Classifications

• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
  • A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
  • A23D9/02—Other edible oils or fats, e.g. shortenings, cooking oils characterised by the production or working-up
  • A23D9/04—Working-up
  • A23D9/05—Forming free-flowing pieces
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
  • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
  • A23L27/10—Natural spices, flavouring agents or condiments; Extracts thereof
  • A23L27/12—Natural spices, flavouring agents or condiments; Extracts thereof from fruit, e.g. essential oils
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
  • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
  • A23L27/70—Fixation, conservation, or encapsulation of flavouring agents
  • A23L27/72—Encapsulation
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
  • A23P10/00—Shaping or working of foodstuffs characterised by the products
  • A23P10/30—Encapsulation of particles, e.g. foodstuff additives

Definitions

• the present invention relates generally to a delivery system that can be used for a wide range of formulations of two or more phases, miscible or immiscible, as well as a process for generation of particles, films, extrudates, agglomerates, filaments, capsules or microcapsules, or other solid forms.
• the delivery system compromises not only a formula, but also a method for selection of the two or more phases.
• the formula is determined by measurement of physical data of the two or more materials that will form the phases of the delivery system.
• a wide range of processes is known for making delivery systems that include two or more phases. Those processes include spray drying, coacervation, emulsion evaporation, drip casting, extrusion and more.
• Those processes include spray drying, coacervation, emulsion evaporation, drip casting, extrusion and more.
• the procedures for developing the phases of a two or more phase delivery system involve trial and error, making the process itself expensive and tiring.
• a method is needed to simplify the development and remove the trial and error guesswork from the development of such deliver systems.
• microcapsules and macrocapsules including those that are seamless.
• U.S. Patent No. 4,251, 195 discloses an apparatus for making miniature capsules having a capsule-forming orifice defined by the open ends of two coaxial conduits.
• the inner conduit defines a central opening in the orifice and the outer conduit defines an annulus circumferentially of the central opening.
• Filter-content material for the individual capsules is extruded as a stream through the central opening and a settable coating liquid material is extruded as a thin film sleeve circumferentially of the filler-content material stream.
• the film sleeve and the stream of filler-content material pass through a cooling liquid which is flowed through a fixed nozzle downstream of the extruding orifice.
• the nozzle has an inlet section with converging inner surfaces and a uniform diameter downstream of the inlet section.
• the cooling fluid, the film sleeve and filler-content stream therein all pass through the nozzle.
• a driven annular vibrator is disposed within the nozzle and develops vibrations in the cooling fluid parallel to the direction of the path of travel of the flow to form discrete droplets of the filler-content material enclosed in a film of the settable material.
• the droplets are recovered as miniature seamless capsules.
• U.S. Patent No. 4,695,466 discloses a method of making seamless capsules.
• the capsules are usually made by simultaneously extruding the shell material and the core material through concentrically aligned nozzles such that the extruded shell material and the extruded core material exit the nozzles as a coaxial jet with the shell material surrounding the core material into a stream of cooled carrier liquid that is flowing downward. While descending in the cooled carrier liquid, the coaxial jet breaks into droplets with the shell material encapsulating the core material.
• the two immiscible or partly miscible streams need to have a certain value of interfacial tension for the streams to form stable droplets.
• U.S. Patent No. 5,595,757 discloses a method and an apparatus for making seamless capsules that are capable of forming seamless capsules that are uniform in size and shape even when carbohydrates are used as the shell materials.
• U.S. Patent No. 6,780,507 discloses a method for the formation of microcapsules which contain a liquid composition in the core, which is surrounded by a polymeric shell, membrane, or coating.
• the microcapsules are produced by simultaneously extruding the liquid core material along with a polymerizable liquid through concentrically-aligned nozzles to form spherically-layered bi-liquid droplets, followed by energy input in the form of heat or light which causes polymerization of the outer layer.
• the capsules formed by this method are capable of containing a variety of liquid materials having a composition ranging from completely aqueous to completely non-aqueous.
• U.S. Patent No. 4,473,438 and Patent No. 4, 171,243 disclose a method for spray drying processes for removing water from aqueous liquids containing solids by spraying such liquids into contact with drying gas which has been heated in a furnace, the drying gas removing water from the liquids and thereby forming a dry product.
