CN117715537A - Bio-based biodegradable compositions and articles made therefrom - Google Patents
Bio-based biodegradable compositions and articles made therefrom Download PDFInfo
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- CN117715537A CN117715537A CN202280050113.5A CN202280050113A CN117715537A CN 117715537 A CN117715537 A CN 117715537A CN 202280050113 A CN202280050113 A CN 202280050113A CN 117715537 A CN117715537 A CN 117715537A
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- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 177
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- ZNOZWUKQPJXOIG-XSBHQQIPSA-L [(2r,3s,4r,5r,6s)-6-[[(1r,3s,4r,5r,8s)-3,4-dihydroxy-2,6-dioxabicyclo[3.2.1]octan-8-yl]oxy]-4-[[(1r,3r,4r,5r,8s)-8-[(2s,3r,4r,5r,6r)-3,4-dihydroxy-6-(hydroxymethyl)-5-sulfonatooxyoxan-2-yl]oxy-4-hydroxy-2,6-dioxabicyclo[3.2.1]octan-3-yl]oxy]-5-hydroxy-2-( Chemical compound O[C@@H]1[C@@H](O)[C@@H](OS([O-])(=O)=O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H]2OC[C@H]1O[C@H](O[C@H]1[C@H]([C@@H](CO)O[C@@H](O[C@@H]3[C@@H]4OC[C@H]3O[C@H](O)[C@@H]4O)[C@@H]1O)OS([O-])(=O)=O)[C@@H]2O ZNOZWUKQPJXOIG-XSBHQQIPSA-L 0.000 claims description 157
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- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 claims description 8
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Disclosed herein are compositions and articles made therefrom that include at least one hydrocolloid, at least one plasticizer, at least one wetting agent or filler, and water. Typically, the components are derived from biological sources, such as seaweed, plants or animals. Typically, the components are prepared from food quality ingredients, thereby making the composition and the article edible. The composition is useful for shaping the article, such as a straw, and the article has desirable flexibility and moisture barrier properties, such as resistance to swelling and biodegradability and/or compostability properties.
Description
Cross Reference to Related Applications
The present application relates to U.S. provisional patent application No. 63/213,887 filed on month 23 of 2021 and U.S. provisional patent application No. 63/243,358 filed on month 13 of 2021, each of which is incorporated herein by reference in its entirety for all purposes.
Background
Disposable articles such as containers (vessel), cups, pipettes, agitators and utensils are typically made of plastic, paper or plastic lined paper and are a common replacement for reusable articles due to their low cost and convenience. Both cups (Dow Chemical) and paper cups can hold hot liquid for extended periods of time. Disposable drinking straws made of plastic materials are also common. However, disposable cups and straws are not environmentally friendly. Because it is not biodegradable, the environment can be filled with refuse or with landfills. In addition, the plastics used in disposable articles are typically derived from fossil fuels.
Plastic products such as plastic straws and the like are ubiquitous. In the united states alone, millions of single use plastics such as plastic straws are thrown away every day, which results in about 750 tens of thousands of plastic straws contaminating the united states shoreline (from 2012 to 2017) and the coastline around the world. However, plastic drinking straws represent about 99% of the worldwide dollar 30-million drinking straw market, and only 9% of them can be recycled due to their size. An alternative solution is urgently needed in view of the average lifetime of plastic drinking straws of 450+ years.
Paper products such as cups and straws provide a sustainable and extensible but more expensive solution than plastics. In addition, poor water barrier properties of paper products such as drinking straws, which begin to crack or undesirably swell after 30-60 minutes of use, lead to reduced shelf life in beverages. In addition, while the feed stream of paper products such as straw or cups is derived from a bio-renewable resource, it is well known that the paper industry consumes more energy and therefore emits more CO than the plastics industry 2 Thus ultimately leading to a greenhouse gas crisis.
Food service industry articles (e.g., cutlery, utensils, and straws) made from bioplastic and bioplastic composites are becoming increasingly popular. Corn-derived polylactic acid (PLA) and polypropylene (PP) are the main components in these formulations. PLA and PP are often blended with natural fibers and starch in order to reduce costs and increase the biodegradability of these materials. Although these materials have improved barrier properties compared to paper products, they still exhibit a number of disadvantages. Although PLA is commercially available as a natural bio-based biodegradable substitute for petroleum-based plastics, PLA is not biodegradable under natural conditions and requires commercial compounding facilities to degrade. Therefore, PLA is not an environmentally friendly alternative to other plastics. Furthermore, the use of corn as a feed stream and concomitant use of agricultural resources such as fresh water and fertilizers to produce these biorenewable monomers and subsequent biopolymers competes with or alters the precious human food source. In addition, the mechanical properties and cost of these materials need to be improved.
Aqueous based (water solution) formulations consisting essentially of alginates (e.g., sodium and potassium salts) may also be used in articles of manufacture, but are more typically used as gelling and thickening agents in the food and cosmetic industries, and in biotechnology for wound dressingsDrug delivery and tissue regeneration. Such formulations are disadvantageous in terms of poor mechanical properties (tensile strength, low brittleness) and barrier properties (rapid loss of moisture or swelling upon contact with aqueous solutions in relatively low humidity environments). Some techniques for addressing these shortcomings include the addition of plasticizers (glycerol, mannitol, etc.), the use of cellulose fibers (microcrystalline cellulose (MCC), thermoplastic cellulose ethers (e.g., ethocell TM (dupont chemical company (DuPont Chemical Company)) and the like), applying a hydrophobic coating (beeswax, soy wax, rice bran wax, and the like), and performing crosslinking, including both ionic crosslinking agents (e.g., using metal ions) and covalent crosslinking agents (e.g., citric acid, tartaric acid, and the like).
Kappa-carrageenan is a linear monosulfated galactosylpolysaccharide that is commonly used as a thickener, gelling agent and protein suspending agent in the food industry, accounting for almost 80% of the total world production. The remainder of the kappa-carrageenan produced is generally classified into pharmaceutical, cosmetic, textile and printing industries, and kappa-carrageenan has been widely used due to its gel forming properties. However, kappa-carrageenan is not typically used in single use food service industry items such as cutlery or drinking straws.
Various biodegradable, edible, and/or biobased formulations, cups, straws, and packages are known in the art, but may be distinguished from the present disclosure in many ways. In addition, the mechanical and/or moisture barrier properties of such known formulations, cups, straws and packages are generally inferior compared to the articles of the present disclosure.
International patent application publication WO 2019/046789 relates to a low or sugar-free edible and/or biodegradable material for maintaining food and liquids for consumption. The present disclosure is incorporated herein by reference in its entirety to demonstrate the latest technology on these materials, the definition and examples of components employed in the materials therein, and the description of the process steps employed therein.
International patent application publication WO 2021/046041 relates to a biodegradable tubular member, such as a straw, comprising a cellulose ester, which may be cellulose acetate, wherein the tubular member comprises a plurality of pores sized and configured in a manner that allows water or bacteria to penetrate or infiltrate into the pores to promote biodegradability. The present disclosure is incorporated herein by reference in its entirety to demonstrate the latest technology on these materials, the definition and examples of components employed in the materials therein, and the description of the process steps employed therein.
Chinese patent application publication CN111875853a relates to a biodegradable, environment-friendly straw comprising sodium alginate, pectin, welan gum (welan gum), modified starch, plasticizer, tea polyphenols, chitosan oligosaccharides, calcium gluconate, tartaric acid and deionized water. The present disclosure is incorporated herein by reference in its entirety to demonstrate the latest technology on such pipettes, the definition and examples of components employed in the pipettes therein, and the description of the processing steps employed therein.
International patent application publication WO 2021/108756 relates to a biodegradable and water-soluble packaging material comprising a biodegradable nonionic polysaccharide, a biodegradable ionic polysaccharide and a plasticizer. The present disclosure is incorporated herein by reference in its entirety to demonstrate the latest technology on these packaging materials, the definition and examples of the components employed in the packaging materials therein, and the description of the processing steps employed therein.
Us patent 6,902,783 relates to edible molded bodies in the form of flat or tubular films suitable for use as sausage casings and food packaging films, said casings/films comprising biopolymers, cut products or derivatives thereof and/or synthetic polymers, at least one edible plasticizer, at least one lubricant and at least one cross-linking agent and fibers. This patent is incorporated herein by reference in its entirety to show the latest technology on such sausage casings and packaging film materials, the definition and examples of the components employed in the packaging film materials therein, and the description of the processing steps employed therein.
U.S. patent application publication 2015/0048554 relates to a biodegradable material comprising a protein gel comprising at least one protein and natural fibers, at least one hygroscopic mineral and water. The present disclosure is incorporated herein by reference in its entirety to demonstrate the latest technology on these materials, the definition and examples of components employed in the materials therein, and the description of the process steps employed therein.
U.S. patent application publication 2019/0248989 relates to biodegradable and edible films and packaging materials comprising biodegradable polymers and polyols, polyacids, or combinations thereof. The present disclosure is incorporated herein by reference in its entirety to demonstrate the latest technology on these materials, the definition and examples of components employed in the materials therein, and the description of the process steps employed therein.
U.S. patent 7,488,503 relates to a packaging composition comprising a mixture of two different food polymers, which can be used to package a package, such as a flavoring agent. This patent is incorporated herein by reference in its entirety to demonstrate the latest technology on these compositions, the definition and examples of the components employed in the compositions, and the description of the processing steps employed therein.
International patent application publication WO 2016/181004 relates to an edible straw comprising water, a gelling agent, sugar, a stabilizer or thickener, and a plasticizer or wetting agent. The present disclosure is incorporated herein by reference in its entirety to demonstrate the latest technology on such pipettes, the definition and examples of components employed in the pipettes, and the description of the processing steps employed therein.
U.S. patent application publication 2007/0292643 relates to a biodegradable composition comprising a foamed gelling hydrocolloid system to which a curing agent and a fibrous material are added. The' 643 disclosure is incorporated herein by reference in its entirety to demonstrate the latest technology on these compositions, the definition and examples of the components employed in the compositions therein, and the description of the processing steps employed therein.
International patent application publication WO 2021/019524 relates to a bio-plastic package or container (container) prepared from seaweed using a method comprising: immersing the seaweed in water for at least 10 minutes, washing and washing the seaweed, cutting the seaweed into pieces smaller than 1cm, and then shaping the seaweed gel or dough by adding water to the cut seaweed. The illustrated straw is rolled from a mixture further comprising rice flour and wheat gluten. The present disclosure is incorporated herein by reference in its entirety to demonstrate the latest technology on such packages or containers, the definition and examples of the components employed in the packages or containers, and the description of the processing steps employed therein.
International patent application publication WO 2021/019525 relates to a biodegradable and edible bioplastic comprising seaweed from Eucheuma sp, sargassum sp, genus renilla, tubers from potato, cassava and sweet potato, protein isolates from soy and gluten, juices from rubber, copal, dammar and jelutong, and additives from glycerol, sorbitol, PEG, food flavors and food dyes. The present disclosure is incorporated herein by reference in its entirety to demonstrate the latest technology on these bioplastics, the definition and examples of components employed in bioplastics, and the description of the processing steps employed therein.
U.S. patent application publication 2009/0099353 relates to alginate and chitosan composite fibers for wound management products, wherein the chitosan polymer is bonded to the alginate polymer along the length of the fiber. Such composite fibers are produced by extruding an alginate solution into a coagulation bath of chitosan. The present disclosure is incorporated herein by reference in its entirety to demonstrate the latest technology on these composite fibers, the definition and examples of the components employed in the composite fibers therein, and the description of the processing steps employed therein.
