Biobased biodegradable composition for injection molding

Abstract

Disclosed herein are compositions for injection molding and articles made therefrom, the compositions and articles comprising at least one hydrocolloid, at least one plasticizer, at least one filler, at least one polycation and / or crosslinking agent, and at least one flowable agent. Typically, the component is derived from a biological source, such as seaweed, plants or animals. Typically, the components are made of biodegradable materials such that the compositions and articles are compostable. The composition is used to form the article by injection molding, such as a disposable food service industry product, and the article has desirable flexibility, tensile strength and water repellency.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 476,471, filed on December 21, 2022, which is incorporated herein by reference in its entirety for all purposes. Background Art

[0003] Plastic waste from takeout orders and food packaging is a growing concern and a major source of the approximately 20 million metric tons of plastic waste generated annually. Americans alone use approximately 560 billion individual plastic items each year. Due to scale and a lack of infrastructure, these items are rarely recycled, so much of it ends up in landfills and waterways.

[0004] Food service products (e.g., cutlery and straws) made from bioplastics and bioplastic composites are becoming increasingly popular. Corn-derived polylactic acid (PLA) and polypropylene (PP) are the primary components of these formulations. To reduce costs and improve the biodegradability of these materials, PLA and PP are often blended with natural fibers and starches. While these materials offer improved barrier properties compared to paper products, they still exhibit a number of disadvantages. PLA and PP will not degrade naturally in the natural environment and require commercial composting facilities. Furthermore, the use of corn as a raw material and agricultural resources (such as fresh water and fertilizer) to produce these biorenewable monomers promote monocropping and competition with human food sources. Furthermore, the mechanical properties and cost of these materials need improvement.

[0005] Several reports have demonstrated the use of starch, cellulose fiber, and chitosan (an amino polysaccharide derived from the exoskeletons of crustaceans and insects) as alternatives to plastic packaging and disposable food service products. While these technologies show promise, they still need to be scaled up and simplified to become economically viable.

[0006] Alternatively, LOLIWARE Inc., a seaweed-based materials technology company, uses biopolymers (specifically, alginate and carrageenan) produced from brown and red seaweed. These two types of seaweed grow rapidly in the ocean and use almost no agricultural resources or fresh water, presenting an ideal renewable and abundant natural resource for large-scale replacement of petroleum-derived plastics and corresponding components used in the food service industry. Furthermore, the energy consumption of extracting 1 kg of alginate from kelp is offset by 2.2 kg of sequestered CO2 in the form of blue carbon, meaning that seaweed-derived biopolymers not only reduce the consumption of fresh water and fertilizer for agriculture, but also reduce the absorption of CO2 in the atmosphere and from seawater. In addition, formulations containing alginate and carrageenan can be processed on conventional plastic processing equipment, particularly twin-screw and single-screw extruders and injection molding machines.

[0007] Typically, carrageenan and carrageenan-based formulations are used as gelling agents and thickeners in the food and cosmetics industries, and in biotechnology for wound dressings and tissue regeneration. Another use of carrageenan-based formulations according to the present invention is their utility as plastic replacements in the manufacture of disposable food service industry products via injection molding. Specifically, the production of utensils, takeout containers, trays, and other disposable food service items. Discarded injection molded parts can be composted under industrial or home compounding conditions to produce soil additives (humus and humic substances) or can be used to produce animal / fish feed.

[0008] The present invention encompasses flexible, strong, biodegradable compositions with improved mechanical and water-barrier properties. These compositions comprise ingredients derived from biorenewable sources and offer a sustainable and inexpensive solution to the problem of single-use plastic pollution, particularly single-use plastic utensils and plastic food packaging. Summary of the Invention

[0009] In order to be an effective alternative to disposable articles (e.g., cups, takeout containers, trays, utensils, or other containers), the articles of the present disclosure preferably have the structural integrity and versatility required to maintain or be in contact with liquids and foods of varying temperatures, especially for extended periods of time. The present invention provides a flexible and biodegradable seaweed-based composition wherein a hydrocolloid is the primary component of the composition. Currently available seaweed-based resins, while manageable and tough, exhibit relatively low flexural strength. Common techniques for addressing these shortcomings in biomaterials include the addition of plasticizers (glycerol, mannitol, and others) and reinforcement with cellulose fibers (MCC, Ethocell, etc.) and fillers (e.g., CaCO 3 , talc, and others).

[0010] The injection moldable compositions disclosed herein address at least some of these and other shortcomings by implementing the addition of low molecular weight ionic polycations and / or crosslinkers (e.g., poly-L-lysine, polyethyleneimine, polyallylamine) or implementing reactive crosslinking during heat treatment of the composition (injection molding process) and, in some aspects, provide components for biodegradable articles that exhibit moderate to high tensile strength and Young's modulus sufficient for use as disposable utensils, take-out containers, trays, and other food service industry products.

[0011] In one aspect, the present disclosure provides an article, pellet, or pretreatment mixture comprising at least one hydrocolloid, at least one plasticizer, at least one filler, at least one polycation and / or cross-linking agent, at least one flow agent, and water.

[0012] In other aspects, the present invention further includes a method for preparing a biodegradable article, the method comprising: combining (i) at least one hydrocolloid, (ii) at least one plasticizer, (iii) at least one filler and (iv) at least one polycation and / or cross-linking agent and (v) water to prepare a pretreatment mixture; optionally blending the pretreatment mixture; optionally mixing the pretreatment mixture into pellets; forming the pretreatment mixture or the pellets into shapes; and drying the shapes to form the article, wherein the at least one hydrocolloid, the at least one plasticizer, the at least one filler, the at least one polycation and / or cross-linking agent and the at least one flow agent are as defined in any of the preceding technical solutions.

[0013] In some aspects, disclosed herein are biodegradable articles, containers, or utensils comprising at least one hydrocolloid, such as alginate, chitosan, agar, kappa-carrageenan, iota-carrageenan, konjac gum, guar gum, locust bean gum, or any combination thereof, typically in combination with other components, such as at least one plasticizer, at least one filler, at least one polycation and / or cross-linking agent, at least one flow agent, and / or water, and optionally additional ingredients including one or more sweeteners (e.g., non-sugars, sugars, honey, etc.), flavorings, coloring agents, active ingredients, edible oils, and preservatives (e.g., natural preservatives). The article may also be coated with an optional edible coating, for example, to enhance water resistance, improve shelf life, and / or reduce the stickiness of the article, or to provide flavor, color, or graphics to the article. The article may be held or in contact with a liquid or food (e.g., moist food) for an extended period of time, preferably greater than about one hour. The article can be in the form of a utensil, container, cup, straw, stirrer, takeout container, tray, lid, or any other suitable form. In some aspects, the article is biodegradable, compostable, or a combination thereof.

[0014] In some aspects, disclosed herein are flexible, firm, bio-based and / or biodegradable articles with improved water-blocking properties, and compositions (such as pre-treatment mixtures) or pellets for the preparation of such articles. These articles, pellets, and compositions comprise ingredients obtained from biorenewable sources, such as seaweed, plants, animals, or a combination thereof, and provide sustainable and cost-effective solutions for the problems associated with disposable plastic pollution (especially disposable plastic appliances or other articles). In some aspects, such compositions are used as substitutes for plastics (such as plastics derived from petroleum) in the manufacture of disposable food service industry articles. In some aspects, the selected components of the mixed composition are continued for a selected time to blend the composition (such as pre-treatment mixtures) to reach the desired consistency suitable for mixing by extrusion and / or by injection molding for further processing. In some aspects, the composition is in the form of pellets for processing by injection molding. In some aspects, pellets are formed by mixing using an extrusion process. In some aspects, pellets have a selected shape, size, and weight suitable for further processing by injection molding.

[0015] In some aspects, such compositions include hydrocolloids, which may be biopolymers (e.g., alginate or carrageenan) derived from seaweed (e.g., kelp or red algae). Seaweed grows unattended in the ocean (e.g., kelp grows several meters per day) and requires almost no agricultural resources or fresh water, thus presenting an ideal renewable and abundant natural resource to replace plastics in disposable items in the food industry. However, in addition to alginate or carrageenan, hydrocolloids (or biopolymers) may also be used, as described elsewhere herein. Additionally, in some aspects, compositions comprising hydrocolloids or biopolymers (e.g., alginate or carrageenan) may be processed on conventional plastics processing equipment (e.g., twin-screw or single-screw cold melt or hot melt extruders), depending on the composition, to enable the use of existing manufacturing techniques (e.g., equipment intended for processing petroleum-derived plastics). For example, compositions (pretreatment mixtures) comprising alginate or dried and ground brown seaweed as the primary component (excluding water) can be produced using cold extrusion, whereas compositions (pretreatment mixtures) comprising kappa-carrageenan or dried and ground red seaweed, even in small amounts (and in some aspects also comprising alginate) can be produced using hot melt extrusion. Articles such as containers or utensils can be produced from such formulations in a scalable and economically viable manner.

[0016] In some aspects, flexible, injection moldable and biodegradable compositions based on alginate and products made therefrom are disclosed, wherein alginate (e.g., sodium alginate) and other biologically derived polysaccharides (e.g., chitin, chitosan, starch, cellulose) are included in the composition and, in some aspects, are the main components of the composition. In some aspects, alginate is the main component (excluding water) of the composition and / or product. In some aspects, the alginate-based product is compounded to form pellets using at least one cold extrusion step.

[0017] In some aspects, flexible, injection moldable, and biodegradable carrageenan-based compositions and articles made therefrom are disclosed, wherein carrageenan (particularly kappa carrageenan and mixtures of kappa carrageenan with other carrageenans) and other bioderived polysaccharides (e.g., chitosan or alginate) are included in the composition and, in some aspects, are the major components of the composition. In some aspects, the carrageenan, which may be a mixture of carrageenans, is the major component of the composition and / or article (excluding water). In some aspects, a product comprising kappa carrageenan is disclosed, the product being flexible, strong, and biodegradable with an extended shelf life (e.g., 6 months or longer under ambient conditions without any packaging). In some aspects, the carrageenan-based article is compounded to form pellets using at least one hot melt extrusion step. In some aspects, cold extrusion is not used to compound the carrageenan-based article. In some aspects, the kappa carrageenan-based article is compounded to form pellets using at least one hot melt extrusion step. In some aspects, cold extrusion is not used to compound the kappa-carrageenan based products.

[0018] In some aspects, disposable food service industry products (e.g., takeout containers) are provided that are composed only of food-grade ingredients, and such features render the products edible. In some aspects, discarded products (e.g., takeout containers) and / or discarded injection-molded parts can be collected and used as fertilizer (e.g., due to the high organic content of the formulation) or as potential feed for animals, fish, or microorganisms. In some aspects, unused injection-molded parts (e.g., pellets that were melted but not incorporated) can be remolded and reincorporated in the injection molding process.

[0019] The compositions disclosed herein can be used to produce food service articles, such as takeout containers, by injection molding. In some aspects, the resulting products (e.g., takeout containers) exhibit moderate to high tensile strength (MPa) and compressive strength (MPa), as well as improved barrier properties, such that the articles remain flexible even in environments with low relative humidity and resist swelling in aqueous solutions (less than 60% by weight). Supporting evidence demonstrating the improved barrier properties, flexibility, resistance to swelling in aqueous solutions, and other mechanical and thermal properties of the components of the compositions disclosed herein can be found in International Application PCT / US2022 / 033527, filed June 15, 2022, which is incorporated herein by reference in its entirety.

[0020] The compositions disclosed herein (particularly compositions comprising kappa-carrageenan) can be used to produce food service articles, such as utensils, wherein the compositions are used as resins in injection molding processes to prepare disposable food service industry products that are sustainable, biorenewable materials. In some aspects, such compositions consist only of food-grade ingredients, making them biodegradable, optionally edible, and suitable for food service environments. In some aspects, the resulting products (e.g., utensils comprising kappa-carrageenan) exhibit moderate tensile strength (e.g., 10 to 60 MPa) and moderate compressive strength (e.g., 10 to 13 MPa), as well as barrier properties sufficient to maintain flexibility and structural integrity for extended periods (e.g., more than 6 months) under environmental conditions without any packaging (e.g., air-blocking and / or moisture-blocking packaging). In some aspects, the resulting products comprising kappa-carrageenan (e.g., takeout containers) exhibit reduced water absorption (compared to paper analogs), wherein swelling in aqueous solution after 1 hour at room temperature is less than 50% by weight, and swelling in aqueous solution after 1 hour at 0°C is less than 30%.

[0021] In one embodiment, some compositions disclosed herein are characterized by a strain at maximum force selected from the range of 2-15%. In one embodiment, some compositions disclosed herein are characterized by a tensile strength equal to or greater than 10 MPa. In one embodiment, some compositions disclosed herein are characterized by a Young's modulus equal to or greater than 2000 MPa, optionally selected from the range of 2000 MPa to 4000 MPa.

[0022] Without wishing to be bound by any particular theory, there may be a discussion herein of the views or understandings of the underlying principles related to the devices and methods disclosed herein. It should be recognized that regardless of the ultimate correctness of any mechanistic explanation or hypothesis, the embodiments of the present invention may still be operational and applicable. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1is a flow chart of an exemplary method of the present disclosure for making an article from an injection moldable formulation.

[0024] Figure 2 The components of the pre-treated mixtures / pellets evaluated in the examples discussed herein are provided. Also shown are exemplary parameters and equipment for the optional compounding step in the methods of the present disclosure. Figure 2 Also depicted are exemplary pellets of the compositions and methods of the present disclosure.

[0025] Figure 3 Results of an exemplary injection molding process are presented, along with the resulting mechanical properties of the compositions tested under the injection molding process parameters.

[0026] Figure 4 Results of an exemplary injection molding process are presented, along with the resulting mechanical properties of the compositions tested under the injection molding process parameters.

[0027] Figure 5 Results of an exemplary injection molding process are presented, along with the resulting mechanical properties of the compositions tested under the injection molding process parameters.

[0028] Figure 6 Results of an exemplary injection molding process are presented, along with the resulting mechanical properties of the compositions tested under the injection molding process parameters.

[0029] Figure 7 Results of an exemplary injection molding process are presented, along with the resulting mechanical properties of the compositions tested under the injection molding process parameters.

[0030] Figure 8 Results of an exemplary injection molding process are presented, along with the resulting mechanical properties of the compositions tested under the injection molding process parameters.

[0031] Figure 9 Results of an exemplary injection molding process are presented, along with the resulting mechanical properties of the compositions tested under the injection molding process parameters.

[0032] Statements about compounds and nomenclature

[0033] In general, the terms and phrases used herein have their generally accepted meanings in the art, which can be found by reference to standard texts, journal references, and context known to those skilled in the art. The following definitions are provided to clarify their specific use in the context of the present invention.

