WO2011063338A2 - Gum bases, chewing gums based thereupon, and methods for making the same - Google Patents
Gum bases, chewing gums based thereupon, and methods for making the same Download PDFInfo
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- WO2011063338A2 WO2011063338A2 PCT/US2010/057636 US2010057636W WO2011063338A2 WO 2011063338 A2 WO2011063338 A2 WO 2011063338A2 US 2010057636 W US2010057636 W US 2010057636W WO 2011063338 A2 WO2011063338 A2 WO 2011063338A2
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- microparticles
- gum base
- chewing gum
- gum
- acrylate
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Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G4/00—Chewing gum
- A23G4/06—Chewing gum characterised by the composition containing organic or inorganic compounds
- A23G4/068—Chewing gum characterised by the composition containing organic or inorganic compounds containing plants or parts thereof, e.g. fruits, seeds, extracts
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G4/00—Chewing gum
- A23G4/06—Chewing gum characterised by the composition containing organic or inorganic compounds
- A23G4/08—Chewing gum characterised by the composition containing organic or inorganic compounds of the chewing gum base
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G4/00—Chewing gum
- A23G4/18—Chewing gum characterised by shape, structure or physical form, e.g. aerated products
Definitions
- INVENTORS XIAOHU XIA, KEN LIN, PHIL SHEPHERD, MICHAEL HAAS, TAWFIK SHARKASI,
- the present invention relates to gum bases and chewing gums. More specifically, this invention relates to improved chewing gum bases and chewing gums with enhanced removability, as well as methods of manufacturing the gum bases.
- a gum base comprises microparticles containing at least one crosslinked polymer. It has been found that such gum bases exhibit desirable chewing properties similar to conventional gum bases. Cuds formed by chewing gum bases containing crosslinked polymer microparticles are easily removable from environmental surfaces such as concrete, fabrics and flooring materials.
- FIG. 1 is a graphical depiction of the shear storage modulus at 37°C of a gum cud prepared from a comparative chewing gum formulation and of a gum cud prepared from a gum base of the present invention.
- FIG. 2 is a graphical depiction of the shear loss modulus at 37°C of a gum cud prepared from one embodiment of a chewing gum formulation and of a gum cud prepared from a gum base of the present invention as described herein.
- FIG 3 is a drawing of a polymer composite microparticle of the present invention.
- FIG 4 is a schematic depiction of a process for preparing hollow shell microparticles of the present invention.
- FIG 5 is a photomicrograph of a hollow shell microparticle of the type claimed in some embodiments of the present invention.
- FIG 6 is a cutaway drawing of a core-shell microparticle of the present invention. DESCRIPTION OF THE INVENTION
- the present invention relates to gum bases which incorporate crosslinked polymer microparticles of a type previously known and used to form pressure sensitive adhesives used in a variety of applications. It has now been surprisingly discovered that such crosslinked polymer microparticles can be used to prepare gum bases having a variety of desirable attributes.
- the crosslinked polymeric microparticles may be nonuniform.
- non-uniform it is meant that the microparticles have a structure other than a chemically and physically homogenous particle.
- the nonuniform crosslinked polymeric microparticles may be in the form of a polymer composite of two or more different crosslinked polymeric microparticle components covalently bonded together at their contacting surfaces.
- the microparticle components are themselves microparticles, the term microparticle components being used to distinguish these from microparticles in finished form which are used in other embodiments of the present invention.
- microparticle components come from different populations of microparticles which differ in some property such as average particle size, polymeric composition, degree of crosslinking or other physical or chemical property or properties such that, if they were used separately, they would convey different properties to a chewing gum product made from them.
- some property such as average particle size, polymeric composition, degree of crosslinking or other physical or chemical property or properties such that, if they were used separately, they would convey different properties to a chewing gum product made from them.
- the non-uniform microparticle will be in the form of a hollow shell.
- hollow shell it is meant that the roughly spherical microparticle is a shell that substantially or completely surrounds a void within the shell. Such voids may constitute 25 to 75% of the volume of the hollow shell microparticle.
- Such hollow shell microparticles will have different textural properties such as a softer texture and greater elasticity as compared to a solid microparticle of the same size and polymeric composition.
- the non-uniform microparticles will be in the form of a core-shell or filled shell.
- the shell substantially or completely surrounds a solid or liquid core.
- the core may be a liquid such as water, vegetable oil, glycerin, hydrogels or an aqueous flavor emulsion or combinations thereof.
- the core may be a solid such as a sugar or sugar alcohol granule or particle, a wax, a solid fat, a polymer having a different polymeric composition from the shell.
- the crosslinked polymer may have a glass transition temperature of less than about 30°C, or less than about 10°C or even less than about 0°C.
- the crosslinked polymer may have a complex modulus (G * ) at 25°C of less than about 10 9 dyne/cm 2 , or less than about 10 7 dyne/cm 2 .
- the crosslinked polymer may desirably have a complex modulus (G * ) of greater than about 10 4 dyne/cm 2 , or greater than about 10 5 dyne/cm 2 .
- the microparticles may have a largest dimension of at least 0.01 microns or at least 0.1 microns or of at least 0.5 microns or at least 10 microns.
- the microparticles may have a largest dimension of less than about 1000 microns, or less than about 500 microns or less than about 100 microns.
- the microparticles may comprise a food grade polymer and may or may not be plasticized.
- the polymer may comprise a polyacrylate, a polyurethane, or copolymers of these.
- the polyacrylate may be prepared from at least one acrylate monomer comprising isooctyl acrylate, 4-methyl-2-pentyl-acrylate, 2-methylbutyl acrylate, isoamyl acrylate, sec-butyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isodecyl methacrylate, isononyl acrylate, isodecyl acrylate or combinations (i.e. copolymers) of these.
- a polyacrylate when desirably used, it may be prepared from isoctyl acrylate, 2-ethylhexyl acrylate, n-butyl acrylate, or copolymers of these.
- the microparticles may comprise the entirety of the gum base or may comprise from about 0.1 weight percent (wt%) to about 99 wt%, or from about 1 wt% to about 70 wt% or from about 5 wt% to about 40 wt%, based upon the total weight of the gum base.
- the gum bases may further comprise at least one removability enhancing component.
- the removability enhancing component may comprise an amphiphilic polymer, a low tack polymer, a polymer comprising hydrolysable units, an ester or ether of a polymer comprising hydrolysable units, block copolymers or combinations of these.
- the inventive gum base may further comprise at least one elastomer, elastomer solvent, softener, plastic resin, filler, emulsifier, or combinations of these.
