WO2020115139A1

WO2020115139A1 - Method of enhancing flavor sensory experience

Info

Publication number: WO2020115139A1
Application number: PCT/EP2019/083687
Authority: WO
Inventors: Nathalie Coursieres; Céline FROMENTIN; Annaïg FALC'HUN; Arnaud PETRI; Jean-Michel Hannetel
Original assignee: V. Mane Fils
Priority date: 2018-12-05
Filing date: 2019-12-04
Publication date: 2020-06-11
Also published as: FR3089391A1; AR117243A1

Abstract

A method for enhancing a flavor sensory experience in a confectionary product is provided. The method includes dispersing 0.1 to 10 wt% of an encapsulated flavor in the confectionary composition. The encapsulated flavor is a microcapsule having an average particle diameter from 400 to 1000 microns with a coefficient of variance of <15%. The capsule includes a shell matrix comprising a gelled hydrocolloid material with an average dried thickness (T) of 20 to 200 microns; and a core portion includes the flavor composition and has an average core diameter (D) of 200 to 950 microns, with a D/T ratio of 1 to 40. The texture characteristic of the dried microcapsule includes a force at break value in a range from 0.05-5 Kg; a stiffness at break value in a range from 0.2-5 Kg/mm; a deformation ratio of 0.1-0.9; or a Young's modulus value in a range from 0.2-10 Kg.

Description

METHOD OF ENHANCING FLAVOR SENSORY EXPERIENCE

TECHNICAL FIELD

[0001] The present invention relates generally to microcapsules, and more particularly to enhanced flavor sensory experiences arising from microcapsules having uniform size and desirable texture properties.

BACKGROUND ART

[0002] Various types of chewable articles are known in commerce. These articles include foodstuff, such as confectionery items. The chewable articles often include various types of active agents or ingredients. Non-limiting examples of typical active ingredients include flavors, sweeteners, colors, medicaments, vitamins, minerals, and sensates.

[0003] A frequent problem associated with the application of flavor systems in chewable articles is the loss of flavor by volatilization and short lasting sensory performance. A common approach to address these problems is the use of encapsulation. Encapsulation is broadly defined as a technology of packaging solids, liquids, or gaseous materials in small, sealed matrices or capsules that can release their contents at controlled rates under specific conditions. In addition to the foregoing, active ingredients may be encapsulated for a variety of other reasons, such as enhanced retention, protection from undesirable interactions with the bulk matrix or other ingredients, guard against either light-induced reactions or oxidation, and/or to effect the controlled release of the ingredient.

[0004] However, the final physical or mechanical properties of the capsules also need to match the requirements of their intended application, such as an ability to withstand processing forces (e.g., shear and/or compression) encountered during incorporation into consumer products, such as stick gum or compressed tablets. In addition, to provide consistent and/or enhanced flavor sensory experience (e.g., sufficient intensity and/or long lasting effect) to chewable articles, it is desirable that the encapsulated materials contain a sufficient quantity of the active ingredient(s) and are homogenously dispersed. Thus, depending on the desired flavor loading, particle size, solubility characteristic, and texture properties, there are several different types of encapsulation techniques to choose from, such as in-situ gelation, coacervation, extrusion, co- extrusion, spray dry, or spray dry granulation.

[0005] Expired U.S. Patent No. 6,436,461 to Bouwmeesters et al. describes using acid polysaccharide (e.g., alginate) beads as food additives, where its matrix contains active ingredients like flavors. The flavor-filled alginate beads are reported to span average particle size diameters from 10 to 5000 microns, and bead sizes were separated using sieves. The larger bead particles (1 to 2 mm) demonstrated higher aroma intensity versus the smaller sizes (i.e., 0.5 to 1 mm; 0.25 to 0.5 mm; 0 to 0.25 mm; and unencapsulated flavors). However, the flavor loading in the particle matrix was only about 20 wt%.

[0006] Expired U.S. Patent No. 6,045,835 to Soper et al. describes a method of encapsulating flavors by controlled water transport across a hydrophilic hydrocolloid shell of a microcapsule into a blank oily core. The microcapsules were prepared by complex coacervation, which generally yields microcapsules less than 800 microns, typically 100 to 400 microns having large particle size distributions. However, complex coacervation particles typically possess thin shell walls, relative to their core, which result in weak texture properties.

[0007] Expired U.S. Patent No. 4,689,235 to Bames et al. describes an extrudable encapsulation system for oils, flavors, etc. comprising maltodextrin and CAPSUL®. While these extruded particles are reported capable of containing up to 40 wt% flavor loadings, the flavor loaded extruded particles require milling and sieving to obtain encapsulated flavor particles with the desired particle size and distribution.

[0008] Expired U.S. Patent No. 5,124,162 to Boskovic et al. describes a mixture of flavor, maltose, maltodextrin, and carbohydrate film former by spray drying the mixture. Spray drying can generally provide particles in a range from 10 to 500 microns, with the most common applications in the 100 to 200 microns diameter range with relatively large particle size distributions.

[0009] Abandoned Published U.S. Patent Application No. 2009/0226529 to Quellet et al. described a method of making granulated compositions by plating or spray drying a flavor composition onto a carrier followed by a coating process that can apply successive layers in a fluidized or non-fluidized bed coating unit. The granulates thereby produced have particle sizes ranging from 0.1 to 10 mm, and typically in the 0.5 to 1 mm range. Similar to spray dried particles, granulates have relatively large particle size distributions.

[0010] Accordingly, there is a need for new encapsulated flavors having desirable rigidity properties, good dispersibility, and monodispersity, and can provide long lasting flavor.

SUMMARY OF INVENTION

[0011] Certain aspects of the present disclosure are described in the appended claims. There are additional features and advantages of the subject matter described herein. They will become apparent as this specification proceeds. In this regard, it is to be understood that the claims serve as a brief summary of varying aspects of the subject matter described herein. The various features in the claims and described below for various embodiments may be used in combination or separately. For example, specified ranges may be inclusive of their recited endpoints, unless explicitly excluded. Any particular embodiment need not provide all features noted above, nor solve all problems or address all issues noted above.

[0012] According to an embodiment of the present invention, a confectionery product having an enhanced flavor profile is provided. The confectionery product comprises a sweetener selected from the group of monosaccharides, disaccharides, polysaccharides, polyol sweeteners, non-nutritive sweeteners, and combinations thereof; and 0.1 wt% to 10 wt% of an encapsulated flavor interspersed in the confectionary matrix, where wt% is based on the entire weight of the confectionery product. The encapsulated flavor is contained in dried microcapsules having an average (or mean) particle diameter in a range from 400 microns to 1000 microns with a coefficient of variance of less than 15%. The dried microcapsules comprise a shell matrix comprising a gelled hydrocolloid gelling agent material and having an average dried thickness of 25 microns to 200 microns; and a core portion comprising a flavor composition and having average core diameter of 200 microns to 950 microns. A ratio between the average core diameter (D) and the average thickness (T) of the shell matrix is in a range from 1 to 40. The texture characteristics of the dried microcapsules include at least one of a force at break value in a range from 0.05 to 5 Kg; a stiffness at break value in a range from 0.2 to 5 Kg/mm; a deformation ratio of 0.1 to 0.9; or a Young’s modulus value in a range from 0.2 to 10 Kg.

[0013] According to another embodiment of the present invention, a method for enhancing a flavor sensory experience in a confectionary product is provided. The method includes dispersing 0.1 wt% to 10 wt% of an encapsulated flavor in the confectionery product, which comprises a sweetener selected from the group of monosaccharides, disaccharides, polysaccharides, polyol sweeteners, non-nutritive sweeteners, and combinations thereof. The encapsulated flavor is a microcapsule having an average particle diameter in a range from 400 microns to 1000 microns with a coefficient of variance of less than 15%. The capsule comprises a shell matrix comprising a crosslinked hydrocolloid material and having a dried average thickness (T) of 20 microns to 200 microns; and a core portion comprising the flavor composition and having an average core diameter (D) of 200 microns to 950 microns, where the D/T ratio is in a range from 1 to 40. The microcapsule is characterized by a texture characteristic of a force at break value in a range from 0.05 to 5 Kg; a stiffness at break value in a range from 0.2 to 5 Kg/mm; a deformation ratio of 0.1 to 0.9; or a Young’s modulus value in a range from 0.2 to 10 Kg. BRIEF DESCRIPTION OF DRAWINGS

[0014] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with a general description of the invention given above, and the detailed description given below, serve to explain the invention.

[0015] [FIG. 1] is a line graph showing mint flavor intensity of an inventive microcapsule over time in a chewing gum matrix in comparison to other flavor delivery systems;

[0016] [FIG. 2] is a line graph showing mint flavor intensity of an inventive microcapsule over time in a chewing gum matrix in comparison to a larger capsule;

[0017] [FIG. 3] is a line graph showing minty freshness intensity of an inventive microcapsule over time in a chewing gum matrix in comparison to other flavor delivery systems;

[0018] [FIG. 4] is a line graph showing minty freshness intensity of an inventive microcapsule over time in a chewing gum matrix in comparison to a larger capsule;

[0019] [FIG. 5] is a line graph showing strawberry flavor intensity of the inventive microcapsules over time in a chewing gum matrix in comparison to other flavor delivery systems;

[0020] [FIG. 6] is a line graph showing strawberry flavor intensity of an inventive microcapsule over time in a chewing gum matrix in comparison to a larger capsule;

[0021] [FIG. 7] is a line graph showing mint flavor intensity of an inventive microcapsule over time in a chewing gum matrix, in comparison to a larger capsule and a combination of both;

[0022] [FIG. 8] is a plot of volume percent (%) versus particle diameter (pm) for an inventive seamless breakable microcapsule, a larger comparative seamless breakable capsule, and a mixture (5:2 weight ratio) thereof; and

[0023] [FIG. 9] is a line graph showing strawberry flavor intensity of an inventive microcapsule over time in a chewing gum matrix in comparison to a larger capsule.

DESCRIPTION OF EMBODIMENTS

[0024] In accordance with embodiments of the present invention, a confectionary com position having an enhanced flavor profile is provided. The confectionary composition comprises at least one encapsulated flavor interspersed in a confectionary matrix. The encapsulated flavor comprises breakable microcapsules that comprise a core and a breakable shell matrix surrounding the core. The microcapsules are advantageously monodispersed and seamless. The breakable microcapsules are advantageously spherical or substantially spherical, and have an average particle diameter in a range of 400 microns to 1000 microns, with a coefficient of variance of less than 15%. The breakable shell matrix comprises a gelled hydrocolloid gelling agent having a dried thickness of 25 microns to 200 microns. The core portion comprises a flavor and has core diameter of 200 microns to 950 microns. The breakable microcapsules are substantially homogenously dispersed in the confectionary matrix.

[0025] Advantageously, the breakable microcapsules are breakable under the application of a sufficient amount of force, but show good resilience to mechanical and thermal stresses experienced during incorporation of the microcapsules into a chewable matrix. Accordingly, the breakable microcapsules are further characterized by one or more of the following texture characteristic: 1) a force at break in a range from 0.05 to 5 Kg; 2) a deformation ratio of 0.1 to 0.9; 3) a stiffness at break in a range from 0.2 to 5 Kg/ mm; or 4) a Young’s modulus in a range from 0.2 to 10 Kg.