[0034] Although certain components of the compositions, pretreatment mixtures, pellets, or articles are described herein as having a given function (e.g., hydrocolloid, plasticizer, etc.), such components may actually provide an entirely different function or functions. Thus, the function of a given component is described as currently understood, but such function is a working theory. For example, chitosan is considered to act as a hydrocolloid in the articles and pretreatment mixtures disclosed herein, but may also serve alternative or additional functions in the pretreatment mixture, pellets, and / or articles.

[0035] As used herein, the term "about" means that, with respect to a composition, a slight variation from the stated value can be used to achieve substantially the same result as the stated value, or with respect to a property, a slight variation from the stated value is acceptable (i.e., not deleterious) for the stated value relative to a given property. In cases where this definition is not applicable or extremely difficult to apply, the term "about" is then used to mean a 10% deviation (plus or minus) from the stated value. In any case, for any individual number or number within a range, it should be understood that a certain variation from the specified value can be accommodated without significant loss of benefit or significant detriment. In this regard, such a non-detrimental variation permitted for a given number or range is generally 10% or less of the stated number or range. Furthermore, the disclosure of ranges is intended to be a continuous range, including every value between the minimum and maximum values ​​recited, as well as any ranges that can be formed from those values. Also disclosed herein are any and all ratios (and ranges of any such ratios) that can be formed by dividing a recited value into any other recited value. Thus, those skilled in the art will appreciate that many such ratios, ranges, and ranges of ratios can be unambiguously derived from the numbers set forth herein, and in all cases, such ratios, ranges, and ranges of ratios represent various embodiments of the present invention.

[0036] As used herein, the term "sugar-free" means that the pre-processed mixture or product is substantially free of dietary sugars, such as glucose, sucrose, and fructose. As used herein, the term "low-sugar" refers to an edible composition, especially in a post-processed form, having less than 10% dietary sugars by weight, and preferably less than about 5% by weight. In some aspects, the products and pre-processed mixtures herein are sugar-free. In some aspects, the products, pellets, and pre-processed mixtures herein are low in sugar.

[0037] As used herein, unless otherwise specified, the percentage of a component in a product, pellet or pre-treatment mixture is a weight percentage. In addition, unless otherwise specified, all weight percentage values ​​are based on the gross weight of the relevant composition, pre-treatment mixture, pellet or product. For example, when disclosing that the pre-treatment mixture has 10 weight % plasticizer, 10 weight % is based on the gross weight (100 weight %) of the pre-treatment mixture including water and other components. In some aspects, the composition, pre-treatment mixture, pellet or product is only composed of dry matter, such as a powdered mixture, wherein weight % is measured on a dry weight basis. For example, if water is not listed as a component of the composition, and the sum of the weight % of the listed components is 100 weight %, then the relevant weight % value is based on the total dry weight % of the relevant composition. In addition, when disclosing that "product, pellet or pre-treatment mixture" "optionally" or "depending on the specific circumstances" has a certain amount of component, such terms mean that any one or all of the product, pellet or pre-treatment mixture can have a specified amount of given component.

[0038] As used herein, the term "edible" refers to an item that is safe to eat by a consumer, but may or may not be palatable or easily eaten.

[0039] As used herein, the term "biopolymer" means a polymer derived from a biological source (e.g., a plant, fungus, or animal), and includes polysaccharides derived from such sources. Particularly suitable biopolymer sources are seaweed, including brown, red, or green algae, as well as green-yellow or golden algae.

[0040] As used herein, the term "biodegradable" refers to an article that can be decomposed into harmless products by the action of organisms (e.g., microorganisms) under typical environmental conditions. In some aspects, an article is biodegradable if it can decompose into harmless products as mentioned above within a time range of about 3 to about 6 months.

[0041] As used herein, the term "chitin" is a long polymer of N-acetylglucosamine derived from biological sources, such as arthropods, such as the exoskeleton of crustaceans (such as crab shells) and insects, or the cell wall of fungi. Chitin can exist as a complex in natural sources, such as in the shell of crustaceans containing calcium carbonate. Pure chitin rather than compound chitin is currently preferred for use in the present disclosure. In some aspects, the viscosity average molecular weight (kDa) of chitin is 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950 or 1000. Each of the aforementioned numbers may be preceded by the words "about," "at least," "at least about," "less than," or "less than about," and any of the aforementioned numbers may be used alone to describe a single point or open-ended range, or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the viscosity-average molecular weight (kDa) of chitin may be 250, about 250, 200 to 300, about 300, 750, about 750, 500 to 800, or less than 350.

[0042] As used herein, the term "chitosan" is a deacetylated form of chitin, which typically has randomly distributed β-(1-4) linked D-glucosamine and N-acetyl-D-glucosamine. Chitin is typically deacetylated by treatment with an alkali (e.g., sodium hydroxide). Commercial chitosan can be characterized by the degree of deacetylation (DD%, typically in the range of 60 to 100%) and the viscosity average molecular weight (typically in the range of 3800 to 800,000 Daltons). In some aspects, chitosan with a viscosity average molecular weight in the range of 50,000 to 400,000 Daltons is used. In some aspects, "low molecular weight chitosan" or "low MW chitosan" is used and refers to chitosan with a viscosity average molecular weight of 50,000 to 190,000 Daltons. Ultra-low molecular weight chitosan (e.g., chitin with a molecular weight of 20,000 Daltons or less) is not preferred for use in the compositions and methods herein. In some aspects, chitosan having a DD% of 75% or higher is used. In some aspects, chitosan having a DD% of 75% to 85% is used.

[0043] As used herein, the term "compostable" refers to items that can be decomposed into harmless natural products under natural composting conditions. Thus, a material is referred to as compostable when it is biodegradable during the composting process, and preferably highly biodegradable by the action of naturally occurring microorganisms under naturally occurring composting conditions and within a specified timeframe. In some aspects, compostable materials degrade to at least about 60%, or at least about 80%, or at least about 90% under natural (home) composting conditions in less than one year, and in some aspects, in less than about 6 months.

[0044] In some aspects, materials are determined to be "biodegradable" and "compostable" according to the definitions provided in EN-13432. According to EN-13432, biodegradability is the ability of a material to be converted into CO2 by the action of microorganisms. This property can be measured using the laboratory standard test method EN-14046 (also published as ISO 14855: Biodegradability under controlled composting conditions). To demonstrate complete biodegradability, a biodegradation level of at least 90% is achieved in 6 months or less.

[0045] In some aspects, the pretreated mixtures, pellets, and / or articles described herein also exhibit high disintegration, i.e., fragmentation and loss of visibility (absence of visible contamination) in the final compost. Disintegration can be measured using a pilot scale composting test (EN 14045), in which a sample of the test material is composted with biowaste for 3 months and the final compost is screened with a 2 mm sieve. The mass of the test material residue greater than 2 mm in size should be less than 10% of the original mass of the test material.

[0046] As used herein, "continuous" refers to a process that is uninterrupted for a duration, or is interrupted, paused, or stopped only temporarily relative to the duration of the process. A hot melt extrusion process is "continuous" when the pretreatment mixture or pellets are fed into the hot melt extruder without interruption or substantially without interruption, or when such hot melt extrusion or pretreatment of the mixture or pellets is not carried out in a batch process.

[0047] As used herein, the term "carrageenan" refers to a linear sulfated polysaccharide typically derived from certain types of seaweed (e.g., Irish moss) by extraction. The polysaccharide comprises repeating galactose units. Carrageenan typically acts as a hydrocolloid in an aqueous environment. There are different classes of carrageenan and they are defined by their sulfate content. As used herein, the term "κ-carrageenan" refers to a carrageenan with one sulfate group per disaccharide, the term "ι-carrageenan" refers to a carrageenan with two sulfate groups per disaccharide, and the term "λ-carrageenan" refers to a carrageenan with three sulfate groups per disaccharide. Carrageenan may contain a mixture of polymers having an average of 1 to 3 sulfate groups per disaccharide, including the κ, ι and λ forms mentioned above, as well as forms having an average number of sulfate groups per disaccharide (e.g., between 1 and 2 or between 2 and 3, excluding 1 and 2 or 1 and 3). Preferred carrageenans for use herein have an average of 1 to 2 (inclusive) sulfate groups per disaccharide. Suitable carrageenans are mixtures of kappa-carrageenan and iota-carrageenan. More suitable carrageenans comprise kappa-carrageenan and less than 10% by weight of other carrageenans. The most suitable carrageenan is kappa-carrageenan.

[0048] As used herein, the terms "crosslinker," "cross-linker," or "crosslinking" have their broadest normal meaning, as readily used by those skilled in the art of polymer or biochemistry. They generally refer to the formation of a covalent bond or other bond (e.g., a hydrogen bond) between two molecules, typically between two oligomers, macromers, or polymers. In some aspects, the article, pretreatment mixture, or pellet comprises an organic crosslinker. In other aspects, the article, pretreatment mixture, or pellet comprises an organic acid crosslinker, such as tannic acid.

[0049] As used herein, the term "flow agent" or "anti-caking agent" refers to an anhydrous compound that prevents particles of a dry material from aggregating and "caking" together. In some aspects, the flow agent comprises functional properties suitable for promoting the flow of the pretreatment mixture during the injection molding process. In some aspects, the flow agent comprises a compound or mixture of compounds that is biocompatible with the pretreatment mixture, such as calcium stearate.

[0050] As used herein, the term "hydrocolloid" refers to a hydrophilic polymer that swells in an aqueous environment by absorbing water. Hydrocolloids affect the rheological properties of the composition, typically resulting in an increase in viscosity. Hydrocolloids are added to aqueous compositions to typically form a gelled network in which the polymer chains of the hydrocolloid interact directly with other polymer chains of the hydrocolloid and / or interact via water, ions, or a combination thereof. Hydrocolloids can be derived from a variety of sources, including plants, animals, or microorganisms, or chemically modified forms thereof. Hydrocolloids can also be prepared synthetically. Hydrocolloids derived from natural sources (e.g., animals or plants), whether chemically modified or not, are referred to herein as "hydrocolloid biopolymers."

[0051] As used herein, the term "pretreatment mixture" refers to a composition that has been molded, extruded, or otherwise formed into an article or pellet. After compounding, injection molding, subsequent drying, or a combination thereof, the amount of a component in the article may differ from the amount of a component in the pretreatment mixture due to leaching (e.g., leaching of the hydrophilic plasticizer during crosslinking and / or rinsing, thereby resulting in a reduction in the amount of hydrophilic plasticizer in the article relative to the pretreatment mixture) and / or drying (e.g., evaporation or other loss of water content, thereby resulting in a reduction in the amount of water in the article relative to the pretreatment mixture). Typically, the relative weight ratios of certain components in the article to other components in the article are the same as the weight ratios in the pretreatment mixture, such as the weight ratios of one or more hydrocolloids to the hydrophobic additive and other hydrophobic components (e.g., a hydrophobic plasticizer, such as tricaprylin, or a hydrophobic additive, such as carnauba wax, lignin powder, etc.), while the weight ratios of other components in the article (e.g., water and a hydrophilic plasticizer, such as glycerol) to other components are different between the pretreatment mixture and the article for the reasons described above. Typically, in aspects where the pretreatment mixture is formed (e.g., cold extruded) into an article that is subjected to a crosslinking bath and then rinsed and dried, the dried article has a water content that is about one-third the water content of the pretreatment mixture (e.g., 85 to 95 wt% compared to 28 to 35 wt%), and the crosslinked and rinsed article also has a hydrophilic plasticizer (e.g., glycerol) content that is about one-third the hydrophilic plasticizer content of the pretreatment mixture (e.g., about 25 to 36 wt% compared to about 8 to 12 wt%). Typically, in aspects where the pretreatment mixture is compounded (e.g., hot melt extruded) into pellets that are not subjected to a crosslinking bath, rinsed, or dried, such pellets have the same or substantially similar (e.g., within 10% of the value) composition and amounts thereof as the pretreatment mixture. Typically, in aspects where the pellets are formed (e.g., injection molded) into articles that are not subjected to a crosslinking bath nor rinsed and such articles are dried, the dried article typically has a moisture content that is the same as or up to about half that of the pellets (e.g., 35 to 50% water by weight in the pellets versus 25 to 35% water by weight in the dried article), and the other components of the article (e.g., hydrophilic plasticizer, hydrophobic plasticizer, filler, hydrophobic additive, etc.) are the same as those in the pellets.

[0052] As used herein, the term "hydrophobicity" relevant to plasticizers or additives means a compound with hydrophobic properties, which generally includes compounds comprising alkyl, ester or aryl groups, and generally has very few or no polar groups, such as compounds of hydroxyl or amino functional groups. For example, alkylated compounds, esterified compounds, waxes, oils, polymers containing alkyl, ester and / or aryl groups, and other similar compounds are hydrophobic. Hydrophobic plasticizers or additives include water-insoluble or only slightly water-soluble plasticizers or additives as understood in the art. Examples of hydrophobic plasticizers especially include citrates, phthalates, adipic acid esters and glycerides, including alkyl esters and fatty acid esters. Examples of hydrophobic additives especially include palmitic stearic acid, carnauba wax, zein and lignin.

[0053] As used herein, the term "hydrophilic" in relation to plasticizers or additives refers to compounds having hydrophilic properties, which generally include compounds containing polar groups, such as hydroxyl and / or amino functional groups. For example, compounds such as glycerol, sugar alcohols, and similar compounds are hydrophilic. Hydrophilic plasticizers or additives include water-soluble plasticizers or additives as understood in the art.

[0054] The terms "glycerol" and "glycerin" are used interchangeably herein and refer to the same compound.

[0055]

[0026] Herein, the term "composition" is used in some aspects to refer to the pretreatment mixture and in some aspects to refer to the article or pellets, as will be clear from the context.

[0056] When numerical values ​​(e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10) are disclosed herein, the following sentence generally follows such numerical values: "Each of the foregoing numbers may be preceded by the terms 'about,' 'at least,' 'at least about,' 'less than,' or 'less than about,' and any of the foregoing numbers may be used alone to describe a single point or open-ended range, or may be used in combination to describe multiple single points or closed ranges." This sentence means that each of the foregoing numbers can be used alone (e.g., 4), can be preceded by the word "about" (e.g., about 8), can be preceded by the phrase "at least about" (e.g., at least about 2), can be preceded by the phrase "at least" (e.g., at least 10), can be preceded by the phrase "less than" (e.g., less than 1), can be preceded by the phrase "less than about" (e.g., less than about 7), or can be used in combination with or without any prefixing words or phrases to define a range (e.g., 2 to 9, about 1 to 4, at least 3, 8 to about 9, 8 to less than 10, about 1 to about 10, etc.). Furthermore, when a range is described as "about X or less," this phrase is equivalent to the range of the combination of "about X" and "less than about X" in the alternative. For example, "about 10 or less" is equivalent to "about 10 or less than about 10." Such interchangeable range descriptions are contemplated herein. Other range formats may be disclosed herein, but differences in format should not be construed to imply that there are substantial differences.

