparative Example.
As shown in Table 2A, and as calculated according to the Headspace Analysis Test Method described herein for the second Comparative Example: the Moisture Sample Headspace Ratio Average is 24.1, and the Moisture Sample Headspace Ratio Maximum is 404.8. These very large ratio values accurately indicate the presence of a moisture-triggered perfume delivery technology (i.e. beta-cyclodextrin) in the product of the second Comparative Example.
The following, in Table 3A, is data related to a third Comparative Example of a deodorant/antiperspirant product known in the prior art (i.e. Degree MOTIONSENSE™ antiperspirant, with “Fresh Energy” fragrance, available in consumer markets and purchased in 2012), wherein the product includes a composition known to have a parent fragrance, a friction-triggered fragrance delivery technology (e.g. gelatin microcapsules), and a moisture-triggered fragrance delivery technology (starch encapsulated accord). The third Comparative Example was subjected to the Headspace Analysis Test Method, which generated the four chromatograms in
As shown in Table 3A, and as calculated according to the Headspace Analysis Test Method described herein for the third Comparative Example: the Friction Sample Headspace Ratio Average is 2.2, and the Friction Sample Headspace Ratio Maximum is 9.3. These somewhat larger ratio values accurately indicate the presence of a friction-triggered perfume delivery technology (e.g. the gelatin microcapsules) in the product of the third Comparative Example.
As shown in Table 3A, and as calculated according to the Headspace Analysis Test Method described herein for the third Comparative Example: the Moisture Sample Headspace Ratio Average is 4.8, and the Moisture Sample Headspace Ratio Maximum is 18.1. These somewhat larger ratio values accurately indicate the presence of a moisture triggered perfume delivery technology (i.e. starch encapsulated accord) in the product of the third Comparative Example.
Following, in Table 4A, is data related to a fourth Example of a deodorant/antiperspirant, wherein the product includes a composition with a parent fragrance, a friction-triggered fragrance delivery technology (polyacrylate microcapsules), and a moisture-triggered fragrance delivery technology (beta-cyclodextrin). The fourth Example was subjected to the Headspace Analysis Test Method, which generated the four chromatograms in
As shown in Table 4A, and as calculated according to the Headspace Analysis Test Method described herein for the fourth Example: the Friction Sample Headspace Ratio Average is 5.6, and the Friction Sample Headspace Ratio Maximum is 52.6. These larger ratio values accurately indicate the presence of a friction-triggered perfume delivery technology (e.g. the polyacrylate microcapsules) in the product of the fourth Example.
As shown in Table 4A, and as calculated according to the Headspace Analysis Test Method described herein for the fourth Example: the Moisture Sample Headspace Ratio Average is 8.6, and the Moisture Sample Headspace Ratio Maximum is 103.1. These larger ratio values accurately indicate the presence of a moisture triggered perfume delivery technology (e.g. beta-cyclodextrin) in the product of the fourth Example.
Apparatus
The following equipment is used for the Headspace Analysis Test Method.
Sampling
For sampling in the Headspace Analysis Test Method, a blotter card is created for each test product. A mass of 0.2 grams of the test product is spread evenly on one side of a perfume blotter card approximately 7.6 cm×12.7 cm in size. Suitable cards included the Professional Aerosol Testing cardboard blotter cards, as supplied by Orlandi Inc. (Farmingdale, N.Y., USA). The creation of the blotter card marks time equals zero for this method.
Each time that headspace is collected in this method it is collected from the blotter card, for five minutes, using a Twister bar, while the card is inside of a closed 125 mL glass jar. Four different headspace samples are collected, as described below, with the card remaining inside the glass jar at all times except where specified.
First, a first headspace sample is collected, with no stimulus, immediately after the creation of the blotter card. The collection of the first headspace sample is intended to provide a sample for assessing the presence and intensity of any parent fragrance in the composition, upon application.
Second, a second headspace sample is collected, with no stimulus, at time equals five hours. The collection of the second headspace sample is intended to provide a sample for assessing the presence and intensity of any parent fragrance, after a period of time.
Third, a third headspace sample is collected, with a stimulus of rubbing, immediately after the second sample is collected. The blotter card is removed from the jar and folded in half (with the side treated with test product, forming the inside), the outside of the card is firmly rubbed with pressure from a thumb tip using 8 strokes, each stroke being one passage in a single direction across the full width of the card, ensuring that the entire area of the card is affected, then the blotter card is returned to the jar, and the third sample is collected. The collection of the third headspace sample is intended to provide a sample for assessing the presence and intensity of any friction triggered perfume delivery technologies, such as friable microcapsules.