[0026] As used herein, the term "capsule" means a delivery system of a core, which is enveloped by a breakable shell. In accordance with embodiments of the present invention, the inventive capsules have an average particle diameter from 400 microns to 1000 microns (0.4 mm to 1 mm), and are thus referred hereinafter as “microcapsules.” Preferably the microcapsules have an average particle diameter greater than 450 microns and less than 950 microns, and more preferably greater than 500 microns and less than 900 microns. It is of particular interest to obtain seamless microcapsules, as the breakability of a welded capsule (also designated in the prior art as softgel or hard capsule) may be influenced by the easy or unwanted rupture of the weld. In an embodiment, the microcapsules are spherical or substantially spherical. The microcapsules may be void of any dyes or colorants, or the microcapsules may be purposefully colored, such as having a colored oily core, a colored shell, or both.

[0027] Unless specified otherwise, the term "substantially" means ± 10% of a numerical value. And when referring to a sphere, it includes a distorted sphere where its shape ratio, which is a ratio of width/length measured by microscopy (SZX9 Olympus microscope with MICRO VISION software), is at least 0.8 or greater.

[0028] As used herein“gellable mixture” means a mixture of a hydrocolloid gelling agent, alone or in combination with one or more other gelling agents, fillers, and/or additives, that is able to convert an aqueous phase from a flowable liquid to a solid or a gel.

[0029] As used herein, “crosslinked” means the linking of one section of the hydrocolloid gelling agent to another section in a gelled matrix. Depending on the chemical nature of the hydrocolloid gelling agent, the specific type of crosslinking may include one or more of ionic interactions, covalent bonding, inter- and intra-strand hydrogen bonding, or Van der Waals forces. In an embodiment, the hydrocolloid gelling agent is a polysaccharide bearing carboxylic or carboxylate groups, where upon exposure to multivalent metal ions, such as Ca2+, bridges are formed between inter- and intra-strand carboxylate groups in the gelled matrix.

[0030] As used herein, the term "breakable” refers to a microcapsule as defined above, wherein the breakable shell can be ruptured under application of a sufficient amount of pressure, which results in the release of the core. The breakable microcapsules may be specifically designed to be incorporated into a variety of matrices, such as powders, gums, melts, gels, pastes, or liquid mediums containing water, to form various forms/ shapes (e.g., tablets, rods, sheets, etc.) of confectionary goods. The microcapsules may be suspended or mixed by any suitable means in order to bring a visual effect of homogeneous dispersion of the microcapsules in the matrices. Accordingly, to avoid undue and premature rupture of the breakable shell, the rigidity of the microcapsule should be greater than that of the matrix into which the microcapsule is incorporated. For example, the Young’s modulus value of the microcapsule should be greater than Young’s modulus value of the confectionary matrix.

[0031] The texture of the microcapsules may be characterized using a TA.XTplus texture analyzer from Stable Micro System Ltd. (Surrey, UK) in compression mode with a 5 Kg load cell; Probe: P0.5 - ½ diameter DELRIN® cylinder; cylinder speed 0.5 mm / sec; resolution of 0.01 Kg. The microcapsule is positioned on the TA.XT plus device between the base and the probe. Vertical compressive force is then continuously applied onto one particle until the breakable shell ruptures and simultaneously the built-in gauge records force (in kilograms (Kg) or newton (N)) and position (in millimeter (mm)). Rupture of the microcapsule results in the release of the core.

[0032] The“force at break” or“hardness” is the maximum force applied at the very moment of the rupture of the microcapsule, (measured in Kg or N).“Deformation” is a ratio of the distance at break and the initial capsule size, where the“distance at break” (in mm) is the distance covered by the probe from the contact of the capsule until the microcapsule’s breaking point, as measured using the TA.XTplus texture analyzer described above.

[0033] As used herein, "rigidity" defines the property of a solid body to resist deformation. Rigidity of the microcapsule may be characterized by its stiffness at break value and/or its Young’s Modulus value. The“stiffness at break” (in Kg/mm or N/mm) is a ratio of the force at break and the distance at break.“Young’s modulus” is defined as a ratio between the force and the deformation at the beginning of the compression (arbitrarily measured at 0.05 sec), in Kg or N. Both of these properties may be measured using the TA.XTplus texture analyzer as described above.

[0034] For texture testing purposes, the dried breakable microcapsule has a water content of 10% or less (measured by Karl Fisher titration); a water activity of 0.8 or less; or both.

[0035] As used herein, the“average particle diameter” of the dried microcapsules is measured using a Beckman Coulter® LS 13 320 laser diffraction particle size analyzer (software version 6.01, firmware version 4.00) using Garnet optical model. As used herein, “average shell thickness” may be determined using a microscope for wet capsules or using a scanning electron microscope (SEM) for dried microcapsules. Prior to SEM measurement, the samples of cut shells were coated using a Quorum Technologies SC7620 Sputter Coater to deposit a thin conductive metal coating; SEM scans were taken using desktop Scanning Electron Microscope - Phenom Pro with standard sample holder. As used herein,“average core diameter” may be determined using a microscope for wet microcapsules, or calculated for the dried microcapsules using the average particle diameter and the average shell thickness of the dried microcapsules.

[0036] The breakable microcapsules of the present invention are useful for numerous applications, such as confectionary applications. In order to withstand the processing stresses encountered during incorporation of the breakable microcapsules into the confectionary application, the dried breakable microcapsules advantageously are characterized by having a force at break of 0.05 Kg to 5 Kg; a deformation ratio of 0.1 to 0.9; a stiffness at break of 0.2 Kg/mm to 5 Kg/mm; and/or a Young’s modulus of 0.2 Kg to 10 Kg.

[0037] BREAKABLE SHELL

[0038] In accordance with embodiments of the present invention, the gellable matrix, which forms the breakable shell of the microcapsule comprises one or more hydrocolloid gelling agents selected from hydrophilic polymers that are dispersible in water. The hydrocolloid gelling agents are selected from a collagen-derived gelling agent, a polysaccharide based gelling agent, or a combination thereof. Non-limiting examples of suitable hydrocolloid gelling agents include gelatin, gellan gum, alginates, agar-agar, kappa- carrageenan, low methoxyl (LM) pectin, pectin, gelifying starch, modified starches, dextran, curdlan, xanthan gum, arabic gum, tara gum, ghatti gum, karaya gum, welan gum, rhamsan gum, pullulan gum, xanthan gum, locust bean gum, modified starches, chitosan, or combinations thereof. Sources of collagen-derived gelling agents include, but are not limited to, gelatins, such as porcine, bovine, or fish derived gelatins, where the gelatin has a Bloom value of at least 200. Non-limiting examples of a suitable gelatins include GELATINE ALIM BOEUF 250 B./30 M. BRESIL / GELITA DEUTCHLAND GMBH; ROUSSELOT® 250 LB 8 / ROUSSELOT SAS; Gelatin Beef 250/30 / PB LEINER USA; GELATINE 240-260 B./30 M. sulf.<10 PPM / PB GELATINS TESSENDERLO CHEMIE SA/NV; GELIKO K FG 250/30 BOVIN HIDES BRAZIL / GELITA DEUTCHLAND GMBH; or GELATINE GAL/F 28 / LAPI GELATINE S.P.A.

[0039] Polysaccharide based gelling agents include, but are not limited to, gellan gum, alginates, agar, kappa-carrageenan, low methoxyl (LM) pectin, or pectin, xanthan gum, arabic gum, tara gum, ghatti gum, karaya gum, dextran, curdlan, welan gum, rhamsan gum, modified starches, or combinations thereof. In an embodiment, the hydrocolloid gelling agent comprises a polysaccharide based gelling agent bearing carboxylic or carboxylate groups, where upon exposure to multivalent metal ions, crosslinking bridges are formed between inter- and intra-strand carboxylate groups.

[0040] In an embodiment, the hydrocolloid gelling agent comprises a gellan gum, include, but not limited to, low acyl gellan gum or deacylated gellan gum. In an embodiment, a suitable gellan gum is KELCOGEL® F gellan gum commercially available from CP Kelco (San Diego, CA). Other exemplary gellan gums include, but are not limited to, GELLAN GUM from DSM Hydrocolloids (Shanghai, China); or Low Acyl Gellan Gum (LA or LAF) ffom Rbbio, DSM Rainbow (Inner Mongolia) Biotechnology, Co. Ltd (Mongolia, China).

[0041] Based on a total mass of the dry weight ingredients, the hydrocolloid gelling agent may be present in the aqueous gellable matrix in an amount in the range from about 0.1 wt% to about 90 wt%. For example, the hydrocolloid gelling agent may be present in the gellable matrix in an amount of 0.1 wt%, 0.2 wt% 0.5 wt%, 0.8 wt%, 1.0 wt%, 1.5 wt% 1.8 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, 3.5 wt%, 4.0 wt%, 4.5 wt%, 5.0 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, or in a range between any two of the foregoing.

[0042] In an embodiment, the hydrocolloid gelling agent comprises gelatin, and the gelatin may be present in an amount from 30 to 90 wt%, such as in an amount of 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, or in a range between any two of the foregoing. In another embodiment, the hydrocolloid gelling agent comprises gellan gum, and the gellan gum may be present in an amount of 0.1 to 10 wt%, such as in an amount of 0.1 wt%, 0.2 wt% 0.5 wt%, 0.8 wt%, 1 wt%, 1.5 wt% 1.8 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, or in a range between any two of the foregoing.

[0043] In an aspect of the invention, the gellable mixture may further comprise a filler, which may be a material that can increase the percentage of dry material in the external liquid phase and thus in the obtained shell after co-extrusion. Increasing the dry material amount in a shell assists in solidifying the shell, as well as reducing the capsule shell’s wet thickness, and may improve drying of the concomitant hydrated (wet) shell. In an aspect, the filler may further act as an antiplasticizer making the breakable shell physically more resistant to deformation or breakage. In another aspect, the filler may further act as a plasticizer, which improves the processability of the gellable mixture and/or the flexibility of the gelled matrix. Exemplary fillers may include, but are not limited to starch derivatives such as dextrin, maltodextrin, innulin, sucrose, allulose, tagatose, cyclodextrin (alpha, beta, gamma, or modified cyclodexrin); cellulose derivatives such as microcrystalline cellulose (MCC) hydroxypropylmethylcellulose (HPMC), hydroxypropylcellulose (HPC), methylcellulose (MC), or carboxymethylcellulose (CMC); a polyvinyl alcohol; polyols with non-plasticizing properties; trehalose; erythritol; maltitol; mannitol; xylitol; glycerol; triacetine; a polyethylene glycol, polyalcohols with plasticizing or humectant properties; or combinations of two or more of the foregoing.

[0044] Based on a total mass of the dry weight ingredients, the filler may be present in the gellable matrix in an amount in the range from about 0.1 to about 60 wt%. For example, the filler may be present in the gellable matrix in an amount of 0.1 wt%, 0.2 wt% 0.5 wt%, 0.8 wt%, 1.0 wt%, 1.5 wt% 2.0 wt%, 2.5 wt%, 3.0 wt%, 4.0 wt%, 5.0 wt%, 7.5 wt%, 10 wt%, 12.5 wt%, 15 wt%, 17.5 wt%, 20 wt%, 25 wt%, 35 wt%, 45 wt%, 50 wt%, 60 wt%, or in a range between any two of the foregoing. In an embodiment, the filler is selected from sorbitol, glycerol, mannitol, sucrose, trehalose, propylene glycol, xylitol, erythritol, or combinations thereof, and may be present in the gellable matrix in a range from 8 wt% to 50 wt%.