- the gum base further comprises a filler, e.g., calcium carbonate, talc, amorphous silica, or combinations of these, in amounts of from about 0 wt% to about 5 wt%, based upon the total weight of the gum base.
- a chewing gum comprising a first gum base comprising a plurality of microparticles comprising at least one crosslinked polymer.
- the first gum base may comprise from about 1 wt% to about 98 wt% of the chewing gum, or from about 10 wt% to about 50 wt%, or from about 20 wt% to about 35 wt% of the chewing gum, based upon the total weight of the gum.
- the chewing gum may comprise the first gum base as the sole gum base component, or, in other embodiments, may comprise a second, conventional gum base.
- the first gum base may comprise from about 0.1 wt% to about 30 wt% of the chewing gum, based upon the total weight of the gum.
- the chewing gum may include at least one removability enhancing component.
- the removability enhancing component included in the chewing gum comprises an emulsifier, that may be encapsulated or spray dried, if desired.
- methods for manufacturing a gum base comprise the steps of adding an aqueous slurry of crosslinked polymeric microparticles to a mixer, adding at least one of an elastomer, an elastomer solvent, a softener, a resin, a filler and/or an emulsifier to the mixer, mixing the components at elevated temperature for a time sufficient to evaporate at least a majority of the water, and discharging the mixture from the mixer.
- ranges are disclosed, the endpoints of all ranges directed to the same component or property are inclusive and independently combinable (e.g., ranges of "up to about 25 wt%, or, more specifically, about 5 wt% to about 20 wt%,” is inclusive of the endpoints and all intermediate values of the ranges of "about 5 wt% to about 25 wt%,” etc.).
- the modifier "about” used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (e.g., includes the degree of error associated with measurement of the particular quantity).
- percents listed herein are weight percents (wt%) and are based upon the total weight of the gum base or chewing gum, as the case may be.
- the present invention provides gum bases and chewing gums, as well as methods of manufacturing the gum bases.
- the gum bases provided herein comprise microparticles further comprising one or more crosslinked polymer(s).
- the polymeric microparticles may render a gum cud comprising the gum base more easily removable from surfaces to which it may have become adhered than gum cuds comprising conventional gum bases.
- the present gum bases also have chew properties consistent with those of conventional gum bases. That is, the gum base comprising the polymeric microparticles is elastic yet deformable, more cohesive than adhesive, and readily recombines if torn apart. As a result, a chewing gum comprising the gum base is expected to enjoy a high consumer-acceptability.
- Polymeric microparticles suitable for use in the chewing gum base described herein should be sufficiently pliable at typical mouth temperatures (e.g., 35-40°C) to give good chewing properties. Further, the polymeric microparticles will desirably be essentially without taste and have an ability to incorporate flavor materials which provide a consumer-acceptable flavor sensation. Typically, the microparticles will have sufficient cohesion such that a chewing gum comprising them retains cohesion during the chewing process and forms a discrete gum cud.
- the polymer(s) used will desirably be crosslinked, either before, during or after the formation thereof into microparticles.
- crosslinked means the linking of the chains of a polymer to one another so that the polymer, as a network, becomes stronger and more resistant to being dissolved. In at least some embodiments all, or most (i.e., greater than 50% of the polymers, based upon the total number thereof), of the polymers within a microparticle will be crosslinked. In other embodiments, the crosslinking may be incomplete and a minority (i.e., less than 50% of the polymers, based upon the total number of polymers) of the polymers within the microparticle will be crosslinked. However, as long as the crosslinking is sufficient to provide at least a portion of the properties described herein to the gum base and/or chewing gum, the amount of crosslinking will be sufficient for use in at least certain embodiments of the present invention.
- the polymers used in the microparticles may desirably be crosslinked to a sufficient degree as to prevent, or reduce the degree of, permanent deformation of the microparticles when exposed to pressures, temperatures and shear forces expected in the course of manufacture, consumption and disposal.
- the polymer(s) should not be crosslinked to an extent that could result in the microparticle being brittle and/or incapable of being temporarily deformed (even if plasticized).
- Insufficient polymer crosslinking may result in excessive difficulty in removing cuds comprising the polymeric microparticles from environmental surfaces.
- excessive polymer crosslinking may result in a gum base that has insufficient adhesion between the microparticles and/or is excessively hard for optimal chewing enjoyment by the consumer.
- Using a crosslinked polymer having an appropriate complex modulus is expected to at least assist in providing the present gum base with appropriate and/or acceptable chew properties.
- crosslinked polymers having a complex modulus G * at 25°C of less than about 10 9 dyne/cm 2 (10 8 Pa), less than about 10 8 dyne/cm 2 (10 7 Pa), less than 10 7 dyne/cm 2 (10 6 Pa) or, in some embodiments, even less than about 10 6 dyne/cm 2 (10 5 Pa) can assist in providing chewing gum bases and chewing gums with desirable chew properties.
- the polymer(s) having a complex modulus G * at 25°C or greater than about 10 7 or 10 8 dyne/cm 2 (10 6 or 10 7 Pa) or even greater it may be desirable to combine the polymer with a plasticizer to reduce effective complex modulus G * to ensure proper chewing texture.
- the polymer may desirably have a complex modulus G * at 25°C of greater than about 10 4 dyne/cm 2 (10 3 Pa) or greater than about 10 5 dyne/cm 2 (10 4 Pa) or even greater than 10 6 dyne/cm 2 (10 5 Pa) to provide a firm texture during chewing.
- crosslinked polymers with an appropriate glass transition temperature may also assist in providing the gum base with appropriate and/or acceptable chew properties.
- Crosslinked polymers having a glass transition temperature of less than about 30°C, or less than about 10°C or even less than about 0°C are expected to at least assist in providing the gum base with chew properties similar to, or better than, conventional gum bases.
- the crosslinked polymer is desirably safe for use in chewing gums, and potentially ingestion.
- the polymer used will be food grade.
- the term 'food grade' is meant to indicate that the polymer meets all legal requirements for use in a food product in the intended market. While requirements for being food grade vary from country to country, food grade polymers intended for use as masticatory substances (i.e.
- gum base may typically have to: i) be approved by the appropriate local food regulatory agency for this purpose; ii) be manufactured under "Good Manufacturing Practices" (GMPs) which may be defined by local regulatory agencies, such practices ensuring adequate levels of cleanliness and safety for the manufacturing of food materials; iii) be manufactured with food grade materials (including reagents, catalysts, solvents and antioxidants) or materials that at least meet standards for quality and purity; iv) meet minimum standards for quality and the level and nature of any impurities present; v) be provided with an adequately documented manufacturing history to ensure compliance with the appropriate standards; and/or vi) be manufactured in a facility that itself is subject to inspection by governmental regulatory agencies.