[0057] In one aspect, the compositions or compounds disclosed herein, such as hydrocolloids or plasticizers, are isolated or substantially purified. In one aspect, the isolated or purified compounds are at least partially isolated or substantially purified as will be understood in the art. In one embodiment, the substantially purified compositions, compounds, or formulations of the invention have a chemical purity of 95%, optionally 99% for some applications, optionally 99.9% for some applications, optionally 99.99% for some applications, and optionally 99.999% for some applications. DETAILED DESCRIPTION

[0058] In the following description, numerous specific details of the devices, device components, and methods of the present invention are set forth in order to provide a thorough explanation of the precise nature of the present invention. However, it will be apparent to those skilled in the art that the present invention can be practiced without these specific details.

[0059] The present invention provides a flexible and biodegradable seaweed-based composition, wherein kappa-carrageenan, iota-carrageenan, and lambda-carrageenan are components of the composition. Currently available biodegradable injection molding formulations primarily contain thermoplastic starch or corn-derived PLA or PHA obtained from the cytoplasm of certain bacteria. While processable, they exhibit poor mechanical properties (low compressive strength, brittleness). Common techniques to address these shortcomings include adding plasticizers (glycerol, mannitol, and others) during the thermal treatment of the composition (injection molding process), reinforcing with cellulose fibers (MCC, Ethocell, etc.) and fillers (CaCO3, talc, BaSO4, Na2SO4, and others), adding polycations, and / or implementing reactive crosslinking.

[0060] Large-scale commercial injection molding processes and equipment. Such compositions can be tough, rigid, hard, and strong after the molding process. The compositions before injection can have good lubricity, elasticity, and can be smooth. Many plastic formulations are suitable for injection molding, and the flexible and biodegradable compositions herein can have properties similar to standard plastic compositions before injection and after the molding process.

[0061] Compared to extrusion processes, injection molding requires a high material flow index, especially for thin-walled products and large components. Extrusion has less stringent material flow requirements because plastic extrusion is open and does not present significant resistance to mold rotation. Therefore, extrusion is generally compatible with resins with low melt flow index (MFI), while injection molding generally requires a high MFI for geometrically demanding parts. Injection molding generally does not have strict requirements for exit swell. Extrusion exit swell can be difficult to manage. Therefore, the control of the viscoelastic properties of injection and extrusion materials differs.

[0062] Extruded products lack the complexity that can be obtained through injection molding, and this lack of complexity limits the number of use cases for extrusion compared to plastic injection molding.

[0063] It was unexpectedly discovered that the addition of polycations (e.g., poly-L-lysine) improved the properties of the resin formulation, making it compatible with injection molding using commercially available injection molding systems. Resin formulations without poly-L-lysine had a lower melt flow index (MFI) and the injection molded products produced were brittle. Surprisingly, adding polycations (in some cases, poly-L-lysine) to the resin increased the (MFI), giving the resin improved flow characteristics and general processability, which is required for the more demanding flow paths of injection molding compared to extrusion. The addition of poly-L-lysine increased the MFI of the resin from about 4 to 5 grams per 10 minutes to about 17 to 55 grams per 10 minutes. Surprisingly, the amount of polycation (in some cases, poly-L-lysine) added to the resin changed the rigidity of the product, with about 2 to 3% poly-L-lysine producing a more flexible product. As the amount of polycation increased by more than 3%, the flexibility of the product decreased. Resins with 1% polylysine have good MFI (suitable for injection molding) and produce products that are more flexible while maintaining their tensile strength compared to resins with 2 to 3% polylysine.

[0064] Without being bound by theory, the formulations described herein can utilize carrageenan as a polyanion to establish a robust network through electrostatic interactions with partially protonated chitosan (as a polycation). The introduction of short, positively charged poly-L-lysine chains can help create a loosely cross-linked, soft, and stretchable secondary network, which is also formed via electrostatic interactions. Polylysine (or other polycations) can also work via other mechanisms. During the formation of these networks, the initial network can retain the integrity of the material, thereby evenly distributing stress throughout the network. At the same time, the network induced by poly-L-lysine can act as a "sacrificial" network, promoting easier bond association and dissociation to dissipate energy. This unique combination can enhance the flexible characteristics of the resulting material.

[0065] These flexible formulations are preferably made from about 40 to 50 weight % hydrocolloid, about 10 to 25 weight % plasticizer, about 40 to 60 weight % water, about 1 to 5 weight % organic acid (e.g., tannic acid or citric acid) as a cross-linking agent, about 15 to 30 weight % filler (e.g., CaCO or NaSO), and other desired additives such as colorants and preservatives. The formulation may have 10 to 40 weight % hydrocolloid, 5 to 20 weight % plasticizer, 5 to 20 weight % filler, 1 to 10 weight % polycation, and 10 to 79 weight % water. The formulation may have 15 to 35 weight % hydrocolloid, 5 to 20 weight % plasticizer, 5 to 20 weight % filler, 1 to 10 weight % polycation, and 15 to 74 weight % water. The formulation can have 20 to 35 % by weight hydrocolloid, 10 to 20 % by weight plasticizer, 5 to 20 % by weight filler, 1 to 10 % by weight polycation and 15 to 64 % by weight water. The formulation can have 20 to 35 % by weight hydrocolloid, 5 to 20 % by weight plasticizer, 10 to 20 % by weight filler, 1 to 10 % by weight polycation and 15 to 64 % by weight water. The formulation can have 20 to 35 % by weight hydrocolloid, 10 to 20 % by weight plasticizer, 10 to 20 % by weight filler, 1 to 10 % by weight polycation and 15 to 59 % by weight water. In one aspect, the polycation of formulation can be polylysine (e.g., 0.1 % by weight, 0.5 % by weight, 1 % by weight, 2 % by weight, 3 % by weight, 4 % by weight or 5 % by weight).

[0066] Preferably, the blended composition is subsequently compounded using a twin-screw extruder with a co-rotating screw, and injection molding is performed using 50 to 150 tons of thermoplastic injection molding machines. In some respects, the plasticizer is a mixture of hydrophilic and hydrophobic plasticizers. In some respects, the plasticizer comprises 5 to 40 wt % hydrophilic plasticizers and 0.5 to 2 wt % hydrophobic plasticizers. In some respects, the filler accounts for 5 to 40 wt % of the pre-treated mixture. In some respects, the filler comprises an organic filler, an inorganic filler, a mineral salt filler or any hydrate thereof. In some respects, the filler comprises a metal hydroxide or its hydrate. In some respects, the filler comprises a carbonate (such as calcium carbonate). In some respects, the filler (or strength modifier) ​​comprises MCC and / or citrus fiber. In some respects, the filler is also used as a wetting agent.

[0067] In some aspects, the hydrocolloid is a mixture of carrageenan (particularly carrageenan comprising kappa carrageenan) and at least one of alginate, chitin, or chitosan. In some aspects, the hydrocolloid is a mixture of kappa carrageenan and at least one of alginate, chitin, or chitosan, and optionally further comprises at least one natural gum, such as guar gum, gum arabic, locust bean gum, konjac gum, or xanthan gum. In some aspects, the hydrocolloid contains 20 to 60% by weight kappa carrageenan and 1 to 30% by weight chitin. In some aspects, the hydrocolloid contains 30 to 50% by weight kappa carrageenan and 1 to 25% by weight chitosan. In some aspects, the hydrocolloid contains 10 to 20% by weight kappa carrageenan and a total of 1 to 10% by weight chitin and / or chitosan. In some aspects, the hydrocolloid contains konjac gum, for example, in an amount of 0 to 3 wt%, 0 to 5 wt%, or 0 to 10 wt%.

[0068] In one aspect, the soft formulation is made with 10-20 wt% carrageenan, 10-20 wt% chitosan, 5-20 wt% glycerol (hydrophilic plus hydrophobic), 5-20 wt% calcium carbonate, 1-10 wt% polylysine, and 10-69 wt% water. In one aspect, the soft formulation is made with 10-20 wt% carrageenan, 10-20 wt% chitosan, 5-20 wt% glycerol (hydrophilic plus hydrophobic), 5-20 wt% calcium carbonate, 1-5 wt% polylysine, and 15-69 wt% water. In one aspect, the soft formulation is made with 10-20 wt% carrageenan, 10-20 wt% chitosan, 5-20 wt% glycerol (hydrophilic plus hydrophobic), 5-20 wt% calcium carbonate, 1-2 wt% polylysine, and 18-69 wt% water.

[0069] A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, and 70 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, and 68 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, and 66 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, and 64 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, and 62 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, and 60 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, and 58 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, and 56 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, and 54 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, and 52 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, and 50 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, and 48 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, and 46 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, and 44 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, and 42 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, and 40 wt% water.

[0070] A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, and 68 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, and 66 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, and 64 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, and 62 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, and 60 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, and 58 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, and 56 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, and 54 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, and 52 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, and 50 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, and 48 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, and 46 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, and 44 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, and 42 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, and 40 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, and 38 wt% water.

[0071] A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, and 66 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, and 64 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, and 62 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, and 60 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, and 58 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, and 56 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, and 54 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, and 52 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, and 50 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, and 48 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, and 46 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, and 44 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, and 42 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, and 40 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, and 38 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, and 36 wt% water.

[0072] A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, and 64 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, and 62 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, and 60 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, and 58 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, and 56 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, and 54 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, and 52 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, and 50 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, and 48 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, and 46 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, and 44 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, and 42 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, and 40 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, and 38 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, and 36 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, and 34 wt% water.

[0073] A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, and 62 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, and 60 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, and 58 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, and 56 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, and 54 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, and 52 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, and 50 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, and 48 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, and 46 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, and 44 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, and 42 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, and 40 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, and 38 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, and 36 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, and 34 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, and 32 wt% water.

[0074] A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, and 60 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, and 58 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, and 56 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, and 54 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, and 52 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, and 50 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, and 48 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, and 46 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, and 44 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, and 42 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, and 40 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, and 38 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, and 36 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, and 34 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, and 32 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, and 30 wt% water.

[0075] A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, and 60 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, and 56 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, and 54 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, and 52 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, and 50 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, and 48 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, and 46 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, and 44 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, and 42 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, and 40 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, and 38 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, and 36 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, and 34 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, and 32 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, and 30 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, and 28 wt% water.

[0076] A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, and 56 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, and 54 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, and 52 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, and 50 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, and 48 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, and 46 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, and 44 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, and 42 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, and 40 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, and 38 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, and 36 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, and 34 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, and 32 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, and 30 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, and 28 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, and 26 wt% water.

[0077] A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, and 54 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, and 52 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, and 50 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, and 48 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, and 46 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, and 44 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, and 42 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, and 40 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, and 38 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, and 36 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, and 34 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, and 32 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, and 30 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, and 28 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, and 26 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, and 24 wt% water.

[0078] A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, and 52 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, and 50 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, and 48 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, and 46 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, and 44 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, and 42 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, and 40 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, and 38 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, and 36 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, and 34 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, and 32 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, and 30 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, and 28 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, and 26 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, and 24 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, and 22 wt% water.

[0079] A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, and 50 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, and 48 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, and 46 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, and 44 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, and 42 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, and 40 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, and 38 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, and 36 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, and 34 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, and 32 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, and 30 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, and 28 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, and 26 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, and 24 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, and 22 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, and 20 wt% water.

[0080] In one aspect, the aforementioned formulations of carrageenan, chitosan, glycerol, and calcium carbonate may further include polylysine (e.g., 0.1%, 1%, 2%, 3%, 4%, or 5% by weight) and / or alginate (e.g., 5 to 20%, or 5%, 10%, 15%, or 20% by weight).

[0081] A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 0.5 wt% polylysine, and 69.5 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 0.5 wt% polylysine, and 67.5 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 0.5 wt% polylysine, and 65.5 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 0.5 wt% polylysine, and 63.5 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 0.5 wt% polylysine, and 61.5 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 0.5 wt% polylysine, and 59.5 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 0.5 wt% polylysine, and 57.5 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 0.5 wt% polylysine, and 55.5 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 0.5 wt% polylysine, and 53.5 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 0.5 wt% polylysine, and 51.5 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 0.5 wt% polylysine, and 49.5 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 0.5 wt% polylysine, and 47.5 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 0.5 wt% polylysine, and 45.5 wt% water.A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 0.5 wt% polylysine, and 43.5 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 0.5 wt% polylysine, and 41.5 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 0.5 wt% polylysine, and 39.5 wt% water.

[0082] A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 0.5 wt% polylysine, and 67.5 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 0.5 wt% polylysine, and 65.5 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 0.5 wt% polylysine, and 63.5 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 0.5 wt% polylysine, and 61.5 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 0.5 wt% polylysine, and 59.5 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 0.5 wt% polylysine, and 57.5 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 0.5 wt% polylysine, and 55.5 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 0.5 wt% polylysine, and 53.5 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 0.5 wt% polylysine, and 51.5 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 0.5 wt% polylysine, and 49.5 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 0.5 wt% polylysine, and 47.5 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 0.5 wt% polylysine, and 45.5 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 0.5 wt% polylysine, and 43.5 wt% water.A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 0.5 wt% polylysine, and 41.5 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 0.5 wt% polylysine, and 39.5 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 0.5 wt% polylysine, and 37.5 wt% water.

[0083] A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 0.5 wt% polylysine, and 65.5 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 0.5 wt% polylysine, and 63.5 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 0.5 wt% polylysine, and 61.5 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 0.5 wt% polylysine, and 59.5 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 0.5 wt% polylysine, and 57.5 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 0.5 wt% polylysine, and 55.5 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 0.5 wt% polylysine, and 53.5 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 0.5 wt% polylysine, and 51.5 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 0.5 wt% polylysine, and 49.5 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 0.5 wt% polylysine, and 47.5 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 0.5 wt% polylysine, and 45.5 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 0.5 wt% polylysine, and 43.5 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 0.5 wt% polylysine, and 41.5 wt% water.A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 0.5 wt% polylysine, and 39.5 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 0.5 wt% polylysine, and 37.5 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 0.5 wt% polylysine, and 35.5 wt% water.