International patent application publication WO 2006/044342 relates to an alginate gel comprising soluble alginate and insoluble alginate/gelling ion particles, wherein the gel is formed from gelling ions of particles that crosslink insoluble alginate polymer particles and soluble alginate polymer. The present disclosure is incorporated herein by reference in its entirety to demonstrate the latest technology regarding these alginate gels, the definition and examples of components employed in the alginate gels, and the description of the processing steps employed therein.
U.S. patent application publication 2018/0192803 relates to a straw containing water, a gelling agent, sugar, a stabilizer or thickener, and a plasticizer or wetting agent. The present disclosure is incorporated herein by reference in its entirety to demonstrate the latest technology on such pipettes, the definition and examples of components employed in the pipettes, and the description of the processing steps employed therein.
International patent application publication WO 2008/044586 relates to a molded article including an amylopectin having a 6- α -maltosyl branched structure and/or a 6- α -maltotetrayl branched structure. The present disclosure is incorporated herein by reference in its entirety to demonstrate the latest technology on these molded articles, definitions and examples of components employed in molded articles, and descriptions of the processing steps employed therein.
International patent application publication WO 2003/035026 relates to polysaccharide networks, in particular starch networks, having a high network density, a high firmness, a low swelling degree and exhibiting reduced water absorption. The present disclosure is incorporated herein by reference in its entirety to demonstrate the latest technology on these polysaccharide networks, the definition and examples of components employed in the polysaccharide networks, and the description of the processing steps employed therein.
International patent application publication WO 2020/174234 relates to a composition comprising seaweed extract, a water-soluble cellulose derivative and water, and a packaging material prepared from said composition. The present disclosure is incorporated herein by reference in its entirety to demonstrate the latest technology on these compositions and packaging materials, the definition and examples of the components employed in the compositions and packaging materials, and the description of the processing steps employed therein.
U.S. patent application publication 2006/0024425 relates to edible film formulations using low viscosity hydrolyzed vegetable gums as film forming components. The present disclosure is incorporated herein by reference in its entirety to demonstrate the latest technology on these films, the definition and examples of components employed in the films therein, and the description of the processing steps employed therein.
International patent application publication WO 1998/042214 relates to edible films and coatings suitable for use as moisture barriers in food products. The present disclosure is incorporated herein by reference in its entirety to demonstrate the latest technology on these films, the definition and examples of components employed in the films therein, and the description of the processing steps employed therein.
International patent application publication WO 2021/028555 relates to compostable tools for eating and drinking, such as drinking straws or tableware. The present disclosure is incorporated herein by reference in its entirety to demonstrate the latest technology regarding these compostable tools, the definition and examples of components employed in the compostable tools, and the description of the processing steps employed therein.
While promising, these techniques have not been scaled and streamlined to be economically viable and there are still various drawbacks in terms of the mechanical, water resistance and other properties of the articles produced from the bio-based compositions and the processability of these compositions into articles.
Thus, there remains a need in the art for biobased articles having desirable characteristics. There is a particular need in the art for biobased articles having resistance to water and other liquids while maintaining flexibility and other mechanical properties such as compressibility and bendability.
Disclosure of Invention
To be an effective replacement for disposable articles such as cups, straws, blenders, utensils, or other containers, the articles of the present disclosure are preferably capable of withstanding the hot and cold temperatures of food and beverages. In particular, in view of the vast consumer demand for coffee and other beverages, cups and straws made from alternative edible materials should be capable of holding or contacting hot or cold liquids. While several examples of edible receptacles or appliances exist today, most lack the structural integrity and versatility required to maintain or contact liquids having different temperatures, particularly for extended periods of time. The compositions and articles thus prepared disclosed herein address at least some of these and other disadvantages and in some aspects provide biodegradable articles that are sufficiently rigid to be used as cups, straws or utensils, while also being able to withstand heat and/or cold beverages for extended periods of time.
In some aspects, disclosed herein are edible and/or biodegradable articles, containers, or appliances comprising a combination of 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 with other components, such as at least one wetting agent, at least one plasticizer, at least one filler (or strength modifier), at least one inorganic cross-linking agent, at least one hydrophobic additive, and/or water, and optionally additional ingredients comprising one or more sweeteners (e.g., non-sugar, honey, etc.), flavoring agents, colorants, active ingredients, edible oils, and preservatives (e.g., natural preservatives). The article may also be coated with, for example, an edible coating to enhance the water repellency of the article, to increase the shelf life of the article, and/or to reduce the tackiness of the article, or to provide a flavor, color, or graphic to the article. The article may remain in or in contact with a liquid or food product (e.g., a moist food product) for an extended period of time, preferably more than about one hour. The article may be in the form of an appliance, container, cup, drinking straw, whisk, or any other suitable form. In some aspects, the article is biodegradable, compostable, or a combination thereof.
In some aspects, disclosed herein are flexible, strong bio-based and/or biodegradable articles having improved water barrier properties, as well as compositions (e.g., pretreatment mixtures) or pellets for making such articles. These articles, pellets and compositions include ingredients obtained from biorenewable sources such as seaweed, plants, animals or combinations thereof and provide a sustainable and cost-effective solution to the problems associated with single-use plastic contamination, particularly single-use plastic drinking straws or other articles. In some aspects, such compositions are used as alternatives to plastics (e.g., petroleum derived plastics) in the manufacture of single use food service industrial articles. In some aspects, the composition (e.g., pretreatment mixture) is in the form of pellets for treatment by thermal extrusion. In some aspects, the pellets are formed by mixing selected components of the composition for a selected time to achieve a desired consistency suitable for further processing. In some aspects, the pellets have a selected shape, size, and weight suitable for further processing by a cold or hot extrusion process.
In some aspects, these compositions include a hydrocolloid, which may be a biopolymer (e.g., alginate or kappa-carrageenan) derived from an alga such as kelp or red algae. Algae grow unattended in the ocean (e.g., kelp grows several meters per day) and do not require agricultural resources or fresh water, thus presenting an ideal renewable and abundant natural resource for replacing plastics in single-use items in the food industry. However, hydrocolloids (or biopolymers) other than or in addition to alginate or kappa-carrageenan may also be employed, as described elsewhere herein. Energy consumption required for extracting alginate (1 kg) from kelp is 2.2kg of CO in the form of blue carbon sequestered 2 Counteracting this means that seaweed-derived biopolymers not only eliminate the need for cultivation consuming valuable land and chemical resources, but also drastically reduce the CO in the atmosphere 2 . In addition, in some aspects, compositions comprising hydrocolloids or biopolymers such as alginate or kappa-carrageenan may be processed on conventional plastic processing equipment such as twin screw or single screw cold or hot melt extruders (depending on the composition) to enable the use of existing manufacturing techniques (e.g., equipment for processing petroleum derived plastics). For example, compositions (pretreatment mixtures) comprising alginate or dried and ground brown algae as the major component (excluding water) may be produced using cold extrusion, while compositions (pretreatment mixtures) comprising kappa-carrageenan or dried and ground red seaweed, even in small amounts (and in some aspects also comprising alginate), may be produced using hot melt extrusion. Articles such as containers or straws may be of this type The formulation is produced in an extensible and economically viable manner at a cost comparable to or lower than the cost of producing paper drinking straws.
In some aspects, an alginate-based flexible and biodegradable composition and articles 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 major components of the composition. In some aspects, alginate is the major component (excluding water) of the composition and/or the article.
In some aspects, a kappa-carrageenan-based flexible and biodegradable composition and articles made therefrom are disclosed, wherein kappa-carrageenan and other biologically derived 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, kappa-carrageenan is the major component (excluding water) of the composition and/or the article. In some aspects, an article comprising kappa-carrageenan is disclosed that is flexible, strong, and biodegradable, has an extended shelf life (e.g., 30 days or more in the absence of any packaging ambient conditions), and also has good water barrier properties (e.g., a swelling rate of less than 50wt.% when in contact with water at room temperature, as disclosed elsewhere herein). In some aspects, the kappa-carrageenan-based article is produced using at least one hot melt extrusion step. In some aspects, the kappa-carrageenan-based article is not produced using cold extrusion.
In some aspects, single-use food service industry products, such as straws, are provided that consist exclusively of food grade ingredients, and such features make the product edible. In some aspects, discarded products, such as straw, may 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.
The compositions disclosed herein can be used to produce food service articles, such as straws, by cold extrusion or hot extrusion. In some aspects, the resulting product, such as a straw, exhibits moderate to high tensile strength (MPa) and compressive strength (MPa) and improved barrier properties, which enable the article to remain flexible even in relatively low humidity environments and to resist swelling in aqueous solutions (less than 60 wt%).
The compositions disclosed herein, particularly compositions containing alginate, may be used to produce food service items such as straws by cold extrusion or hot extrusion, but are preferably treated by cold extrusion. In some aspects, the resulting product, such as a straw, comprising alginate exhibits moderate to high tensile strength (MPa) and compressive strength (MPa) and improved barrier properties, which enable the article to remain flexible even in relatively low humidity environments and to resist swelling (less than 60 wt%) in aqueous solutions.
The compositions disclosed herein, or more particularly including kappa-carrageenan, may be used to produce food service items, such as straws, wherein the compositions are used as resins in a continuous Hot Melt Extrusion (HME) process to prepare single use food service industrial products that are sustainable biorenewable materials. In some aspects, such compositions consist exclusively of food-grade ingredients, which render them biodegradable, edible, and suitable for use in a food service environment. In some aspects, the resulting product, such as a straw comprising kappa-carrageenan, exhibits moderate tensile strength (e.g., 20-25 MPa) and moderate compressive strength (e.g., 10-13 MPa) and barrier properties sufficient to maintain flexibility and structural integrity for extended periods of time (e.g., over 30 days) in the absence of any packaging (e.g., air and/or moisture barrier packaging) environmental conditions. In some aspects, the resulting product, such as a straw comprising kappa-carrageenan, exhibits reduced water absorption (as compared to paper analogs), a swelling ratio of less than 50% by weight after 1 hour at room temperature in aqueous solution, and a swelling ratio of less than 30% after 1 hour at 0 ℃ in aqueous solution.
In some aspects, the pretreatment mixture includes about 10wt.% to 20wt.% sodium alginate, about 20wt.% to 30wt.% plasticizer, about 30-50wt.% water, about 1-3wt.% wetting agent, and other desired optional additives, such as colorants, cross-linking agents, and preservatives. In some aspects, the pretreatment mixture or the article comprises (1) about 10wt.% to 20wt.% kappa-carrageenan; (2) About 10wt.% to 20wt.% of an additional hydrocolloid (e.g., a biopolymer or polysaccharide), wherein the hydrocolloid comprises chitosan, alginate (e.g., sodium alginate), iota-carrageenan, or any combination thereof; (3) about 5wt.% to 20wt.% of a plasticizer; (4) About 5wt.% to 20wt.% of a filler (e.g., an organic filler or strength modifier (e.g., MCC), an inorganic filler or a mineral salt filler); (5) about 30wt.% to 50wt.% water; and (6) optional additives such as colorants, fragrances, and/or preservatives. In some aspects, the pretreatment mixture or the article comprises (1) about 10wt.% to 20wt.% kappa-carrageenan; (2) About 10wt.% to 20wt.% of an additional hydrocolloid (e.g., a biopolymer or polysaccharide), wherein the hydrocolloid comprises chitosan, alginate (e.g., sodium alginate), iota-carrageenan, or any combination thereof; (3) about 5wt.% to 20wt.% of a plasticizer; (4) about 0wt.% to 10wt.% of a wetting agent; (5) about 30wt.% to 50wt.% water; and (6) optional additives such as colorants, fragrances, and/or preservatives. However, any of the components may be used in the amounts described elsewhere herein, and these compositions may or may not include any of the components described elsewhere herein. In some aspects, the pretreatment mixture includes about 5-35wt.% hydrocolloid, 20-40wt.% plasticizer, and 0.5wt.% to 10wt.% wetting agent, as well as optional ingredients and water. In some aspects, the pretreatment mixture or the article includes about 15-35wt.% hydrocolloid, about 5-20wt.% plasticizer, and about 5-10wt.% filler (e.g., organic filler (e.g., MCC), inorganic filler, or mineral salt filler), as well as optional ingredients and water. In some aspects, the pretreatment mixture or the article comprising kappa-carrageenan further comprises at least one of a filler (e.g., strength modifier, inorganic filler, and/or organic filler), a cross-linking agent (e.g., inorganic cross-linking agent), a plasticizer (hydrophobic and/or hydrophilic plasticizer), and a hydrophobic additive, or any combination thereof, or a combination of all of its components.