- GMPs Good Manufacturing Practices
- Any polymer(s) capable of exhibiting at least a portion of the desired properties may be suitable for use in the microparticles, and thus gum base, described herein.
- Polymers that are capable of exhibiting the desired properties if plasticized sufficiently are also suitable for use. Examples of such polymers include, but are not limited to, grafted acrylic polymers, polyurethanes and grafted polyolefins with side groups greater than four carbon atoms. Graft or block copolymers of these are also suitable
- polymers that are expected to exhibit the desired properties for use in the formation of the microparticles without the use of substantial amounts of plasticizer, include, but are not limited to polyacrylates, polyurethanes, graft or block copolymers of these.
- Other crosslinked polymers which might otherwise be above the desirable T g and/or modulus ranges may be used if the crosslinked polymers are suitably plasticized to reduce the T g and/or modulus values to within the desirable ranges. Combinations of any of these are also suitable.
- the desired polymer may typically be prepared from one or more monomer(s). Suitable monomers will depend upon the polymer desirably being prepared.
- the polymer comprises at least one crosslinked polyacrylate that, in further preferred embodiments may be prepared from one or more acrylate monomers.
- Suitable acrylate monomers include monofunctional unsaturated acrylate and/or methacrylate esters of non-tertiary alkyl alcohols, wherein the alkyl groups contain from about 4 to about 14 carbon atoms, and a multifunctional crosslinking agent.
- Examples of monofunctional acrylate monomers suitable for use in preparing the polyacrylate thus include, but are not limited to, isooctyl acrylate, 4-methyl-2-pentyl- acrylate, 2-methylbutyl acrylate, isoamyl acrylate, sec-butyl acrylate, n-butyl acrylate, 2- ethylhexyl acrylate, isodecyl methacrylate, isononyl acrylate, isodecyl acrylate and mixtures thereof.
- isooctyl acrylate, 2-ethylhexyl acrylate, n-butyl acrylate or combinations of these are preferred for use in some embodiments of the gum base.
- At least one crosslinking agent may be used to produce the crosslinked polymer.
- the crosslinking agent(s) chosen, and effective amounts thereof, will depend on the polymer desirably crosslinked, and can be readily selected and optimized by those of ordinary skill in the art.
- suitable crosslinking agents include multifunctional acrylates, such as trimethylolpropane triacrylate (TMPTA); epoxy group containing compounds; alkylenimines; organoalkoxysilanes; or combinations of these.
- the crosslinked polymer is desirably provided in the form of a microparticle., i.e., a particle having a largest dimension of at least about 0.1 microns or at least about 0.5 microns or at least about 10 microns.
- the microparticles may have a largest dimension of less than about about 1000 microns, or less than about 500 microns or less than about 100 microns.
- providing the crosslinked polymer in such a form can assist in enhancing the removability of the gum bases and chewing gums, e.g., since the microparticles are of a size that will not allow them to flow into the topography of many environmental surfaces, while yet preserving the chewability of the gum bases and chewing gums.
- the shape of the microparticles is not critical and they may be irregularly shaped, or of any shape, e.g., the particles may be in the form of rods, cylinders, spheres, cubes, ovals, etc.
- the microparticles may be generally spherical.
- the generally spherical microparticles may desirably have diameters of from about 0.1 microns to about 1000 microns, or from about 0.5 microns to about 500 microns, or even from about 10 microns to about 100 microns.
- the desired polymer may be formed into microparticles by any of a number of techniques known to those of ordinary skill in the art. Or, the desired polymer may be purchased in a microparticle form from any of a number of commercial sources. Polyacrylate microparticles, for example, are commercially available from Avery Dennison (Pasadena, California) under the tradename Ultra-Removable Adhesive.
- the polymers may be provided in a microparticle form by a suspension polymerization process in which one or more monofunctional monomers are reacted along with at least one multifunctional crosslinking agent.
- the reactants will be present as suspended droplets, preferably by subjecting them to mechanical dispersion in an appropriate continuous phase.
- the particle size of the microparticles can be controlled by adjusting the ratio of the phases, with a greater imbalance in the ratio tending to produce smaller microparticles. Particle size may also be controlled via use of a surfactant, and the adjustment of any amounts thereof or through variations in the temperature of the reaction. Increasing the intensity of agitation will also tend to produce smaller microparticles.
- microparticles are provided in the form of a water dispersion, they may be mechanically separated from the dispersion medium by mechanical means such as centrifugation, precipitation or filtration before blending with other gum base or chewing gum components
- Non-uniform microparticles in the form of a polymer composite can be prepared as follows. First, two batches of crosslinked polymeric microparticles having different chemical or physical properties (such as size) are prepared under an inert (i.e. oxygen- free) atmosphere to prevent termination of the polymerization reaction as previously described. After the microparticles are substantially formed, the surfaces of the microparticles of both batches stay active for further growth. The two batches are then combined while maintaining the inert atmosphere. This allows the microparticles to react and covalently and/or ionically bond with each other on their surfaces to produce the polymer composite. Finally, oxygen is introduced into the atmosphere to terminate the reaction.
- a microparticle in the form of a polymer composite having a large diameter microparticle component (1 ) and a number of smaller diameter microparticle components (2) covalently bonded to its surface is illustrated in Figure 3.
- Non-uniform microparticles in the form of a hollow shell can be prepared as follows.
- a template particle such as a particle of silicon dioxide is introduced into a monomer emulsion or suspension. Polymerization is allowed to occur which results in a polymeric coating on the surface of the template particle. After polymerization is complete, the coated particles are collected and etched with using a reagent capable of dissolving the template particle but not the polymeric coating, such as a hydrofluoric acid solution. After the reagent has dissolved the template particles, the hollow polymeric microparticles are collected and washed to remove the reagent. This process is illustrated in Figure 4.
- Non-uniform microparticles in the form of a core-shell can be prepared by surface- initiated atom transfer radical polymerization (ATRP).
- ATRP surface- initiated atom transfer radical polymerization
- Such processes are disclosed in the following papers which are hereby incorporated by reference: PLGA-Lecithin-PEG Core-Shell Nanoparticles for Controlled Drug Delivery, by Robert Langer et al, Biomaterials 30 (2009), 1627-1634; Preparation of Core-Shell Type Polymer Microspheres from Anionic Block Copolymers, by Koji Ishizu, Fumihiro Naruse and Reiko Saito Polymer, 34, 18, 1993, 3929-3933); Synthesis of Core-Shell Polymer Microspheres by Two-Stage Distillation-Precipitation Polymerization, by Donglai Qi, Feng Bai, Xinlin Yang and Wenqiang Huang, European Polymer Journal, 41 , 10, 2005, 2320-2328; and Inorganic-Polymer Core Shell Hy
- Microparticles in the form of nanoparticles can be prepared by altering the conditions used to make larger crosslinked polymeric microparticles. Such modifications may include using a higher emulsifier level to increase the critical micelle concentration (CMC), more vigorous agitation of the emulsion or a combination of these methods.