• the spray drying apparatus includes a spray drying tower with an inlet for a liquid composition to be dried to provide a solid product, an outlet for the solid product, an inlet for a heated drying gas, and an outlet for the drying gas as well as a furnace for heating the drying gas, the furnace having inlets to supply fuel and to supply air, and an outlet for the heated gas.
• microcapsules can be used to deliver a range of active materials such as: breath-freshening agents, flavorings, pharmaceutical active agents, nutrients, gluing systems, textile additives, phase change materials and the like. They generally consist of a two phase system where the outer phase is in many cases, but not limited to, water- and non- water-soluble polymers, plasticizers, waxes/fats and emulsifiers as shell materials. Selection of particular wall materials and plasticizers is based on considerations of the capsule wall properties needed. Thus, it is conventional to employ a water-soluble polymer that is capable of forming strong gels with good mechanical strength; plasticizers are chosen to provide elasticity and pliability to the microcapsule wall charge distribution.
• active materials such as: breath-freshening agents, flavorings, pharmaceutical active agents, nutrients, gluing systems, textile additives, phase change materials and the like. They generally consist of a two phase system where the outer phase is in many cases, but not limited to, water- and non- water-soluble polymers, plasticizer
• the inner phase can contain, but is not limited to, oils, non-water soluble liquids, solvents, water, water soluble materials, waxes, polymers, metals, ceramics and others.
• This invention shows an encapsulation system, where its components are determined by measurement of physical substance properties and a deterministic approach, as well as novel type solid forms that encapsulate actives in favorable ways.
• the methods described are also versatile and adaptive for solving a large number of old and new problems or encapsulation in a quick, cost efficient and effective way.
• the encapsulation system determined to have favorable delivery system formation can be transformed into a solid form.
• the reforming and solid forming processes can be of various natures, including one or several nozzles or sets of nozzles, but are suitable to manipulate the viscosity and surface tension of the encapsulation system by other than chemical means. Also, a setup that generates an additional interfacial layer to enhance or manipulate the surface energy effect on the outermost phase is possible, changing the value of the interfacial energy to a desired range.
• One delivery system for extrudates, agglomerates, particles, seamless or non- seamless microcapsules or macrocapsules, seamless or non-seamless microspheres or macrospheres, films, and filaments that is designed by the measurement of interfacial tension, density, and viscosity of a first phase and a second phase includes a first phase comprising a first surface active agent having an interfacial tension of 1 to 50 mN/m, and a second phase comprising a second surface active agent having an interfacial tension of 1 to 50 mN/m.
• the first phase and the second phase are different from one another and have a viscosity ratio of smaller than 1000: 1 and a density ratio of 1 : 1 to 1 : 10.
• the first surface active agent and the second surface active agent have an interfacial tension of about 8.5 to 35.3 mN/m and may have a viscosity ratio of about 10: 1 to 1 : 1 and a density ratio of about 1 : 1 to 1 :4.
• the delivery system is a capsule, sphere, or particle and the first phase is a core phase and the second phase is an outer phase that forms the capsule shell, sphere shell, or particle shell that houses the core phase.
• the capsule, sphere, or particle may include one or more layers of a coating applied thereto.
• a method for determining the interfacial tension of two or more immiscible or partly miscible phases, such method being especially applicable for use in the formation of droplets between immiscible or partly miscible phases and useful to develop stable formulations of microcapsules or microspheres.
• the immiscible or partly miscible phases being comprised of a liquid, solid, or gas composition as the core phase, which is surrounded by a carrier shell.
• Another aspect of this invention is that a range of encapsulation systems is disclosed which share unique properties for applications.
• encapsulation systems disclosed can be applied to a number of industrial processes, some of them well established, others still in their early stages, as for example: emulsification, flotation, coating, detergency, lubrication, dispersion of powders, coacervation, phase separation, and microencapsulation.
• emulsification, flotation, coating, detergency, lubrication, dispersion of powders, coacervation, phase separation, and microencapsulation We disclose here how to apply such encapsulation system to those industrial processes to yield novel and advantageous products.
• these novel encapsulation systems are used for seamless capsule, film and extrudate forming, to deliver a range of active materials such as: breath-freshening agents, flavorings, pharmaceutical active agents, nutrients, gluing systems, textile additives, phase change materials (PCMs) and the like.
• active materials such as: breath-freshening agents, flavorings, pharmaceutical active agents, nutrients, gluing systems, textile additives, phase change materials (PCMs) and the like.