[0045] In an embodiment, the shell matrix comprises a filler in an amount in a range from 0.1 to 90 wt%, wherein wt% is based on the entire weight of the dry weight ingredients.

[0046] Advantageously, in an embodiment, the filler comprises a partially-gelatinized, high amylose starch, such as that described in a patent application FR1872369 by Falc’hun et al, filed on December 5, 2018. The partially-gelatinized, high amylose starch is derived from a high amylose starch (HAS) having an amylose content of at least 50 wt%, such as 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75% wt%, 80 wt%, 90 wt%, 95 wt%, or in a range between any two of the foregoing, and wherein wt% is based on the dry weight of the starch. The HAS may be chemically modified to include a hydroxyalkyl C2-C6 group to form an ether modified high amylose starch, or chemically modified by reaction with a reactive acyl group (e.g., an anhydride of a carboxylic acid) to form an ester-modified high amylose starch. In accordance with an embodiment, the high amylose starch is chemically modified by reaction with about 2 wt% to about 7 wt% acetic anhydride to form a low acyl modified, high amylose starch.

[0047] Non-limiting examples of HAS include, AMYLOMAIS M400G marketed by Roquette Freres Corporation; HYLON® VII, HI-MAIZE® 260, or CRISP FILM® from Ingredion Incorporated; BATTERCRISP 90240 or AMYLOGEL 030031 from Cargill; high amylose Native Pea Starch marketed by Emsland Starke GmbH; or combinations thereof.

[0048] Based on a total mass of the dry weight ingredients, the modified HAS is present in the gellable matrix in an amount in the range from about 10 wt% to about 90 wt%. For example, the modified HAS may be present in the gellable matrix at 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or in a range between any two of the foregoing, where wt% is based on the total dry ingredient weight.

[0049] In accordance with an embodiment, heating an aqueous mixture of the HAS to a temperature above the starch’s threshold gelatinization temperature (gel T°) initiates the gelatinization process. When the desired degree of gelatinization is achieved, the temperature of the mixture may be lowered to a temperature that is sufficiently lower than the starch’s gel T° in order to stabilize the starch against further gelatinization, as well as stabilize the viscosity of the starch-containing solution. In another embodiment of the present invention, the entirety of the dry ingredients (e.g., hydrocolloid gelling agent, HAS, filler, etc.) making up the gellable matrix may be all combined in water and heated together above the gel T° of the HAS for a sufficient duration to achieve the desired degree of gelatinization, which may be correlated to dynamic viscosity of the HAS mixture.

[0050] A coloring agent may be added to impart color to the breakable shell of the microcapsule. Accordingly, the gellable mixture may further include one or more synthetic or natural coloring agents that is water soluble or capable of forming a water- stable suspension. Exemplary coloring agents include, but are not limited to, pigments, titanium dioxide, iron oxides, carbon black, or any type of food, oral care, cosmetic or pharmaceutical pigments, such as Covasorb colors distributed by LCW. Natural coloring agents may also be obtained from Kancor Ingredients, Ltd (Kerala, India), including the natural pigments sold under Kancor’s C-CAPTURE’s colour stabilisation process. Additionally, the gellable mixture may further include other additives, such as actives, sweeteners, sensates, pH modifiers.

[0051] In accordance with embodiments of the present invention, the gellable mixture comprises an aqueous mixture of the hydrocolloid gelling agent, filler, etc. in water. A typical weight ratio of water to the non- water (dry) ingredients is in a range from 1 : 1 to 20:1. Preferably, the water used for the external phase is purified water, such as distilled water, deionized water, or reverse osmosis water, but processing (tap) water is viable. If processing water, which may contain alkali or alkaline earth metal salts, is used with an anionic polysaccharide hydrocolloid gelling agent, a sequestering or complexing agent, may be added to the gellable mixture to minimize undesirable or uncontrollable gelling during the coextrusion. More specifically, cations can affect the viscosity and gelling behavior of these type of hydrocolloid gelling agents. The sequestering or complexing agent allows the entrapment of cations, such as alkali metals, alkaline earth metals, metals, or other cations, that could be present in the components of the liquid phase including the water. Thus, the use of a sequestering agent, preferably of a calcium ion sequestering agent, allows gellan gum, as well as other anionic polysaccharide gelling agents, to be co-extruded without undesirable or uncontrollable gelling during the coextrusion. The amount of sequestering agent is at most 2 wt%, preferably at most 1 wt% and even more preferably at most 0.5 wt%, wherein wt% is based on the total dry weight of the shell ingredients. The sequestering agent may comprise a salt, preferably selected from the group comprising trisodium citrate, trisodium phosphate, tetrasodium pyrophosphate, sodium hexametaphosphate, and mixtures thereof.

[0052] In this particular embodiment employing the use of the sequestering agent in the gellable matrix, once the capsules are formed, the uncrosslinked shell of the formed capsules may be treated with a curing solution that comprises one or more crosslinking agents, for example a cation containing salt in the composition, which serves to enhance the setting ability of the gelling agents. Preferably, the salt comprises cations such as K+, Li+, Na+, NH4+, Ca2+, or Mg2+, etc. The amount of cations is less than 5 wt%, preferably less than 3 wt%, more preferably 0.01 wt% to 3 wt%, even more preferably 0.5 wt% to 2 wt%, especially 0.01 to 1 wt%, wherein wt% is based on the dry weight ingredients in the hydrophilic external liquid phase.

[0053] Alternatively, a hydrophilic external liquid phase containing an anionic polysaccharide gelling agent may further include a cationic crosslinking agent. Exemplary cationic crosslinking agents include a salt, such as salts comprising K+, Li+, Na+, NH4+, Ca2+, Mg2+, or combinations thereof. The concentration of the cationic crosslinking agent in the hydrophilic external liquid phase solution may be less than 2 wt%, wherein wt% is based on the dry weight ingredients (e.g., hydrocolloid, filler, etc.) in the hydrophilic gelling matrix. For example, the cationic crosslinking agent may be present in an amount of 0.1 wt%, 0.25 wt%, 0.5 wt%, 0.75 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, 1.25 wt%, 1.50 wt%, 1.75 wt%, 1.9 wt%, 2.0 wt%, or in a range between any two of the foregoing. Variations in the amount of cationic crosslinking agent, relative to the amount of anionic polysaccharide gelling agent, provides an aspect for tuning the viscosity of the gellable matrix and the texture properties of the microcapsule.

[0054] The hydrophilic external liquid phase can also further include preservatives or bac- tericides such as benzoate, parabens, diols, cetylpyridinium chloride, diazolidinyl urea or any preservatives used for food, pharmaceutical or cosmetic products. Such preservatives may be useful if the seamless microcapsules are not sufficiently dried to inhibit growth of bacteria, molds, and yeasts (i.e., a water activity (Aw) equal to 0.6 or less). Water activity (Aw), as known by one skilled in the art, is sometimes referred to as“free” or“available” water in a system that is not bound to non-aqueous con- stituents. It can properly be defined as the partial vapor pressure of food moisture divided by the equilibrium vapor pressure of pure water at the same temperature. Water activity value can be measured using a LabMaster- aw by Novasina AG (Lachen, Switzerland), at 25°C.

[0055] In accordance with embodiments of the present invention, the dynamic viscosity of the gellable mixture, which is the external aqueous liquid phase in the coextrusion process, is in a range between from 5 to 350 mParscc, where the dynamic viscosity is measured at 70°C using MARSIII Haake Rheometer; cone 35mm/2°; shear rate from 0.01 to 1000 s-1; rotations in isothermal increments. For example, the dynamic viscosity of the external aqueous liquid phase, measured at 70 °C, and shear of lOs-1, may be 5 mParscc, 10 mPa*sec, 15 mPa*sec, 20 mPa*sec, 25 mPa*sec, 30 mPa*sec, 50 mPa*sec, 70 mPa*sec, 90 mPa^»sec, 100 mPa^»sec, 110 mPa^»sec, 125 mPa^»sec, 140 mPa^»sec, 160 mPa^»sec, 175 mPa^»sec, 200 mPa^»sec, 250 mPa^»sec, 300 mPa^»sec, 350 mPa^»sec, or in a range between any two of the foregoing. In an embodiment, the dynamic viscosity of the aqueous external phase, is in a range from 35 to 140 mPa^»sec, measured at 70 °C, and shear of 10s- 1.

[0056] OILY CORE

[0057] In accordance with embodiments of the present invention, the oily core component of the breakable microcapsules comprises a liquid solution, emulsion, or dispersion of one or more active ingredients in a lipophilic liquid. The oily core may be a fluid or a low melting solid. However, the oily core component should be a fluid at its extrusion temperature to enable being pumped through the coextrusion nozzle. The oily core may comprise one or more of the following ingredients flavors, fragrances, solvents, diluents, sweeteners, sensates, coloring agents, vitamins, vegetable extracts, thickening agents, weightening agents, pH-modifiers, antioxidants, emulsifiers, nutritionals, taste modifiers, and microorganisms such as probiotics. The core portion of the breakable capsule may comprise a mixture of materials or products that are lipophilic or partially soluble in ethanol, or of molecules formulated as oil/water/oil emulsions. The core of the microcapsule according to embodiments of the invention may be of the order of 10 wt% to 80 wt%, such as in a range from 15 wt% to 70 wt%, wherein wt% is based on the total weight of the dried microcapsule. For example, the core may be 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 75 wt%, 80 wt%, or in a range between any two of the foregoing.

[0058] In general, the oily core in the breakable microcapsule can be liquid, viscous, or even a low melting solid that is a liquid at its extrusion temperature. Thus, at its extrusion temperature, the core liquid has a dynamic viscosity of 1 to 500 mParscc, more preferably of 2 to 300 mParscc, even more preferably of 3 to 200 mParscc and most preferably 5 to 99 mParscc, where the dynamic viscosity may be determined at its extrusion temperature using Thermo Scientific MARSIII™ HAAKE™ Rheometer; cone 35mm/2°; shear rate from 0.01 to 1000 s-1; rotations in isothermal increments. In an embodiment, the dynamic viscosity of the core liquid, measured at 25°C and shear rate lOs-1, is in a range from 2 to 300 mParscc, such as in a range from 3 to 200 mParscc. For example, dynamic viscosity may be 2 mParscc, 3 mPa*sec, 4 mPa*sec, 5 mPa*sec, 10 mPa*sec, 15 mPa*sec, 25 mPa*sec, 50 mPa*sec, 70 mPa*sec, 90 mPa*sec, 100 mPa*sec, 120 mPa*sec, 150 mPa*sec, 175 mPa*sec, 200 mPa*sec, 225 mPa^»sec, 250 mPa^»sec, 275 mPa^»sec, 300 mPa^»sec, or in a range between any two of the foregoing, measured at 70 °C, and shear rate of lOs-1.