- CMC critical micelle concentration
- the above described methods of forming the crosslinked polymeric microparticles of the present invention are exemplary only and the present invention is not limited to the described processes. The use of other methods, whether or not currently known, are specifically contemplated. Any method of producing the described crosslinked polymeric microbeads is acceptable.
- the gum bases described herein contain at least one population of the microparticles described herein, although it is to be understood that the gum base may comprise any number of such populations. In such embodiments, each population may comprise the same polymer, but may be processed differently or comprise different additional components, so that the properties of each population are different. Or, each of the populations may comprise the same polymer, but one population of microparticles may have a different particle size distribution or average largest dimension than the other(s).
- a population of nanoparticles may be combined with populations of microparticles having greater average largest dimension.
- each of the populations may also comprise a different polymer, or combinations of polymers, etc.
- populations of microparticles in the form of polymer composite microparticles, hollow shell microparticles and core-shell microparticles may be combined with each other or with populations of solid microparticles which comprise a single polymer or copolymer in any desired combination. The blending of different populations of microparticles provides greater control and flexibility over the texture and chewing properties of the finished product.
- the microparticles may be the sole component of the gum base described herein, or the gum base may comprise additional ingredients, if desired.
- the microparticles may comprise from about 0.1 wt% to about 99 wt%, or from about 1 wt% to about 70 wt%, or from about 5 wt% to about 40 wt%, based upon the total weight of the gum base.
- additives such as emulsifiers and amphiphilic polymers may be added.
- Another additive which may prove useful is a polymer having a straight or branched chain carbon-carbon polymer backbone and a multiplicity of side chains attached to the backbone as disclosed in WO 06-016179 hereby incorporated by reference herein in its entirety for any and all purposes, to the extent that it is not contradictory to the teachings provided herein.
- Still another additive which may enhance removability is a polymer comprising hydrolyzable units or an ester and/or ether of such a polymer.
- One such polymer comprising hydrolyzable units is a copolymer sold under the Trade name Gantrez®. Addition of such polymers at levels of from about 1 wt% to about 20 wt% based upon the total weight of the chewing gum base may reduce adhesion of discarded gum cuds.
- Another approach to enhancing removability of the present invention involves formulating gum bases to contain less than 5% (i.e. 0 to 5%) of a calcium carbonate and/or talc filler and/or 5 to 40% amorphous silica filler.
- Formulating gum bases to contain 5 to 15% of high molecular weight polyisobutylene is also effective in enhancing removability.
- the gum base desirably includes ingredients or components in addition to the microparticles
- any components typically found in gum bases may be included.
- the microparticles may be combined with one or more elastomers, elastomer solvents, softeners, resins, fillers, colors, antioxidants, emulsifiers or mixtures thereof and other conventional gum base components.
- the microparticles may be used as the sole elastomer, while in others, the microparticles may be combined with other base elastomers, and elastomer solvents suitable for use in gum bases.
- significant amounts are not incorporated into a gum base of the present invention, i.e., the elastomer component of gum bases disclosed herein may contain up to about 100 wt% of the microparticles disclosed herein.
- the present gum bases may include at least about 10 wt%, or at least about 30 wt%, or at least about 50 wt% or even at least about 70 wt% microparticles by weight of the total elastomer content, in combination with any other desired elastomer(s).
- a typical elastomeric component of the gum bases described herein contains between 10 wt% to 100 wt% microparticles and preferably 50 wt% to 100 wt% microparticles.
- a gum base having an elastomer component containing from about 75 wt% to about 90 wt%, or from about 90 wt% to about 100 wt.% microparticles is also useful.
- Suitable other elastomers include synthetic elastomers including polyisobutylene, isobutylene-isoprene copolymers (butyl rubber), styrene-butadiene copolymers, polyisoprene and combinations thereof.
- Natural elastomers that can be used include natural rubbers such as chicle, jelutong, lechi caspi, perillo, sorva, massaranduba balata, massaranduba chocolate, nispero, rosindinha, chicle, gutta hang kang, and combinations thereof.
- biopolymers such as those based on modified or unmodified proteins and carbohydrates, may be used as elastomers.
- Elastomer solvents commonly used for synthetic elastomers may be optionally used in this invention including but are not limited to, natural rosin esters, often called estergums, such as glycerol esters of partially hydrogenated rosin, glycerol esters of polymerized rosin, glycerol esters of partially or fully dimerized rosin, glycerol esters of rosin, pentaerythritol esters of partially hydrogenated rosin, methyl and partially hydrogenated methyl esters of rosin, pentaerythritol esters of rosin, glycerol esters of wood rosin, glycerol esters of gum rosin; synthetics such as terpene resins derived from alpha-pinene, beta-pinene, and/or d-limonene; and any suitable
- Softeners may be added to gum bases in order to optimize the chewability and mouth feel of a chewing gum based upon the same.
- Softeners/emulsifiers that typically are used include tallow, hydrogenated tallow, hydrogenated and partially hydrogenated vegetable oils, cocoa butter, mono- and di- glycerides such as glycerol monostearate, glycerol triacetate, lecithin, paraffin wax, microcrystalline wax, natural waxes and combinations thereof.
- Lecithin and mono- and di-glycerides also function as emulsifiers to improve compatibility of the various gum base components.
- a typical gum base may include at least about 5 wt%, or at least about 10 wt% softener, or up to about 30 wt% and more typically up to about 40 wt% softener, based upon the total weight of the gum base.
- the gum bases of the present invention may optionally include plastic resins. These include polyvinyl acetate, vinyl acetate-vinyl laurate copolymer having vinyl laurate content of about 5 to about 50 percent by weight of the copolymer, and combinations thereof. Preferred weight average molecular weights (by GPC) for polyvinyl acetate are 2,000 to 90,000 or 10,000 to 65,000 (with higher molecular weight polyvinyl acetates typically used in bubble gum bases). For vinyl acetate-vinyl laurate, vinyl laurate content of from about 10 wt% to about 45 wt% of the copolymer is preferred. Where used, plastic resins may constitute 5 to 35 wt.% of the gum base composition.
- Fillers/texturizers typically are inorganic, water-insoluble powders such as magnesium and calcium carbonate, ground limestone, silicate types such as magnesium and aluminum silicate, clay, alumina, talc, titanium oxide, mono-, di- and tri-calcium phosphate and calcium sulfate.