[0084] A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 0.5 wt% polylysine, and 63.5 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 0.5 wt% polylysine, and 61.5 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 0.5 wt% polylysine, and 59.5 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 0.5 wt% polylysine, and 57.5 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 0.5 wt% polylysine, and 55.5 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 0.5 wt% polylysine, and 53.5 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 0.5 wt% polylysine, and 51.5 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 0.5 wt% polylysine, and 49.5 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 0.5 wt% polylysine, and 47.5 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 0.5 wt% polylysine, and 45.5 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 0.5 wt% polylysine, and 43.5 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 0.5 wt% polylysine, and 41.5 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 0.5 wt% polylysine, and 39.5 wt% water.A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 0.5 wt% polylysine, and 37.5 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 0.5 wt% polylysine, and 35.5 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 0.5 wt% polylysine, and 33.5 wt% water.

[0085] A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 0.5 wt% polylysine, and 61.5 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 0.5 wt% polylysine, and 59.5 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 0.5 wt% polylysine, and 57.5 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 0.5 wt% polylysine, and 55.5 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 0.5 wt% polylysine, and 53.5 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 0.5 wt% polylysine, and 51.5 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 0.5 wt% polylysine, and 49.5 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 0.5 wt% polylysine, and 47.5 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 0.5 wt% polylysine, and 45.5 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 0.5 wt% polylysine, and 43.5 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 0.5 wt% polylysine, and 41.5 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 0.5 wt% polylysine, and 39.5 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 0.5 wt% polylysine, and 37.5 wt% water.A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 0.5 wt% polylysine, and 35.5 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 0.5 wt% polylysine, and 33.5 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 0.5 wt% polylysine, and 31.5 wt% water.

[0086] A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 0.5 wt% polylysine, and 59.5 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 0.5 wt% polylysine, and 57.5 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 0.5 wt% polylysine, and 55.5 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 0.5 wt% polylysine, and 53.5 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 0.5 wt% polylysine, and 51.5 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 0.5 wt% polylysine, and 49.5 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 0.5 wt% polylysine, and 47.5 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 0.5 wt% polylysine, and 45.5 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 0.5 wt% polylysine, and 43.5 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 0.5 wt% polylysine, and 41.5 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 0.5 wt% polylysine, and 39.5 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 0.5 wt% polylysine, and 37.5 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 0.5 wt% polylysine, and 35.5 wt% water.A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 0.5 wt% polylysine, and 33.5 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 0.5 wt% polylysine, and 31.5 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 0.5 wt% polylysine, and 29.5 wt% water.

[0087] A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 0.5 wt% polylysine, and 59.5 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 0.5 wt% polylysine, and 55.5 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 0.5 wt% polylysine, and 53.5 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 0.5 wt% polylysine, and 51.5 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 0.5 wt% polylysine, and 49.5 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 0.5 wt% polylysine, and 47.5 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 0.5 wt% polylysine, and 45.5 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 0.5 wt% polylysine, and 43.5 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 0.5 wt% polylysine, and 41.5 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 0.5 wt% polylysine, and 39.5 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 0.5 wt% polylysine, and 37.5 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 0.5 wt% polylysine, and 35.5 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 0.5 wt% polylysine, and 33.5 wt% water.A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 0.5 wt% polylysine, and 31.5 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 0.5 wt% polylysine, and 29.5 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 0.5 wt% polylysine, and 27.5 wt% water.

[0088] A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 0.5 wt% polylysine, and 55.5 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 0.5 wt% polylysine, and 53.5 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 0.5 wt% polylysine, and 51.5 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 0.5 wt% polylysine, and 49.5 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 0.5 wt% polylysine, and 47.5 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 0.5 wt% polylysine, and 45.5 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 0.5 wt% polylysine, and 43.5 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 0.5 wt% polylysine, and 41.5 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 0.5 wt% polylysine, and 39.5 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 0.5 wt% polylysine, and 37.5 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 0.5 wt% polylysine, and 35.5 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 0.5 wt% polylysine, and 33.5 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 0.5 wt% polylysine, and 31.5 wt% water.A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 0.5 wt% polylysine, and 29.5 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 0.5 wt% polylysine, and 27.5 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 0.5 wt% polylysine, and 25.5 wt% water.

[0089] A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 0.5 wt% polylysine, and 53.5 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 0.5 wt% polylysine, and 51.5 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 0.5 wt% polylysine, and 49.5 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 0.5 wt% polylysine, and 47.5 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 0.5 wt% polylysine, and 45.5 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 0.5 wt% polylysine, and 43.5 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 0.5 wt% polylysine, and 41.5 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 0.5 wt% polylysine, and 39.5 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 0.5 wt% polylysine, and 37.5 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 0.5 wt% polylysine, and 35.5 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 0.5 wt% polylysine, and 33.5 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 0.5 wt% polylysine, and 31.5 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 0.5 wt% polylysine, and 29.5 wt% water.A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 0.5 wt% polylysine, and 27.5 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 0.5 wt% polylysine, and 25.5 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 0.5 wt% polylysine, and 23.5 wt% water.

[0090] A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 0.5 wt% polylysine, and 51.5 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 0.5 wt% polylysine, and 49.5 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 0.5 wt% polylysine, and 47.5 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 0.5 wt% polylysine, and 45.5 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 0.5 wt% polylysine, and 43.5 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 0.5 wt% polylysine, and 41.5 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 0.5 wt% polylysine, and 39.5 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 0.5 wt% polylysine, and 37.5 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 0.5 wt% polylysine, and 35.5 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 0.5 wt% polylysine, and 33.5 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 0.5 wt% polylysine, and 31.5 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 0.5 wt% polylysine, and 29.5 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 0.5 wt% polylysine, and 27.5 wt% water.A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 0.5 wt% polylysine, and 25.5 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 0.5 wt% polylysine, and 23.5 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 0.5 wt% polylysine, and 21.5 wt% water.

[0091] A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 0.5 wt% polylysine, and 49.5 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 0.5 wt% polylysine, and 47.5 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 0.5 wt% polylysine, and 45.5 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 0.5 wt% polylysine, and 43.5 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 0.5 wt% polylysine, and 41.5 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 0.5 wt% polylysine, and 39.5 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 0.5 wt% polylysine, and 37.5 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 0.5 wt% polylysine, and 35.5 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 0.5 wt% polylysine, and 33.5 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 0.5 wt% polylysine, and 31.5 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 0.5 wt% polylysine, and 29.5 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 0.5 wt% polylysine, and 27.5 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 0.5 wt% polylysine, and 25.5 wt% water.A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 0.5 wt% polylysine, and 23.5 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 0.5 wt% polylysine, and 21.5 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 0.5 wt% polylysine, and 19.5 wt% water.

[0092] A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 1 wt% polylysine, and 69 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 1 wt% polylysine, and 67 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 1 wt% polylysine, and 65 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 1 wt% polylysine, and 63 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 1 wt% polylysine, and 61 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 1 wt% polylysine, and 59 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 1 wt% polylysine, and 57 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 1 wt% polylysine, and 55 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 1 wt% polylysine, and 53 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 1 wt% polylysine, and 51 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 1 wt% polylysine, and 49 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 1 wt% polylysine, and 47 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 1 wt% polylysine, and 45 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 1 wt% polylysine, and 43 wt% water.A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 1 wt% polylysine, and 41 wt% water. A soft formulation can be made with 10 wt% carrageenan, 10 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 1 wt% polylysine, and 39 wt% water.

[0093] A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 1 wt% polylysine, and 67 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 1 wt% polylysine, and 65 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 1 wt% polylysine, and 63 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 1 wt% polylysine, and 61 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 1 wt% polylysine, and 59 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 1 wt% polylysine, and 57 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 1 wt% polylysine, and 55 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 1 wt% polylysine, and 53 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 1 wt% polylysine, and 51 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 1 wt% polylysine, and 49 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 1 wt% polylysine, and 47 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 1 wt% polylysine, and 45 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 1 wt% polylysine, and 43 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 1 wt% polylysine, and 41 wt% water.A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 1 wt% polylysine, and 39 wt% water. A soft formulation can be made with 11 wt% carrageenan, 11 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 1 wt% polylysine, and 37 wt% water.

[0094] A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 1 wt% polylysine, and 65 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 1 wt% polylysine, and 63 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 1 wt% polylysine, and 61 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 1 wt% polylysine, and 59 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 1 wt% polylysine, and 57 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 1 wt% polylysine, and 55 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 1 wt% polylysine, and 53 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 1 wt% polylysine, and 51 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 1 wt% polylysine, and 49 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 1 wt% polylysine, and 47 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 1 wt% polylysine, and 45 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 1 wt% polylysine, and 43 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 1 wt% polylysine, and 41 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 1 wt% polylysine, and 39 wt% water.A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 1 wt% polylysine, and 37 wt% water. A soft formulation can be made with 12 wt% carrageenan, 12 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 1 wt% polylysine, and 35 wt% water.

[0095] A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 1 wt% polylysine, and 63 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 1 wt% polylysine, and 61 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 1 wt% polylysine, and 59 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 1 wt% polylysine, and 57 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 1 wt% polylysine, and 55 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 1 wt% polylysine, and 53 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 1 wt% polylysine, and 51 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 1 wt% polylysine, and 49 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 1 wt% polylysine, and 47 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 1 wt% polylysine, and 45 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 1 wt% polylysine, and 43 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 1 wt% polylysine, and 41 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 1 wt% polylysine, and 39 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 1 wt% polylysine, and 37 wt% water.A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 1 wt% polylysine, and 35 wt% water. A soft formulation can be made with 13 wt% carrageenan, 13 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 1 wt% polylysine, and 33 wt% water.

[0096] A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 1 wt% polylysine, and 61 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 1 wt% polylysine, and 59 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 1 wt% polylysine, and 57 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 1 wt% polylysine, and 55 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 1 wt% polylysine, and 53 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 1 wt% polylysine, and 51 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 1 wt% polylysine, and 49 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 1 wt% polylysine, and 47 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 1 wt% polylysine, and 45 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 1 wt% polylysine, and 43 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 1 wt% polylysine, and 41 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 1 wt% polylysine, and 39 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 1 wt% polylysine, and 37 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 1 wt% polylysine, and 35 wt% water.A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 1 wt% polylysine, and 33 wt% water. A soft formulation can be made with 14 wt% carrageenan, 14 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 1 wt% polylysine, and 31 wt% water.

[0097] A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 1 wt% polylysine, and 59 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 1 wt% polylysine, and 57 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 1 wt% polylysine, and 55 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 1 wt% polylysine, and 53 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 1 wt% polylysine, and 51 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 1 wt% polylysine, and 49 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 1 wt% polylysine, and 47 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 1 wt% polylysine, and 45 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 1 wt% polylysine, and 43 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 1 wt% polylysine, and 41 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 1 wt% polylysine, and 39 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 1 wt% polylysine, and 37 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 1 wt% polylysine, and 35 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 1 wt% polylysine, and 33 wt% water.A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 1 wt% polylysine, and 31 wt% water. A soft formulation can be made with 15 wt% carrageenan, 15 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 1 wt% polylysine, and 29 wt% water.

[0098] A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 1 wt% polylysine, and 59 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 1 wt% polylysine, and 55 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 1 wt% polylysine, and 53 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 1 wt% polylysine, and 51 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 1 wt% polylysine, and 49 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 1 wt% polylysine, and 47 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 1 wt% polylysine, and 45 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 1 wt% polylysine, and 43 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 1 wt% polylysine, and 41 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 1 wt% polylysine, and 39 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 1 wt% polylysine, and 37 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 1 wt% polylysine, and 35 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 1 wt% polylysine, and 33 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 1 wt% polylysine, and 31 wt% water.A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 1 wt% polylysine, and 29 wt% water. A soft formulation can be made with 16 wt% carrageenan, 16 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 1 wt% polylysine, and 27 wt% water.

[0099] A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 1 wt% polylysine, and 55 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 1 wt% polylysine, and 53 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 1 wt% polylysine, and 51 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 1 wt% polylysine, and 49 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 1 wt% polylysine, and 47 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 1 wt% polylysine, and 45 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 1 wt% polylysine, and 43 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 1 wt% polylysine, and 41 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 1 wt% polylysine, and 39 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 1 wt% polylysine, and 37 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 1 wt% polylysine, and 35 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 1 wt% polylysine, and 33 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 1 wt% polylysine, and 31 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 1 wt% polylysine, and 29 wt% water.A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 1 wt% polylysine, and 27 wt% water. A soft formulation can be made with 17 wt% carrageenan, 17 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 1 wt% polylysine, and 25 wt% water.

[0100] A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 1 wt% polylysine, and 53 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 1 wt% polylysine, and 51 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 1 wt% polylysine, and 49 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 1 wt% polylysine, and 47 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 1 wt% polylysine, and 45 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 1 wt% polylysine, and 43 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 1 wt% polylysine, and 41 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 1 wt% polylysine, and 39 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 1 wt% polylysine, and 37 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 1 wt% polylysine, and 35 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 1 wt% polylysine, and 33 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 1 wt% polylysine, and 31 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 1 wt% polylysine, and 29 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 1 wt% polylysine, and 27 wt% water.A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 1 wt% polylysine, and 25 wt% water. A soft formulation can be made with 18 wt% carrageenan, 18 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 1 wt% polylysine, and 23 wt% water.

[0101] A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 1 wt% polylysine, and 51 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 1 wt% polylysine, and 49 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 1 wt% polylysine, and 47 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 1 wt% polylysine, and 45 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 1 wt% polylysine, and 43 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 1 wt% polylysine, and 41 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 1 wt% polylysine, and 39 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 1 wt% polylysine, and 37 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 1 wt% polylysine, and 35 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 1 wt% polylysine, and 33 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 1 wt% polylysine, and 31 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 1 wt% polylysine, and 29 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 1 wt% polylysine, and 27 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 1 wt% polylysine, and 25 wt% water.A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 1 wt% polylysine, and 23 wt% water. A soft formulation can be made with 19 wt% carrageenan, 19 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 1 wt% polylysine, and 21 wt% water.