In some aspects, the hydrocolloid is a mixture of alginate, chitosan, and at least one natural gum, such as guar gum, gum arabic (gum arabic), locust bean gum, konjac gum, or xanthan gum. In some aspects, the hydrocolloid comprises 5-15wt.% alginate and 0.5-10 wt.% chitosan. In some aspects, the hydrocolloid contains 0.5wt.% to 5wt.% natural gum. In some aspects, the plasticizer is a mixture of a hydrophilic plasticizer and a hydrophobic plasticizer. In some aspects, the plasticizer is 20-35wt.% hydrophilic plasticizer and 0.5wt.% to 5wt.% hydrophobic plasticizer. In some aspects, the wetting agent comprises 1-4wt.% of the pretreatment mixture. In some aspects, the wetting agent comprises a metal salt or a hydrate thereof. In some aspects, the wetting agent comprises a metal hydroxide or a hydrate thereof.
In some aspects, the hydrocolloid is carrageenan, particularly a mixture of carrageenan including kappa-carrageenan with at least one alginate, chitin or chitosan. In some aspects, the hydrocolloid is a mixture of kappa-carrageenan with at least one of alginate, chitin, or chitosan, optionally additionally comprising at least one natural gum, such as guar gum, gum arabic, locust bean gum, konjac gum, or xanthan gum. In some aspects, the hydrocolloid comprises 10-20wt.% kappa-carrageenan and 5-15wt.% chitin. In some aspects, the hydrocolloid comprises 10-20wt.% kappa carrageenan and 5-15wt.% chitosan. In some aspects, the hydrocolloid comprises 10-20wt.% kappa carrageenan and a total of 5-15wt.% chitin and/or chitosan. In some aspects, the hydrocolloid contains, for example, konjac gum in an amount of 0-3wt.%, 0-5wt.%, or 0-10 wt.%. In some aspects, the plasticizer is a mixture of a hydrophilic plasticizer and a hydrophobic plasticizer. In some aspects, the plasticizer comprises 5-15wt.% hydrophilic plasticizer and 0.5wt.% to 2wt.% hydrophobic plasticizer. In some aspects, the filler comprises 5-10wt.% of the pretreatment mixture. In some aspects, the filler comprises an organic filler, an inorganic filler, a mineral salt filler, or any hydrate thereof. In some aspects, the filler comprises a metal hydroxide or a hydrate thereof. In some aspects, the filler comprises a carbonate (e.g., calcium carbonate). In some aspects, the filler (or strength modifier) comprises MCC and/or citrus fiber.
In some aspects, the pretreatment mixture or the pellet comprises 10-40wt.% hydrocolloid (e.g., 5-10wt.% agar, 4-9wt.% carrageenan in combination with 1-5wt.% xanthan gum), 15-30wt.% plasticizer (e.g., 10-20wt.% hydrophilic plasticizer, such as a combination of one or more sugar alcohols with 1-3wt.% hydrophobic plasticizer, such as one or more alkylated sugar alcohols), 0.1-5wt.% wetting agent (e.g., calcium sulfate or a hydrate thereof), and balance water. In some aspects, the pretreatment mixture or the pellets comprise about 5-35wt.% of hydrocolloid (e.g., 5-15wt.% of alginate (e.g., having 1-5wt.% of high M block alginate and 8-16wt.% of high G block alginate), 0.5-10wt.% of chitosan in combination with 0.5-10wt.% of guar gum), 20-35wt.% of hydrophilic plasticizer (e.g., glycerin), 0.5-2wt.% of hydrophobic plasticizer (e.g., glyceryl tricaprylate), 0.5-10wt.% of wetting agent (e.g., aluminum hydroxide or a hydrate thereof), 40-60wt.% of water, and optional ingredients (e.g., colorants, fragrances, etc.). In some aspects, the pretreatment mixture or the pellets comprise about 17-21wt.% hydrocolloid (e.g., 10-14wt.% alginate (e.g., 1-4wt.% high M block alginate and 9-13wt.% high G block alginate), 1-5wt.% chitosan in combination with 1-5wt.% guar gum), 28-33wt.% hydrophilic plasticizer (e.g., glycerin), 0.5-2wt.% hydrophobic plasticizer (e.g., glyceryl tricaprylate), 1-4wt.% wetting agent (e.g., aluminum hydroxide or a hydrate thereof), 44-54wt.% water, and optional ingredients (e.g., 0.1-0.5wt.% colorant provided in the form of an aqueous solution). In some aspects, the pretreatment mixture or the pellets comprise about 3-30wt.% of hydrocolloid (e.g., 5-15wt.% of alginate (e.g., 4-10wt.% of high M block alginate and 4-10wt.% of high G block alginate), 0.5-4wt.% of chitosan in combination with 2-10wt.% of locust bean gum), 30-45wt.% of hydrophilic plasticizer (e.g., sorbitol), 1.5-8wt.% of wetting agent (e.g., metal oxide (e.g., magnesium oxide) or a hydrate thereof), 40-60wt.% of water, and optional ingredients (e.g., colorants, fragrances, etc.). Articles or pellets prepared from such a pretreatment mixture typically have the same weight ratio of hydrocolloid, hydrophobic plasticizer and wetting agent. In some aspects, the article or the pellet produced from the pretreatment mixture comprises about 34-41wt.% of hydrocolloid (e.g., 24-29wt.% of alginate (e.g., 3-8wt.% of high M block alginate and 18-25wt.% of high G block alginate), 3-8wt.% of chitosan in combination with 2-7wt.% of guar gum), 17-24wt.% of hydrophilic plasticizer (e.g., glycerin), 2-6wt.% of hydrophobic plasticizer (e.g., glyceryl tricaprylate), 2-7wt.% of wetting agent (e.g., aluminum hydroxide or a hydrate thereof), 30-40wt.% of water, and optional ingredients (e.g., 0.4-0.9wt.% of colorant).
In some aspects, a pretreatment mixture, pellet, or article is disclosed that includes: 8-33wt.% hydrocolloid (e.g., 5-15wt.% kappa-carrageenan, 0-5wt.% alginate (e.g., alginate Protanal) TM 6650 3-10wt.% chitosan (e.g., low MW crustaceans) and 20-40wt.% guar gum), 0-5wt.% wetting agent (e.g., aluminum hydroxide or a hydrate thereof), 20-45wt.% plasticizer (e.g., 20-40wt.% glycerin in combination with 0-5wt.% glyceryl tricaprylate), 0-5wt.% filler/strength modifier (e.g., microcrystalline cellulose (MCC)), 35-60wt.% water, and optional ingredients such as colorants and/or preservatives. In some aspects, a pretreatment mixture, pellet, or article is disclosed that includes: 13-33wt.% of a hydrocolloid (e.g., 10-20wt.% kappa-carrageenan, 3-10wt.% chitosan (e.g., low MW crustacean) in combination with 0-3wt.% guar gum), 0-5wt.% wetting agent (e.g., aluminum hydroxide or a hydrate thereof), 20-45wt.% plasticizer (e.g., 20-40wt.% glycerol in combination with 0-5wt.% glyceryl tricaprylate), 0-5wt.% filler/strength modifier (e.g., MCC), 35-65wt.% water, and Optional ingredients such as colorants and/or preservatives. In some aspects, a pretreatment mixture, pellet, or article is disclosed that includes: 23-63wt.% hydrocolloid (e.g., 5-15wt.% kappa-carrageenan, 5-15wt.% iota-carrageenan, 10-20wt.% alginate (e.g., alginate Protanal) TM 6650 3-10wt.% chitosan (e.g., low MW crustaceans) in combination with 0-3wt.% guar gum), 0-5wt.% wetting agent (e.g., aluminum hydroxide or a hydrate thereof), 20-45wt.% plasticizer (e.g., 20-40wt.% glycerin in combination with 0-5wt.% glyceryl tricaprylate), 0-5wt.% filler/strength modifier (e.g., MCC), 35-65wt.% water, and optional ingredients such as colorants and/or preservatives. In some aspects, a pretreatment mixture, pellet, or article is disclosed that includes: 10-28wt.% of a hydrocolloid (e.g., 10-20wt.% of kappa-carrageenan, 0-5wt.% of iota-carrageenan in combination with 0-3wt.% of guar gum), 0-5wt.% of a wetting agent (e.g., aluminum hydroxide or a hydrate thereof), 20-45wt.% of a plasticizer (e.g., 20-40wt.% of glycerol in combination with 0-5wt.% of glyceryl tricaprylate), 0-5wt.% of a filler/strength modifier (e.g., MCC), 35-65wt.% of water, and optional ingredients such as colorants and/or preservatives. In some aspects, a pretreatment mixture, pellet, or article is disclosed that includes: 13-33wt.% of a hydrocolloid (e.g., 10-20wt.% of kappa-carrageenan, 3-10wt.% of chitosan (e.g., low MW crustaceans) in combination with 0-3wt.% of locust bean gum), 0-5wt.% of a wetting agent (e.g., aluminum hydroxide or a hydrate thereof), 20-45wt.% of a plasticizer (e.g., 20-40wt.% of glycerol in combination with 0-5wt.% of glycerol trioctanoate), 0-5wt.% of a filler/strength modifier (e.g., MCC), 35-65wt.% of water, and optional ingredients such as colorants and/or preservatives. In some aspects, a pretreatment mixture, pellet, or article is disclosed that includes: 20-23wt.% of a hydrocolloid (e.g., 10-20wt.% of a combination of kappa-carrageenan and 0-3wt.% of konjac gum), 0-5wt.% of a wetting agent (e.g., aluminum hydroxide or a hydrate thereof), 20-45wt.% of a plasticizer (e.g., 20-40wt.% of glycerin in combination with 0-5wt.% of glyceryl tricaprylate), 0-5wt.% of a filler/strength A degree modifier (e.g., MCC), 35-65wt.% water, and optional ingredients such as colorants and/or preservatives. In some aspects, a pretreatment mixture, pellet, or article is disclosed that includes: 10-35wt.% of a hydrocolloid (e.g., 10-30wt.% of a combination of kappa-carrageenan and 0-5wt.% of konjac gum), 25-45wt.% of a plasticizer (e.g., 25-40wt.% of glycerol and 0-5wt.% of glyceryl trioctanoate), 5-15wt.% of a hydrophobic additive (e.g., palm stearin), 0-5wt.% of a filler/strength modifier (e.g., MCC), 30-50wt.% of water, and optional ingredients such as colorants and/or preservatives. In some aspects, a pretreatment mixture, pellet, or article is disclosed that includes: 10-35wt.% of a hydrocolloid (e.g., 10-30wt.% of a combination of kappa-carrageenan and 0-5wt.% of konjac gum), 25-45wt.% of a plasticizer (e.g., 25-40wt.% of glycerol and 0-5wt.% of glyceryl trioctanoate), 5-15wt.% of a hydrophobic additive (e.g., carnauba wax), 0-5wt.% of a filler/strength modifier (e.g., MCC), 30-50wt.% of water, and optional ingredients such as colorants and/or preservatives. In some aspects, a pretreatment mixture, pellet, or article is disclosed that includes: 10-35wt.% of a hydrocolloid (e.g., 10-30wt.% of a combination of kappa-carrageenan and 0-5wt.% of konjac gum), 25-45wt.% of a plasticizer (e.g., 25-40wt.% of glycerol and 0-5wt.% of glyceryl trioctanoate), 0-3wt.% of a hydrophobic additive (e.g., zein), 0-5wt.% of a filler/strength modifier (e.g., MCC), 30-60wt.% of water, and optional ingredients such as colorants and/or preservatives. In some aspects, a pretreatment mixture, pellet, or article is disclosed that includes: 10-35wt.% of a hydrocolloid (e.g., 10-30wt.% of a combination of kappa-carrageenan and 0-5wt.% of konjac gum), 0-15wt.% of a filler/strength modifier (e.g., 0-10wt.