- Insoluble organic fillers including cellulose polymers such as wood as well as combinations of any of these also may be used. If used, fillers may typically be included in amounts from about 4 wt% to about 50 wt% filler, based upon the total weight of the gum base.
- common inorganic fillers be minimized such as by limiting their use to less than 5 wt.% and preferably less than 3 wt.% or even 0 percent as a means of further reducing the adhesive properties of the chewed cud.
- Colorants and whiteners may include FD&C-type dyes and lakes, fruit and vegetable extracts, titanium dioxide, and combinations thereof.
- Antioxidants such as BHA, BHT, tocopherols, propyl gallate and other food acceptable antioxidants may be employed to prevent oxidation of fats, oils and elastomers in the gum base.
- the gum base described herein may include wax or be wax-free.
- An example of a wax-free gum base is disclosed in U.S. Patent No. 5,286,500, the disclosure of which is incorporated herein by reference to the extent that it is consistent with the teachings provided herein. It is preferred that the gum bases of the present invention be free of paraffin wax.
- a typical gum base useful in this invention may include from about 0.1 wt% to about 98 wt% microparticles, from about 0 wt% to about 20 wt% synthetic elastomer, from about 0 wt% to about 20 wt% natural elastomer, from about 0 wt% to about 40 wt% elastomer solvent, from about 0 wt% to about 50 wt% filler/texturizer, from about 0 wt% to about 40 wt.% softener/em ulsifier, from about 5 wt% to about 35 wt% plastic resin, and about 2 wt% or less, or less than about 1 wt% of miscellaneous ingredients such as colorants, antioxidants, and the like.
- the microparticles may be processed into the gum base according to any known method of doing so.
- the microparticles may be used as prepared or purchased, typically in an aqueous suspension.
- the microparticle suspension may be dehydrated prior to inclusion in, or use as, the gum base.
- one exemplary method of manufacturing a gum base comprising the polymeric microparticles includes adding the microparticle suspension to a mixer followed by at least one of an elastomer, an elastomer solvent, a filler/texturizer, emulsifier/softener, plastic resin, color and/or antioxidant to the mixer, the desired components are mixed at elevated temperature, e.g., from about 100°C to about 120°C, for a time sufficient to evaporate at least a majority of the liquid, and discharging the gum base from the mixer. Any desired additional ingredients may be added by conventional batch mixing processes or continuous mixing processes. Process temperatures are generally from about 120°C to about 180°C in the case of a batch process.
- the conventional elastomers be formulated into a conventional gum base before combining with the microparticle gum base.
- the elastomers are typically first ground or shredded along with at least a portion of any desired filler. Then the ground elastomer is transferred to a batch mixer for compounding. Any standard, commercially available mixer (e.g., a Sigma blade mixer) may be used for this purpose. Compounding typically involves combining the ground elastomer with filler and elastomer solvent and mixing until a homogeneous mixture is produced, typically for about 30 to about 70 minutes.
- a standard, commercially available mixer e.g., a Sigma blade mixer
- any desired additional filler and elastomer plasticizer(s) are added followed by softeners, while mixing to homogeneity after each addition. Minor ingredients such as antioxidants and color may be added at any time in the process.
- the conventional base is then blended with the microparticle-containing gum base in the desired ratio.
- the completed base may be extruded or cast into any desirable shape (e.g., balls, pellets, sheets or slabs) and allowed to cool and solidify. In some cases, it may be preferable to use an underwater peptization process for this purpose.
- the gum base may be compounded with both conventional elastomers and microparticles, or, any desired conventional elastomers and the polymeric microparticles may be added separately to a gum base mixing operation along with other chewing gum components.
- Continuous processes using mixing extruders may also be used to prepare the gum base.
- initial ingredients including ground elastomer, if used
- extruder ports various points along the length of the extruder corresponding to the batch processing sequence.
- a metering extruder or other specialized means to meter the microparticles into the compounding extruder may be used.
- the balance of the base ingredients are metered into ports or injected at various points along the length of the extruder. Typically, any remainder of elastomer component or other components are added after the initial compounding stage.
- the composition is then further processed to produce a homogeneous mass before discharging from the extruder outlet. Typically, the transit time through the extruder will be less than an hour.
- Exemplary methods of extrusion include the following, the entire contents of each being incorporated herein by reference to the extent that they do not contradict the teachings herein: (i) U.S. Pat. No. 6,238,710, which describes a method for continuous chewing gum base manufacturing, which entails compounding all ingredients in a single extruder; (ii) U.S. Pat. No. 6,086,925 which discloses the manufacture of chewing gum base by adding a hard elastomer, a filler and a lubricating agent to a continuous mixer; (iii) U.S. Pat. No.
- a typical gum base comprising the microparticles as described herein may desirably have a shear modulus (the measure of the resistance to the deformation) of from about 1 kPa (10000 dyne/cm 2 ) to about 600 kPa (6 x 10 6 dyne/cm 2 ) at 40°C (measured on a Rheometric Dynamic Analyzer with dynamic temperature steps, 0-100°C at 3°C/min; parallel plate; 0.5% strain; 10 rad/s).
- a shear modulus the measure of the resistance to the deformation
- a preferred gum base according to some embodiments of the present invention may have a shear modulus of from about 5 kPa (50000 dyne/cm 2 ) to about 300 kPa (3 x 10 6 dyne/cm 2 ), or even from about 10 kPa (1 x 10 5 dyne/cm 2 ) to about 70 kPa (7 x 10 5 dyne/cm 2 ).
- a variety chewing gum formulations including the gum bases described herein can be created and/or manufactured in accordance with the present invention. Because of the inclusion of the polymeric microparticles described herein into the inventive gum base and chewing gum, a gum cud formed from the chewing gum is more easily removed from surfaces onto which it may become adhered than gum cuds formed from chewing gums comprising conventional gum bases.
- the gum base described herein may constitute from about 0.1 wt% to about 98 wt% by weight of the chewing gum. More typically, the inventive gum base may constitute from about 10 wt% to about 50 wt% of the chewing gum and, in various preferred embodiments, may constitute from about 20 wt% to about 35% by weight of the chewing gum.
- the gum bases described herein may be used to replace conventional gum bases in chewing gum formulas.
- the gum base may comprise from about 15 wt% to about 50 wt% of the chewing gum.
- the gum bases described herein may be used in combination with conventional gum bases, in any amount or ratio.
- the gum base described herein may comprise from about 0.1 wt% to about 30 wt% of the chewing gum.
- any of the removability enhancing components discussed herein may also be added to the chewing gum, either instead of, or in addition to, any amount thereof added to the gum base.