[0102] A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 5 wt% glycerol (hydrophilic plus hydrophobic), 5 wt% calcium carbonate, 1 wt% polylysine, and 49 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 6 wt% glycerol (hydrophilic plus hydrophobic), 6 wt% calcium carbonate, 1 wt% polylysine, and 47 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 7 wt% glycerol (hydrophilic plus hydrophobic), 7 wt% calcium carbonate, 1 wt% polylysine, and 45 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 8 wt% glycerol (hydrophilic plus hydrophobic), 8 wt% calcium carbonate, 1 wt% polylysine, and 43 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 9 wt% glycerol (hydrophilic plus hydrophobic), 9 wt% calcium carbonate, 1 wt% polylysine, and 41 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 10 wt% glycerol (hydrophilic plus hydrophobic), 10 wt% calcium carbonate, 1 wt% polylysine, and 39 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 11 wt% glycerol (hydrophilic plus hydrophobic), 11 wt% calcium carbonate, 1 wt% polylysine, and 37 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 12 wt% glycerol (hydrophilic plus hydrophobic), 12 wt% calcium carbonate, 1 wt% polylysine, and 35 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 13 wt% glycerol (hydrophilic plus hydrophobic), 13 wt% calcium carbonate, 1 wt% polylysine, and 33 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 14 wt% glycerol (hydrophilic plus hydrophobic), 14 wt% calcium carbonate, 1 wt% polylysine, and 31 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 15 wt% glycerol (hydrophilic plus hydrophobic), 15 wt% calcium carbonate, 1 wt% polylysine, and 29 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 16 wt% glycerol (hydrophilic plus hydrophobic), 16 wt% calcium carbonate, 1 wt% polylysine, and 27 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 17 wt% glycerol (hydrophilic plus hydrophobic), 17 wt% calcium carbonate, 1 wt% polylysine, and 25 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 18 wt% glycerol (hydrophilic plus hydrophobic), 18 wt% calcium carbonate, 1 wt% polylysine, and 23 wt% water.A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 19 wt% glycerol (hydrophilic plus hydrophobic), 19 wt% calcium carbonate, 1 wt% polylysine, and 21 wt% water. A soft formulation can be made with 20 wt% carrageenan, 20 wt% chitosan, 20 wt% glycerol (hydrophilic plus hydrophobic), 20 wt% calcium carbonate, 1 wt% polylysine, and 19 wt% water.

[0103] In some respects, goods, pellet or pre-treatment mixture comprise one or more coloring agents (sometimes referred to as developer in this article). Coloring agent can be added in pre-treatment mixture as optional composition, can be applied on goods as edible coating, or can be poured into goods or pellet. In some respects, coloring agent is derived from plant origin, and is present in goods, pellet or pre-treatment mixture with the amount of about 0.1 % by weight to about 10 % by weight or about 0.1 % by weight to about 0.3 % by weight. Representative coloring agent can be available from DDW Color House, Food Ingredient Solutions, GNT, Natural Flavors Inc., Sun Chemical, Fire Dots and Sensient Food Colors. Depending on selected coloring agent or reagent, goods (such as edible goods) can be translucent, opaque or transparent. In some aspects, the colorant is a pigment, such as cyan, red, blue, yellow, green, purple, or any other desired color, which can be in any form, such as an aqueous solution. In some aspects, the colorant is a photonic flake, such as titanium dioxide-coated mica, carbon black-coated mica, or self-assembled polymer flakes in a color range from purple to red, and is supplied in powdered form. In some aspects, the article, pellets, or pre-treatment mixture does not utilize any colorant. Colorants can be applied to provide a specific appearance, such as streaks, blocks of color, fading from one color to another, overall color change, tie-dye, marbleization, or any combination thereof.

[0104] In some aspects, the product, pellet, or pre-treated mixture comprises one or more preservatives (e.g., natural preservatives). In some aspects, the preservative comprises an antioxidant, such as tocopherol. In some aspects, the preservative comprises citric acid. In some aspects, the preservative comprises lemon juice, lemon powder, ascorbic acid, tartaric acid, malic acid, acid salt, or any combination thereof. In some aspects, any combination of preservatives may be used.

[0105] In some aspects, the article or pellet comprises a coating, e.g., to enhance water resistance, extend shelf life (e.g., as a preservative), or a combination thereof. In some aspects, the coating is edible. In some aspects, the coating improves the gas and water vapor barrier properties of the article. In some aspects, the coating reduces the stickiness of the article and / or pellet. In some aspects, the coating (or coating component) comprises a vegetable oil, including but not limited to coconut oil, palm oil, beechnut oil, castor oil, cottonseed oil, groundnut oil, hazelnut oil, olive oil, palm kernel oil, peanut oil, pericarp oil, blackcurrant seed oil, linseed oil, amaranth oil, apricot oil, grapeseed oil, rapeseed oil, rice bran oil, safflower oil, sesame oil, sunflower seed oil, star palm oil, soybean oil, almond oil, Brazil nut oil, cashew oil, macadamia oil, mongongo nut oil, pine nut oil, pistachio oil, walnut oil, or any combination thereof; short-chain or medium-chain or long-chain triglycerides, monoglycerides, diglycerides, or any combination thereof; a confectioner's glaze; an acetylated monoglyceride; a wax, such as beeswax, soy wax, rice bran wax, shellac; or any combination of any coating materials or coating components listed herein. In some aspects, the coating or coating component comprises a wax, such as beeswax, rice bran wax, carnauba wax, soy wax, shellac, or any combination thereof. In some aspects, the wax is an edible wax. In some aspects, the coating is applied to the article or pellet with the aid of a coating solution comprising a coating component (e.g., a coating component that is or comprises any of the coatings or coating materials described herein). For example, in some aspects, the coating solution comprises, in an amount (wt %) of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, or 35 of a coating component (e.g., an oil, an edible wax, a combination of edible waxes, or a combination of one or more oils and one or more edible waxes), based on the total weight of the coating solution. Each of the aforementioned numbers may be preceded by the words "about," "at least," "at least about," "less than," or "less than about," and any of the aforementioned numbers may be used alone to describe a single point or open-ended range, or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the coating solution comprises a coating component in an amount (wt %) of 0 to 15, 10 to 20, less than 18, 30, 25 to 35, 28 to 33, about 5, or 2 to 8. In some aspects, the coating solution comprises a coating component (e.g., an edible wax) dissolved in a 1:1, 1:2, 1:3, or 1:4 mixture of water:acetone. In some aspects, the coating (e.g., coating solution) is applied to the article after the article has been formed and dried or extruded and dried. In some aspects, the coating (e.g., coating solution) is applied to the article during the drying process.In some aspects, the coating (e.g., a coating solution) is applied by spraying, immersing, dipping, brushing, edible inkjet printing, coextrusion, or any combination thereof, or otherwise applied to the interior and / or exterior surface of the article. In some aspects, the article or pellet can be coated using any known coating agent (e.g., the coating agents / materials / components described herein) as known in the art to coat the article (e.g., a straw). In some aspects, the method comprises optionally applying a coating to the pellet by spraying, immersing, dipping, brushing, edible inkjet printing, coextrusion, or any combination thereof, wherein the coating comprises an oil coating, a wax coating, a confectionery glaze, or any combination thereof, or any other coating disclosed herein.

[0106] In some aspects, the coated article has any suitable contact angle when measured using a Rame-Hart Model 90CA version with DropImage software and using water as the liquid. For example, in some aspects, the static contact angle (°) is 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, or 115. Each of the foregoing numbers may be preceded by the words "about," "at least," "at least about," "less than," or "less than about," and any of the foregoing numbers may be used alone to describe a single point or open-ended range, or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the static contact angle is 95 to 115, 100, about 100, 98 to 105, 97 to 110, 100 to 115, 100 to 110, or 105 to 112. In some aspects, an article can have such a static contact angle when any suitable coating disclosed herein is present on the article, the coating including, for example, beeswax, a combination of beeswax and carnauba, carnauba, oil, confectioners' glaze, soy wax, the like, or any combination thereof.

[0107] In some aspects, the pellets and / or articles herein do not include a coating, such as a coating comprising rubber.

[0108] Aspects of the Invention

[0109] Various aspects are covered herein, several of which are described in the following paragraphs. It is expressly contemplated that any aspect or portion thereof may be combined to form a single aspect. Furthermore, it is expressly contemplated that any aspect (e.g., Aspect A13) that references an aspect (e.g., Aspect A1) for which there are sub-aspects (e.g., Aspects A1a, A1b, A1c, etc.) with the same top-level number necessarily includes reference to those sub-aspects A1a, A1b, A1c, etc. In other words, if Aspect A13 refers to Aspect A1, and Aspects A1a and A1b exist, then Aspect A13 refers to either Aspect A1a or A1b. Furthermore, although the following aspects are subdivided into Aspects A, B, C, D, etc., it is expressly contemplated that aspects of each of the subdivisions A, B, C, D, etc. may be combined in any manner. In addition, the term "any of the preceding aspects" means any aspect that comes before the aspect containing such a phrase (in other words, the sentence "Aspect B13: a method as in any of Aspects B1 to B12 or any of the preceding aspects" means any aspect that comes before Aspect B13, including Aspects B1 to B12 and all "A" aspects). For example, it is contemplated that any method or composition of any of the following aspects can optionally be used or combined with any other aspect provided below. Also, for example, it is contemplated that any embodiment described elsewhere herein (including above this paragraph) can optionally be combined with any of the aspects listed below. In some cases below or elsewhere herein, the disclosure that two open-ended ranges can be combined into one range. For example, the disclosure that "at least X" can be combined with "less than Y" to form a range, where X and Y are numerical values. For the purposes of forming ranges herein, it is expressly contemplated that "at least X" combined with "less than Y" forms a range of XY (including the value X and the value Y), even if "less than Y" in isolation does not include Y.

[0110] Aspect A1: An article, pellet or pre-treated mixture comprising:

[0111] at least one hydrocolloid,

[0112] at least one plasticizer,

[0113] at least one filler,

[0114] at least one polycation and / or cross-linking agent, and

[0115] At least one flow agent.

[0116] Aspect A2: The article, pellet or pretreatment mixture of Aspect A1, wherein said at least one hydrocolloid is derived from a biological source.

[0117] Aspect A3: The article, pellet or pre-treatment mixture of Aspect A1 or Aspect A2, wherein the at least one hydrocolloid comprises alginate, chitin, chitosan, carrageenan, pectin, gelatin, isomalt, konjac, lecithin, maltodextrin, methylcellulose, natural gum or any combination thereof.

[0118] Aspect A3a: The article, pellet or pretreatment mixture of any of Aspects A1 to A3, wherein the at least one hydrocolloid comprises at least one natural gum, such as guar gum, gum arabic, locust bean gum or xanthan gum.

[0119] Aspect A4: The article, pellet, or pretreatment mixture of any of Aspects A1 to A3a, wherein the at least one hydrocolloid comprises carrageenan.

[0120] Aspect A4a: The article, pellet, or pretreatment mixture of any of Aspects A1 to A4, wherein the at least one hydrocolloid comprises kappa-carrageenan, iota-carrageenan, lambda-carrageenan, or any combination thereof.

[0121] Aspect A5: The article, pellet, or pretreatment mixture of any of Aspects A1 to A4a, wherein the at least one hydrocolloid comprises kappa-carrageenan.

[0122] Aspect A6: The article, pellet, or pretreatment mixture of any of Aspects A1 to A5, wherein the at least one hydrocolloid comprises a combination of carrageenan and at least one of chitosan or chitin.

[0123] Aspect A7: The article, pellet or pre-treated mixture of Aspect A6 or any preceding aspect, wherein the chitosan and / or chitin is a low molecular weight crustacean chitosan and / or chitin.

[0124] Aspect A8: The article, pellet, or pretreatment mixture according to any one of Aspects A1 to A7, optionally comprising a total amount of 10% to 70% by weight (e.g., 10% to 70% by weight, 10% to 60% by weight, 10% to 50% by weight, 10% to 40% by weight, 10% to 30% by weight, 10% to 20% by weight, 20% to 70% by weight, 20% to 30% by weight, 20% to 40% by weight, 20% to 50% by weight, 20% to 50% by weight, 20% to 3 ...30% by weight, % to 40 wt %, 20 wt % to 30 wt %, 30 wt % to 70 wt %, 30 wt % to 60 wt %, 30 wt % to 50 wt %, 30 wt % to 40 wt %, 40 wt % to 70 wt %, 40 wt % to 60 wt %, 40 wt % to 50 wt %, 50 wt % to 70 wt %, or 50 wt % to 60 wt %.

[0125] Aspect A9: The article, pellet, or pretreatment mixture of any one of Aspects A1 to A8, wherein the at least one hydrocolloid comprises:

[0126] carrageenan in an amount between 20% and 60% by weight (e.g., between 20% and 60%, between 20% and 55%, between 20% and 50%, between 20% and 40%, between 20% and 30%, between 25% and 60%, between 25% and 55%, between 25% and 50%, between 25% and 40%, between 25% and 30%, between 30% and 60%, between 30% and 55%, between 30% and 50%, between 30% and 40%, between 40% and 60%, between 40% and 55%, between 40% and 50%, or between 50% and 60%), and

[0127] Chitin or chitosan or a mixture thereof in an amount of 1% to 30% by weight (e.g., 1% to 30% by weight, 1% to 25% by weight, 1% to 20% by weight, 1% to 16% by weight, 1% to 12% by weight, 1% to 8% by weight, 1% to 5% by weight, 1% to 4% by weight, 1% to 3% by weight, 2% to 30% by weight, 2% to 25% by weight, 2% to 20% by weight, 2% to 16% by weight, 2% to 12% by weight, 2% to 8% by weight, 2% to 5% by weight, 2% to 4% by weight, 3% to 5% by weight % to 30 wt%, 3 wt% to 25 wt%, 3 wt% to 20 wt%, 3 wt% to 16 wt%, 3 wt% to 12 wt%, 3 wt% to 8 wt%, 3 wt% to 5 wt%, 3 wt% to 4 wt%, 4 wt% to 30 wt%, 4 wt% to 25 wt%, 4 wt% to 20 wt%, 4 wt% to 16 wt%, 4 wt% to 12 wt%, 4 wt% to 8 wt%, 5 wt% to 30 wt%, 5 wt% to 25 wt%, 5 wt% to 20 wt%, 5 wt% to 16 wt%, 5 wt% to 15 wt%, 5 wt% to 12 wt%, 5% to 10% by weight, 5% to 8% by weight, 6% to 30% by weight, 6% to 25% by weight, 6% to 20% by weight, 6% to 16% by weight, 6% to 12% by weight, 6% to 8% by weight, 7% to 30% by weight, 7% to 25% by weight, 7% to 20% by weight, 7% to 16% by weight, 7% to 14% by weight, 7% to 12% by weight, 7% to 8% by weight; 8% to 30% by weight, 8% to 25% by weight, 8% to 20% by weight, 8% to 16% by weight, 8% to 12% by weight % to 30 wt %, 9 wt % to 25 wt %, 9 wt % to 20 wt %, 9 wt % to 18 wt %, 9 wt % to 16 wt %, 9 wt % to 12 wt %, 9 wt % to 10 wt %, 10 wt % to 30 wt %, 10 wt % to 25 wt %, 10 wt % to 20 wt %, 10 wt % to 18 wt %, 10 wt % to 16 wt %, 10 wt % to 15 wt %, 10 wt % to 14 wt %, 10 wt % to 13 wt %, 10 wt % to 12 wt %, or 10 wt % to 11 wt %,

[0128] This is based on the total weight of the article, pellets or pre-treated mixture as appropriate.