[0059] The oily core may include one or more hydrophobic oils or solvents conventionally used in the food, pharmaceutical, or cosmetic industries. The hydrophobic oils or solvents may be triglycerides, and in particular medium chain triglycerides (MCT), such as triglycerides of caprylic or capric acids, borage oil, vegetable oil, olive oil, sunflower oil, com oil, pecan nut oil, pistachio kernel oil, rapeseed oil, rice germ oil, sesame seed oil, Soya oil, groundnut oil, hazelnut oil, walnut oil, coconut oil, pumpkin seed oil, linseed oil, maize germ oil, macadamia nut oil, almond oil, grapeseed oil, wheatgerm oil, thistle oil, castor oil, mineral oils, silicone oils; or fractionated coconut oils, which mainly have fatty acid residues with a length of between six and eight carbon atoms (C6- to C8-fatty acids). Diluent solvents may also be used, such as propylene glycol, diacetine (glycerine diacetate), triacetine (glycerine triacetate), benzyl alcohol, triethyl citrate, ethyl lactate, isopropanol, ethanol, glycerine, or combinations thereof.

[0060] For low melting substances, such as low melting waxes, fatty acids, triglycerides, polyglycerol esters, or the like, the melting point of the substance should be in a range from about room temperature to less than the co-extrusion temperature, such as in a range from 25 °C to 90 °C. Non-limiting examples of low melting substances include cocoa butter oil, coprah oil, bees waxes, castor oil, butter fat, or the like.

[0061] The fragrance and flavoring substances are mixed with one or more of the above- mentioned oils or solvents and then used in accordance with the embodiments described herein. Preferably the flavor used according to the invention comprises lipophilic flavor substances. Lipophilic flavoring substances are preferably used in the context of the present invention and thus preferably used in the core of the microcapsule. They belong to various chemical groups, such as the group comprising hydrocarbons, aliphatic alcohols, aliphatic aldehydes and the acetals thereof, aliphatic ketones and oximes thereof, aliphatic sulfur-containing compounds, aliphatic nitriles, aliphatic carboxylic acids esters, acyclic terpene alcohols, acyclic terpene aldehydes and ketones, cyclic terpene alcohols, cyclic terpene aldehydes and ketones, cyclic alcohols, cycloaliphatic carboxylic acids, aromatic hydrocarbons, araliphatic alcohols, esters of araliphatic alcohols and aliphatic carboxylic acids, araliphatic ethers, aromatic and araliphatic aldehydes, aromatic and araliphatic ketones, aromatic and araliphatic carboxylic acids and the esters, nitrogenous aromatic compounds, phenols, phenyl ethers, phenyl esters heterocyclic compounds, lactones, and combinations thereof.

[0062] The lipophilic flavoring substances particularly preferably used in the context of the present invention have a log POW of higher than 1.0 are preferably selected from the group consisting of: acetophenone, allyl capronate, alpha-ionone, beta-ionone, anisaldehyde, anisyl acetate, anisyl formate, benzaldehyde, benzothiazole, benzyl acetate, benzyl alcohol, benzyl benzoate, beta-ionone, butyl butyrate, butyl caproate, butylidene phthalide, carvone, camphene, caryophyllene, cineol, cinnamyl acetate, citral, citronellol, citronellal, citronellyl acetate, cyclohexyl acetate, cymol, damascone, decalactone, dihydrocoumarin, dimethyl anthranilate, dimethyl anthranilate, dode- calactone, ethoxyethyl acetate, ethylbutyric acid, ethyl butyrate, ethyl caprinate, ethyl capronate, ethyl crotonate, ethyl furaneol, ethyl guajacol, ethyl isobutyrate, ethyl iso- valerate, ethyl lactate, ethyl methyl butyrate, ethyl propionate, eucalyptol, eugenol, ethyl heptylate, 4-(p-hydroxyphenyl)-2-butanone, gamma-decalactone, geraniol, geranyl acetate, geranyl acetate, grapefruit aldehyde, methyl dihydrojasmonate (e.g. hedione), heliotropin, 2-heptanone, 3-heptanone, 4-heptanone, trans-2-heptenal, cis-4- heptenal, trans-2-hexenal, cis-3-hexenol, trans-2-hexenoic acid, trans-3-hexenoic acid, cis-2- hexenyl acetate, cis-3-hexenyl acetate, cis-3-hexenyl capronate, trans-2-hexenyl capronate, cis-3-hexenyl formate, cis-2-hexyl acetate, cis-3 -hexyl acetate, trans-2-hexyl acetate, cis-3- hexyl formate, para-hydroxy benzyl acetone, isoamyl alcohol, isoamyl isovalerate, isobutyl butyrate, isobutyraldehyde, isoeugenol methyl ether, isopropylmethylthiazole, lauric acid, levulinic acid, linalool, linalool oxide, linalyl acetate, menthol, menthofuran, methyl anthranilate, methylbutanol, methylbutyric acid, 2-methylbutyl acetate, methyl capronate, methyl cinnamate, 5-methyl furfural, 3,2,2-methyl cyclopentenolone, 6,5,2-methyl heptenone, methyl di- hydrojasmonate, methyl jasmonate, 2-methyl methyl butyrate, 2-methyl-2- pentenoic acid, methylthiobutyrate, 3,1-methylthiohexanol, 3-methylthiohexyl acetate, nerol, neryl acetate, trans,trans,2,4-nonadienal, 2,4-nonadienol, 2,6-nonadienol,2,4-nonadienol, nootkatone, delta-octalactone, gamma-octalactone, 2-octanol, 3-octanol, 1,3-octenol, 1 -octyl acetate, 3-octyl acetate, palmitic acid, paraldehyde, phellandrene, pentanedione, phenylethyl acetate, phenylethyl alcohol, phenylethyl alcohol, phenylethyl iso valerate, piperonal, propionaldehyde, propyl butyrate, pulegone, pulegol, sinensal, sulfurol, terpinene, terpineol, terpinolene, 8,3-thiomenthanone, 4,4,2-thiomethyl pentanone, thymol, delta-undecalactone, gamma-undecalactone, valencene, valeric acid, vanillin, acetoin, ethyl vanillin, ethyl vanillin isobutyrate, 2,5-dimethyl-4-hydroxy-3(2H)-furanone, homofuraneol, ho- mofuronol, 5-ethyl-

2-methyl-4-hydroxy-3(2H)-furanone, maltol and maltol derivatives, coumarin and coumarin derivatives, gamma-lactones, gamma-unde- calactone, gamma-nonalactone, gamma- decalactone, delta-lactones, 4-methyl delta de- calactone, massoia lactone, delta decalactone, tuberose lactone, methyl sorbate, di- vanillin, 4-hydroxy-2(or 5)-ethyl-5(or 2)-methyl- 3(2H)furanone, 2-hydroxy-3-methyl-2-cyclopentenone, 3-hydroxy-4,5-dimethyl-2(5H)- furanone, acetic acid isoamyl ester, butyric acid ethyl ester, butyric acid-n-butyl ester, butyric acid isoamyl ester, 3 -methylbutyric acid ethyl ester, n-hexanoic acid ethyl ester, n- hexanoic acid allyl ester, n-hexanoic acid-n-butyl ester, n-octanoic acid ethyl ester, ethyl-3 -methyl-3 - phenyl glycidate, ethyl-2-trans-4-cis-decadienoate, 4-(p-hydroxyphenyl)-2-butanone, 1,1- dimethoxy-2,2,5-trimethyl-4-hexane, 2,6-dimethyl-5-hepten- 1 -al and phenyl-acetaldehyde, 2- methyl-3-(methylthio)furan, 2-methyl-3-furanthiol, bis(2-methyl-3-furyl)disulfide, furfuryl mercaptan, methional, 2-acetyl-2-thiazoline, 3-mercapto-2-pentanone, 2,5-dimethyl-3- furanthiol, 2,4,5-trimethylthiazole, 2-acetylthiazole, 2,4-dimethyl-5-ethylthiazole, mercapto-

3 -methyl- 1 -butanol, 2-acetyl- 1-pyrro line, 2-methyl-3-ethylpyrazine, 2-ethyl-3,5- dimethylpyrazine, 2-ethyl-3,6-dimethylpyrazine, 2,3-diethyl-5-methylpyrazine,3-isopropyl- 2-methoxypyrazine, 2-isobutyl-2-methoxypyrazine, 2-acetylpyrazine, 2-pentylpyridine, (E,E)-2,4-decadienal, (E,E)-2,4-nonadienal, (E)-2-octenal, (E)-2-nonenal, 2-undecenal, 12- methyltridecanal, l-penten-3-one, 4-hydroxy-2,5-dimethyl-3(2H)-furanone, guaiacol, 3- hydroxy-4,5-dimethyl-2(5H)-furanone, 3-hydroxy-4-methyl-5-ethyl-2(5H)-furanone, cinnamaldehyde, cinnamyl alcohol, methyl salicylate, isopulegol and further stereoisomers, enantiomers, positional isomers, diastereomers, cis/trans-isomers or epimers (not expressly mentioned) of these substances.

[0063] The core of the microcapsule may include natural or synthetic aromas and/or fragrances. Non-limiting examples of suitable fragrances are fruity, confectionery, floral, sweet, woody fragrances. Examples of suitable aromas are vanilla, coffee, chocolate, cinnamon, mint.

[0064] Non-limiting examples of suitable flavorings include peppermint oils, spearmint oils, eucalyptus oils, wintergreen oils, cinnamon oils, cassia oils, aniseed oils, bitter almond oils, clove oils, parsley seed oils, citrus oils, vanilla (extracts), fruity flavoring com positions having tastes oriented towards, for example, apple, pear, peach, grape, strawberry, raspberry, cherry, or pineapple are preferably used.

[0065] In addition, suitable individual substances as part of the flavorings are those having a cooling refreshing effect in the throat or in the oral or nasal cavity. Non-limiting examples include menthol, menthone, menthone glycerin acetate, menthyl acetate, menthyl methyl ether, methone acetals, menthol carbonates, menthyl lactate, menthyl succinates (such as monomenthyl succinate sold under the tradename PHYSCOOL®), substituted menthyl-3- carboxamides (for example menthyl-3 -carboxylic acid-N-ethylamide), 2-isopropyl-N-2,3- trimethylbutanamide, substituted cyclohexane car- boxamides, 3-menthoxypropane-l,2-diol, 2-hydroxyethyl menthyl carbonate, 2-hydroxypropyl menthyl carbonate, N-acetylglycine menthyl ester, isopulegol, hy- droxycarboxylic acid menthyl esters (for example menthyl-3- hydroxybutyrate), 2-mercaptocyclodecanone, menthyl-2-pyrrolidin-5-onecarboxylate, 2,3- dihydroxy-p-menthane, 3,3,5-trimethylcyclohexanone glycerol ketal, 2-menthyl-3,6-di- and - tri- oxaalkanoates, 3-menthyl methoxyacetate, icilin, 1,8-cineol (eucalyptol), carvone, alpha- terpineol, thymol, methyl salicylate, 2'-hydroxypropiophenone, or a combination of two or more of the foregoing.