- a polymer comprising hydrolysable units or an ester or ether of such a polymer may be added to the chewing gum at levels of from about 1 wt% to about 7 wt% based upon the total weight of the chewing gum.
- high levels of emulsifiers such as powdered lecithin may be incorporated into the chewing gum at levels of 3 to 7% by weight of the chewing gum in order to enhance the removability of gum cuds produced therefrom.
- removability of gum cuds formed from the chewing gums comprising the gum bases disclosed herein can be further enhanced by incorporating at least one of from about 0 wt% to about 5 wt% of a calcium carbonate or talc filler, from about 5 wt% to about 40 wt% amorphous silica filler, from about 5 wt% to about 15 wt% high molecular weight polyisobutylene, from about 1 wt% to about 20 wt% of a polymer having a straight or branched chain carbon-carbon polymer backbone and a multiplicity of side chains attached to the backbone, based upon the total weight of the gum base, into the gum base.
- the gum base according to this embodiment may then be formed into a chewing gum further comprising 3 to 7% of an emulsifier, such as lecithin, which is preferably encapsulated such as by spray drying.
- chewing gum typically includes a bulk portion which may include bulking agents, high intensity sweeteners, one or more flavoring agents, water-soluble softeners, binders, emulsifiers, colorants, acidulants, antioxidants, and other components that provide attributes desired by consumers of chewing gum. Any or all of these may be included in the present chewing gums.
- one or more bulking agent(s) or bulk sweetener(s) may be provided in chewing gums described herein to provide sweetness, bulk and texture to the chewing gum.
- Bulking agents may also be selected to allow marketing claims to be used in association with the chewing gums. That is, if it is desirable to promote a chewing gum as low calorie, low calorie bulking agents such as polydextrose may be used, or, if the chewing gum is desirably promoted as comprising natural ingredients, natural bulking agents such as isomaltulose, inulin, agave syrup or powder, erythritol, starches and some dextrins may be used. Combinations of any of the above bulking agents may also be used in the present invention.
- Typical bulking agents include sugars, sugar alcohols, and combinations thereof.
- Sugar bulking agents generally include saccharide-containing components commonly known in the chewing gum art, including, but not limited to, sucrose, dextrose, maltose, dextrin, dried invert sugar, fructose, levulose, galactose, corn syrup solids, and the like, alone or in combination.
- sugar alcohols such as sorbitol, maltitol, erythritol, isomalt, mannitol, xylitol and combinations thereof are substituted for sugar bulking agents.
- Bulking agents typically constitute from about 5 wt% to about 95 wt% of the total weight of the chewing gum, more typically from about 20 wt% to about 80 wt% and, still more typically, from about 30 wt% to about 70 wt% of the total weight of the chewing gum.
- the microparticles/gum base may comprise up to about 98 wt% of the chewing gum.
- a low caloric bulking agent can be used.
- low caloric bulking agents include, but are not limited to, polydextrose; Raftilose; Raftilin; fructooligosaccharides (NutraFlora®); Palatinose oligosaccharide; Guar Gum Hydrolysate (Sun Fiber®); or indigestible dextrin (Fibersol®).
- the caloric content of a chewing gum can also be reduced by increasing the relative level of gum base while reducing the level of caloric sweeteners in the product. This can be done with or without an accompanying decrease in piece weight.
- high intensity artificial sweeteners can be used alone or in combination with the bulk sweeteners.
- Preferred sweeteners include, but are not limited to sucralose, aspartame, salts of acesulfame, alitame, neotame, saccharin and its salts, cyclamic acid and its salts, glycyrrhizin, stevia and stevia derivatives such as Rebaudoside A, dihydrochalcones, lo han guo, thaumatin, monellin, etc., or combinations of these.
- the artificial sweetener In order to provide longer lasting sweetness and flavor perception, it may be desirable to encapsulate or otherwise control the release of at least a portion of the artificial sweetener. Techniques such as wet granulation, wax granulation, spray drying, spray chilling, fluid bed coating, coacervation, and fiber extrusion may be used to achieve the desired release characteristics.
- usage level of the artificial sweetener will vary greatly and will depend on such factors as potency of the sweetener, rate of release, desired sweetness of the product, level and type of flavor used and cost considerations. Generally speaking, appropriate levels of artificial sweeteners thus may vary from about 0.02 wt% to about 8 wt%. When carriers used for encapsulation are included, the usage level of the encapsulated sweetener will be proportionately higher.
- Flavoring agents may include essential oils, natural extracts, synthetic flavors or mixtures thereof including, but not limited to, oils derived from plants and fruits such as citrus oils, fruit essences, peppermint oil, spearmint oil, other mint oils, clove oil, oil of wintergreen, anise and the like.
- Artificial flavoring agents and components may also be used. Sensate components which impart a perceived tingling or thermal response while chewing, such as a cooling or heating effect, also may be included. Such components include cyclic and acyclic carboxamides, menthol and menthol derivatives such as menthyl esters of food acceptable acids, and capsaicin among others. Acidulants may be included to impart tartness.
- the desired flavoring agent(s) can be used in amounts of from approximately 0.1 wt% to about 15 wt% of the gum, and preferably, from about 0.2 wt% to about 5 wt%.
- Water-soluble softeners which may also be known as water-soluble plasticizers, plasticizing agents, binders or binding agents, generally constitute between approximately 0.5 wt% to about 15 wt% of the chewing gum.
- Water-soluble softeners may include glycerin, propylene glycol, and combinations thereof.
- Syrups or high-solids solutions of .sugars and/or sugar alcohols such as sorbitol solutions, hydrogenated starch hydrolysates (HSH), corn syrup and combinations thereof, may also be used.
- sugar alcohols such as sorbitol solutions, hydrogenated starch hydrolysates (HSH), corn syrup and combinations thereof
- HSH hydrogenated starch hydrolysates
- corn syrups and other dextrose syrups which contain dextrose and significant amounts higher saccharides
- These include syrups of various DE levels including high-maltose syrups and high fructose syrups.
- low-moisture syrups can replace some or all of the bulking agents typically use, in which case usage levels of the syrup may extend up to 50 wt.% or more of the total gum composition.
- solutions of sugar alcohols including sorbitol solutions and hydrogenated starch hydrolysate syrups are commonly used.
- syrups such as those disclosed in US 5,651 ,936 and US 2004-234648 which are incorporated herein by reference. Such syrups serve to soften the initial chew of the product, reduce crumbliness and brittleness and increase flexibility in stick and tab products. They may also control moisture gain or loss and provide a degree of sweetness depending on the particular syrup employed.