[0129] Aspect A10: The article, pellet, or pretreatment mixture of any one of Aspects A1 to A9, wherein the at least one hydrocolloid comprises:

[0130] a. carrageenan in an amount of 30% to 50% by weight (e.g., 30% to 50% by weight, 30% to 40% by weight, 35% to 50% by weight, 35% to 40% by weight, 40% to 60% by weight, 40% to 55% by weight, 40% to 50% by weight, or 45% to 50% by weight), and

[0131] b. chitin or chitosan or a mixture thereof, optionally in an amount of 1% to 25% by weight (e.g., 1% to 25%, 1% to 20%, 1% to 16%, 1% to 12%, 1% to 10%, 1% to 8%, 1% to 5%, 1% to 4%, 1% to 3%, 2% to 25%, 2% to 20%, 2% to 16%, 2% to 12%, 2% to 20%, 2% to 10%, 2% to 25%, 2% to 20%, 2% to 16%, 2% to 12%, 2% to 20%, 2% to 10%, 2% to 25%, 2% to 20%, 2% to 16%, 2% to 12%, 2% to 20%, 2% to 10%, 2% to 25%, 2% to 20%, 2% to 16%, 2% to 12%, 2% to 10 ...0%, 2% to 10%, 2% to 20%, 2% to 10%, 2% to 20%, 2% to 10%, 2% to 10%, 2% to 20%, 2% to 10%, 2% to 10%, 2% to 10%, 2% to 10%, 2% to 10%, 2% to 10%, 2% to 10%, 2% to 10%, 2% to 10%, 2% to 10%, 2% to 10%, % to 8 wt%, 2 wt% to 5 wt%, 2 wt% to 4 wt%, 3 wt% to 25 wt%, 3 wt% to 20 wt%, 3 wt% to 16 wt%, 3 wt% to 12 wt%, 3 wt% to 8 wt%, 3 wt% to 5 wt%, 3 wt% to 4 wt%, 4 wt% to 25 wt%, 4 wt% to 20 wt%, 4 wt% to 16 wt%, 4 wt% to 12 wt%, 4 wt% to 8 wt%, 5 wt% to 25 wt%, 5 wt% to 20 wt%, 5 wt% to 16 wt%, 5 wt% to 15 wt %, 5 wt % to 12 wt %, 5 wt % to 10 wt %, 5 wt % to 8 wt %, 6 wt % to 25 wt %, 6 wt % to 20 wt %, 6 wt % to 16 wt %, 6 wt % to 12 wt %, 6 wt % to 8 wt %, 7 wt % to 25 wt %, 7 wt % to 20 wt %, 7 wt % to 16 wt %, 7 wt % to 14 wt %, 7 wt % to 12 wt %, 7 wt % to 8 wt %; 8 wt % to 25 wt %, 8 wt % to 20 wt %, 8 wt % to 16 wt %, 8 wt % to 12 wt %, % to 12 wt %, 8 wt % to 10 wt %, 9 wt % to 25 wt %, 9 wt % to 20 wt %, 9 wt % to 18 wt %, 9 wt % to 16 wt %, 9 wt % to 12 wt %, 9 wt % to 10 wt %, 10 wt % to 25 wt %, 10 wt % to 20 wt %, 10 wt % to 18 wt %, 10 wt % to 16 wt %, 10 wt % to 15 wt %, 10 wt % to 14 wt %, 10 wt % to 13 wt %, 10 wt % to 12 wt %, or 10 wt % to 11 wt %.

[0132] Aspect A11: The article, pellet or pre-treated mixture of any one of Aspects A1 to A10, wherein the at least one plasticizer comprises a sugar alcohol (e.g., glycerol, mannitol, sorbitol), microcrystalline cellulose, gum arabic, genepin, nanoemulsion, algal oil, coconut oil, processed shea butter, ester gum, palmitic stearic acid, thermoplastic cellulose ether, zein, citrate esters, phthalate esters, adipate esters, fatty acids or any alkylated or esterified forms thereof, or any combination thereof.

[0133] Aspect A12: The article, pellet, or pretreatment mixture of any of Aspects A1 to A11, wherein the at least one plasticizer comprises a combination of: a hydrophilic plasticizer and a hydrophobic plasticizer.

[0134] Aspect A13: The article, pellet, or pretreatment mixture according to any of Aspects A1 to A12, optionally comprising a plasticizer in a total amount of 1 wt.% to 40 wt.%, based on the total weight of the article, pellet, or pretreatment mixture.For example, the article, pellet, or pretreatment mixture may optionally comprise a total amount of 1% to 40% by weight, 1% to 30% by weight, 1% to 25% by weight, 1% to 20% by weight, 1% to 16% by weight, 1% to 12% by weight, 1% to 8% by weight, 1% to 5% by weight, 1% to 4% by weight, 1% to 3% by weight, 2% to 40% by weight, 2% to 30% by weight, 2% to 25% by weight, 2% to 20% by weight, 2% to 16% by weight, 2% to 12% by weight, 2% to 8% by weight, 2% to 5% by weight, 2% to 4 wt%, 3 wt% to 40 wt%, 3 wt% to 30 wt%, 3 wt% to 25 wt%, 3 wt% to 20 wt%, 3 wt% to 16 wt%, 3 wt% to 12 wt%, 3 wt% to 8 wt%, 3 wt% to 5 wt%, 3 wt% to 4 wt%, 4 wt% to 40 wt%, 4 wt% to 30 wt%, 4 wt% to 25 wt%, 4 wt% to 20 wt%, 4 wt% to 16 wt%, 4 wt% to 12 wt%, 4 wt% to 8 wt%, 5 wt% to 40 wt%, 5 wt% to 30 wt%, 5 wt% to 25 wt%, 5 wt% to 20 wt%, 5 wt% to 16 wt%, 5 wt% to 15 wt%, 5 wt% to % to 12 wt%, 5 wt% to 10 wt%, 5 wt% to 8 wt%, 6 wt% to 40 wt%, 6 wt% to 30 wt%, 6 wt% to 25 wt%, 6 wt% to 20 wt%, 6 wt% to 16 wt%, 6 wt% to 12 wt%, 6 wt% to 8 wt%, 7 wt% to 40 wt%, 7 wt% to 30 wt%, 7 wt% to 25 wt%, 7 wt% to 20 wt%, 7 wt% to 16 wt%, 7 wt% to 14 wt%, 7 wt% to 12 wt%, 7 wt% to 8 wt%, 8 wt% to 40 wt%, 8 wt% to 30 wt%, 8 wt% to 25 wt%, 8 wt% to 20 wt%, 8 wt% to 16 wt% %, 8 wt % to 12 wt %, 8 wt % to 10 wt %, 9 wt % to 40 wt %, 9 wt % to 30 wt %, 9 wt % to 25 wt %, 9 wt % to 20 wt %, 9 wt % to 18 wt %, 9 wt % to 16 wt %, 9 wt % to 12 wt %, 9 wt % to 10 wt %, 10 wt % to 40 wt %, 10 wt % to 30 wt %, 10 wt % to 25 wt %, 10 wt % to 20 wt %, 10 wt % to 18 wt %, 10 wt % to 16 wt %, 10 wt % to 15 wt %, 10 wt % to 14 wt %, 10 wt % to 13 wt %, 10 wt % to 12 wt %, or 10 wt % to 11 wt % of a plasticizer.

[0135] Aspect A14: The article, pellet, or pretreated mixture of any one of Aspects A1 to A13, wherein the at least one filler comprises starch, microcrystalline cellulose (MCC), guar gum, carboxymethyl cellulose, citrus fiber, a mineral salt, calcium carbonate or a hydrate thereof, sodium sulfate or a hydrate thereof, barium sulfate or a hydrate thereof, talc, a salt or a compound that is a hydroxide, sulfate, chloride, carbonate, oxide, aluminate, silicate, acetate, silicon dioxide, pentasodium triphosphate, sepiolite, silica, zeolite, or any hydrate thereof, or any combination thereof.

[0136] Aspect A15: The article, pellet or pretreatment mixture according to any of Aspects A1 to A14, optionally comprising a filler in a total amount of 5% to 40% by weight, based on the total weight of the article, pellet or pretreatment mixture. For example, the article, pellet, or pretreatment mixture may optionally comprise a total amount of 5% to 40% by weight, 5% to 30% by weight, 5% to 25% by weight, 5% to 20% by weight, 5% to 16% by weight, 5% to 15% by weight, 5% to 12% by weight, 5% to 10% by weight, 5% to 8% by weight, 6% to 40% by weight, 6% to 30% by weight, 6% to 25% by weight, 6% to 20% by weight, 6% to 16% by weight, 6% to 12% by weight, 6% to 8% by weight, 7% to 40% by weight, 7% to 30% by weight, 7% to 25% by weight, 7% to 20% by weight, 7% to 16% by weight, 7% to 14% by weight, 7% to 12% by weight, 7% to 8% by weight, 8 wt %, 8 wt % to 40 wt %, 8 wt % to 30 wt %, 8 wt % to 25 wt %, 8 wt % to 20 wt %, 8 wt % to 16 wt %, 8 wt % to 12 wt %, 8 wt % to 10 wt %, 9 wt % to 40 wt %, 9 wt % to 30 wt %, 9 wt % to 25 wt %, 9 wt % to 20 wt %, 9 wt % to 18 wt %, 9 wt % to 16 wt %, 9 wt % to % to 12 wt%, 9 wt% to 10 wt%, 10 wt% to 40 wt%, 10 wt% to 30 wt%, 10 wt% to 25 wt%, 10 wt% to 20 wt%, 10 wt% to 18 wt%, 10 wt% to 16 wt%, 10 wt% to 15 wt%, 10 wt% to 14 wt%, 10 wt% to 13 wt%, 10 wt% to 12 wt%, or 10 wt% to 11 wt% of filler.

[0137] Aspect A16: The article, pellet or pretreatment mixture according to any of Aspects A1 to A15, wherein said at least one polycation and / or cross-linking agent comprises an organic acid.

[0138] Aspect A17: The article, pellet or pretreatment mixture according to any of Aspects A1 to A16, wherein the at least one polycation and / or cross-linking agent comprises carboxylic acid, malic acid, succinic acid, adipic acid, citric acid, tannic acid, caffeic acid, catechin, ferulic acid or a combination thereof.

[0139] Aspect A18: The article, pellet or pretreatment mixture of any of Aspects A1 to A17, optionally comprising a polycation and / or cross-linking agent in a total amount of 0.5% to 10% by weight, based on the total weight of the article, pellet or pretreatment mixture. For example, the article, pellet or pretreatment mixture may optionally comprise a total amount of 0.5% to 10% by weight, 0.5% to 8% by weight, 0.5% to 5% by weight, 0.5% to 4% by weight, 0.5% to 3% by weight, 0.5% to 2% by weight, 0.5% to 1% by weight, 1% to 10% by weight, 1% to 8% by weight, 1% to 5% by weight, based on the total weight of the article, pellet or pretreatment mixture. % to 8 wt %, 2 wt % to 5 wt %, 2 wt % to 4 wt %, 2 wt % to 3 wt %, 3 wt % to 10 wt %, 3 wt % to 8 wt %, 3 wt % to 5 wt %, 3 wt % to 4 wt %, 4 wt % to 10 wt %, 4 wt % to 8 wt %, or 4 wt % to 5 wt % of the polycation and / or cross-linking agent.

[0140] Aspect A19: The article, pellet, or pretreatment mixture according to any of Aspects A1 to A18, wherein the at least one flow agent comprises calcium stearate, zinc stearate, or a combination thereof.

[0141] Aspect A20: The article, pellet, or pretreatment mixture according to any of Aspects A1 to A19, optionally comprising a flow agent in a total amount of 0.5% to 5% by weight (e.g., 0.5% to 5%, 0.5% to 4%, 0.5% to 3%, 0.5% to 2%, 0.5% to 1%, 1% to 5%, 1% to 4%, 1% to 3%, 1% to 2%, or 2% to 5% by weight), based on the total weight of the article, pellet, or pretreatment mixture.

[0142] Aspect A21 : The article, pellet or pretreatment mixture of any of Aspects A1 to A20, further comprising a colorant.

[0143] Aspect A22: The preparation, pellet or pre-treatment mixture according to any of Aspects A1 to A21, further comprising a preservative.

[0144] Aspect A23: The pretreated mixture of any of Aspects A1 to A22, comprising a water content of 30% to 70% by weight (e.g., 30% to 70% by weight, 30% to 60% by weight, 30% to 50% by weight, 30% to 40% by weight, 40% to 70% by weight, 40% to 60% by weight, 40% to 50% by weight, 50% to 70% by weight, 50% to 60% by weight, or 60% to 70% by weight).

[0145] Aspect A24: The article, pellet, or pretreated mixture according to any of Aspects A1 to A23, exhibiting a pressure of at least 10 MPa (e.g., at least any of 10 MPa, 12 MPa, 15 MPa, 20 MPa, 25 MPa, or 30 MPa, optionally at least any of 35 MPa, 40 MPa, 45 MPa, 50 MPa, 55 MPa, 60 MPa, 65 MPa, 70 MPa, 75 MPa, 80 MPa, 85 MPa, or 90 MPa). 0 MPa, optionally, at least any of the following: 100 MPa, 150 MPa, 200 MPa, 250 MPa, 300 MPa, 350 MPa, 400 MPa, 450 MPa or 500 MPa, optionally, less than any of the following: 1000 MPa, 950 MPa, 900 MPa, 850 MPa, 800 MPa, 750 MPa, 700 MPa, 650 MPa, 600 MPa or 550 MPa) of tensile strength.

[0146] Aspect A25: The article, pellet, or pretreatment mixture of any of Aspects A1 to A24, exhibiting a Young's modulus of at least 2000 MPa. For example, the article, pellet, or pretreated mixture may exhibit a strength of 2000 MPa to 2200 MPa, 2000 MPa to 2400 MPa, 2000 MPa to 2600 MPa, 2000 MPa to 2800 MPa, 2000 MPa to 3000 MPa, 2000 MPa to 3200 MPa, 2000 MPa to 3400 MPa, 2000 MPa to 3600 MPa, 2000 MPa to 3800 MPa, 2000 MPa to 4000 MPa, 2400 MPa to 2600 MPa, 2400 MPa to 2800 MPa, 2400 MPa to 3000 MPa, 2400 MPa to 3200 MPa, 2400 MPa to 3400 MPa, 2400 MPa to 3600 MPa, MPa, and optionally a Young's modulus of less than any of 10,000 MPa, 9,500 MPa, 9,000 MPa, 8,500 MPa, or 8,000 MPa.