Fourth, a fourth headspace sample is collected, with a stimulus of moisture, immediately after the third sample is collected. The blotter card is removed from the jar and, while fully opened, a fine mist of distilled water is sprayed on the side treated with test product, then the blotter card is returned to the jar, and the fourth sample is collected. The collection of the fourth headspace sample is intended to provide a sample for assessing the presence and intensity of any moisture triggered perfume delivery technologies, such as starch based microcapsules.
Analysis
After sampling, the Twister bar is transferred to the Gerstel Thermal Desorption Unit. The collected headspace sample is thermally desorbed using the automated Gerstel TDU before cryofocusing and gas chromatography mass spectrometry analysis. The sample is transferred to the proper sample tray in the unit, then loaded and analyzed. A cryogenic trap is cooled to −80° C. and helium (flowing at a rate of about 50 ml/min) is used to purge the trap. The desorption temperature is ramped from 30° C. to 265° C. and the tube is purged for 3 minutes. The cryo-trap is then heated to remove the trapped fragrances (up to 275° C. and held for 3 minutes), followed by the start of the gas chromatography mass spectrometry analysis (run in splitless mode). The following temperature program is used: an initial temperature of about 40° C. which is held for 1 minute, and an increase in the initial temperature at a rate of about 8° C./min until a temperature of about 250° C. is reached, then an increase of 20° C./min to 275° C., to be held for about 3 minutes. The gas chromatography software uses mass spectrometry libraries to identify the components of the fragrances in the collected headspace sample, to integrate detected peaks, and to graphically display their presence on a gas chromatography chart.
Calculating
For each fragrance ingredient identified in the analyzing of a test product, the intensity value for each ingredient is normalized to the intensity of the first headspace sample—that is, the absolute value of each headspace sample is divided by the absolute value of the first headspace sample, such that the first headspace value is represented as a 1, and each of the second, third, and fourth headspace values is represented by a unitless number that is a multiple of the first headspace value. So, for each component, each of the second, third, and fourth headspace values is a ratio of that headspace value to the first headspace value.
Since the third headspace value is collected with the stimulus of rubbing, the Friction Sample Headspace Ratio Average for a product is calculated as the sum of all of third headspace values for that product, divided by the number of components. The Friction Sample Headspace Ratio Maximum is determined to be the largest value among all of the third headspace values, for that product.
Since the fourth headspace value is collected with the stimulus of moisture, the Moisture Sample Headspace Ratio Average for a product is calculated as the sum of all of fourth headspace values for that product, divided by the number of components. The Moisture Sample Headspace Ratio Maximum is determined to be the largest value among all of the fourth headspace values, for that product.
Fracture Strength Test Method
One skilled in the art will recognize that various protocols may be constructed for the extraction and isolation of microcapsules from finished products, and will recognize that such methods require validation via a comparison of the resulting measured values, as measured before and after the microcapsules' addition to and extraction from the finished product. The isolated microcapsules are then formulated in de-ionized (DI) water to form a slurry for characterization.
To calculate the percentage of microcapsules which fall within a claimed range of fracture strengths, three different measurements are made and two resulting graphs are utilized. The three separate measurements are namely: i) the volume-weighted particle size distribution (PSD) of the microcapsules; ii) the diameter of at least 10 individual microcapsules within each of 3 specified size ranges, and; iii) the rupture-force of those same 30 or more individual microcapsules. The two graphs created are namely: a plot of the volume-weighted particle size distribution data collected at i) above; and a plot of the modeled distribution of the relationship between microcapsule diameter and fracture-strength, derived from the data collected at ii) and iii) above. The modeled relationship plot enables the microcapsules within a claimed strength range to be identified as a specific region under the volume-weighted PSD curve, and then calculated as a percentage of the total area under the curve.
The identified area under the PSD curve is then calculated as a percentage of the total area under the PSD curve. This percentage indicates the percentage of microcapsules falling with the specified range of fracture strengths.
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, 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 with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. 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 | |
|---|---|---|---|
| 61703587 | Sep 2012 | US | |
| 61703616 | Sep 2012 | US |