% of calcium carbonate or a hydrate thereof in combination with 0-5wt.% of MCC), 10-30wt.% of a plasticizer (e.g., 10-25wt.% of a combination of glycerol and 0-5wt.% of glyceryl tricaprylate), 20-80wt.% of water, and optional ingredients such as colorants and/or preservatives. In some aspects, a pretreatment mixture, pellet, or article is disclosed that includes: 15-40w t.% hydrocolloid (e.g., 15-30wt.% kappa-carrageenan in combination with 0-10wt.% konjac gum), 0-15wt.% filler (e.g., 0-10wt.% calcium carbonate or hydrate thereof in combination with 0-5wt.% MCC), 0-5wt.% inorganic crosslinker (e.g., zirconium potassium carbonate or hydrate thereof (e.g., zirmel) TM 1000 5-25wt.% > (e.g., a combination of 5-20wt.% glycerin with 0-5wt.% glyceryl tricaprylate), 30-80wt.% water, and optional ingredients such as colorants and/or preservatives). In some aspects, a pretreatment mixture, pellet, or article is disclosed that includes: 10-40wt.% of hydrocolloid (e.g., 10-30wt.% of kappa-carrageenan in combination with 0-10wt.% of konjac gum), 0-15wt.% of filler (e.g., 0-10wt.% of calcium carbonate or a hydrate thereof in combination with 0-5wt.% of MCC), 0-3wt.% of inorganic cross-linking agent (e.g., alum (e.g., KAl (SO) 4 ) 2 *12H 2 O), 5-25wt.% of a plasticizer (e.g., a combination of 5-20wt.% glycerin with 0-5wt.% glyceryl tricaprylate), 40-80wt.% water, and optional ingredients such as colorants and/or preservatives. In some aspects, a pretreatment mixture, pellet, or article is disclosed that includes: 10-40wt.% of a hydrocolloid (e.g., 10-30wt.% of a combination of kappa-carrageenan and 0-10wt.% of konjac gum), 0-15wt.% of a filler (e.g., 0-10wt.% of calcium carbonate or a hydrate thereof in combination with 0-5wt.% of MCC), 0-3wt.% of an inorganic cross-linking agent (e.g., zirconium acetate), 5-25wt.% of a plasticizer (e.g., 5-20wt.% of glycerol in combination with 0-5wt.% of glyceryl tricaprylate), 40-80wt.% of water, and optional ingredients such as colorants and/or preservatives. In some aspects, a pretreatment mixture, pellet, or article is disclosed that includes: 10-40wt.% of a hydrocolloid (e.g., 10-30wt.% of a combination of kappa-carrageenan and 0-10wt.% of konjac gum), 5-15wt.% of a filler (e.g., calcium carbonate or a hydrate thereof), 5-25wt.% of a plasticizer (e.g., 5-20wt.% of glycerol in combination with 0-5wt.% of glyceryl tricaprylate), 40-80wt.% of water, and optional ingredients such as colorants and/or preservatives. In some aspects, a pretreatment mixture, pellet, or article is disclosed that includes: 10-50wt.% hydrocolloid (e.g., 10-30wt.% kappa) Carrageenan, a combination of 0-10wt.% chitosan (e.g. low MW crustaceans) with 0-10wt.% konjac gum), 5-15wt.% filler (e.g. calcium carbonate or a hydrate thereof), 5-25wt.% plasticizer (e.g. a combination of 5-20wt.% glycerol with 0-5wt.% glyceryl tricaprylate), 40-80wt.% water and optional ingredients such as colorants and/or preservatives. In some aspects, a pretreatment mixture, pellet, or article is disclosed that includes: 10-50wt.% of a hydrocolloid (e.g., 10-30wt.% of kappa-carrageenan, 0-10wt.% of chitin (e.g., from crustaceans) in combination with 0-10wt.% of konjac gum), 5-15wt.% of a filler (e.g., calcium carbonate or a hydrate thereof), 5-25wt.% of a plasticizer (e.g., 5-20wt.% of glycerol in combination with 0-5wt.% of glyceryl tricaprylate), 40-80wt.% of water, and optional ingredients such as colorants and/or preservatives. In some aspects, a pretreatment mixture, pellet, or article is disclosed that includes: 10-50wt.% of a hydrocolloid (e.g., 10-30wt.% of kappa-carrageenan, 0-10wt.% of chitosan and 0-10wt.% of chitin (e.g., from crustaceans) in combination with 0-10wt.% of konjac gum), 5-15wt.% of a filler (e.g., calcium carbonate or a hydrate thereof), 5-25wt.% of a plasticizer (e.g., 5-20wt.% of glycerol in combination with 0-5wt.% of glyceryl tricaprylate), 40-80wt.% of water, and optional ingredients such as colorants and/or preservatives. In some aspects, a pretreatment mixture, pellet, or article is disclosed that includes: 10-40wt.% of a hydrocolloid (e.g., 10-30wt.% of a combination of kappa-carrageenan and 0-10wt.% of konjac gum), 5-20wt.% of a plasticizer (e.g., glycerol), 0-10wt.% of a hydrophobic additive (e.g., lignin powder)), 0-10wt.% of a filler/strength modifier (e.g., calcium carbonate or a hydrate thereof), 40-70wt.% of water, and optional ingredients such as colorants and/or preservatives.
In some aspects, a method for producing an edible and/or biodegradable article or pellet is disclosed. In some aspects, the method includes introducing a mixture including a hydrocolloid (e.g., including alginate or kappa-carrageenan), a water-based liquid, a wetting agent, a plasticizer, and optional ingredients into a mold including at least one internal form and one or more external forms, thereby allowing the hydrocolloid to set, removing the external mold form, dehydrating the hydrocolloid while on the internal mold form, and removing the article from the internal mold form. In some aspects, the method includes introducing a mixture including a hydrocolloid, a water-based liquid, a wetting agent, a plasticizer, and optional ingredients into a mold including at least one internal form and one or more external forms, thereby allowing the hydrocolloid to set, removing the internal mold form, dehydrating the hydrocolloid while on the external mold form, and removing the article from the external mold form. In some aspects, the method includes introducing a mixture including a hydrocolloid, a water-based liquid, a wetting agent, a plasticizer, and optional ingredients into a mold including at least one internal form and one or more external forms, thereby allowing the hydrocolloid to set, dehydrating the hydrocolloid while on the internal and external mold forms, and removing the article from the internal and external mold forms. In some aspects, the composition is mixed and extruded (e.g., cold extruded and/or hot extruded) into an article (e.g., a straw, cup, or appliance). In some aspects, the extruded article is immersed in a crosslinking bath, then rinsed to eliminate excess crosslinking agent, and dried to eliminate excess water.
In some aspects, a method for producing an edible and/or biodegradable article or pellet, particularly an article comprising kappa-carrageenan, is disclosed. In some aspects, the method includes compounding the pretreatment mixture into pellets using a twin screw hot melt extruder. In some aspects, the pellets are processed into a desired form, such as an article or a straw, on conventional machinery, including an extruder and/or an injection molding machine. In some aspects, the pellets are extruded into articles such as straws using a single screw extruder. In some aspects, the pellets are extruded into articles such as straws using a single screw extruder with a universal screw and a tubular die. In some aspects, the universal screw has a compression ratio of 3:1. In some aspects, the resulting article, such as a straw, is air cooled and cut to length. In some aspects, extrusion into pellets and/or articles is performed at elevated temperatures relative to typical room temperatures, e.g., each extrusion temperature is independently 70-100 ℃, 70-99 ℃, 70-95 ℃, 75-95 ℃, or 85-100 ℃.
In some aspects, a pretreatment mixture or pellet comprising a hydrocolloid, a wetting agent, and a plasticizer is disclosed that produces an article that is biodegradable, flexible, strong, and water resistant in some aspects.
In some aspects, a pretreatment mixture or pellet comprising a hydrocolloid, a filler, and a plasticizer is disclosed that produces an article that is biodegradable, flexible, strong, and water resistant in some aspects.
Various aspects are contemplated herein, several of which are set forth in the following paragraphs. It is expressly contemplated that any aspect or portion thereof may be combined to form an aspect.
Aspect 1: an article, pellet, or pretreatment mixture comprising, consisting of, or consisting essentially of: at least one hydrocolloid, at least one plasticizer, at least one wetting agent, or at least one filler, or a combination thereof, and water, each of which is described elsewhere herein.
Aspect 2: the article, pellet, or pretreatment mixture of aspect 1 comprising, consisting of, or consisting essentially of: at least one hydrocolloid, at least one plasticizer, at least one wetting agent, and water, each of which are described elsewhere herein.
Aspect 3: the article, pellet, or pretreatment mixture of aspect 2, comprising, consisting of, or consisting essentially of no filler.
Aspect 4: the article, pellet, or pretreatment mixture of aspect 1 comprising, consisting of, or consisting essentially of: at least one hydrocolloid, at least one plasticizer, at least one filler, and water, each of which are described elsewhere herein.
Aspect 5: the article, pellet, or pretreatment mixture of aspect 4, comprising, consisting of, or consisting essentially of no wetting agent.
Aspect 6: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one hydrocolloid is derived from a biological source.
Aspect 7: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one hydrocolloid comprises alginate, agar, chitin, chitosan, pectin, carrageenan (e.g., kappa, iota, lambda, or a combination thereof), gelatin, cornstarch, natural gum, gellan gum (gellan gum), guar gum, acacia gum, isomalt, konjac gum, lecithin, locust bean gum, maltodextrin, methylcellulose, sodium alginate, xanthan gum, tapioca flour, or any combination thereof.
Aspect 8: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one hydrocolloid comprises an alginate and chitosan.
Aspect 9: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one hydrocolloid comprises a high G block alginate and a high M block alginate.
Aspect 10: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one hydrocolloid comprises, as the case may be, based on the total weight of the article, pellet, or pretreatment mixture: an alginate in an amount of about 5wt.% to about 30 wt.%; chitosan and/or chitin in an amount of about 0.5wt.% to about 10 wt.%; and guar gum in an amount of about 0.5wt.% to about 10 wt.%.