• the aim of the methods is the generation of successful solid forms of multiphase materials or the design of an encapsulation system by selection of compatible shell and core materials based on measurement of interfacial tension, density and viscosity analysis, and utilization of the physical measurement of the two or more phases and correlating the same to favorable formation of a delivery system. The correlation is relied upon to produce the sold forms.
• FIG. 1 is a pendant drop profile showing the Young-Laplace equation expressed as 3 dimensionless first order equations.
• FIG. 2 is an image of a droplet formed during interfacial analysis of an oil alone with Polymer Solution I such as the vegetable oil or the MCT oil tested in Example 1.
• FIG. 3 is an image of a droplet formed during interfacial tension analysis of 80% MCT oil with 20% menthol in Polymer Solution I. A 70% MCT oil with 30% menthol appeared similarly oblong during interfacial tension analysis.
• FIG. 4 is an image of a droplet formed during interfacial analysis of 80% vegetable oil with 20% menthol in Polymer Solution I.
• FIG. 5 is a photograph of seamless capsules of 80% vegetable oil with 20% methanol encapsulated within a capsule wall formed from Polymer Solution I (an agar pullulan blend).
• FIG. 6 is an image of a droplet formed during interfacial analysis of mint oil with 0.5% menthol in Polymer Solution II.
• Interfacial tension is considered to be a result of the atomic or molecular interactions of the interface layer.
• Surface energy exists between any interface layer in a macroscopic sense, possibly being an interface between gaseous, liquid, solid and any other macroscopic state in any combination.
• the surface energy is considered to be generated by Van der Waals interactions, polarity properties of the molecules in consideration, and also by the Gibbs free energy, enthalpy and entropy interactions.
• miscibility between two substances is an important factor in formulation of chemical systems.
• the reason for being miscible or immiscible is not the polarity of two substances alone, but also the surface energy generated between the two, here called interfacial tension.
• interfacial tension With miscible materials, the direction of the forces in the phase layer between the two phases is directed in all directions, meaning that at last, part of the force is directed into the other phase - to an extent that is correlated to the overall miscibility ratio of the two.
• the force is not directed into the other phase. This means that the force is only directed alongside the phase layer surface and into the phase, effectively pushing out the other phase.
• the formation of "oil droplets in water” can be observed.
• the surface tension of the water pushes the oil into a droplet shape that has the smallest surface to volume ratio and the lowest potential energy.
• the surface energy can be measured as the surface tension (typically against air) or as interfacial tension between two phases and is usually expressed as a figure equaling an energy/area relation.
• the common units for surface energy are dynes/cm or mN/m, which are equivalent.
• the quality of the encapsulation varies with the amount of excess energy until a "breakpoint" is reached, at which an encapsulation is no longer possible.
• the method disclosed herein indicates that the excess surface energy between two faces can be balanced to a degree that an encapsulation system is formed, made possible by the measurement of excess surface energy between the two phases to be incorporated into the delivery system.
• This is not limited to core-shell encapsulation (including seamless capsules), but is also valid for many other forms of encapsulation such as films, strips, particles, pellets, sprays, extrudates, microspheres, emulsions, suspensions, or other forms of encapsulation systems.
• the methods disclosed herein are also valid for other delivery systems of two or more phases made by processes including spray drying, coacervation, emulsion evaporation, drip casting, extrusion, in-situ polymerization, phase separation, and interfacial polymerization.
• a direct way to measure and witness the excess surface energy is to generate and analyze the shape and form of a drop of liquid in a second liquid, forming thus a liquid-liquid interaction and making the excess surface energy directly quantifiable.
• the surface energy can be calculated with the following formulas:
• ⁇ difference in density between fluids at interface
• ⁇ shape factor
• the shape factor can be defined through the Young-Laplace equation expressed as three dimensionless first order equations as shown in FIG. 1.
• the Young-Laplace equation for ⁇ can be solved with modern computational methods using iterative calculations.
• the surface energy may be measured based and calculated as a solution of the Young-Laplace equation.
• this represents a significant improvement, from other, more traditional methods.
• it is possible with this method to use very small volumes of liquid, measure very low surface energies and even analyze melts and many other forms of liquids and liquefiable products.
• video-based optical contact angle measuring systems like OCA 20 made by Data Physics GmbH.
• polarity refers to a separation of electric charge leading to a molecule having an electric dipole
• polar molecules can bond together due to dipole-dipole intermolecular forces between one molecule (and part of a large molecule) with asymmetrical charge distribution and another molecule also with asymmetrical charge distribution.