[0147] Aspect A26: The article, pellet, or pretreatment mixture of any of Aspects A1 to A25, optionally comprising carrageenan in an amount of 40% to 60% by weight (e.g., 30% to 60% by weight, 30% to 55% by weight, 30% to 50% by weight, 30% to 40% by weight, 40% to 60% by weight, 40% to 55% by weight, 40% to 50% by weight, or 50% to 60% by weight), based on the total weight of the article, pellet, or pretreatment mixture; % by weight (e.g., 1% to 10%, 1% to 8%, 1% to 5%, 1% to 4%, 1% to 3%, 2% to 10%, 2% to 8%, 2% to 5%, 2% to 4%, 2% to 3%, 3% to 10%, 3% to 8%, 3% to 5%, 3% to 4%, 4% to 10%, 4% to 8% or 4% to 5%) of chitin or chitosan or mixtures thereof; at least one plasticizer in an amount of 10% to 35% by weight (e.g., 10% to 35% by weight, 15% to 35% by weight, 20% to 35% by weight, 25% to 35% by weight, or 30% to 35% by weight); at least one filler in an amount of 15% to 30% by weight (e.g., 15% to 30% by weight, 20% to 30% by weight, or 25% to 30% by weight); at least one filler in an amount of 1% to 5% by weight (e.g., 1% to 5% by weight, 1% to 4% by weight); %, 1 wt % to 3 wt %, 1 wt % to 2 wt %, 2 wt % to 5 wt %, 2 wt % to 4 wt % of a polycation and / or a cross-linking agent; and at least one flow agent in an amount of 0.5 wt % to 5 wt % (e.g., 0.5 wt % to 5 wt %, 0.5 wt % to 4 wt %, 0.5 wt % to 3 wt %, 0.5 wt % to 2 wt %, 0.5 wt % to 1 wt %, 1 wt % to 5 wt %, 1 wt % to 4 wt %, 1 wt % to 3 wt %, 1 wt % to 2 wt %, or 2 wt % to 5 wt %).

[0148] Aspect A26a: The article, pellet, or pretreatment mixture of Aspect A26 or any one of the preceding aspects, wherein the carrageenan comprises kappa-carrageenan.

[0149] Aspect A26b: The article, pellet or pre-treated mixture of Aspect A26 or Aspect A26a or any of the preceding aspects, wherein the chitin and / or chitosan is a low molecular weight crustacean chitosan and / or chitin.

[0150] Aspect A27: The article, pellet or pretreatment mixture of any of Aspects A1 to A26b, wherein the at least one plasticizer comprises glycerol.

[0151] Aspect A28: The article, pellet or pretreatment mixture of any one of Aspects A1 to A27, wherein the at least one plasticizer comprises a mixture of glycerol and esterified or alkylated glycerol, wherein the esterified or alkylated glycerol has 4 to 15 carbon atoms in the ester or alkyl group (e.g., 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 carbon atoms in the ester or alkyl group).

[0152] Aspect A29: The article, pellet or pretreatment mixture according to any one of Aspects A1 to A28, wherein the at least one filler comprises calcium carbonate or a hydrate thereof, or sodium sulfate or a hydrate thereof.

[0153] Aspect A30: The article, pellet or pretreatment mixture according to any of Aspects A1 to A29, wherein said at least one polycation and / or cross-linking agent comprises polylysine, tannic acid or citric acid.

[0154] Aspect A31 : The preparation, pellet or pretreatment mixture according to any of Aspects A1 to A30, wherein the at least one flow agent comprises calcium stearate.

[0155] Aspect A32: The pretreated mixture of any of Aspects A1 to A31, comprising a water content of 40% to 60% by weight (e.g., 40% to 60% by weight, 45% to 60% by weight, 50% to 60% by weight, 55% to 60% by weight, 40% to 50% by weight, or 40% to 55% by weight).

[0156] Aspect B1: A method for preparing a biodegradable article, the method comprising:

[0157] combining (i) at least one hydrocolloid, (ii) at least one plasticizer, (iii) at least one filler, (iv) at least one polycation and / or cross-linking agent, and (v) at least one flow agent to prepare a pretreatment mixture; and

[0158] optionally blending the pretreatment mixture;

[0159] optionally compounding the pretreated mixture into pellets;

[0160] forming the pretreated mixture or pellets into shapes; and

[0161] drying the shape to form the article,

[0162] The at least one hydrocolloid, the at least one plasticizer, the at least one filler, the at least one polycation and / or cross-linking agent and the at least one flow agent are as defined in any one of the above technical solutions.

[0163] Aspect B2: The method of Aspect B1 or any of the preceding aspects, wherein the compounding is performed and comprises extrusion.

[0164] Aspect B3: The method of aspect B2 or any of the preceding aspects, wherein the extruding comprises a twin-screw extruder having co-rotating screws.

[0165] Aspect B4: The method of aspect B2 or B3 or any of the preceding aspects, wherein the extrusion is a continuous hot melt extrusion process.

[0166] Aspect B5: The method of any one of aspects Bl to B4 or any of the preceding aspects, wherein the pretreatment mixture is compounded into pellets and the pellets are formed into the shape.

[0167] Aspect B6: The method of Aspect B5 or any of the preceding aspects, wherein the pellets are characterized by a diameter in the range of 2 to 10 mm.

[0168] Aspect B7: The method of aspect B5 or B6 or any of the preceding aspects, wherein the pellets are characterized by a thickness in the range of 2 to 10 mm.

[0169] Aspect B8: The method of any one of aspects Bl to B7 or any of the preceding aspects, wherein the forming comprises injection molding.

[0170] Aspect B9: The method of any of aspects Bl to B8 or any of the preceding aspects, wherein the forming comprises thermoplastic injection molding.

[0171] Aspect B10: The method of aspect B8 or B9 or any of the preceding aspects, wherein the injection molding comprises a 50 to 150 ton injection molding machine.

[0172] Aspect B11: The method of any of aspects B1 to B10 or any of the preceding aspects, further comprising a post-processing step after forming the pre-treated mixture or pellets into a shape.

[0173] Aspect B12: A method as described in Aspect B11 or any of the preceding aspects, wherein the post-treatment step comprises annealing the shape at a temperature in the range of 50 to 150°C for a period of 1 to 12 hours (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 hours).

[0174] Aspect B13: A method as described in any of Aspects B1 to B12 or any of the preceding aspects, wherein drying the shape to form the article comprises exposing the shape to environmental conditions for a period of 24 to 48 hours (e.g., 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47 or 48 hours).

[0175] Aspect B14: A method as described in Aspect B13 or any of the preceding aspects, wherein the environmental conditions comprise an ambient temperature in the range of 15 to 25°C (e.g., 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25°C) and an ambient relative humidity in the range of 30 to 50% (e.g., 30 to 50%, 35 to 50%, 40 to 50% or 45 to 50%).

[0176] Aspect B15: The method of any one of aspects Bl to B14 or any of the preceding aspects, wherein said blending is performed and comprises using a ribbon blender.

[0177] Aspect B16: The method of any one of aspects B1 to B15 or any of the preceding aspects, wherein the combining step further comprises a colorant.

[0178] Aspect B17: The method of any one of aspects B1 to B16 or any of the preceding aspects, wherein the combining step further comprises a preservative.

[0179] Figure 1 Describe the flow chart of the exemplary method for forming an exemplary composition for injection molding of the present disclosure. The exemplary flow chart provides a method for producing an article with desired mechanical and thermal properties by injection molding. In certain embodiments, all ingredients (components) including at least one hydrocolloid, at least one filler, at least one plasticizer, at least one polycation and / or cross-linking agent, at least one flow agent and any optional colorant or preservative or other additive are combined to form a pre-treated mixture. In an embodiment, all components are in a non-liquid state (i.e., dry ingredients), such as powder form or crystalline form. In other embodiments, one or more components of the composition are in liquid form. In certain embodiments, the components of the composition are combined to form a pre-treated mixture using a ribbon blender or similar mixing device.

[0180] like Figure 1As shown in FIG, in some embodiments, a pretreatment mixture is mixed. In some aspects, the pretreatment mixture comprises both a liquid component and a solid component. In aspects where the pretreatment mixture consists only of dry ingredients, water is introduced to facilitate mixing the pretreatment mixture into pellets. In some aspects, the dry pretreatment mixture is mixed with various amounts of water, such as 30, 40, 50, 60, or 70% by weight. As shown in the flow chart, in some aspects, mixing is carried out by a twin-screw extruder. In other aspects, mixing is carried out by a single-screw extruder. In aspects, the extruder can be a continuous hot melt extruder. After mixing, in some aspects, the pretreatment mixture is mixed into filaments. In aspects, the filaments are cut into pellets. In aspects, the pellets are characterized by a diameter within the range of 2 mm to 10 mm. In some aspects, the pellets are characterized by a thickness within the range of 2 mm to 10 mm.

[0181] Further in Figure 1 , pellets are introduced into an injection molding machine. In aspects of the invention, the injection molding machine is a 50 to 150 ton injection molding machine. In some aspects, the injection molding machine is a thermoplastic injection molding machine. In some aspects, injection molding results in the formation of an article. In aspects of the invention, the shape of the article is determined by a custom mold. In embodiments, the custom mold comprises pre-hardened steel, aluminum, beryllium copper alloy, or any combination thereof. In embodiments, the custom mold comprises a mold for disposable food service industry products, such as utensils and take-out containers.

[0182] Figure 1 1 illustrates an aspect in which the resulting article is subjected to testing for mechanical and thermal properties. In some aspects, the mechanical and thermal properties include biodegradability, flexibility, tensile strength, and water resistance.

[0183] Figure 2 The components of the pre-treatment mixtures / pellets evaluated in the following Examples 1 to 4 are provided. Also shown are exemplary parameters and equipment for the optional compounding step in the methods of the present disclosure. Figure 2 Also depicted are exemplary pellets of the compositions and methods of the present disclosure.

[0184] The present invention can be further understood by reference to the following non-limiting examples.

[0185] Examples

[0186] The following examples are provided to illustrate some of the concepts described within this disclosure. Although each example is considered to provide a specific individual embodiment of the composition, preparation and use methods, the examples should not be considered as limiting the more general embodiments described herein.

[0187] In the following examples, efforts have been made to ensure accuracy with respect to numbers used (eg, amounts, temperature, etc.), but some experimental errors and deviations should be accounted for.

[0188] Instrument usage / method:

[0189] Experimental process overview: Use Figure 1 The following experiment was conducted using the exemplary process flow chart depicted in . All pre-measured dry ingredients of the composition (including kappa-carrageenan, chitosan, calcium carbonate, glycerol, tricaprylin, tannic acid, and calcium stearate) were combined and then blended using a Ross ribbon blender to form a pre-treated mixture. As described in more detail below, the pre-treated mixture was introduced into a twin-screw extruder where it was compounded into filaments. The filaments produced by the twin-screw extruder were cut into pellets. The resulting pellets were then processed through a 50 to 150 ton thermoplastic injection molding machine to form articles. The articles were then subjected to various mechanical tests, with the results analyzed using a universal tester.

[0190] Twin-Screw Extruder: The pretreatment mixture was compounded using a Theysohn 21 mm co-rotating twin-screw extruder. In the examples, the pretreatment compositions were processed to form pellets at a temperature of 130 to 250°F, a screw speed of 150 to 350 rpm, and a melt pressure of 20 to 80 psi at the liquid to solid feed ratios indicated in the examples below. In these examples, DI (deionized) HO was the reference liquid in the liquid to solid feed ratios. In the examples below, a 1:1 ratio indicates that 50% by weight of DIHO was added during the compounding and extrusion process, based on the total weight percent of DIHO and solid components of the pretreatment mixture. Additionally, a 2:3 ratio indicates that 40% by weight of DIHO was added during the compounding and extrusion process, based on the total weight percent of DIHO and solid components of the pretreatment mixture. Similarly, in the following examples, a 3:2 ratio indicates that 60 wt% of DIH2O was added during the compounding and extrusion process, based on the total wt% of DIH2O and solid components of the pre-treated mixture.

[0191] Injection Molding Machine: The pre-treated mixture and / or pellets are processed to form articles using a 50 to 150 ton thermoplastic injection molding machine. The examples provided herein describe the following exemplary parameters for processing the pre-treated mixture and / or pellets via injection molding: zone temperature: 150 to 350°F; set maximum pressure: 5,000 to 50,000 psi; peak pressure: 2,000 to 20,000 psi; hold pressure: 2,000 to 10,000 psi; hold time: 1 to 60 seconds; and clamp tonnage: 20 to 100 tons.

[0192] Young's modulus measurements: All Young's modulus values ​​were determined using a universal tester (34SC-1, Instron, Norwood, MA, USA) and a load cell rated at 1 kN. To meet the structural integrity requirements of disposable food service industry products (e.g., utensils, takeout containers, trays, lids, etc.), acceptable formulations are expected to have a tensile strength of at least 10 MPa, a modulus of at least 2000 MPa, and a percent strain at maximum force of at least 2%, optionally selected from the range of 2 to 15%.

[0193] Materials / Components:

[0194] Table 1 presents the components of the pretreatment mixtures tested in Experiments 4, 15, and 16 (Examples 1, 2, and 3, respectively) described below.

[0195] Table 1: Figure 2 The components of the pre-treated mixture / pellets are shown in FIG.

[0196]

[0197] *Dry weight %.

[0198] Example 1-(Experiment 4) : This example compares the mechanical properties of biodegradable articles produced under different process parameters.

[0199] like Figure 3-5 As shown in FIG, Experiment 4 compares the effects of various liquid to solid ratios employed during compounding on the resulting mechanical properties of injection molded articles. Specifically, liquid:solid ratios include 3:2 ( Figure 3 )、1:1( Figure 4 ) and 2:3( Figure 5 ).

[0200] In addition, Experiment 4 compared the effects of post-treatment drying parameters on the resulting mechanical properties of injection molded articles. Specifically, some samples were air-dried for 24 to 48 hours after injection molding and then annealed at 50 to 150°C for 1 to 12 hours. Other samples were equilibrated at 30 to 50% relative humidity after injection molding ("equilibrated at RH" in Table 2) and then annealed at 50 to 150°C for 1 to 12 hours. The results are shown in Table 2 as a comparison of the mechanical properties of the injection molded articles. Figure 3-5 A supplement to the graphical representation in .

[0201] Table 2

[0202]

[0203]

[0204] As shown in Table 2, all samples except Sample 1 exhibited acceptable tensile strength and modulus for disposable food service industry products (ie, a tensile strength of at least 10 MPa and a modulus of at least 2000 MPa).

[0205] Example 2-(Experiment 15): This example compares the mechanical properties of biodegradable articles produced under different process parameters.