Aspect 11: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one hydrocolloid comprises carrageenan.
Aspect 12: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one hydrocolloid comprises kappa-carrageenan.
Aspect 13: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one hydrocolloid comprises a combination of carrageenan and at least one of alginate, chitin, or chitosan.
Aspect 14: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one hydrocolloid comprises, as the case may be, based on the total weight of the article, pellet, or pretreatment mixture: kappa-carrageenan in an amount of 10 to 20 wt.%; and chitin and/or chitosan in a total amount of 5wt.% to 15 wt.%.
Aspect 15: the article, pellet or pretreatment mixture of any of the preceding aspects, wherein the at least one hydrocolloid comprises chitosan, optionally the chitosan comprises crustacean chitosan, and optionally the crustacean chitosan comprises low molecular weight crustacean chitosan.
Aspect 16: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one hydrocolloid comprises chitin, optionally the chitin comprises milled chitosan, and optionally the chitin comprises low molecular weight crustacean chitin.
Aspect 17: the article, pellet or pretreatment mixture according to any of the preceding aspects, comprising a total amount of 1 to 40wt.% hydrocolloid, as the case may be, based on the total weight of the article, pellet or pretreatment mixture.
Aspect 18: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one plasticizer comprises glycerin, sugar alcohol, microcrystalline cellulose, acacia, shellac, genipin (genepin), nanoemulsion, algae oil, coconut oil, treated shea butter, ester gum, carnauba wax, palm stearin, thermoplastic cellulose ether (e.g., ethocell) TM ) Zein, citrate, phthalate, adipate, fatty acid or any alkylated or esterified version thereof or any combination thereof.
Aspect 19: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one plasticizer comprises glycerin.
Aspect 20: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one plasticizer comprises a combination of: hydrophilic plasticizers and hydrophobic plasticizers.
Aspect 21: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one plasticizer comprises a combination of: glycerol and/or sugar alcohols, and alkylated or esterified glycerol or alkylated or esterified sugar alcohols.
Aspect 22: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one plasticizer comprises a combination of: glycerol and esterified or alkylated glycerol, wherein the esterified or alkylated glycerol has 4 to 15 carbon atoms in the ester group or alkyl group.
Aspect 23: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the total amount of the at least one plasticizer is 15wt.% to 40wt.%.
Aspect 24: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one plasticizer comprises a hydrophilic plasticizer in an amount of 15wt.% to 40wt.% and a hydrophobic plasticizer in an amount of 0.5wt.% to 10 wt.%.
Aspect 25: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one plasticizer comprises a hydrophilic plasticizer in an amount of 5wt.% to 15wt.% and a hydrophobic plasticizer in an amount of 0.5wt.% to 5 wt.%.
Aspect 26: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one filler is present and comprises a starch (e.g., corn starch), microcrystalline cellulose (MCC), guar gum, carboxymethyl cellulose, citrus fiber, mineral salts, calcium carbonate, or a hydrate thereof, a salt or compound that is a hydroxide, sulfate, chloride, carbonate, oxide, aluminate, silicate, acetate, silica (silica), pentasodium triphosphate, sepiolite, silica (silica), zeolite, or any hydrate thereof, or any combination thereof.
Aspect 27: the article, pellet or pretreatment mixture according to any of the preceding aspects, wherein the at least one wetting agent is present and comprises a salt or compound that is a hydroxide, sulfate, chloride, carbonate, oxide, aluminate, silicate, acetate, silica (silica), pentasodium triphosphate, sepiolite, silica (silica dioxide), zeolite or any hydrate thereof, or any combination thereof.
Aspect 28: the article, pellet, or pretreatment mixture of aspect 27 or any of the preceding aspects, wherein the salt or the compound is a salt of an alkali metal, an alkaline earth metal, aluminum, or any combination thereof.
Aspect 29: the article, pellet, or pretreatment mixture of aspect 27 or any of the preceding aspects, wherein the hydroxide comprises aluminum hydroxide, calcium hydroxide, or a hydrate thereof; the sulfate includes calcium sulfate, magnesium bisulfate, sodium sulfate, sodium bisulfate, alum (e.g., KAl (SO) 4 ) 2 ) Or a hydrate thereof; the chloride comprises calcium chloride, magnesium chloride or a hydrate thereof; the carbonate includes calcium carbonate, potassium carbonate, magnesium carbonate, zirconium potassium carbonate (e.g., zirmel TM 1000 Or a hydrate thereof; the oxide comprises calcium oxide, magnesium oxide, aluminum oxide or hydrate thereof; the aluminate comprises calcium aluminate or a hydrate thereof; the silicate comprises calcium silicate, potassium silicate, lithium silicate, magnesium silicate or a hydrate thereof; or the acetate salt comprises sodium acetate, potassium acetate, zirconium acetate or a hydrate thereof; or any combination thereof.
Aspect 30: the article, pellet, or pretreatment mixture of any of the preceding aspects, further comprising a colorant, a flavoring agent, or a combination thereof.
Aspect 31: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one wetting agent is present and comprises a hydrochloride salt or a hydrate thereof.
Aspect 32: the article, pellet, or pretreatment mixture of aspect 31 or any of the preceding aspects, wherein the hydroxide is a salt of an alkali metal, alkaline earth metal, or aluminum.
Aspect 33: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one wetting agent is present in an amount of 0.5wt.% to 10wt.% as the case may be, based on the total weight of the article, pellet, or pretreatment mixture.
Aspect 34: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the water is present in an amount of 20wt.% to 70 wt.%.
Aspect 35: an article, pellet or pretreatment mixture according to any of the preceding aspects comprising a weight ratio of total hydrocolloid to wetting agent of from 5:1 to 15:1.
Aspect 36: the article, pellet or pretreatment mixture according to any of the preceding aspects comprising a weight ratio of total hydrocolloid to total plasticizer of from 0.1:1 to 5:1.
Aspect 37: an article, pellet or pretreatment mixture according to any of the preceding aspects comprising a weight ratio of total hydrocolloid to hydrophobic plasticizer of from 1:1 to 20:1.
Aspect 38: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one hydrocolloid comprises at least one alginate, and wherein the article, the pellet, or the pretreatment mixture comprises a weight ratio of total alginate to total plasticizer of from 0.07:1 to 0.8:1.
Aspect 39: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one hydrocolloid comprises at least one alginate, and wherein the article, the pellet, or the pretreatment mixture comprises a weight ratio of total alginate to hydrophobic plasticizer of from 1:1 to 10:1.
Aspect 40: the article, pellet or pretreatment mixture of any of the preceding aspects, wherein the at least one hydrocolloid comprises at least one alginate, and wherein the article, pellet or pretreatment mixture comprises a weight ratio of total alginate to chitosan of from 1:1 to 10:1.
Aspect 41: the article, pellet or pretreatment mixture of any of the preceding aspects, wherein the at least one hydrocolloid comprises at least one alginate, and wherein the article, pellet or pretreatment mixture comprises a weight ratio of total alginate to wetting agent of from 1:1 to 10:1.
Aspect 42: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one filler is present and comprises calcium carbonate or a hydrate thereof.
Aspect 43: the article, pellet, or pretreatment mixture of any of the preceding aspects, wherein the at least one filler is present in an amount of 5wt.% to 15wt.% as the case may be, based on the total weight of the article, pellet, or pretreatment mixture.
Aspect 44: the article, pellet, or pretreatment mixture according to any of the preceding aspects, further comprising at least one inorganic crosslinking agent.
Aspect 45: the article, pellet, or pretreatment mixture of aspect 44 or any of the preceding aspects, wherein the at least one inorganic crosslinking agent is present in an amount of 1wt.% to 10wt.% as the case may be, based on the total weight of the article, pellet, or pretreatment mixture.
Aspect 46: the article, pellet, or pretreatment mixture of aspects 44 or 45 or any of the preceding aspects, wherein the at least one inorganic crosslinking agent comprises zirconium acetate, potassium zirconium carbonate (e.g., zirmel TM 1000 Ammonium zirconium carbonate (e.g. available from Luxfer MEL technology)Bacote obtained from department (Luxfer MEL Technologies) TM ) Alum (e.g., KAl (SO) 4 ) 2 ) Calcium chloride, or any combination thereof.
Aspect 47: the article, pellet, or pretreatment mixture according to any of the preceding aspects, further comprising at least one hydrophobic additive.
Aspect 48: the article, pellet, or pretreatment mixture of aspect 47 or any of the preceding aspects, the at least one hydrophobic additive being present in an amount of 1wt.% to 15wt.% as the case may be, based on the total weight of the article, pellet, or pretreatment mixture.
Aspect 49: the article, pellet, or pretreatment mixture of aspect 47 or aspect 48, wherein the at least one hydrophobic additive comprises palm stearin, carnauba wax, zein, lignin, a hydrophobic plasticizer, an edible oil, a coating, or any combination thereof.
Aspect 50: the article, pellet or pretreatment mixture of any of the preceding aspects, wherein the at least one hydrocolloid comprises kappa-carrageenan and the article, pellet or pretreatment mixture comprises a weight ratio of kappa-carrageenan to total plasticizer of from 0.5:1 to 4:1.
Aspect 51: the article, pellet or pretreatment mixture of the preceding aspect, wherein the at least one hydrocolloid comprises kappa-carrageenan and the article, pellet or pretreatment mixture comprises a weight ratio of kappa-carrageenan to hydrophilic plasticizer of from 0.6:1 to 4:1.
Aspect 52: the article, pellet or pretreatment mixture of any of the preceding aspects, wherein the at least one hydrocolloid comprises kappa-carrageenan and the article, pellet or pretreatment mixture comprises a weight ratio of kappa-carrageenan to hydrophobic plasticizer of from 5:1 to 40:1.
Aspect 53: the article, pellet or pretreatment mixture of any of the preceding aspects, wherein the at least one hydrocolloid comprises kappa-carrageenan and the article, pellet or pretreatment mixture comprises a weight ratio of kappa-carrageenan to total filler of from 1:1 to 4:1.
Aspect 54: the article, pellet or pretreatment mixture of any of the preceding aspects, wherein the at least one hydrocolloid comprises kappa-carrageenan, and the weight ratio of kappa-carrageenan to total other hydrocolloids of the article, the pellet or the pretreatment mixture is from 0.6:1 to 4:1.
Aspect 55: a method for preparing an article, the method comprising, consisting of, or consisting essentially of: combining at least one hydrocolloid, at least one plasticizer, at least one wetting agent or filler, or a combination thereof, water, and optionally at least one colorant to prepare a pretreatment mixture; optionally, compounding the pretreatment mixture into a pellet; shaping the pre-treatment mixture or the pellets into a shape; optionally, immersing the shape in a crosslinking bath to shape the crosslinked shape; optionally, rinsing the crosslinked shape to remove excess crosslinking agent; and drying the shape, optionally cross-linking, to shape the article, optionally shaping the article on a mandrel; wherein the at least one hydrocolloid, the at least one plasticizer and the at least one filler are as defined in any one of the preceding aspects.
Aspect 56: the method of aspect 55, wherein the at least one hydrocolloid comprises carrageenan and at least one of chitosan and chitin.
Aspect 57: the method of aspect 56, wherein the shaping comprises molding, extruding, casting, or any combination thereof.
Aspect 58: the method of aspect 56 or aspect 57, wherein the shaping comprises hot melt extrusion.
Aspect 59: the method of aspect 58, wherein the hot melt extruding comprises a single screw extruder utilizing a universal screw with a compression ratio of 3:1 and a tubular die at a temperature of 75 ℃ to 95 ℃ and at a screw speed of 5rpm to 50 rpm.