• Molecular polarity is dependent on the difference in electro-negativity between atoms in a compound and the asymmetry of the compound's structure.
• a molecule surrounded by the same molecules in all directions will not add to the surface energy due to the polarity; however, other effects like an increase of the boiling point or melt point due to strengthening of the Van der Waals interactions between the polar groups and salt solubility will occur. Those also influence the stability of an encapsulation system. Nevertheless, the strongest effect a polar molecule will have is on the interface surface, where the forces are directed into the liquid and on the surface. The higher the polarity, the higher the surface tension typically is.
• Polarity itself is typically measured as a relation to the dielectric constant of a molecule. This is not a precise correlation, but a good indication of the polarity, where typically a value of less than 15 is considered to be classified as non-polar.
• the dielectric constant is correlated to the solvent's ability to reduce the field strength of the electric field surrounding a charged particle immersed in it. The Table below shows some examples of dielectric constant and dipole moment.
• the surface tension is an intrinsic property of substances. However, it can be modified to large extents by use of surface active agents. It is in no way a linear correlation, but it depends on the intra-molecular interactions in the phases.
• a polar liquid - here also called a solvent - can dissolve a salt that is built by positive and negative charged ions. Those ions however "attach" to the positive or negative charged parts of the molecule of the solvent. This will block the interaction with other solvent molecules, the forces between the solvent molecules change, i.e. are reduced.
• the macroscopic effect of this change in the polarity and finally surface energy is the reduction of the melt point of a material, which can be witnessed in winter when salt is used to reduce the melt point of water below the temperature, causing snow and ice to melt.
• a molecular level which is a solution, a sol or gel, or a suspension, on a macroscopic level.
• the method described in detail herein shows that by choosing the right surface active agents, like salts, detergents, additive and/or the active agent to be encapsulated, the properties of the surface tension can be designed in an encapsulation system to fulfill the intended purpose.
• temperature of the phase plays an important role in adjusting not only viscosity and density, but also surface tension, as Brownian molecular movement increases with raising temperature, which weakens the surface tension.
• surface tension is not strong enough to keep the molecules in the liquid, so the molecules enter the gas phase.
• the encapsulation systems described herein contain at last two phases, where the innermost can be considered a core phase.
• the core phase may be a liquid, solid, or gas composition.
• the core phase composition may include one or more solvents and/or one or more surface active agents.
• Suitable solvents include, but are not limited to, oils such as vegetable oil, olive oil, mineral oil, safflower oil, sesame seed oil, corn oil, soybean oil, hydrogenated vegetable oil, mono-glycerides, medium chain triglycerides, canola oil, silicon oil, cottonseed oil, linseed oil, palm oil, peanut oil, castor oil, animal waxes, vegetable waxes, synthetic waxes, and petroleum waxes, water, organic solvents such as alcohols, acids, meltable substances, dispersions, emulsions or other, generally liquid materials with limited viscosities in a range of 0.1 to 10000 mPa*s.
• oils such as vegetable oil, olive oil, mineral oil, safflower oil, sesame seed oil, corn oil, soybean oil, hydrogenated vegetable oil, mono-glycerides, medium chain triglycerides, canola oil, silicon oil, cottonseed oil, linseed oil, palm oil, peanut oil, castor oil, animal
• the surface active agents may be any material having a desirable characteristic, for example, a flavor, a fragrance, a therapeutic effect, catalyst, reactive agent, or other agents such as those listed below.
• Suitable surface active agents include, but are not limited to, salts, sugars, amino-acids, polysaccharides, enzymes, peptides, proteins or carbohydrates, food supplements, food additives, hormones, bacteria, plant extracts, medicaments, drugs, nutrients, chemicals for agro-chemical or cosmetic applications, carotenoids, vitamins, antioxidants, monosaccharides, disaccharides and polysaccharides such as xylose, ribose, glucose (dextrose), mannose, galactose, fructose (levulose), sucrose (sugar), maltose, water soluble artificial sweeteners such as the soluble saccharin salts, i.e., sodium or calcium saccharin salts, cyclamate salts dipeptide based sweeteners, such a L-aspartic acid derived sweeteners, such as L-aspartyl-L-phenylalaine methyl ester (aspartame), dextromethorphan,
• Typical shell materials being gelatin, agar, pullulan, gellan gum, alginate, pectin, hydrocarbon waxes, hydrocarbon polymers, alkyl cellulose, water-soluble polymers such as hydroxyalkyl cellulose, water-soluble polyvalent alcohols or water-soluble derivatives thereof such as polyglycerin, sorbitol, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, oligosaccharide, sugar ester, glyceride, sorbitan ester, corn starch, potato starch, rice starch, tapioca starch, maize starch, sorghum starch, sago starch wheat starch or sodium starch glycolate; or any native starch that has been chemically modified, e.g.