[0066] The oily core may also comprise one or more sweeteners, with the use of solubilizing agents, if appropriate. In general, applicable sweeteners for the core material include saccharin (optionally as sodium, potassium, or calcium salt), aspartame, cyclamate (optionally as sodium or calcium salt), acesulfam-K, neohesperidin dihydrochalcone. Furthermore, other sweeteners, such as steviols, stevioside, rebaudioside A, glycyrrhizin, osladin, brazzein, miraculin, pentadin, phyllodulcin, dihydrochalcone, arylureas, trisubstituted guanidines, glycyrrhizin, superaspartam, suosan, sucralose (trichlorogalactosesucrose or TGS), alitame, monellin, as well as other natural or artificial sweeteners may also be used.

[0067] If the core is to be colored, suitable colorants include oil soluble colors, oil stable suspensions, or W/O emulsions. Nonlimiting examples of colors suitable for imparting color to the core include lactoflavin (riboflavin), beta-carotene, riboflavin-5 '-phosphate, alpha-carotene, gamma-carotene, cantaxanthin, erythrosine, curcumin, quinoline yellow, yellow orange S, tartrazine, bixin, norbixin (annatto, orlean), capsanthin, capsorubin, lycopene, beta-apo-8'-carotenal, beta-apo-8'-carotenic acid ethyl ester, xantophylls (flavoxanthin, lutein, cryptoxanthin, rubixanthin, violaxanthin, rodoxanthin), fast carmine (carminic acid, cochineal), azorubin, cochineal red A (Ponceau 4 R), beetroot red, betanin, anthocyanins, guaiazulene, amaranth, patent blue V, indigotine I (indigo-carmine), chlorophylls, copper compounds of chlorophylls, acid brilliant green BS (lissamine green), brilliant black BN, vegetable carbon, titanium dioxide, iron oxides and hydroxides, calcium carbonate, aluminum, silver, gold, pigment rubine BK (lithol rubine BK), methyl violet B, victoria blue R, victoria blue B, acilan brilliant blue FFR (brilliant wool blue FFR), naphthol green B, acilan fast green 10 G (alkali fast green 10 G), ceres yellow GRN, Sudan blue II, ultramarine, ph- thalocyanine blue, phthalocayanine green, or fast acid violet R. Further naturally obtained colorants, such as those commercially available from Rancor Ingredients Ltd. (Kerala, India), e.g., anthocyanins, betatins, bixins, norbixins, carmines, carotenoids, chlorophyls, curcumins, spirulinas, etc., can be used for coloring purposes. The so- called aluminum lakes: FD & C Yellow 5 Lake, FD & C Blue 2 Lake, FD & C Blue 1 Lake, Tartrazine Lake, Quinoline Yellow Lake, FD & C Yellow 6 Lake, FD & C Red 40 Lake, Sunset Yellow Lake, Carmoisine Lake, Amaranth Lake, Ponceau 4R Lake, Erythrosyne Lake, Red 2G Lake, Allura Red Lake, Patent Blue V Lake, Indigo Carmine Lake, Brilliant Blue Lake, Brown HT Lake, Black PN Lake, Green S Lake, and mixtures thereof, may also be used.

[0068] Preferred antioxidants including substances which can reinforce an antioxidative effect are for example naturally occurring tocopherols and derivatives thereof (for example vitamin E-acetate), vitamin C and the salts or derivatives thereof (for example ascorbyl palmitate, Mg-ascorbyl phosphate, ascorbyl acetate), vitamin A and derivatives (vitamin A- palmitate), tocotrienols, flavonoids, alpha-hydroxy acids (for example citric acid, lactic acid, malic acid, tartaric acid) and the Na+, K+ and Ca+2 salts thereof, flavonoids, quercetin, phenolic benzylamines, propyl gallate, octyl gallate, dodecyl gallate, butylhydroxyanisol (BHA, E320), butyl hydroxytoluene (BHT, 2,6-di-tert-butyl-4-methyl-phenol, E321), lecithins, mono- and diglycerides of edible fatty acids esterified with citric acid, carotenoids, carotenes (for example a- carotene, b-carotene, lycopene) and derivatives thereof, phytic acid, lactoferrin, EDTA, EGTA), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, ferulic acid and derivatives thereof, zinc and derivatives thereof (for example ZnO, ZnS04), selenium and derivatives thereof (for example selenium methionine), orthophosphates and Na+, K+, and Ca+2 salts of monophosphoric acid as well as in gredients isolated from plants, extracts or fractions thereof, for example, from tea, green tea, algae, grape seeds, wheatgerm, camomile, rosemary and oregano.

[0069] The liquid or viscous core may contain substances or substance mixtures, which are active in nutritional physiology (nutraceuticals). Nutraceuticals in the meaning of the invention are substances or mixtures of substances that add a healthy benefit to the capsules according to the invention. Examples of such substances are especially vitamins, minerals, trace elements, micronutrients, probiotics, and/or antioxidants. The following might be named by way of example: panthenol, pantothenic acid, essential fatty acids, vitamin A and derivatives, carotenes, vitamin C (ascorbic acid), vitamin E (tocopherol) and derivatives, vitamins of the B and D series, such as vitamin B6 (nicotinamide), vitamin B12, vitamin Dl, vitamin D3, vitamin F, folic acid, biotin, amino acids, oil soluble compounds of the elements magnesium, silicon, phosphorus, calcium, manganese, iron or copper, coenzyme Q10, unsaturated fatty acids, omega-3-fatty acids, polyunsaturated fatty acids, g-linolenic acid, oleic acid, eicosapentaenoic acid, docosahexaenoic acid and derivatives thereof, bisabolene, chloramphenicol, caffeine, capsaicin, prostaglandins, thymol, camphor, g-oryzanol, salmon oil, mustard oil such as allyl isothiocyanate (AITC), oil soluble or oil miscible extracts, concretes or residues of plant and animal origin, or probiotics such as bifidobacterium- containing compositions.

[0070] Antitussive actives can be added and include e.g. dextromethorphan, chlophedianol, carbetapentane, caramiphen, nosciapine, diphenylhydramine, codeine, hydrocodone, hydromorphone, fominoben and benzonatate. Oral anesthetic actives can be added and include e.g. phenol, lidocaine, dyclonine, benzocaine, menthol, salicyl alcohol and hexylresorcinol.

[0071] The core may also comprise one or more weighting agents as used in aromatic emulsions, such as dammar gum, wood resins of the ester gum type, sucrose acetate isobutyrate (SAIB), or brominated vegetable oils. The function of these weighting agents is to adjust the density of the liquid core.

[0072] The core may also include one or more captive agents, including but not limited to, Betahydrane™ (3-benzyl-tetrahydropyran); Antillone™ (9-decen-2-one); Noreenal™ ((±)-6,8-Dimethylnon-7-enal); and/or Pescagreen™ (2-(2,4,4-trimethyl-cyclopentyl)- acrylonitrile).

[0073] MICROCAPSULE FORMATION

[0074] In accordance with embodiments of the present invention, the seamless breakable microcapsules may be formed using co-extrusion techniques. The general method includes preparing the gellable matrix, which will form the shell component of the breakable microcapsule, and preparing an oily liquid phase, which will form the core component of the breakable microcapsule. The co-extrusion step is a synchronous extrusion of two liquids: the external hydrophilic liquid phase and the internal lipophilic liquid phase, though a coaxial nozzle assembly thereby forming a coaxial composite stream. The discharge of the coaxial nozzle is directed into a cooled stream of fluid to sufficiently lower the temperature of the gellable matrix to induce gel formation.

[0075] In order to break the coaxial composite stream into spherical mononuclear droplets having the desired capsule size, vibrational, electrostatic, mechanical, or hydrodynamic methods may be utilized, of which the most commonly used method is vibrational. For example, expired US. Patent No. 4,251,195 to Suzuki et al. and assigned to Morishita Jintan Company, Ftd. describes the use of a ring or cylinder body that vibrates with a certain frequency along the lengthwise direction of the coaxial composite stream, and thus imparts vibrational energy causing the formation of waves that ultimately break into spherical particles due to the interfacial tension of the fluids. Abandoned German Patent Application DE19617924A1 to Thorsten and assigned to Brace GmbH describes the induction of vibration excitation to the liquid being dripped before the nozzles or at least a short distance away from the nozzle device. The direct introduction of the vibration can happen in different ways: 1) mechanical vibration transmission of an elastic body or an elastic membrane in the nozzle assembly or in the supply line just before the nozzle assembly; 2) a vibrating plunger may be inserted into the nozzle assembly; or integrating a piezoelectric crystal or an ultrasonic probe into the nozzle assembly or in the supply line just before the nozzle. And PCT Application Publ. No. WO0213786 to Kim et al. and assigned to the Board of Trustees of the University of Illinois, describes implementing an acoustic-type vibrational wave to break an accelerated cylindrical jet of a composite stream into droplets.

[0076] The vibration energy may be applied to the core component, the shell component, or both. Alternatively, the vibrational energy may be applied to the coaxial nozzle. One or more of a variety of vibration methods, including but not limited to, acoustic vibration, vibrating nozzle, a piezoelectric vibrator, etc., breaks the composite jet into droplets having a size related to the vibration frequency. Several other process parameters may be set or controlled, including the coaxial nozzle diameters, the feed rates of the oily core liquid and/or the gellable matrix, the flow rate of the coaxial composite stream, and the viscosity of the extruded liquid. Without being bound by any particular theory, it is generally held that for a given nozzle diameter, the two major factors affecting optimal droplet formation are vibrational frequency and composite stream velocity.

[0077] Thus, in accordance with an embodiment, the inner nozzle supplying the oily core material may have an inner diameter in a range from 100 microns to 1500 microns, such as 100 microns, 150 microns, 200 microns, 250 microns, 300 microns, 350 microns, 400 microns, 450 microns, 500 microns, 550 microns, 600 microns, 650 microns, 700 microns, 750 microns, 800 microns, 900 microns, 1000 microns, 1100 microns, 1200 microns, 1300 microns, 1400 microns, 1500 microns, or in range between any two of the foregoing. The outer nozzle supplying the gellable matrix for forming the shell may have an inner diameter in a range from 300 microns to 3000 microns, such as 300 microns, 400 microns, 500 microns, 600 microns, 700 microns, 800 microns, 900 microns, 1000 microns, 1100 microns, 1200 microns, 1300 microns, 1400 microns, 1500 microns, 1600 microns, 1700 microns,

1800 microns, 1900 microns, 2000 microns, 2100 microns, 2200 microns, 2300 microns,

2400 microns, 2500 microns, 2600 microns, 2700 microns, 2800 microns, 2900 microns,

3000 microns, or in a range between any two of the foregoing.

[0078] The feed rate of the oily core material through the inner nozzle may be in a range from 1 to 150 mL/min, such as 1 mL/min, 2 mL/min, 5 mL/min, 10 mL/min, 25 mL/min, 50 mL/min, 75 mL/min, 100 mL/min, 125 mL/min, 150 mL/min, or in a range between any two of the foregoing. The feed rate of the gellable matrix forming the shell may be in a range from 5 to 500 mL/min, such as 5 mL/min, 10 mL/min, 25 mL/ min, 50 mL/min, 100 mL/min, 200 mL/min, 300 mL/min, 400 mL/min, 500 mL/min, or in a range between any two of the foregoing. As noted above, the breakable microcapsule component dimensions (e.g., shell thickness and core diameter) may be controlled by the relative nozzle dimensions, as well as the volumetric flowrates of the inner and outer phases. According to an aspect, a ratio between the feed rate of the outer nozzle to the inner nozzle is in a range from about 1 :2 to about 20:1, depending on a variety of parameters such as desired shell thickness, core diameter, microcapsule diameter, etc. For example, the ratio may be 1 :2. 2:3, 1 : 1, 3:2, 2:1, 3: 1, 4:1, 5:1, 6: 1, 7: 1, 8:1, 9:1, 10: 1, 11 :1, 12: 1, 13:1, 14: 1, 15:1, 20:1, or in a range between any two of the foregoing.