Aspect 60: the method of any one of aspects 55 to 59, wherein the method is a continuous hot melt extrusion process.
Aspect 61: the method of any one of aspects 55 to 60, wherein the compounding is performed.
Aspect 62: the method of any one of aspects 55 to 61, further comprising applying a coating or optionally an edible coating to the article.
Aspect 63: the method of aspect 62, wherein the applying comprises spraying, dipping, brushing, edible inkjet printing, co-extrusion, or any combination thereof.
Aspect 64: the method of aspect 62, wherein the applying comprises immersing the article in a solution of a coating component in a solvent.
Aspect 65: the article or pellet of aspect 62, wherein the coating or the edible coating comprises an oil coating, a wax coating, a confectionary's glaze, or a combination thereof.
Aspect 66: the article or pellet of aspect 62, wherein the coating or the edible coating comprises the wax coating and the wax coating comprises beeswax, carnauba wax, soy wax, rice bran wax, shellac, or a combination thereof.
Aspect 67: the article of any one of the preceding aspects, which exhibits a tensile strength of from 10MPa to 30MPa.
Aspect 68: the article of any one of the preceding aspects, which exhibits a Young's modulus (Young's modulus) of from 50MPa to 250MPa.
Aspect 69: the article according to any one of the preceding aspects, which exhibits a compressive strength of from 10MPa to 25MPa.
Aspect 70: the article according to any one of the preceding aspects, which exhibits a swelling ratio in room temperature water of 0% to 50%.
Aspect 71: the article according to any one of the preceding aspects, which exhibits a swelling ratio in a cold non-alcoholic beverage of 0% to 40%.
Aspect 72: the article according to any one of the preceding aspects, which exhibits a swelling ratio in cold alcoholic beverages of 0% to 50%.
Aspect 73: the article of any one of the preceding aspects, which exhibits a swelling ratio in a cold carbonated beverage of from 0% to 50%.
Aspect 74: a process for preparing a pellet, the process comprising, consisting of, or consisting essentially of: combining at least one hydrocolloid, at least one plasticizer, at least one filler or wetting agent or combination thereof, water, and optionally at least one colorant to prepare a pretreatment mixture; compounding the pre-treatment mixture into the pellets; and optionally applying a coating to the pellet by spraying, immersing, dipping, brushing, edible ink-jet printing, coextrusion, or any combination thereof, wherein the coating comprises an oil coating, a wax coating, a sugar coating of a confectionary, or any combination thereof; wherein the at least one hydrocolloid, the at least one plasticizer and the at least one filler are as defined in any one of the preceding aspects.
Aspect 75: the method of aspect 74, wherein the compounding comprises extruding with a twin screw hot melt extruder at a temperature of 85 ℃ to 100 ℃, at a screw speed of 200-300rpm, and at a feed weight ratio of solids to liquid of 0.25:1 to 1:1.
Aspect 76: the method of any one of aspects 55 to 75, wherein the at least one hydrocolloid comprises alginate and chitosan.
Aspect 77: the method according to any one of aspects 55 to 75, wherein the at least one hydrocolloid is a combination of carrageenan with chitin and/or chitosan.
Aspect 78: the method of aspect 77, wherein the carrageenan comprises kappa-carrageenan.
Without wishing to be bound by any particular theory, there may be a discussion herein of the belief or understanding of the underlying principles related to the apparatus and methods disclosed herein. It should be appreciated that embodiments of the present invention may still be operable and useful regardless of any mechanical interpretation or assumed final correctness.
Drawings
Figure 1 shows carbon dioxide (CO) for preparing a single straw made of different materials 2 ) And (3) generating. The technology disclosed herein uses CO 2 To provide fuel for the production of seaweed.
FIG. 2 is a flow chart illustrating an exemplary method of the present disclosure for molding an exemplary article, particularly a beverage straw.
Detailed Description
Statement regarding chemical compounds and terms
In general, terms and phrases used herein have their art-recognized meanings, which can be found by standard text, journal references, and the context known to those skilled in the art. The following definitions are provided to illustrate specific uses thereof in the context of the present invention.
As used herein, the term "about" means that minor variations from the recited value can be used to achieve substantially the same result as the recited value with respect to the composition, or that minor variations from the recited value are acceptable (i.e., not deleterious) to the recited value with respect to a given property with respect to the property. In the case where the present definition is not applicable or very difficult to apply, the term "about" means a 10% deviation (positive or negative) from the stated value. In any event, for any individual number or number within a certain range, it is understood that certain variations in the specific values may be adjusted without losing significant benefit or causing significant damage. In this regard, such non-detrimental variations allowed for a given number or range are typically 10% or less of the recited number or range. Likewise, the disclosure of a range is intended to be a continuous range, including every value between the minimum and maximum values recited, as well as any ranges that may be formed from such 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, the skilled artisan will recognize that many such ratios, ranges, and ranges of ratios can be explicitly deduced from the values presented herein; and in all cases such ratios, ranges, and ranges of ratios are indicative of the various embodiments of the invention.
As used herein, the term "sugar-free" means that the pretreatment mixture or preparation is substantially free of dietary sugars, such as glucose, sucrose, and fructose. As used herein, the term "low sugar" refers to an edible composition having less than 10% by weight of dietary sugar, and preferably less than about 5% by weight, particularly in its post-processed form. In some aspects, the articles and pretreatment mixtures herein are sugar-free. In some aspects, the articles, pellets, and pretreatment mixtures herein are low sugar.
As used herein, unless otherwise indicated, the percentages of the components in the article, pellet, or pretreatment mixture are weight percentages. Furthermore, unless otherwise indicated, all weight percent values are based on the total weight of the relevant composition, pretreatment mixture, pellet, or article. For example, when the pretreatment mixture is disclosed as having 10wt.% plasticizer, the 10wt.% is based on the total weight of the pretreatment mixture (100 wt.%) including water and other components. Furthermore, when "article, pellet, or pretreatment mixture" is disclosed as having "as the case may be," or "as the case may be" an amount of a component, such term means that any or all of the article, pellet, or pretreatment mixture may have the specified amount of the given component.
As used herein, the term "edible" refers to an item that may be safely consumed by a consumer, but may or may not be palatable or readily edible.
As used herein, the term "biopolymer" refers to a polymer derived from biological sources such as plants, fungi, or animals, and comprises polysaccharides derived from such sources. One particularly useful source of biopolymers is algae, including brown, red or green algae, and green yellow or golden algae.
As used herein, the term "biodegradable" refers to an article that is capable of decomposing into harmless products under typical environmental conditions by the action of living matter (e.g., microorganisms). In some aspects, an article is biodegradable if the article can be broken down into harmless products as mentioned above in a time frame of about 3 months to about 6 months.
As used herein, the term "chitin" is a long polymer of N-acetylglucosamine derived from biological sources, such as arthropods, such as crustaceans (e.g., crab shells) and exoskeletons of insects, or cell walls of fungi. Chitin may be present in the form of complexes in natural sources, for example complexes with calcium carbonate in crustacean shells. Pure chitin is presently preferred for use in the present disclosure rather than complex chitin. It is believed that chitin acts as a hydrocolloid in the articles, pellets, and pretreatment mixtures disclosed herein, but may also serve an alternative or additional function in the pretreatment mixtures, pellets, and/or articles. In some aspects, chitin has a viscosity average molecular weight (kDa) of 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or 1000. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, chitin can have a viscosity average molecular weight (kDa) of 250, about 250, 200 to 300, about 300, 750, about 750, 500 to 800, or less than 350.
As used herein, the term "chitosan" is a deacetylated form of chitin, typically with randomly distributed β - (1-4) -linked D-glucosamine and N-acetyl-D-glucosamine. Chitin is typically deacetylated by treatment with a base such as sodium hydroxide. Commercially available chitosan can be characterized by a Degree of Deacetylation (DD), typically in the range of 60% to 100%, and a viscosity average molecular weight, typically in the range of 3800 daltons to 800,000 daltons. In some aspects, chitosan having a viscosity average molecular weight in the range of 50,000 daltons to 400,000 daltons is employed. In some aspects, "low molecular weight chitosan" or "low MW chitosan" is employed and refers to chitosan having a viscosity average molecular weight of 50,000 daltons to 190,000 daltons. Ultra-low molecular weight chitosan (e.g., chitin having 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 greater is employed. In some aspects, chitosan having a DD% of 75% -85% is employed.
It is believed that chitosan acts as a hydrocolloid in the articles and pretreatment mixtures disclosed herein, but may also serve an alternative or additional function in the pretreatment mixtures, pellets and/or articles.
As used herein, the term "compostable" refers to an item that is capable of decomposing into harmless natural products under natural composting conditions. Thus, a material is said to be compostable when it can be biodegradable during composting and is preferably biodegradable by the action of naturally occurring microorganisms under naturally occurring composting conditions and highly biodegradable within a defined time frame. In some aspects, the compostable materials degrade under natural (home) composting conditions in less than one year, and in some aspects, to an extent of at least about 60% or at least about 80% or at least about 90% in less than about 6 months.
In some aspects, materials are determined to be "biodegradable" and "compostable" according to the definition provided in EN-13432. According to EN-13432, biodegradability is the conversion of a material into CO by the action of microorganisms 2 Is provided). This property can be measured by the laboratory standard test method EN-14046 (also published as ISO 14855: biodegradability under controlled composting conditions). To exhibit complete biodegradability, a level of biodegradability of at least 90% is reached in 6 months or less.
In some aspects, the pretreatment mixtures, pellets, and/or articles described herein also exhibit high disintegration, i.e., breaking and losing visibility (no visible contamination) in the final compost. Disintegration can be measured using a test-scale composting test (EN 14045) in which samples of test material are composted with biowaste for 3 months and the final compost is screened with a 2mm screen. The mass of the test material residue with a size greater than 2mm should be less than 10% of the original mass of the test material.
As used herein, "continuous" means a process that is not interrupted for its duration, or is only temporarily interrupted, paused, or suspended relative to the duration of the process. A hot melt extrusion process is "continuous" when the preconditioning mixture or pellet is fed into the hot melt extruder without interruption or substantial interruption, or such hot melt extrusion or preconditioning mixture or pellet is not performed in a batch process.
As used herein, the term "carrageenan" refers to seaweed derived from certain species (e.g., irish moss), typically derived from linear sulfated polysaccharides by extraction from the species. The polysaccharide comprises repeating galactose units. Carrageenan generally functions as a hydrocolloid in an aqueous environment. There are different classes of carrageenan, and it is defined in terms of sulfate content. As used herein, the term "kappa-carrageenan" refers to carrageenan having one sulfate group per disaccharide, the term "iota-carrageenan" refers to carrageenan having two sulfate groups per disaccharide, and the term "lambda-carrageenan" refers to carrageenan having three sulfate groups per disaccharide. Carrageenan may contain a polymer mixture comprising on average 1-3 sulfate groups per disaccharide, including the kappa, iota and lambda forms mentioned above, and each disaccharide having an intermediate average number of sulfate groups (e.g. between 1 and 2 or between 2 and 3, exclusively). Preferred carrageenans for use herein have on average between 1 and 2 (including 1 and 2) sulfate groups per disaccharide. Useful carrageenans are mixtures of kappa-carrageenan and iota-carrageenan. More useful carrageenans include kappa-carrageenan and less than 10wt.% other carrageenans. The most useful carrageenan is kappa-carrageenan.