• methyl celluloses and mixed ethers thereof such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose, ethyl methyl cellulose, and carboxymethyl methyl cellulose; ethyl cellulose and mixed ethers thereof such as ethyl hydroxyethyl cellulose; hydroxyalkyl cellulose ethers such as hydroxy ethyl cellulose, hydroxypropyl cellulose, hydroxyethyl hydroxypropyl cellulose, and carboxymethyl hydroxyethyl cellulose, animal waxes, vegetable waxes, synthetic waxes, petroleum, and mixtures thereof.
• Microcapsule production may be achieved by physical methods such as spray drying or by centrifugal and fluidized beds. However, it is desirable to use co-extrusion nozzles with or without vibrational support for optimized product quality.
• the microencapsulated material(s) may be provided using any suitable capsule chemistry.
• Chemical techniques may be used, such as dispersing droplets of the molten core phase in an aqueous solution and to form walls around the droplets using simple or complex coacervation, interfacial polymerization and in situ polymerization all of which are well known in the art.
• methods are well known in the art to form gelatin capsules by coacervation, polyurethane or polyurea capsules by interfacial polymerization, and urea-formaldehyde, urea-resorcinol-formaldehyde, and melamine formaldehyde capsules by in situ polymerization.
• the outer phase may be a composition comprising one or more phases containing at least one surface active agent.
• the outer phase includes a surface active agent that may be known as a hydrocolloid.
• a surface active agent that may be known as a hydrocolloid.
• a vibrational nozzle process as supplied by BRACE GmbH, Germany, is used.
• the inner phase and the outer phase (or a first phase and a second phase, which may both include one or more phases therein) are coextruded in a laminar flow through one or many orifices (annular gap nozzles) and the liquids are subject to a vibration in resonance, either via the nozzle or nozzle plate, or via the liquid(s) itself.
• the resulting droplet which is already the precursor capsule in shape and form, is solidified, depending on the out phase system used, either with cold gas, cold liquid, reaction in liquid or gas phase.
• an alginate-pectin system for example cooled oil is used, for an alginate-pectin system a calcium chloride or calcium lactate solution.
• materials as ethyl cellulose, alginate, carboxymethylcellulose, gelatine, pullulan, guar gum, gellan gum, various poly- cat- or poly-anions as poly-L-lysin, or others.
• Ethylcellulose, alginate and gelatine are use for many widely applicable processes.
• the microcapsules will typically have a relatively high payload of the core composition of about 10% to 90%.
• the core composition is present at about 70% to 80% by weight.
• the core composition may include one or more of the surface active agents in one or more of the solvents described above.
• the size of the microspheres or microcapsules is typically in the range from about 10 to about 10000 ⁇ and more typically from about 30 to about 6000 ⁇ .
• the capsule size selected will depend on the application in which the microcapsule is used. For example, flavor microcapsules of 800-1200 ⁇ are used in chewing gum products, whereas microcapsules of 30-1000 ⁇ are used in construction for delivering phase change material, humidified or anti-fouling agents into concrete. In textiles microcapsules of 1 to 500 ⁇ are used for anti-allergic mattresses, other applications include food applications like probiotic microcapsule formulations or fermentation agents in champagne production. [0059]
• the microcapsules may be made of different wall thicknesses.
• the wall material should be thick enough to contain the core composition according to the desired properties. Desired properties can include, but is not limited to, protection against the environment, full enclosure without leaks or diffusion out of the capsule, slow diffusion, triggered release, sustained or controlled release, etc.
• the wall thickness may be about 0.1 to about 500 ⁇ . In one embodiment, the wall may be about 0.2 to about 0.6 ⁇ thick with a nominal (mean) thickness of about 0.4 ⁇ .
• the shell can be designed to withstand rupture under high pressure to rupture under minimal pressure, dissolution under change of pH, presence of humidity or other solvents, time dissolution, etc.