[0079] In accordance with an embodiment, the vibrational energy is imparted to the coaxial composite stream via a piezoelectric vibrator stack. Upon application of electrical energy at a sufficient voltage, the layers of ceramic piezoelectric materials (e.g., modified lead zirconate titanate) provide a longitudinal expansion having an amplitude of displacement (Ad) in a range of 0 < Ad < 100 microns, such as 1 micron, 2 microns, 5 microns, 10 microns, 15 microns, 20 microns, 30 microns, 40 microns, 50 microns, 60 microns, 70 microns, 80 microns, 90 microns, 100 microns, or in a range between any two of the foregoing. For example, the amplitude of displacement (Ad) of the piezoelectric stack may be in a range from 0 < Ad < 32 microns. In turn, the dis- placement is transferred as vibrational energy through a flexible membrane (e.g., thin layer of stainless steel) in direct fluid contact with the inner core fluid, the outer gellable shell matrix, or both. The operating voltage range of the piezo electric vibrator assembly may be from 0.5 volts to 180 volts, such as 0.5 volts, 1 volt, 2 volts, 5 volts, 10 volts, 20 volts, 30 volts, 40 volts, 50 volts, 75 volts, 100 volts, 125 volts, 150 volts, 180 volts, or in a range between any two of the foregoing. In an example, the electrical voltage may be in a range from 1 volt to 50 volts.

[0080] In accordance with an aspect of the invention, the vibration frequency of the piezo- electric stack may be in a range from 50 Hz to 3500 Hz. For example, the vibration frequency may be 50 Hz, 75 Hz, 100 Hz, 200 Hz, 300 Hz, 400 Hz, 500 Hz, 600 Hz, 700 Hz, 800 Hz, 900 Hz, 1000 Hz, 1250 Hz, 1500 Hz, 1750 Hz, 2000 Hz, 2500 Hz, 3000 Hz, 3500 Hz, or in a range between any two of the foregoing. In an example, the vibrational frequency of the piezoelectric stack is in a range from 200 to 2000 Hz.

[0081] The co-extrusion can be performed using an apparatus and processes as described in expired U.S. Patent No. 5,882,680 by Takei assigned to Freund Industrial Co., Ltd or U.S. Patent No. 6,719,933 by Nakamura et al. assigned Chugai.

[0082] In accordance with an embodiment, the co-extrusion is performed at a temperature less than about 70°C. Advantageously, the co-extrusion is performed at a temperature below 40°C. Of course, the acceptable temperature range for conducting the co extrusion step is related to the gelling temperature of the gellable matrix, and should be conducted at a temperature at or sufficiently below the gelling temperature. In an embodiment, the co-extrusion is performed near room temperature, which means between 5 °C and 30 °C, preferably 15 °C to 20 °C under atmospheric pressure. In another embodiment, the co-extrusion is performed at a temperature in a range from 3 °C to 20 °C, such as at a temperature of 3 °C, 5 °C, 10 °C, 15°C, 20°C, 25°C, or in a range between any two of the foregoing.

[0083] According to another embodiment of the invention, after the co-extrusion step the microcapsules may be further subjected to a solidification step, which is performed while maintaining the microcapsules cold in order to ensure sufficient gelling of the shell by contacting them with a cold bath, for example. Moreover, if the shells of the microcapsules comprise anionic polysaccharide gelling agents and are not already crosslinked (i.e., crosslinking agent not included in the gellable matrix prior to extrusion), the cold bath may comprise an aqueous solution or an emulsion containing a curing agent which comprises a cationic salt (e.g., alkali metals, alkaline earth metals, metals, or other cations), and optionally an acid. The effect of the immersion step is to wash out residual oil remaining at the periphery of the microcapsule, and to gradually strengthen the shell, notably through crosslinking, dehydration, and osmotic equilibrium. The curing agent preferably comprises divalent metal ions, or a mixture of divalent metal ions, such as calcium ions or magnesium ions. Thus, the cold bath may be a cold oil (e.g., MCT) or a cold emulsion. The bath temperature may be maintained at a value less than the gelation temperature of the gellable matrix. For example, the bath temperature may be below 18°C, such as about 2°C to about 10°C, or about 4°C to about 6°C.

[0084] The aqueous solution or emulsion containing the curing agent is preferably a divalent alkaline earth metal salt solution, preferably containing calcium or magnesium salts, more preferably, calcium dichloride, calcium carbonate, calcium sulfate or dicalcium phosphate. This solution may be the aqueous phase of an oil-in-water emulsion. This solution can be at a temperature comprised between 2 °C and room temperature. Advantageously, the aqueous solution containing the curing agent is maintained under acid conditions of pH, and preferably at a pH less than 5, more preferably from 2 to 4. According to an embodiment of the invention, the aqueous solution or emulsion containing a curing agent is a 1 wt% calcium chloride solution having a pH of 3 to 4.

[0085] The microcapsules may be optionally dried in a current or air at controlled tem perature and humidity. The relative humidity of the drying air may be in a range from 20% to 60%, preferably 30 to 50%; the temperature of the drying air is in a range from 15 °C to 80 °C, preferably 35 °C to 55 °C. According to an embodiment of the invention, after immersion, the microcapsules can be dried under the same conditions as mentioned above. According to another embodiment of the invention, after immersion, the microcapsules are not dried.

[0086] If the cold bath is an oil or if the microcapsules are extruded with a submerged (in chilled oil) co-extrusion nozzle, the microcapsules may be centrifuged in order to remove the surplus oil. Additionally or alternatively, the microcapsules may be washed with organic solvent (such as acetone, ethyl acetate, ethanol, petroleum ether, etc.) to remove the surplus oil.

[0087] The microcapsules manufactured in accordance with an embodiment of the invention are spherical or substantially spherical, are monodispersed in size (i.e., a coefficient of variance of 15% or less), and have an average dried particle diameter from 400 microns to about 1000 microns. For example, the average dried particle diameter may be 400 microns, 450 microns, 500 microns, 550 microns, 600 microns, 650 microns, 700 microns, 750 microns, 800 microns, 850 microns, 900 microns, 950 microns, 1000 microns, or in a range between any two of the foregoing. In an embodiment, the average dried particle diameter is in a range between 500 microns to 900 microns, 550 microns to 850 microns, or 600 microns to 800 microns. In an embodiment, the co- efficient of variance of average particle diameter of the dried capsules is 15% or less, such as 14%, 13%, 12%, 11%, 10%, or less. Advantageously, the average shell thickness of the microcapsule is 25 to 200 microns, preferably 30 to 180 microns, more preferably 35 to 150 microns, where the shell thickness is a measured on dried capsules using scanning electron microscopy technique described above. The flavor- containing core portion may have an average core diameter of 200 microns to 950 microns, preferably 225 microns to 800 microns, more preferably 250 microns to 700 microns.

[0088] In an embodiment, the ratio between the average core diameter (D) and the average shell thickness (T) is in a range between 1 to 40, preferably 2 to 30, more preferably 2 to 20, such as a D:T ratio within a range between 2 to 15.

[0089] The total weight of the dried capsule of the invention depends on its diameter, shell thickness, flavor loading, and its final moisture content. According to an embodiment of the invention, the total weight of the dried capsule is within the range of 0.2 to 1 mg, preferably 0.3 to 0.9 mg, more preferably 0.4 to 0.8 mg. The flavor loading within the microcapsules may range from 30 wt% to 80 wt%, preferably 40 wt% to 75 wt%, more preferably 50 wt% to 70 wt%.

[0090] According to a preferred embodiment, the dried breakable microcapsules according to the invention are characterized as having one or more of the following properties: force at break value in a range from 0.05 to 5 Kg; a stiffness at break value in a range from 0.2 to 5 Kg/mm; a deformation ratio of 0.1 to 0.9; or a Young’s modulus value in a range from 0.2 to 10 Kg. In another embodiment, the dried breakable microcapsules are characterized as having a force at break value in a range from 0.05 to 5 Kg; a stiffness at break value in a range from 0.2 to 5 Kg/mm; a deformation ratio of 0.1 to 0.9; and a Young’s modulus value in a range from 0.2 to 10 Kg. As noted above, the foregoing texture properties are measured on dried breakable microcapsules having a moisture content of 10% or less, a water activity of 0.8 or less, or both.

[0091] In accordance with another embodiment of the present invention, a method for enhancing a sensory experience for a flavor composition in a confectionary com- position is provided. The method includes: dispersing 0.1 wt% to 10 wt% of an encapsulated flavor in the confectionary com- position, wherein wt% is based on the entire weight of the confectionery composition, wherein the encapsulated flavor is a dried microcapsule having an average particle diameter in a range from 400 microns to 1000 microns with a coefficient of variance of less than 15%, wherein the dried microcapsule comprises: a shell matrix comprising a gelled hydrocolloid gelling agent and having an average thickness of 25 microns to 200 microns; and a core portion comprising the flavor composition and having an average core diameter of 200 microns to 950 microns, wherein a ratio between the average core diameter and the average thickness of the shell matrix is in a range between 1 to 40; wherein the dried microcapsule is characterized by a texture characteristic of a force at break value in a range from 0.05 to 5 Kg; a stiffness at break value in a range from 0.2 to 5 Kg/mm; a deformation ratio of 0.1 to 0.9; or a Young’s modulus value in a range from 0.2 to 10 Kg; and wherein the confectionery composition further comprising a sweetener selected from the group of monosaccharides, disaccharides, polysaccharides, polyol sweeteners, non-nutritive sweeteners, and combinations thereof.

[0092] Confectionery products include chewable products comprising a sweetener selected from the group of monosaccharides, disaccharides, polysaccharides, polyol sweeteners, non-nutritive sweeteners, and combinations thereof. When flavor compositions, which are encapsulated within the breakable microcapsules according to the present invention, are homogenously dispersed in the confectionary products, such as compressed chewing gum tablets or chewing gum mini-stick, the sensory experience for an encapsulated flavor composition in the confectionary composition is surprisingly enhanced, relative to other encapsulated techniques. During mastication, the breakable microcapsules are broken thereby releasing their flavor contents. Applicants have discovered that the inventive monodispersed microcapsules (having an average particle diameter and coefficient of variance within the range(s) disclosed herein) provide an enhanced flavor-filled experience, both in intensity and longer lasting experience, relative to other flavor delivery systems.