- an active agent such as a drug, a dental health ingredients or dietary supplement can be used in combination with the gums and gum bases of the present invention.
- the active agent may be incorporated into the gum base, the chewing gum or into associated non-gum portions of a finished product such as into a coating or a candy layer.
- the active may be encapsulated to control its release or to protect it from other product ingredients or environmental factors.
- the chewing gum formulations provided herein may also comprise one or more other ingredients conventional in the art, such as gum emulsifiers, colorants, acidulants, fillers, antioxidants and the like. Such ingredients may be used in the present chewing gum formulations in amounts and in accordance with procedures well known in the art of chewing gum manufacture.
- Chewing gum is generally manufactured by sequentially adding the various chewing gum ingredients, including the gum base, to commercially available mixers known in the art. After the ingredients have been thoroughly mixed, the chewing gum mass is discharged from the mixer and shaped into the desired form, such as by rolling into sheets and cutting into sticks, tabs or pellets or by extruding and cutting into chunks.
- the chewing gum may be prepared according to a batch process.
- the ingredients are mixed by first melting the gum base and adding it to the running mixer.
- the gum base may alternatively be melted in the mixer.
- Color and emulsifiers may be added at this time.
- a chewing gum softener such as glycerin can be added next along with a portion of the bulking agent. Further portions of the bulking agent may then be added to the mixer. Flavoring agents are typically added with the final portion of the bulking agent. The entire mixing process typically takes from about five to about fifteen minutes, although longer mixing times are sometimes required.
- Chewing gums of the present invention may be prepared by a continuous process comprising the steps of: a) adding gum base ingredients into a high efficiency continuous mixer; b) mixing the ingredients to produce a homogeneous gum base, c) adding at least one sweetener and at least one flavor into the continuous mixer, and mixing the sweetener and flavor with the remaining ingredients to form a chewing gum product; and d) discharging the mixed chewing gum mass from the single high efficiency continuous mixer.
- a finished gum base may be metered into a continuous extruder along with other gum ingredients to continuously produce a chewing gum composition.
- the resultant chewing gums may be formed into sticks, tabs, chunks, tapes, coated or uncoated pellets or balls or any other desired form.
- the chewing gum formulation may be used as a component of a greater confectionery product, for example as a center in a hard candy such as a lollipop or as one or more layers of a layered confection which also comprises non-gum confectionery layers.
- Polyacrylate Microparticles Polyacrylate microparticles (Ultra-Removable Adhesive) were acquired from Avery Dennison.
- Gum Bases Three gum bases_were prepared, the formulas of which are provided below in Table 1 . Briefly, Gum Base A was used as a control, and was based upon a commercial formula known to be strongly adhesive to concrete. Gum Base B was formulated to have reduced adhesion to environmental surfaces. Gum Base C comprised polyacrylate microparticles as described herein.
- Gum Base A was made in a sigma blade mixer at 120°C. For a batch of 3000 gram, gum base A was made in according to the sequence shown in Table 2, below.
- Gum Base B was made in a sigma blade mixer at 120°C. For a batch of 3000 gram, Gum Base B was made in according to the sequence shown in Table 3, below.
- Example 1 a comparative formulation, was prepared using Gum Base A, known to be strongly adhesive to concrete.
- Example 2 was prepared using Gum Base B and so appropriate for use as a reduced adhesion control/comparative example.
- Examples 3-6 were prepared using a combination of Gum Base B (reduced adhesion control) and inventive Gum Base C.
- Chewing Gums 1 -6 were made in a 1000 gram batch sigma blade mixer.
- the gum base and bulk sweeteners (sorbitol) were pre-heated in 70°C oven for 30 minutes.
- the blend of gum base and sorbitol was then added in the running mixer (front blade speed 32 rpm), the other ingredients (except flavor) were added immediately and mixed for four to five minutes.
- the flavor was then added and mixed for an additional 4 to 5 minutes until a homogeneous appearance was achieved.
- Removability Test Power Wash (1550 PSI). The nozzle angle was set at 60 degrees from the ground, and the spray pattern was set to a fan shape covering 3 cm width on ground when the nozzle was held 40 cm from the cud. The cud was washed for up to 1 minute. A photo was taken before and after the removal test, using a one cent coin as a reference mark for photographic analysis. The percentage of residue remaining after pressure washing was estimated from the after photo. If the cud was completely removed during power wash, the removal time was recorded.
- each of the inventive chewing gums not only showed superior removability as compared to the adhesive control chewing gum formulation, but also showed superior removability as compared to the reduced adhesion control.
- Chewing Gum A chewing gum according to the present invention, comprising polyacrylate microparticles as a total replacement for gum base, was made according to the formula in Table 6.
- the polyacrylate microparticles were provided as a 45% aqueous suspension to which was added the sorbitol, calcium carbonate and glycerin. The composition was mixed for 10 minutes to obtain a homogeneous white suspension. The mixture was then heated with continued mixing to obtain a thick but pourable suspension. Flavor was added and the mixture was allowed to dry in an oven at 50°C overnight.
- Each gum cud was applied to a piece of concrete and covered by silicone coated paper before stepping on it for 2 seconds.
- the adhered samples were placed in an oven at 50°C for 24 hours.
- the concrete was then taken out of the oven and allowed to cool to room temperature before attempting to remove the adhered cuds using fingers.
- the Doublemint® gum cud left a large amount of residue that was very hard to remove.
- the Orbit® gum cud gave a long string and also left a large amount of residue.
- the gum cud of Example 7 was removed cleanly by hand leaving no residue.
- Example 7 The gum cud of Example 7 was placed on a piece of 100% cotton fabric from a sport shirt and heavy thumb pressure was applied. It was cleanly removable from the cotton fabric using only fingers.