[0206] like Figure 6-7 Experiment 15, as shown in

[15] , compared the effects of post-processing drying parameters on the resulting mechanical properties of injection molded articles. Specifically, some samples were air-dried for 24 to 48 hours after injection molding, followed by annealing at temperatures between 50 and 150°C for 1 to 12 hours. Other samples were equilibrated at a relative humidity between 30 and 50% after injection molding, followed by annealing at temperatures between 50 and 150°C for 1 to 12 hours. The results are shown in Table 3 for the results of the experiment. Figure 6-7 A supplement to the graphical representation in .

[0207] Table 3

[0208]

[0209] As shown in Table 3, all samples exhibited tensile strength and modulus acceptable for disposable food service industry products.

[0210] Example 3-(Experiment 16) : This example compares the mechanical properties of biodegradable articles produced under different process parameters.

[0211] like Figure 8-9 As shown in FIG, Experiment 16 compares the effects of two liquid to solid ratios employed during compounding on the resulting mechanical properties of injection molded articles, the two liquid to solid ratios including 1:1 ( Figure 8 ) and 2:3( Figure 9 ).

[0212] Experiment 16 also compared the effects of post-processing drying parameters on the resulting mechanical properties of injection molded articles. Specifically, some samples were air-dried for 24 to 48 hours after injection molding, followed by annealing at temperatures ranging from 50 to 150°C for 1 to 12 hours. Other samples were equilibrated at 30 to 50% relative humidity after injection molding, followed by annealing at temperatures ranging from 50 to 150°C for 1 to 12 hours. The results are shown in Table 4 for the results of the experiment. Figure 8-9 A supplement to the graphical representation in .

[0213] Table 4

[0214]

[0215] As shown in Table 4, all samples except Sample 18 exhibited acceptable tensile strength and modulus for disposable food service industry products (ie, a tensile strength of at least 10 MPa and a modulus of at least 2000 MPa).

[0216] Example 4 : This example compares the mechanical properties of the pre-treated mixtures of Experiments 4, 15, and 16, which were evaluated using substantially the same parameters (1:1 liquid:solid and air dried).

[0217] Table 5: Comparison of pretreatment mixture components

[0218]

[0219] Additionally, the percent shrinkage of the pre-treated mixture was measured. The percent shrinkage was calculated by comparing the weight percent of the components before treatment with the corresponding weight percent of the components after drying. The percent shrinkage for the above samples ranged from 3 to 30%, with acceptable formulations exhibiting a percent shrinkage in the range of 10 to 30%.

[0220] Example 5 :This example provides additional pre-treated mixtures and / or pellets that include various components compatible with injection molding processes. Prior to injection molding, the components are optionally blended and optionally compounded using a twin-screw extruder with a liquid to solid feed ratio of 1:1, 2:3, 3:2, 7:3, or 3:7 to form pellets. In examples where the components are not compounded into pellets, the components are optionally blended and mixed with DiH2O to produce a liquid to solid ratio of 1:1, 2:3, 3:2, 7:3, or 3:7 to form the pre-treated mixture. The pre-treated mixture and / or pellets are then injection molded using a 50 to 150 ton injection molding machine to form the article.

[0221] Table 6: Components of exemplary pre-treated mixtures and / or pellets for injection molding*

[0222] κ-Carrageenan 20-60 wt% Chitosan and / or chitin 1-30 wt% hydrophilic plasticizer 5-30% by weight Hydrophobic plasticizer 0.5-5% by weight Fillers 5 wt% to 40 wt% Polycations and / or cross-linkers 0.5 wt% to 10 wt% Flowing agent 0.5 wt% to 5 wt% Optional ingredients (e.g., preservatives, colorants) <1 wt%

[0223] *Dry wt %. The wt % of each listed component is adjusted within the given range so that the total amount of the components is 100 wt %.

[0224] Articles prepared from the exemplary pretreated mixtures or pellets of Table 5 are expected to exhibit moderate to high tensile strength and Young's modulus, biodegradability, flexibility, and water resistance. Thus, the articles of this Example 5 are suitable for use as food service items, in particular, utensils, trays, containers, and lids.

[0225] Example 6:This example provides additional pre-treated mixtures and / or pellets that contain various components that are compatible with the injection molding process.

[0226] The following pre-treatment mixture was prepared and used in an injection molding process using commercially available equipment.

[0227] Carrageenan 8-15% by weight Chitosan 8-15% by weight Hydrophilic plasticizer (glycerin) 5-12% by weight Hydrophobic plasticizer (tricaprylin) 0.1-2.0 wt% Filler (calcium carbonate) 5 wt% to 12 wt% Optional polycation (polylysine) 0.1 wt% to 5 wt% water 50% to 70% by weight Optional ingredients (e.g., preservatives, colorants) <1 wt%

[0228] *The weight percent of each listed component is adjusted within the given range so that the total amount of the components is 100 weight percent.

[0229] Including polylysine in the formulation increased the MFI of the extruded formulation from 4.2 to 17 to 55, which is suitable for injection molding processes and equipment.

[0230] When the polylysine in the pre-treated mixture is increased to 0.5 to 5.0%, the resin formulation can be used for injection molding and the products produced. Polylysine in the range of 0.5 to 1.5 weight percent produces products with increased Young's modulus, and when polylysine is increased beyond this range, the Young's modulus decreases.

[0231] A water content of 50% is also advantageous for producing pre-treated resins that result in products with increased Young's modulus.

[0232] Statement Regarding Incorporation by Reference and Variations

[0233] All references throughout this application, such as patent documents, including issued or granted patents or their equivalents, patent application publications, and non-patent literature documents, or other source materials, are hereby incorporated by reference in their entirety, as if individually incorporated by reference, to the extent that each reference is at least partially not inconsistent with the disclosure in this application (e.g., a partially inconsistent reference is incorporated by reference except for the partially inconsistent portion of the reference).

[0234] The terms and expressions used herein are used as terms of description rather than limitation, and in the use of such terms and expressions, it is not intended to exclude any equivalents of the features shown and described or parts thereof, but it should be recognized that various modifications are possible within the scope of the invention claimed. Therefore, it should be understood that although the present invention has been specifically disclosed by preferred embodiments, exemplary embodiments and optional features, those skilled in the art may adopt modifications and variations of the concepts disclosed herein, and such modifications and variations are considered to be within the scope of the invention as defined by the appended claims. The specific embodiments provided herein are examples of applicable embodiments of the present invention, and it will be apparent to those skilled in the art that the present invention can be carried out using a large number of variations of the devices, device components, and method steps described in this specification. As will be apparent to those skilled in the art, methods and devices suitable for the methods of the present invention may include a large number of optional compositions and processing elements and steps.

[0235] Unless the context clearly dictates otherwise, as used herein and in the appended claims, the singular forms "a," "an," and "the" include plural references. Thus, for example, reference to "a cell" includes a plurality of such cells and equivalents thereof known to those skilled in the art. Likewise, the terms "a" (or "an"), "one or more," and "at least one" are used interchangeably herein. It should also be noted that the terms "comprising," "including," and "having" are used interchangeably. The phrase "as set forth in any one of claims XX to YY" (wherein XX and YY refer to claim numbers) is intended to provide multiple dependent claims in an alternative form and, in some embodiments, is interchangeable with the phrase "as set forth in any one of claims XX to YY."

[0236] When a group of substituents is disclosed herein, it is understood that all individual members and all subgroups of the group are disclosed separately, including any isomers, enantiomers, and diastereomers of the group members. When Markush groups or other groupings are used herein, all individual members of the group and all possible combinations and subcombinations of the group are intended to be included individually in the present disclosure. When a compound is described herein so that a specific isomer, enantiomer, or diastereomer of the compound is not specified, for example, in a formula or chemical name, the description is intended to include each isomer and enantiomer of the compound described individually or in any combination. In addition, unless otherwise specified, all isotopic variants of the compounds disclosed herein are intended to be covered by the present disclosure. For example, it is understood that any one or more hydrogens in the disclosed molecules may be replaced by deuterium or tritium. Isotopic variants of molecules are generally suitable for use as standards in molecular analysis and chemical and biological research related to molecules or their uses. Methods for preparing such isotopic variants are known in the art. Specific names of compounds are intended to be exemplary, as it is known that one of ordinary skill in the art may name the same compound differently.

[0237] Certain molecules disclosed herein may contain one or more ionizable groups [groups from which a proton can be removed (e.g., -COOH) or a proton can be added (e.g., an amine) or a group that can be quaternized (e.g., an amine)]. All possible ionic forms of such molecules and their salts are intended to be individually included in the disclosure herein. With respect to the salts of the compounds herein, one of ordinary skill in the art can select from a wide variety of available counterions suitable for preparing salts of the present invention for a given application. In particular applications, the choice of a given anion or cation for preparing a salt may result in increased or decreased solubility of the salt.

[0238] Unless otherwise stated, every device, system, formulation, compositional combination, or method described or illustrated can be used to practice the invention.

[0239] Whenever a range is given in this specification (e.g., a temperature range, a time range, or a composition or concentration range), all intermediate ranges and subranges, as well as all individual values, included in the given range are intended to be included in the disclosure. It should be understood that any subrange or individual value within a range or subrange included in the description herein may be excluded from the claims herein.

[0240] All patents and publications mentioned in this specification indicate the skill level of those skilled in the art to which the present invention belongs. The references cited herein are incorporated herein by reference in their entirety to indicate the current state of the art as of their disclosure or filing date, and it is hoped that this information can be used herein to exclude specific embodiments in the prior art when necessary. For example, when claiming a composition of matter, it should be understood that compounds known and available in the art prior to the present invention proposed by the applicant, including compounds that provide enabling disclosures in the references cited herein, are not intended to be included in the composition of matter claimed herein.

[0241] As used herein, "comprising" is synonymous with "including," "containing," or "characterized by," and is inclusive or open-ended and does not exclude additional unlisted elements or method steps. As used herein, "consisting of excludes any element, step, or ingredient not specified in the claimed element. As used herein, "consisting essentially of does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. In each case herein, any one of the terms "comprising," "consisting essentially of," and "consisting of" may be replaced by any one of the other two terms. The invention illustratively described herein may be suitably practiced in the absence of any one or more elements, one or more limitations not specifically disclosed herein.

[0242] Those skilled in the art will appreciate that starting materials, biological materials, reagents, synthesis methods, purification methods, analytical methods, assay methods, and biological methods other than those specifically exemplified may be employed in the practice of the present invention without resorting to undue experimentation. All functional equivalents known in the art of any such materials and methods are intended to be included in the present invention. The terms and expressions employed are used as descriptive rather than restrictive terms, and any equivalents of the features shown and described, or portions thereof, are not intended to be excluded in the use of the terms and expressions, but it should be recognized that various modifications are possible within the scope of the present invention. Therefore, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modifications and variations of the concepts disclosed herein may be adopted by those skilled in the art, and such modifications and variations are deemed to be within the scope of the present invention as defined by the appended claims.

Claims

1. A product, pellet or pre-treated mixture comprising: a. at least one hydrocolloid, b. at least one plasticizer, c. at least one filler, and d. at least one polycation.

2. The article, pellet or pretreatment mixture of claim 1, wherein the at least one hydrocolloid comprises chitosan, carrageenan or any combination thereof.

3. The article, pellet or pretreatment mixture according to any one of claims 1 to 2, wherein the at least one hydrocolloid comprises carrageenan.

4. The article, pellet or pretreatment mixture of any one of claims 1 to 3, wherein the at least one hydrocolloid comprises a combination of carrageenan and at least one of chitosan or chitin.

5. The pretreatment mixture according to any one of claims 1 to 4, comprising a total amount of 10 to 40 wt% of hydrocolloid, based on the total weight of the pretreatment mixture.

6. The pretreatment mixture according to any one of claims 1 to 5, wherein the at least one hydrocolloid comprises, based on the total weight of the pretreatment mixture: a. carrageenan in an amount of 10% to 20% by weight, and b. Chitin or chitosan or a mixture thereof in an amount of 10 to 20 wt%.

7. The article, pellet or pretreatment mixture of any one of claims 1 to 6, wherein the at least one plasticizer comprises a combination of a hydrophilic plasticizer and a hydrophobic plasticizer.

8. The pretreatment mixture according to any one of claims 1 to 7, comprising a total amount of 5 to 20 wt% plasticizer, based on the total weight of the pretreatment mixture.

9. The article, pellet or pre-treated mixture of any one of claims 1 to 8, wherein the at least one filler comprises calcium carbonate or a hydrate thereof.

10. The pretreatment mixture according to any one of claims 1 to 9, comprising, where appropriate, fillers in a total amount of 5% to 20% by weight, based on the total weight of the pretreatment mixture.

11. The article, pellet or pretreatment mixture of any one of claims 1 to 10, wherein the at least one polycation comprises polylysine.

12. The pretreatment mixture according to any one of claims 1 to 10, comprising a total amount of 0.5% to 5% by weight of polycations, based on the total weight of the pretreatment mixture.

13. The pretreatment mixture according to any one of claims 1 to 12, comprising a water content of 10% to 69% by weight.

14. The article, pellet or pre-treated mixture of any one of claims 1 to 13, exhibiting a Young's modulus of at least 2000 MPa.

15. The article, pellet or pretreatment mixture of any one of claims 1 to 14, wherein the at least one plasticizer comprises glycerol.

16. A method for preparing a biodegradable article, the method comprising: a. combining (i) at least one hydrocolloid, (ii) at least one plasticizer, (iii) at least one filler and (iv) at least one polycation to prepare a pretreatment mixture; and b. optionally blending the pretreated mixture; c. optionally compounding the pretreated mixture into pellets; d. forming the pretreated mixture or pellets into shapes; and e. drying the shape to form the article, wherein the at least one hydrocolloid, the at least one plasticizer, the at least one filler and the at least one polycation are as defined in any one of the preceding claims. The method of claim 16 , wherein the forming comprises injection molding.

18. The method of any one of claims 16-17, wherein the forming comprises thermoplastic injection molding.

19. The method according to any one of claims 16 to 18, further comprising a post-processing step after forming the pre-treated mixture or pellets into a shape.

20. The method of claim 19, wherein the post-processing step comprises annealing the shape at a temperature in the range of 50 to 150°C for a period of 1 to 12 hours.

21. The method of any one of claims 16 to 20, wherein drying the shape to form the article comprises exposing the shape to ambient conditions for a period of 24 to 48 hours.

22. The method of claim 21, wherein the environmental conditions comprise an ambient temperature in the range of 15 to 25°C and an ambient relative humidity in the range of 30 to 50%.

23. The method of any one of claims 16 to 22, wherein the blending is performed and comprises using a ribbon blender.

24. The method of any one of claims 16 to 23, wherein the combining step further comprises a colorant.

25. The method of any one of claims 16 to 24, wherein the combining step further comprises a preservative.

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