[0093] In an embodiment, the confectionary comprises a chewing gum base, which can also contain any of a variety of traditional ingredients such as plasticizers or softeners such as lanolin, stearic acid, sodium stearate, potassium stearate, glyceryl triacetate, glycerine and the like and/or waxes, for example, natural waxes, petroleum waxes, such as polyethylene waxes, paraffin waxes and microcrystalline waxes, to obtain a variety of desirable textures and consistency properties. These individual additional materials are generally employed in amounts of up to about 30% by weight and preferably in amounts of from about 3% to about 20% by weight of the final chewing gum base composition. The chewing gum base composition may additionally include conventional additives such as emulsifiers such as lecithin and glyceryl monostearate; and additional fillers such as aluminum hydroxide, magnesium hydroxide, alumina, aluminum silicates, calcium carbonate, and talc and combinations thereof. These fillers may be used in the chewing gum base in various amounts. Preferably the amount of fillers when used will vary from about 4 to about 30% by weight of the final chewing gum base. The chewing gum embodiments of the present invention containing the flavor-filled, breakable microcapsules may further include a one or more flavor delivery systems selected from liquid, spray dry, spray dry granulation, gel beads, or other encapsulations techniques.

[0094] All the features described previously regarding the confectionary product also apply to the method of the invention.

[0095] Non-limiting examples of embodiments of the present invention, in accordance with the description and in comparison with non-inventive embodiments, are now disclosed below. These examples are merely for the purpose of illustration and are not to be regarded as limiting the scope of the invention or the manner in which it can be practiced. Other examples and/or applications will be appreciated by a person having ordinary skill in the art. EXAMPLES

[0096] Co-extruded microcapsules and capsules were prepared in accordance with the method and principles described herein. Exemplary flavor compositions of mint, mint and PHYSCOOL®, and strawberry were used to evaluate flavor sensory performance in a stick chewing gum confectionary application.

[0097] Exemplary Gelatin Microcapsules and Capsules: An external hydrophilic liquid phase (shell solution) comprising 19.8 wt% gelatin (bovine, 250 bloom, 19.8 wt%), and 2.7 wt% sorbitol in 77.7 wt% water was prepared and coextruded with an internal lipophilic liquid phase comprising the desired flavor composition to make flavor-filled gelatin microcapsules. The external hydrophilic liquid phase was prepared by adding the desired mass of water in a bain-marie mixer, followed by the appropriate mass of sorbitol and gelatin powders to achieve the desired weight percentages. The mixture was heated to 65°C with stirring until complete solubilization of the powders is achieved. Stirring was discontinued and the solution was allowed to degas while maintaining the temperature at 65°C, until co extruding.

[0098] The internal lipophilic liquid phase (core solution) was prepared (flavor oils, solvents, etc.) and maintained at 25°C, until co-extruding. The external hydrophilic liquid phase and the internal lipophilic liquid phase are separately pumped to the coxial nozzle assembly, and simultaneously extruded through the coaxial nozzles into an MCT cooling fluid at 15°C, forming concentric drops with a core / shell ratio of about 30 / 70. The external hydrophilic liquid phase containing the gelatin hydrocolloid gelling agent gelifies around the flavored core due to the temperature decrease. The wet gelified capsules were collected and stored in cold MCT at +4°C for about an hour to allow the shell’s gelled matrix to further solidify. Afterwards, the MCT was removed by centrifugation.

[0099] The centrifuged capsules and a portion of dessicating agent (e.g., silica or starch) were mixed and then dried in a fluid bed dryer with air at 42°C / 120 m3/h until the capsule bed reaches approximately 32 °C. The dried capsules were collected and sieved to remove excess dessicating agent(s). Physical testing of the capsules (e.g., texture properties, water activity, water content, average particle diameter, and shell thickness) were conducted on the dried capsules and are shown in Tables 1 and 3.

[0100] Exemplary Hydrocolloid and HAS Microcapsules: An external hydrophilic liquid phase (shell solution) comprising 0.5 wt% gellan gum (Kelcogel® F), 4 wt% sorbitol, 10 wt% HAS (AMYLO M-400G) and 0.05 wt% CaC12*2H20 in 85.45 wt% osmosis water is prepared and is coextruded with an internal lipophilic liquid phase (core solution) comprising the desired flavor composition to make flavor-filled hydrocolloid/ HAS microcapsules. A measured quantity of osmosis water is heated and the gellan gum hydrocolloid gelling agent mixed therein until complete dissolution is achieved. The high amylose starch (HAS) and filler (sorbitol) are added and the resultant mixture is stirred at a sufficient temperature (e.g., 75°C) to affect a controlled partial gelatinization of the HAS. After achieving the desired extent of gelatinization, the temperature of the mixture is then lowered by adding a cooler solution of the crosslinking agent (50% aqueous CaC12*2H20) and additionally cooling, if needed, to stabilize the mixture until it is coextruded to make the breakable microcapsule. The holding temperature is near or below the threshold gelatinization temperature (Gel °T) of the HAS and above the gelling or gelification temperature of the gellable mixture.

[0101] The internal lipophilic liquid phase is prepared (flavor oils, solvents, etc.) and maintained at 25°C, until co-extruding. The external hydrophilic liquid phase and the internal lipophilic liquid phase are separately pumped to the coxial nozzle assembly, and simultaneously extruded through the coaxial nozzles into an MCT cooling fluid at 18°C, forming concentric drops with a core / shell ratio of about 10 / 90. The external hydrophilic liquid phase containing the partially-gelatinized HAS and gellan hydrocolloid gelling agent gelifies around the flavored core due to the temperature decrease. The wet gelified capsules are collected and stored in cold MCT at +4°C for about an hour to allow the shell’s gelled matrix to further solidify. Afterwards, the MCT is removed by centrifugation.

[0102] The centrifuged capsules and a portion of dessicating agent (e.g., silica or starch) are mixed and then dried in a fluid bed dryer with air at 42°C / 120 m3/h until the capsule bed reaches approximately 32 °C. The dried capsules may be collected and sieved to remove excess dessicating agent(s).

[0103] Exemplary Gellan-based Microcapsules (method 1) : An external hydrophilic liquid phase (shell solution) comprising 1 wt% gellan gum (Kelcogel® F), 1 wt% K- carraghenan, 8 wt% sorbitol, and 7 wt% dextrin, and 0.05 wt% CaC12*2H20 in 82.95 wt% osmosis waster is prepared and coextruded with an internal lipophilic liquid phase (core solution) comprising the desired flavor composition to make flavor-filled gellan- based microcapsules. A measured quantity of osmosis water is heated to 85°C and the gellan gum and K-carraghenan hydrocolloid gelling agents are mixed therein until complete dissolution is achieved. The sorbitol, dextrin, and CaC12*2H20 are added. The mixture is maintained at 85°C with stirring until complete solubilization of the powders is achieved. Stirring is discontinued and the solution is allowed to degas while maintaining the temperature at 85°C, until co-extruding.

[0104] The internal lipophilic liquid phase was prepared (flavor oils, solvents, etc.) and maintained at 25°C, until co-extruding. The external hydrophilic liquid phase and the internal lipophilic liquid phase are separately pumped to the coxial nozzle assembly, and simultaneously extruded through the coaxial nozzles into an MCT cooling fluid at 18°C, forming concentric drops with a core / shell ratio of about 30 / 70. The external hydrophilic liquid phase containing the gellan and k-carraghenan hydrocolloid gelling agents gelifies around the flavored core due to the temperature decrease. The wet gelified capsules are collected and stored in cold MCT at +4°C for about an hour to allow the shell’s gelled matrix to further solidify. Afterwards, the MCT is removed by centrifugation.

[0105] The centrifuged capsules and a portion of dessicating agent (e.g., silica or starch) are mixed and then dried in a fluid bed dryer with air at 42°C / 120 m3/h until the capsule bed reaches approximately 32 °C. The dried capsules may be collected and sieved to remove excess dessicating agent(s).

[0106] Exemplary Gellan-based Microcapsules (method 2) : An external hydrophilic liquid phase (shell solution) comprising 1 wt% gellan gum (Kelcogel® F), 1 wt% K- carraghenan, 8 wt% sorbitol, 2 wt% betacyclodextrine, and 11.7 wt% dextrin, and 0.2 wt% sodium citrate dihydrate in 83.1 wt% osmosis waster is prepared and coextruded with an internal lipophilic liquid phase (core solution) comprising the desired flavor composition to make flavor-filled gellan-based microcapsules. A measured quantity of osmosis water is heated to 85°C and the sodium citrate sequestering agent is dissolved therein. The gellan gum, K-carraghenan, and sorbitol are mixed therein until complete dissolution is achieved. The dextrin and betacyclodextrin are added. The mixture is maintained at 85°C with stirring until complete solubilization of the ingredients is achieved. Stirring is discontinued and the solution is allowed to degas while maintaining the temperature at 85°C, until co-extruding.

[0107] The internal lipophilic liquid phase is prepared (flavor oils, solvents, etc.) and maintained at 25°C, until co-extruding. The external hydrophilic liquid phase and the internal lipophilic liquid phase are separately pumped to the coxial nozzle assembly, and simultaneously extruded through the coaxial nozzles into an MCT cooling fluid at 18°C, forming concentric drops with a core / shell ratio of about 30 / 70. The external hydrophilic liquid phase containing the gellan gum and k-carraghenan hydrocolloid gelling agents gelifies around the flavored core due to the temperature decrease. The wet gelified capsules are collected and stored in cold MCT at +4°C for about an hour to allow the shell’s gelled matrix to further solidify. Afterwards, the MCT is removed by centrifugation. The centrifuged capsules are then crosslinked by immersion in a 5 wt% CaCl*2H20 solution, stirred for 15 minutes, and then may be isolated by centrifuging to remove the excess water.

[0108] The centrifuged capsules and a portion of dessicating agent (e.g., silica or starch) are mixed and then dried in a fluid bed dryer with air at 42°C / 120 m3/h until the capsule bed reaches approximately 32 °C. The dried capsules may be collected and sieved to remove excess dessicating agent(s)

[0109] [Table 1]

[0110] In Table 2, details regarding the comparison samples are provided.

[0111] [Table 2]

[0112] In Table 3, texture property measurements of the seamless capsules and micro- capsules are provided.

[0113] [Table 3]

[0114] The sensory performance for the various flavor delivery systems was studied in a stick chewing gum matrix. Flavored sticks of gum were prepared by softening the gum base in the microwave, mixing the gum base and half of the mass of the powder ingredients for 5 min. The maltitol syrup was added and mixed for 5 min, following by addition of the remaining mass of the powders, the glycerin, the lecithin, and the flavor (encapsulated or liquid). The entire quantity of ingredients was mixed for another 5 min, after which the flavored chewing gum matrix was rolled, detailed, and packaged. A listing of the stick chewing gum ingredients and their respective amounts are listed in Table 4. Despite the varied flavor loadings in the different encapsulation technologies (see Tables 1 and 2), it should be noted that the total amount of the flavor in the chewing gum application was substantially the equivalent in the compared samples.

[0115] [Table 4]

[0116] Protocol for Evaluation: For each inventive example and comparative example, trained sensory panelists (11 < n < 18) were provided samples of the flavored stick chewing gums. The sensory panel followed a general chewing and testing protocol, where a single sample of the flavored chewing gum was place in the panelist's mouth at time zero, and the panelist began chewing regularly. Observations and numerical scores (1-10) were recorded at specific time intervals. For the mint and mint/PHYSCOOF® flavors, the sensory panel evaluated freshness and mint intensity. For the strawberry flavor, the sensory panel evaluated its intensity. Observations were recorded after 5 seconds, 15 seconds, 30 seconds, 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, and 10 minutes. Mean scores and coefficient of variances were calculated. In some instances, student T-values and associated probabilities were calculated to verify significance of the sensory panel testing results.