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Abstract
Description
Claims
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10832323.9A EP2503898A4 (en) | 2009-11-23 | 2010-11-22 | Gum bases, chewing gums based thereupon, and methods for making the same |
CA2781389A CA2781389C (en) | 2009-11-23 | 2010-11-22 | Gum bases, chewing gums based thereupon, and methods for making the same |
JP2012541141A JP2013511289A (en) | 2009-11-23 | 2010-11-22 | Gum base, chewing gum based on this gum base, and method for producing the same |
AP2012006321A AP2012006321A0 (en) | 2009-11-23 | 2010-11-22 | Gum bases, chewing gums based thereupon, and methods for making the same. |
CN201080052984.8A CN102724883B (en) | 2009-11-23 | 2010-11-22 | Matrix, based on its chewing gum and manufacture method thereof |
MX2012005867A MX346257B (en) | 2009-11-23 | 2010-11-22 | Gum bases, chewing gums based thereupon, and methods for making the same. |
BR112012012084A BR112012012084A2 (en) | 2009-11-23 | 2010-11-22 | chewing gum base and method of manufacturing a gum base |
RU2012125860/13A RU2533035C2 (en) | 2009-11-23 | 2010-11-22 | Chewing gum base (versions) and its manufacture method |
AU2010321710A AU2010321710B2 (en) | 2009-11-23 | 2010-11-22 | Gum bases, chewing gums based thereupon, and methods for making the same |
ZA2012/03580A ZA201203580B (en) | 2009-11-23 | 2012-05-16 | Gum bases, chewing gums based thereupon, and methods for making the same |
HK13102273.9A HK1174796A1 (en) | 2009-11-23 | 2013-02-22 | Gum bases, chewing gums based thereupon, and methods for making the same |
Applications Claiming Priority (2)
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US26346209P | 2009-11-23 | 2009-11-23 | |
US61/263,462 | 2009-11-23 |
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WO2011063338A3 WO2011063338A3 (en) | 2011-09-22 |
WO2011063338A4 WO2011063338A4 (en) | 2011-11-17 |
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PCT/US2010/057636 WO2011063338A2 (en) | 2009-11-23 | 2010-11-22 | Gum bases, chewing gums based thereupon, and methods for making the same |
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EP (1) | EP2503898A4 (en) |
JP (1) | JP2013511289A (en) |
CN (1) | CN102724883B (en) |
AP (1) | AP2012006321A0 (en) |
AU (1) | AU2010321710B2 (en) |
CA (1) | CA2781389C (en) |
HK (1) | HK1174796A1 (en) |
MX (1) | MX346257B (en) |
RU (1) | RU2533035C2 (en) |
WO (1) | WO2011063338A2 (en) |
ZA (1) | ZA201203580B (en) |
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WO2012097253A1 (en) * | 2011-01-14 | 2012-07-19 | Avery Dennison Corporation | Removable composition with polymer microspheres |
WO2014008186A2 (en) | 2012-07-05 | 2014-01-09 | Wm. Wrigley Jr. Company | Gum bases based on crosslinked polymeric microparticles |
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US9848619B2 (en) | 2012-08-10 | 2017-12-26 | Wm. Wrigley Jr. Company | Chewing gums and gum bases comprising block copolymers having crystallizable hard blocks |
US9854831B2 (en) | 2012-01-20 | 2018-01-02 | Altria Client Services Llc | Oral product |
US9854830B2 (en) | 2012-01-20 | 2018-01-02 | Altria Client Services Llc | Oral tobacco product |
US9884015B2 (en) | 2012-01-20 | 2018-02-06 | Altria Client Services Llc | Oral product |
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US9986756B2 (en) | 2012-01-20 | 2018-06-05 | Altria Client Services Llc | Exhausted-tobacco oral product |
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DE102011082981A1 (en) * | 2011-09-19 | 2013-03-21 | Wacker Chemie Ag | Non-stick chewing gum base, chewing gum preparation made therefrom, and method of making the same |
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- 2010-11-22 WO PCT/US2010/057636 patent/WO2011063338A2/en active Application Filing
- 2010-11-22 CN CN201080052984.8A patent/CN102724883B/en not_active Expired - Fee Related
- 2010-11-22 AP AP2012006321A patent/AP2012006321A0/en unknown
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- 2010-11-22 JP JP2012541141A patent/JP2013511289A/en active Pending
- 2010-11-22 RU RU2012125860/13A patent/RU2533035C2/en not_active IP Right Cessation
- 2010-11-22 AU AU2010321710A patent/AU2010321710B2/en not_active Ceased
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WO2012097253A1 (en) * | 2011-01-14 | 2012-07-19 | Avery Dennison Corporation | Removable composition with polymer microspheres |
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US9884015B2 (en) | 2012-01-20 | 2018-02-06 | Altria Client Services Llc | Oral product |
EP2804897B1 (en) | 2012-01-20 | 2016-07-13 | Altria Client Services LLC | Oral product |
US11541001B2 (en) | 2012-01-20 | 2023-01-03 | Altria Client Services Llc | Oral product |
US9854831B2 (en) | 2012-01-20 | 2018-01-02 | Altria Client Services Llc | Oral product |
US9854830B2 (en) | 2012-01-20 | 2018-01-02 | Altria Client Services Llc | Oral tobacco product |
US9986756B2 (en) | 2012-01-20 | 2018-06-05 | Altria Client Services Llc | Exhausted-tobacco oral product |
US11864578B2 (en) | 2012-01-20 | 2024-01-09 | Altria Client Services Llc | Oral product |
US9930909B2 (en) | 2012-01-20 | 2018-04-03 | Altria Client Services Llc | Oral product |
US9872516B2 (en) | 2012-01-20 | 2018-01-23 | Altria Client Services Llc | Oral product |
US10602768B2 (en) | 2012-01-20 | 2020-03-31 | Altria Client Services Llc | Oral tobacco product |
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WO2014008186A2 (en) | 2012-07-05 | 2014-01-09 | Wm. Wrigley Jr. Company | Gum bases based on crosslinked polymeric microparticles |
CN104427883A (en) * | 2012-07-05 | 2015-03-18 | Wm.雷格利Jr.公司 | Gum bases based on crosslinked polymeric microparticles |
EP2869711A4 (en) * | 2012-07-05 | 2016-03-09 | Wrigley W M Jun Co | Gum bases based on crosslinked polymeric microparticles |
US9848619B2 (en) | 2012-08-10 | 2017-12-26 | Wm. Wrigley Jr. Company | Chewing gums and gum bases comprising block copolymers having crystallizable hard blocks |
Also Published As
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HK1174796A1 (en) | 2013-06-21 |
RU2533035C2 (en) | 2014-11-20 |
AP2012006321A0 (en) | 2012-06-30 |
CA2781389A1 (en) | 2011-05-26 |
EP2503898A2 (en) | 2012-10-03 |
CN102724883A (en) | 2012-10-10 |
WO2011063338A4 (en) | 2011-11-17 |
AU2010321710A1 (en) | 2012-06-21 |
EP2503898A4 (en) | 2014-01-08 |
AU2010321710B2 (en) | 2013-03-07 |
CN102724883B (en) | 2015-10-07 |
JP2013511289A (en) | 2013-04-04 |
MX346257B (en) | 2017-03-13 |
ZA201203580B (en) | 2013-07-31 |
CA2781389C (en) | 2016-05-17 |
WO2011063338A3 (en) | 2011-09-22 |
MX2012005867A (en) | 2012-06-14 |
RU2012125860A (en) | 2013-12-27 |
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