As used herein, the term "wetting agent" refers to a substance that helps to retain moisture in a given product (e.g., article or pellet) or composition (e.g., pretreatment mixture). Typically, the wetting agent is a hygroscopic substance, but this is not necessarily so. The wetting agent may comprise organic substances, inorganic substances or substances having organic and inorganic characteristics.
As used herein, the term "hydrocolloid" refers to a hydrophilic polymer that swells in an aqueous environment by absorbing water. The hydrocolloids affect the rheology of the composition, which generally results in an increase in viscosity. The addition of hydrocolloid to an aqueous composition typically forms a gelled network in which the polymer chains of the hydrocolloid interact with other polymer chains of the hydrocolloid directly and/or mediated by water, ions or a combination thereof. The hydrocolloid may be derived from a number of sources, including plants, animals or microorganisms, or chemically modified versions thereof. Hydrocolloids may also be prepared synthetically. Hydrocolloids of natural origin, such as animals or plants, whether chemically modified or not, are referred to herein as "hydrocolloid biopolymers". While it is believed that certain components herein function as hydrocolloids, such components, even if classified as hydrocolloids, may actually have additional or alternative functionality, and such components are still considered "hydrocolloids" as defined herein.
As used herein, the term "pretreatment mixture" refers to a composition that is molded, extruded, or otherwise shaped into an article or pellet. After extrusion, rinsing, subsequent drying, or a combination thereof, the amount of components in the article may differ from the amount of components in the pretreatment mixture due to leaching (e.g., the hydrophilic plasticizer leaches during crosslinking and/or rinsing, thereby resulting in a reduction in the amount of hydrophilic plasticizer in the article relative to the amount of hydrophilic plasticizer in 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 amount of water in the pretreatment mixture). Typically, the relative weight ratio of certain components in the article to other components in the article is the same as the relative weight ratio of hydrocolloid to wetting agent and other hydrophobic components (e.g., hydrophobic plasticizers such as glyceryl tricaprylate or hydrophobic additives such as carnauba wax, lignin powder, etc.) in the pretreatment mixture, while the weight ratio of other components in the article (such as water and hydrophilic plasticizers, e.g., glycerol) to other components varies between the pretreatment mixture and the article for the reasons described above. Typically, in shaping (e.g., cold extrusion) the pretreatment mixture into an article that is subjected to a crosslinking bath and then rinsed and dried, the water content of the dried article is about one third (e.g., 85-95wt.% versus 28-35 wt.%) of the water content of the pretreatment mixture, and the hydrophilic plasticizer (e.g., glycerin) content in the crosslinked and rinsed article is also about one third (e.g., about 25-36wt.% versus about 8-12 wt.%) of the hydrophilic plasticizer content of the pretreatment mixture. Typically, in terms of shaping (e.g., hot melt extrusion) the pretreatment mixture into pellets that are not subjected to a crosslinking bath, flushing, or drying, such pellets have the same or substantially similar (e.g., within 10% of the value) composition and amount thereof as the pretreatment mixture. Generally, in shaping (e.g., hot melt extrusion) the pellets into an article that is not subjected to a crosslinking bath nor is rinsed, and drying such articles, the water content of the dried article is typically the same as or at most about half of the water content of the pellets (e.g., 35-50wt.% water in the pellets versus 25-35wt.% water in the dried article), and other components of the article (e.g., hydrophilic plasticizers, hydrophobic plasticizers, fillers, hydrophobic additives, etc.) are the same as the other components in the pellets.
As used herein, the term "hydrophobic" in connection with plasticizers or additives means compounds having hydrophobic properties, which generally comprise compounds comprising alkyl, ester or aryl groups, and in which there is typically little or no polar group, such as a hydroxyl or amino functional group. 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 comprise plasticizers or additives which are insoluble or only slightly soluble in water as understood in the art. Examples of hydrophobic plasticizers include, inter alia, citric acid esters, phthalic acid esters, adipic acid esters, and glycerol esters, including alkyl esters and fatty acid esters. Examples of hydrophobic additives include, inter alia, palm stearin, carnauba wax, zein, lignin, and the like.
As used herein, the term "hydrophilic" in connection with plasticizers or additives refers to compounds having hydrophilic character, which generally comprise compounds comprising polar groups, such as hydroxyl and/or amino functional groups. For example, compounds such as glycerol, sugar alcohols, and the like are hydrophilic. Hydrophilic plasticizers or additives comprise plasticizers or additives which are water soluble as understood in the art.
The terms "glycerol" and "glycerin" are used interchangeably herein and refer to the same chemical compound.
The term "composition" is used in some aspects to refer to a pretreatment mixture, and in some aspects to refer to an article or pellet, as will be apparent from the context.
Although certain components of the pretreatment mixture, pellet, or article are described herein as having a given function (e.g., hydrocolloid, plasticizer, etc.), these components may actually serve a completely different function or functions. Thus, the function of a given component is described as currently understood, but such function is a theory of operation.
When values are disclosed herein, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, the following sentences will generally follow these values: "each of the foregoing numbers may be preceded by the word 'about', 'at least about', 'less than' or 'less than about', and any of the foregoing numbers may be used individually to describe a single point or open 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 begin with the word "about" (e.g., about 8), can begin with the phrase "at least about" (e.g., at least about 2), can begin with the phrase "at least" (e.g., at least 10), can begin with the phrase "less than" (e.g., less than 1), can begin with the phrase "less than about" (e.g., less than about 7), or can be used in any combination with or without any prefix word or phrase 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.). Further, when a range is described as "about X or less," the range of combinations of "about X" and "less than about X" in this phrase and alternative is the same. For example, "about 10 or less" is the same as "about 10 or less than about 10". Such interchangeable range descriptions are contemplated herein. Other range formats may be disclosed herein, but differences in formats should not be construed as implying substantial differences.
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 compound is at least partially isolated or substantially purified, as understood in the art. In one embodiment, the substantially purified composition, compound, or formulation of the invention is 95% pure in chemical purity, optionally 99% pure for some applications, optionally 99.9% pure for some applications, optionally 99.99% pure for some applications, and optionally 99.999% pure for some applications.
In the following description, numerous specific details of the compositions, pretreatment mixtures, pellets, articles and methods made therefrom are set forth in order to provide a thorough explanation of the precise nature of the invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced without these specific details.
In some aspects, the pretreatment mixtures, pellets, and articles described herein include at least one hydrocolloid, such as an alginate, at least one plasticizer, such as glycerol, and at least one wetting agent, such as aluminum hydroxide or a hydrate thereof. In some aspects, the pretreatment mixtures, pellets, and articles described herein include at least one hydrocolloid, such as kappa-carrageenan, at least one plasticizer, such as glycerol and/or glyceryl tricaprylate, and at least one filler, such as calcium carbonate or a hydrate thereof, and/or MCC. The preconditioning mixtures, pellets, and articles such as containers, cups, utensils, or straws, may further include additional ingredients comprising one or more of sugar or non-sugar sweeteners, flavoring agents, coloring agents, active ingredients, plasticizers, humectants, hydrocolloids, edible oils, fillers (e.g., organic or inorganic), hydrophobic additives, cross-linking agents (e.g., inorganic or ionic), and natural preservatives. The article may also be coated with an edible coating to enhance the water repellency of the article, to increase the shelf life of the article, and/or to reduce the tackiness of the article or to provide a flavor, color, or graphic to the article. The article may remain in or in contact with the liquid (hot or cold) for an extended period of time, in some aspects, for more than about one hour (e.g., more than about 2 hours, more than about 3 hours, more than about 4 hours, or more than about 5 hours).
In some aspects, a method for producing a pretreatment mixture, pellets, and articles is disclosed. In one aspect, the method includes introducing a pretreatment mixture including a hydrocolloid (e.g., alginate and/or kappa-carrageenan), water, a plasticizer, and a wetting agent, and optionally additional ingredients, into a mold including at least one internal form and one or more external forms, thereby allowing the hydrocolloid to set, removing the external mold form, dehydrating the hydrocolloid while on the internal mold form, and removing the article from the internal mold form. In another aspect, a pretreatment mixture comprising hydrocolloid, plasticizer, wetting agent, water, and optional additional ingredients is extruded to provide an article, and then optionally crosslinked. In some aspects, two hydrocolloids (e.g., one or more alginates, kappa-carrageenan, and chitosan) are mixed together in the form of a powder, and the powder mixture is added to one or more plasticizers (e.g., glycerol and glycerol trioctanoate), followed by the addition of a wetting agent (e.g., aluminum hydroxide or a hydrate thereof) or filler (e.g., calcium carbonate and/or MCC). In some aspects, such mixtures are mixed and then water is added to make a dough that is heat blended and then cooled to below 50 ℃, at which point additional optional ingredients (e.g., flavor, color, or both) may be added. In some aspects, such mixtures are then extruded (e.g., hot or cold), crosslinked, rinsed, and dried.
In some aspects, a method for producing an edible and/or biodegradable article or pellet (particularly an article comprising kappa-carrageenan) is disclosed. In some aspects, the method includes compounding the pre-treatment mixture into pellets using a twin screw hot melt extruder in a continuous process at a temperature ranging from 85 ℃ to 100 ℃ and at a screw speed ranging from 200-300rpm at a feed ratio of solids to liquid ranging from any value from 1:1 to 1:4. In some aspects, the pellets are processed into a desired form, such as an article or a straw, on conventional machinery, including an extruder and/or an injection molding machine. In some aspects, the pellets are extruded into articles such as straws using a single screw extruder. In some aspects, the pellets are extruded into articles such as straws using a single screw extruder with a universal screw and a tubular die. In some aspects, the compression ratio of the universal screw is 3:1, and the extrusion is performed at a temperature in the range of 75 ℃ to 95 ℃ and at a screw speed in the range of 5rpm to 50 rpm. In some aspects, the resulting article (e.g., straw) is air cooled and cut to length.
Article of manufacture
In some aspects, the articles disclosed herein that result from pre-treating the mixture or pellets can be any suitable articles. For example, in some aspects, the article is a container, cup, lid, drinking vessel, dish, or appliance. In some aspects, the appliance is a straw (e.g., drinking straw), fork, knife, spoon, chopstick, toothpick, or whisk (e.g., drink whisk). In some aspects, the lid is a lid for a cup, a lid for a container, a lid for a tray, a lid for a dish, or an insulating lid thereof. In some aspects, the article may be any suitable article that contacts a food or beverage and facilitates preparation, consumption, service, presentation, or storage of the food or beverage. In some aspects, the article is edible, derived from a plant or animal (i.e., biobased), biodegradable, compostable, or any combination thereof. In some aspects, the article is a wound dressing. In some aspects, the article is not intended to be in contact with a food or beverage, e.g., a container for storing an item, which provides a strong but biodegradable alternative to a plastic or foam storage container.
In some aspects, the article is a drinking straw or a beverage blender. In some aspects, the drinking straw or whisk is also adapted to consume or whisk cold or hot drinks for an extended period of time without significantly reducing functionality, preferably for more than an hour or more. In some aspects, the drinking straw or stirrer may have any configuration, such as a cylindrical drinking straw or stirrer, a spoon straw or stirrer, a cocktail straw or stirrer, a foam tea straw, and the like. In some aspects, the straw or stirrer may have an inner diameter of about 2mm to about 15mm or about 3mm to about 10mm or less (particularly for stirrers, such as about 0.5mm to about 1.5 mm). In some aspects, the stirrer is hollow. In some aspects, the stirrer is not hollow.