[0117] In reference to FIG. 1, six different stick chewing gum compositions comprising about 0.7 wt% of mint flavor were subjected to evaluation of mint intensity by the sensory panelists. Example 1 (600mhi microcapsule) and Comp. Ex. 16 (1.1 mm capsule) gave enhanced mint intensity over the range of about 1 to 3 minutes, relative to Comp. Ex. 15 (liquid), Comp. Ex. 17 (extruded), Comp. Ex. 6 (spray granulation), and Comp. Ex. 7 (spray granulation).

[0118] In reference to FIG. 2, a comparison of Example 1 and Comp. Ex. 16 shows that the larger 1.1 mm capsule provided an enhanced mint intensity for the first minute, but a higher mint intensity was observed after about 3 minutes for the smaller Example 1 microcapsule.

[0119] In reference to FIG. 3, the same six different stick chewing gum compositions evaluated for mint intensity in FIG. 1 were also evaluated by the sensory panelists for freshness intensity. While Comp. Ex. 16 showed that the larger 1.1 mm capsule provided an enhanced freshness intensity for the first minute, the smaller Example 1 microcapsule demonstrated a higher mint intensity after about 3 minutes. This longer lasting freshness intensity provide by the smaller Example 1 microcapsules is more evident when comparing a simplified graph of just Comp. Ex. 16 and Example 1, as shown in FIG. 4.

[0120] In reference to FIG. 5, six different stick chewing gum compositions comprising about 0.5 wt% of strawberry flavor were subjected to evaluation of strawberry flavor intensity by the sensory panelists. After two minutes, Example 3 (670pm microcapsule) gave enhanced strawberry flavor intensity relative to Comp. Ex. 19 (1.1 mm capsule), Comp. Ex. 18 (liquid), Comp. Ex. 11 (extruded), Comp. Ex. 8 (spray granulation), and Comp. Ex. 9 (spray granulation). This longer lasting strawberry flavor intensity provided by the smaller Example 3 microcapsules is even more evident when comparing a simplified graph of just Comp. Ex. 19 and Example 3, as shown in FIG. 6.

[0121] In order to determine if a combination of two difference capsules could provide an improved sensory profile with an upfront intensity contribution by the larger capsule followed by a longer lasting flavor intensity provided by the smaller microcapsule, samples of three different stick chewing gum compositions comprising about 0.7 wt% of mint & PHYSCOOL® flavor were subjected to evaluation of mint intensity by the sensory panel. The contribution of the flavor loading came from each (0.5 wt% of Example 14, 705mhi microcapsule, 8.9% std. dev.; and 0.2 wt% of Comp. Ex. 5, 1.1 mm capsule, 6.5% std. dev.) in the combined chewing gum sample. Surprisingly, the flavor sensory enhancement (i.e., longer lasting effect) provided by the smaller Example 14 microcapsules was not observed in the combined chewing gum sample, as shown in FIG. 7.

[0122] Without being bound by any particular theory, it was postulated that the combination of these two different sized seamless capsules, each having monodispersity, normal distribution, and relatively small coefficient of variances, performs in the chewing gum matrix like a single sample having a broad particle size distribution with a bi-disperse particle size profile. Thus, even though the average particle diameter of the mixture would clearly still reside within the range described and claimed herein, the coefficient of variance of the mixture would reside outside of the claimed range. In reference to FIG. 8, an analysis of volume particle size distributions are shown for Example 14, Comp. Ex. 5, and a 5:2 weight ratio of a mixture of the two and two comparative examples (Comp. Ex. 5 and 13). The average (mean) particle diameter of the bi- dispersed mixture was 834 microns with a coefficient of variance of 22.7%. The effect of larger particle diameters and coefficients of variance can be seen in FIG. 9, where the smaller microcapsule (Ex. 2) with the lower coefficient of variance outperformed the comparative sample (Comp. 12).

[0123] The unexpected discovery of enhanced flavor sensory performance may be attributed to a combination of monodispersed flavor-filled seamless breakable microcapsules (e.g., average particle diameter in a range from 400 micron to 1000 micron with a co- efficient of variance of less than 15%), and a sufficient flavor loading (e.g., a ratio between the average core diameter and the average thickness of the shell matrix in a range between 1 to 40). This combination of characteristics is believed to provide a more homogenously dispersed, flavor-filled confectionary composition. According, the compressive and shearing forces during mastication cause the rupture of the seamless, breakable microcapsules of the present invention over a longer duration thereby providing a longer lasting effect.

[0124] While the present invention has been illustrated by the description of one or more embodiments thereof, and while some embodiments have been described in considerable detail, they are not intended to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modification will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative product and method, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the scope of the general inventive concept embraced by the following claims.

[0125] WHAT IS CLAIMED IS.

Claims

[Claim 1] A confectionery product having an enhanced flavor profile, comprising:

a confectionery matrix comprising a sweetener selected from the group of monosaccharides, disaccharides, polysaccharides, polyol sweeteners, non-nutritive sweeteners, and combinations thereof; and

0.1 wt% to 10 wt% of an encapsulated flavor interspersed in the confectionary matrix, wherein wt% is based on the entire weight of the confectionery product, wherein the encapsulated flavor is a dried microcapsule having an average particle diameter in a range from 400 microns to 1000 microns with a coefficient of variance of less than 15%, wherein the dried microcapsule comprises:

a shell matrix comprising a gelled hydrocolloid gelling agent and having an average thickness of 25 microns to 200 microns; and

a core portion comprising a flavor and having an average core diameter of 200 microns to 950 microns, wherein a ratio between the average core diameter and the average thickness of the shell matrix is in a range between 1 to 40; and

wherein the dried microcapsule is characterized as having a texture characteristic of a force at break value in a range from 0.05 to 5 Kg; a stiffness at break value in a range from 0.2 to 5 Kg/mm; a deformation ratio of 0.1 to 0.9; or a Young’s modulus value in a range from 0.2 to 10 Kg.

[Claim 2] The confectionery product according to claim 1, wherein the confectionary matrix has a base Young’s modulus value that is less than the microcapsule Young’s modulus value.

[Claim 3] The confectionery product according to claim 1 or 2, wherein the shell matrix further comprises a filler in an amount in a range from 0.1 to 90 wt%, wherein wt% is based on the entire weight of the dry weight ingredients.

[Claim 4] The confectionary product according to claim 3, wherein the filler is selected from the group consisting of a dextrin, a maltodextrin, a cyclodextrin, innulin, sucrose, allulose, tagatose, a microcrystalline cellulose, a hydroxypropylmethylcellulose, a hydroxypropylcellulose, a methylcellulose, a carboxymethylcellulose, a polyvinyl alcohol, trehalose, erythritol, maltitol, mannitol, xylitol, glycerol, triacetine, a polyethylene glycol, and combinations thereof.

[Claim 5] The confectionary product according to any claim 1 to 4, wherein the shell matrix is derived from a hydrocolloid gelling agent selected from a collagen-derived gelling agent, a polysaccharide based gelling agent or a combination thereof

[Claim 6] The confectionary product according to any one of claims 1 to 5, wherein the gelled hydrocolloid gelling agent of the shell matrix is selected from the group consisting of gelatin, gellan gum, alginates, kappa-carrageenan, low methoxyl (LM) pectin, pectin, agar-agar, gelifying starch, modified starches, dextran, curdlan, tara gum, ghatti gum, karaya gum, welan gum, rhamsan gum, pullulan gum, xanthan gum, locust bean gum, gum arabic, and combinations thereof

[Claim 7] The confectionary product according to any one of claims 1 to 6, wherein the gelled hydrocolloid gelling agent of the shell matrix is derived from a polysaccharide bearing carboxylic or carboxylate groups, where upon exposure to multivalent metal ions, crosslinking bridges are formed between inter- and intra- strand carboxylate groups.

[Claim 8] The confectionary product according to any one of claims 1 to 7, where the gelled hydrocolloid gelling agent of the shell matrix comprises gelatin.

[Claim 9] The confectionary product according to any one of claims 1 to 8, wherein the ratio between the average core diameter and the average thickness of the shell matrix is in a range between 2 to 15.

[Claim 10] A method for enhancing a flavor sensory experience for a flavor com- position in a confectionary composition, comprising:

dispersing 0.1 wt% to 10 wt% of an encapsulated flavor in the confectionary composition, wherein wt% is based on the entire weight of the confectionery composition, wherein the encapsulated flavor is a dried microcapsule having an average particle diameter in a range from 400 microns to 1000 microns with a coefficient of variance of less than 15%, wherein the dried microcapsule comprises:

a core portion comprising the flavor composition and having an average core diameter of 200 microns to 950 microns, wherein a ratio between the average core diameter and the average thickness of the shell matrix is in a range between 1 to 40;

wherein the dried microcapsule is characterized by a texture characteristic of a force at break value in a range from 0.05 to 5 Kg; a stiffness at break value in a range from 0.2 to 5 Kg/mm; a deformation ratio of 0.1 to 0.9; or a Young’s modulus value in a range from 0.2 to 10 Kg; and wherein the confectionery composition further comprising a sweetener selected from the group of monosaccharides, disaccharides, polysaccharides, polyol sweeteners, non-nutritive sweeteners, and com- binations thereof.

[Claim 11] The method according to claim 10, wherein the confectionary matrix has a base Young’s modulus value that is less than the Young’s modulus value of the dried microcapsule.

[Claim 12] The method according to claim 10 or 11, wherein the shell matrix further comprises a filler in an amount in a range from 0.1 to 90 wt%, wherein wt% is based on the entire weight of the dry weight ingredients.

[Claim 13] The method according to claim 12, wherein the filler is selected from the group consisting of a dextrin, a maltodextrin, a cyclodextrin, innulin, sucrose, allulose, tagatose, a microcrystalline cellulose, a hy- droxypropylmethylcellulose, a hydroxypropylcellulose, a methyl- cellulose, a carboxymethylcellulose, a polyvinyl alcohol, trehalose, erythritol, maltitol, mannitol, xylitol, glycerol, triacetine, a polyethylene glycol, and combinations thereof.

[Claim 14] The method according to any one of claims 10 to 13, wherein the gelled hydrocolloid gelling agent comprises a collagen-derived gelling agent or a polysaccharide based gelling agent.

[Claim 15] The method according to any one of claims 10 to 14, wherein the gelled hydrocolloid gelling agent is selected from the group consisting of gelatin, gellan gum, alginates, kappa- carrageenan, low methoxyl (LM) pectin, pectin, agar-agar, gelifying starch, modified starches, dextran, curdlan, tara gum, ghatti gum, karaya gum, welan gum, rhamsan gum,pullulan gum, xanthan gum, locust bean gum, gum arabic, and combinations thereof.

[Claim 16] The method according to any one of claims 10 to 15, wherein the gelled hydrocolloid gelling agent comprises a polysaccharide bearing carboxylic or carboxylate groups, where upon exposure to multivalent metal ions, crosslinking bridges are formed between inter- and intra strand carboxylate groups.

[Claim 17] The method according to any one of claims 10 to 16, where the gelled hydrocolloid gelling agent of the shell matrix comprises gelatin.

[Claim 18] The method according to any one of claims 10 to 17, wherein the ratio between the average core diameter and the average thickness of the shell matrix is in a range between 2 to 15.