• capsule size and wall thickness may be varied by many known methods, for instance, adjusting the amount of mixing energy applied to the materials immediately before wall formation commences.
• Capsule wall thickness is also dependent upon many variables, including the typical process parameters as, but not limited to, flow rate, frequency of droplet generation, amplitude, temperature, viscosity, and speed of the mixing unit used in the encapsulation process.
• microencapsulation processes known in the art or otherwise found to be suitable for use with the invention may be employed.
• a plurality of microencapsulated PCMs having the same or different encapsulation may be contained in "macrocapsules" as disclosed in U.S. Patents No. 6,703, 127 and No. 5,415,222, herein incorporated by reference in their entirety.
• Macrocapsules may provide a thermal energy storage composition that more efficiently absorbs or releases thermal energy during a heating or a cooling process than individual microencapsulated PCMs.
• the delivery system may be a film or a filament.
• the two phases to be combined in the film or filament formulation are tested using the same methods described above for the capsule systems.
• the pendent drop method is used to measure the interfacial tension and to view the droplet formation.
• round end, evenly shaped droplets correlate to favorable delivery system formation and oblong droplets do not.
• the two phases may include one film forming phase that may contain film forming agents and the second phase includes a surface active agent.
• the surface active agent may be any of those listed above, the like, or equivalents thereof.
• the film forming agent may include, but is not limited to, . . . .
• water-soluble non-starch polysaccharides such as carboxymethylcellulose (CMC), methylcellulose, hydroxypropylmethylcellulose (HPMC), guar gum, locust bean gum, xanthum gum, carrageenan, algins, propylene glycol, levan, elsinan, pullulan, pectins, chitosan, and gum arabic; native starches such as corn starch, waxy maize starch, high-amylose corn starch, potato, tapioca, rice and wheat starch; modified starches such as those that have been acid modified, bleached, oxidized, esterified, etherified, crosslinked, and treated enzymatically; starch hydrolyzed products such as maltodextrin; protein such as albumen, gelatin, casein, salts of casein, whey, wheat gluten, zein, and protein derived from soybeans; polymers such as polyvinyl pyrrolidone, methycrylate copolymer, and
• softeners can also be employed to ensure the flexibility of the film, thereby reducing brittleness.
• the softeners which are also known as plasticizers, may include tallow, hydrogenated tallow, hydrogenated and partially hydrogenated vegetable oils, cocoa butter, sorbitol and other polyols, including polyoxyethylene sorbitan monooleate, glycerin, polyethylene glycol, propylene glycol, invert sugars, corn syrup, lecithin, hydrogenated lecithin, mono-, di- and triglycerides, acetylated monoglycerides, fatty acids (e.g.
• the softener may constitute 0% to about 20% by dry weight of the film, or about 2% to about 10% by dry weight of the film.
• the film formulation may be formed into a film using any known techniques.
• the film formulation may be coated onto a release paper using a knife- over-roll coating head.
• the coated paper is then dried in a drying tunnel and a film matrix is formed.
• the film matrix has a paper wafer like consistency.
• the film matrix may be cut into desirable shapes and packaged.
• Polymer Solution I and oil samples were analyzed to determine the physical parameters of density and viscosity of oil samples, and determine interfacial tension between polymer solution and oil blend samples at temperature of 68 °C using Pendant drop method.
• Polymer Solution I was comprised of a solution made with de-ionized water, blend of agar and pullulan water soluble polymers, and glycerin as a plasticizer. Table 1 lists measurement of density and viscosity of the oil samples.
• Table 2 lists measurement of interfacial tension between Polymer Solution I and oil blend samples at temperature of 68°C using Pendant drop method.
• the interfacial tension was measured using a Data Physics GmbH's video-based optical contact angle measuring system OCA 20 with software SCA20, 22.
• FIG. 2 is an image of the droplet formed during interfacial analysis of Sample No. 6 from Table 2 of a Medium Chain Triglyceride ("MCT") oil core phase collected in a Polymer Solution I carrier phase.
• MCT Medium Chain Triglyceride
• the interfacial tension value for the MCT oil was the highest value and resulted in the most spherical droplet for the oils tested with Polymer Solution I. Accordingly, the MCT oil and Polymer Solution I were scaled up as described below to produce seamless capsules.
• Seamless capsules were prepared by using a vibrational nozzle process, as supplied by BRACE GmbH, Germany, with a concentrically aligned multiple orifice system having an inner orifice and an outer orifice.
• the inner orifice had an outside diameter of 0.07 cm, and the outer orifice had an outside diameter of 0.16 cm.
• Polymer Solution I was used as the carrier solution, and maintained in a tank at 60°C. This mixture had an actual viscosity of 85 mPa*s at 60°C, and a density of 1.00 g/ml.
• the mixture was then fed to the outer orifice as the shell material at a temperature of 60°C and a volumetric flow rate of 5 ml/min.
• MCT oil having a density of 0.9 g/ml was supplied to the inner orifice as the core material at ambient temperature and a volumetric flow rate of 5 ml/min.
• the shell material and the core material were then simultaneously extruded from the outer and inner orifices; the coaxial jet descended through air for 10 cm and broke down into droplets to allow encapsulation to take place.
• the capsules then descended into a cooled mineral oil bath.
• the resultant capsules collected had a diameter of about 4.5 mm.
• With an additional coating applied by ethanol-ethyl cellulose bath (5% ethyl cellulose) the capsule was finalized and subsequently dried in a rotary drum drier.
• Polymer Solution I and mixtures of oil and surface active agents were analyzed to determine the physical parameters of density and viscosity of mixture of oil and surface active agent samples, and determine interfacial tension between polymer solution and oil blend samples at temperature of 68°C using Pendant drop method.
• Menthol was selected as the surface active agent for Example 2.
• MCT had the highest interfacial tension in Example 1 and formed successful seamless microcapsules with Polymer Solution I, so the interfacial tension of MCT with menthol in the Polymer Solution I was measured. Additionally, the oil that had the second highest interfacial tension measurement in Example 1, vegetable oil, was also selected for measurement of the interfacial tension with menthol in the Polymer Solution I.
• Polymer Solution I as indicated above, comprised of a solution made with de-ionized water, blend of agar and pullulan water soluble polymers, and glycerin as a plasticizer. Table 3 lists measurement of density and viscosity of the mixture of oil and surface active agent samples.
• Table 4 lists measurement of interfacial tension between Polymer Solution I and oil blend samples at temperature of 68°C using Pendant drop method.
• the interfacial tension was measured using a Data Physics GmbH's video-based optical contact angle measuring system OCA 20 with software SCA20, 22. The same procedure for taking the interfacial tension measurements described above in Example 1 was used here.
• FIG. 3 is an image of a droplet formed during interfacial tension analysis of Sample 5 from Table 4 of 80% MCT Oil: 20% Menthol and Polymer Solution I. At the higher menthol concentrations in MCT, stable spherical droplet formation during interfacial tension analysis was not achieved. The droplets formed were oblong in shape as shown in FIG. 3. When menthol is present, the interfacial tension measurements, droplet formation during the interfacial tension measurements, and the decrease in viscosity correlates to unfavorable seamless capsule formation.
• FIG. 4 is an image of a droplet formed during interfacial tension analysis of Sample 2 from Table 4 of a 80% Vegetable Oil: 20% Menthol and Polymer Solution I. At the higher menthol concentrations in Vegetable Oil, stable spherical droplet formation during interfacial tension analysis was achieved. The droplets formed were spherical in shape as shown in FIG. 4. When menthol is present, the interfacial tension measurements, droplet formation during the measurements, and increase in viscosity experienced by the vegetable oil correlate to favorable seamless capsule formation.
• a mixture of 80% MCT oil: 20% menthol having a density of 0.9 g/ml was supplied to the inner orifice as the core material at ambient temperature and a volumetric flow rate of 5 ml/min.
• the shell material and the core material were then simultaneously extruded from the outer and inner orifices; the coaxial jet descended through air for 10 cm and broke down into droplets to allow encapsulation to take place.
• the droplets were then separated into two separate streams and descended into a cooled mineral oil bath.
• the resultant spheres collected had a diameter of about 4.5 mm, but were empty, i.e., the spheres only contained shell material. Unfavorable seamless capsule formation occurred as expected from the data reported above.
• the capsules in FIG. 5 also include a coating applied by a carboxymethyl- cellulose bath (2.5% carboxymethyl cellulose) after capsule formation. After coating with the carboxymethyl cellulose, the capsules were dried in a rotary drum drier.
• EXAMPLE 3 MCT oil with Orange Oil as the Surface Active Agent in an
• the surface active agent was used for the inner phase a mixture of an MCT and orange oil.
• the external phase a solution of alginate (1%) and pectin (1.5%) was used, which included polyethylene glycol 1500 (0.5%).
• the measurement of interfacial tension using the pendant drop method resulted in the formation of a round end evenly shaped droplet at room temperature. This correlates to favorable capsule formation, which did result in filled capsules as shown below.
• Seamless capsules were prepared by using a vibrational nozzle process, as supplied by BRACE GmbH, Germany, with a 36 fold concentrically aligned multiple orifice system having an inner orifice and an outer orifice.
• the inner orifice had an outside diameter of 0.2 mm, and the outer orifice had an outside diameter of 0.3 mm.
• the outer and inner phases were both used at room temperature. With a flow rate of 144 mL/min for the inner phase and 420 mL/min for the outer phase droplets of 600 ⁇ were produced. Those droplets were solidificated in a 4% CaC3 ⁇ 4 solution.
• the capsules from above were collected after 5 minutes in the CaC3 ⁇ 4 solution and then transferred to a 1% alginate solution for 10 minutes. After this, they have been washed and dried in a rotary drum drier. This produced capsules with a load of 88%o and a crush force of 15+-3N.
• Example 4 A Mint Oil with Coolact 10 as the Surface Active Agent in a
• Polymer Solution II and mint flavor oils with surface active agents were analyzed to determine the physical parameters of density and viscosity of mixture of mint oil with surface active agent samples, and determine interfacial tension between polymer solution and oil blend samples at temperature of 68°C using Pendant drop method.
• Polymer Solution II was comprised of a solution made with de-ionized water, blend of tapioca starch, tapioca dextrin and gelatin water soluble polymers, and sorbitol as a plasticizer. Coolact 10 was used as the surface active agent. Table 5 lists measurement of density and viscosity of the mixture of oil and surface active agent samples.
• Table 6 lists measurement of interfacial tension between Polymer Solution I and oil blend samples at temperature of 68°C using Pendant drop method as set forth in Example 1.
• the interfacial tension was measured using a Data Physics GmbH's video- based optical contact angle measuring system OCA 20 with software SCA20, 22. The same procedure described in Example 1 for taking the interfacial tension measurements was used here.
• the measurement of interfacial tension using the pendant drop method resulted in the formation of a round end evenly shaped droplet at room temperature for both samples.
• FIG. 6 is an image of a droplet formed during interfacial tension analysis of mint oil with 0.5% Coolact 10 in Polymer Solution II. This correlates to favorable capsule formation for both concentrations of surface active agent, which did result in filled capsules.
• EXAMPLE 5 Film Formation with a first phase and second phase
• Phase 1 was comprised of a solution made with de-ionized water, tapioca starch, tapioca dextrin, sorbitol, polysorbate 80, and protein.
• Phase 2 consisted of Mint Flavor 2.
• Phase 1 and Phase 2 were analyzed to determine the interfacial tension between the two phases using Data Physics GmbH's video-based optical contact angle measuring system OCA 20 with software SCA20, 22.
• the interfacial tension measurement for Phase 1/ Phase 2 was 20.2 dynes/cm (mN/m) and a round end, evenly shaped droplet was seen. This correlates to favorable formation of a delivery system comprising the two phases.
• a mono-layer film containing mint oil with active agents was prepared as follows. For Phase 1, two solutions were made, the first being a starch solution and the second being a protein solution.
• Starch Solution 10 grams of Tapioca Starch and 10 grams Tapioca Dextrin were added to 180 ml of de-ionized water with high shear mixing until a clear solution was formed.
• Protein Solution 20 grams Pork Gelatin was added to 180 ml of de-ionized water with high shear mixing until a clear solution was formed.
• Phase 1 consisted of a mixture of the starch solution, 75% sorbitol solution, polysorbate 80, and the protein solution. Phase 1 was mixed together until homogenous.
• Phase 2 consisted of a flavor agent, here mint flavor 2. Phase 2 was emulsified into the mixture with mixing until no lumps are present.
• the coating formula was coated onto a polyethylene coated differential release paper using a knife-over-roll coating head.
• the coated paper was then dried in a drying tunnel and film matrix was formed.
• Film matrix has a paper wafer like consistency. Pieces were then tested for sensory response of flavor release in the oral cavity. The films dissolved quickly in the mouth to provide bursts of flavor sensations to the oral cavity.

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