In some aspects, the article may be in the form of other containers, lids, utensils, and other desktop containers using the same ingredients in addition to the cup, straw, and whisk. In some aspects, the article includes a drinking vessel, such as a teacup, mug, goblet, cocktail cup, low ball cup, and high ball cup; flat utensils such as spoons, knives, forks and utensils; tableware such as trays, tea trays and bowls; serving utensils, such as trays, serving bowls, pitchers, and kettles.
In some aspects, the article includes an edible shell or cup for containing a food filling. In some aspects, the edible films, skins and shells may be used to form confectioneries, pasta such as pasta, dumplings, wontons, mochi, and tortilla skins used to encase or encase food fillings such as syrups, jellies, whipped cream, chocolate, meats, vegetables, cheeses, fruits, nuts, ice cream, sauce, peanut butter, syrup, sugar, and candy. In some aspects, edible food shells or cups for holding or wrapping the food filling may also be frozen to hold frozen ingredients such as ice cream. In some aspects, the edible material may include a frozen casing for holding a flavoring for injection into the beverage.
In some aspects, the article is an edible and/or biodegradable film, coating, or packaging. In some aspects, the article is a film, coating, or package for containing a concentrate (e.g., powder) of a liquid (e.g., emulsion, soap, shampoo, or conditioner) to be dripped into water or a water-based liquid and mixed to dissolve the film, coating, or package and release the contents, thereby producing a beverage, soup, or other consumable liquid, or for topical application. In some aspects, the article is, for example, a water-soluble film, coating, or packaging for a dishwasher tablet.
In some aspects, the article is an edible garment for, for example, the intimate industry, such as edible undergarments, edible accessories, and toys. In some aspects, the concentration of the ingredients used to prepare the edible material can be adjusted by weight to produce a softer, more pliable material or a harder, more rigid material, optionally containing desired flavoring and/or coloring agents.
In some aspects, the articles disclosed herein are not in the form of sausage casings or food packaging films.
In some aspects, the article may have any suitable characteristics. For example, the article (e.g., drinking straw or beverage mixer) has a tensile strength (MPa) of 5, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, or 30. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the article (e.g., straw or stirrer) has a tensile strength of about 10 to about 30, about 8 to about 24, about 18 to about 28, at least about 14, at least 16, or at least 18. Tensile strength may be measured by any accepted method, particularly those applied to plastic sheets. For example, tensile strength may be measured using a 25mm initial gap tester (4443; instron, nerwood, mass., USA) based on ASTM D882-12 (2012).
In some aspects, the article may have any suitable characteristics. For example, an article (e.g., drinking straw or beverage mixer) has a young's modulus (MPa) of 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, or 270. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the young's modulus of the article (e.g., straw or stirrer) is about 40 to about 270, about 50 to about 250, about 140 to about 240, about 170 to about 210, at least about 150, at least 180, at least 190, at least 200, at least 210, about 150 to 230, or less than about 260. Young's modulus may be measured by any accepted method, particularly those applied to plastic sheets. For example, young's modulus may be derived from a stress-strain curve obtained according to ASTM D882-12 (2012) with an initial gap of 25mm using a tester (4443; instron, norwood, massa, USA).
In some aspects, the article may have any suitable characteristics. For example, the article (e.g., drinking straw or beverage mixer) has a compressive strength (MPa) of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, or 27. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the compressive strength of the article (e.g., straw or stirrer) is from about 5 to about 27, from about 10 to about 25, from about 8 to about 12, from about 6 to about 20, or at least about 7. Compressive strength may be measured by any accepted method, particularly those applied to plastic sheets. For example, compressive strength may be measured based on ASTM D695-15 (2018) and ASTM D2412-11 (2018) using a tensile strength tester (4443; instron, norwood, massa, USA). In this determination, both the axial configuration and the radial configuration for compression were tested, using a compression rate test of 10 mm/min for the axial configuration using a sample with a length/diameter ratio of 2, and a compression rate test of 1 mm/min for the radial configuration with a length/diameter ratio of greater than 8.
In some aspects, the article may have any suitable characteristics. For example, an article (e.g., drinking straw or beverage mixer) has a breaking force (psi) of 50, 60, 80, 90, 100, 120, 140, 160, 180, 200, 220, 24, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 480, or 500. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the breaking force (psi) is 100 to 500, 120 to 440, 200 to 360, 140 to 320, 180 to 240, or 160 to 280. The breaking force (psi) of the article was measured based on ASTM D882-12 (2012) using a universal tester (34 SC-1, instron company, norwood, ma) fitted with a 1kN load cell and an initial gap of 25 mm.
In some aspects, the article may have any suitable characteristics. For example, an article (e.g., drinking straw or beverage mixer) has an elongation at break (%) of 0.4, 1, 2, 4, 6, 8, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, or 380. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the elongation at break (%) is 0.4 to 320, 1 to 300, 1 to 20, 20 to 60, 20 to 100, 80 to 220, 100 to 340, 140 to 340, 180 to 360, 180 to 320, 200 to 320, or 80 to 260. Elongation at break (%) of the article was measured using a universal tester (34-SC-1, instron, norwood, massa, USA) equipped with a 1kN load cell and an initial gap of 25 mm. Elongation at break is determined according to the following formula: the%= (final gauge length-initial gauge length)/initial gauge length x 100.
In some aspects, different articles may have different target mechanical properties, such as flexibility, compressibility, tensile strength, young's modulus, compressive strength, or any combination thereof, depending on the identity or intended use of a given article. For example, drinking straws are typically flexible, i.e., the straw need not be flexible, but in any event, consumers typically desire a straw having some level of flexibility, even though the straw typically does not need such flexibility to function properly (e.g., to drink liquid from a cup). In contrast, utensils such as forks, knives and spoons generally do not need to be flexible, even though they may be, but rather more rigid characteristics are suitable for such utensils in view of their intended use for cutting and/or supporting food. In some aspects, the mechanical or swelling properties disclosed elsewhere herein can be improved and/or affected by the formulation components and amounts thereof.
In some aspects, the article may have any suitable characteristics. For example, the article (e.g., drinking straw or beverage mixer) is stable under room temperature water, as measured by a swell ratio of between about 0% and about 65%, or between about 0% and about 50%, or between about 0% and about 40%, or between about 0% and about 30%, or between about 0% and about 20%, or between about 0% and about 10%, wherein the article is immersed in room temperature water and the weight change is recorded after 1 hour. The percent swell is the percentage of weight increase of the article due to the absorption of water.
In some aspects, the article may have any suitable characteristics. For example, the article (e.g., drinking straw or beverage mixer) is stable in cold non-alcoholic beverages, exhibiting a swelling rate of between about 0% and about 65%, or between about 0% and about 50%, or between about 0% and about 40%, or between about 0% and about 30%, or between about 0% and about 20%, or between about 0% and about 10%, wherein the article is immersed in the cold non-alcoholic beverage and the weight change is recorded after 1 hour. The percent swell is the percentage of weight increase of the article due to the absorption of water.
In some aspects, the article may have any suitable characteristics. For example, the article (e.g., drinking straw or beverage stirrer) is stable in a cold alcoholic beverage having about 20vol.% alcohol, exhibiting a swelling ratio of between about 0% and about 65%, or between about 0% and about 50%, or between about 0% and about 40%, or between about 0% and about 30%, or between about 0% and about 20%, or between about 0% and about 10%, wherein the article is immersed in the cold alcoholic beverage and the weight change is recorded after 1 hour. The percent swell is the percentage of weight increase of the article due to the absorption of water.
In some aspects, the article may have any suitable characteristics. For example, the article (e.g., drinking straw or beverage mixer) is stable in a cold carbonated beverage, exhibiting a swelling ratio of between about 0% and about 65%, or between about 0% and about 50%, or between about 0% and about 40%, or between about 0% and about 30%, or between about 0% and about 20%, or between about 0% and about 10%, wherein the article is immersed in the cold carbonated beverage and the weight change is recorded after 1 hour. The percent swell is the percentage of weight increase of the article due to the absorption of water.
In some aspects, swelling may be reduced, e.g., reduced or prevented, by increasing the crosslink density.
In some aspects, the article may have any suitable characteristics. For example, the article (e.g., drinking straw or beverage blender) exhibits a material transfer to a liquid having a fumarwell turbidity unit (FNU) of between about 0 and about 1, as measured by immersing thirty articles (e.g., straw) in 1L of room temperature water for 24 hours and measuring turbidity and determining FNU.
In some aspects, the article maintains suitable flexibility, moisture barrier properties, and structural integrity for an extended period of time at room temperature and 50% relative humidity without any packaging (e.g., packaging with moisture and/or air barrier properties). In some aspects, an "extended period of time" is the shelf life of the article. In some aspects, an "extended period of time" is 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 365, 370, 380, 390, 400, 450, 500, 550, 600, 650, 700, 800, or 1000. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the extended period of time (days) is at least 10 days, at least 20 days, at least 26 days, at least 28 days, at least 30 days, at least 32 days, at least 40 days, 20 days to 40 days, about 24 days to about 36 days, 28 days to 60 days, at least 150 days, 30 days to 120 days, 120 days to 365 days, 150 days to 365 days, 30 days to 1000 days, or 24 days to 48 days. In some aspects, the article does not exhibit any change in mechanical properties (e.g., one or more of tensile strength, young's modulus, compressive strength, or swelling rate in room temperature water) when the article is maintained at room temperature and 50% relative humidity for an extended period of time.
In some aspects, the article has a neutral odor. In some aspects, the product has a neutral taste. In some aspects, the article has a neutral odor and a neutral taste. In some aspects, neutral odor and/or taste is achieved without the addition of any fragrances and/or perfumes. In some aspects, whether the article has a neutral odor and/or taste is determined by investigating a panel of panelists who are not biased (i.e., panelists who are not at risk for the outcome of the odor/taste evaluation).
In some aspects, the pretreatment mixture and/or the article does not comprise a plurality of pores. In some aspects, the pretreatment mixture and/or article does not include a plurality of pores sized and configured in such a way as to allow water or bacteria to penetrate or penetrate into the pores to promote biodegradability. In some aspects, the pretreatment mixture and/or the article does not comprise pores having a diameter of about 500nm or less. In some aspects, the pretreatment mixture and/or article has a density other than about 0.6g/cm 3 To about 1.3g/cm 3 . In some aspects, the pretreatment mixture and/or article has a porosity that is not at least 10%, at least 15%, at least 20%, at least 25%, or at least 30%.
Pellet material
In some aspects, the pre-treatment mixture may first be shaped (e.g., compounded) into pellets. In some aspects, the pellets are then used to shape an article, such as a drinking straw. In some aspects, the preconditioning mixture is compounded into pellets using a twin screw hot melt extruder at a temperature ranging from 70-100 ℃ (e.g., 85-100 ℃). In some aspects, the screw speed is from 150rpm to 450rpm (e.g., 200-300 rpm), as described elsewhere herein. In some aspects, the feed weight ratio of solids to liquids ranges from 1:1 to 1:6, e.g., 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, or 1:6, as described elsewhere herein. Each of the foregoing ratios may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing ratios may be used alone to describe a single point or open range, or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the solids to liquid feed weight ratio is from 1:1 to 1:4, from about 1:1.5 to 1:5.5, or from 1:3 to 1:4.5.
In some aspects, the composition of the pellets is the same as the composition of the pretreatment mixture used to prepare the pellets. Specifically, in some aspects, the pellets contain the same amount (e.g., and at the same ratio) of the same components as in the pretreatment mixture used to prepare the pellets. In some aspects, the pellets contain the same relative amount of each component (e.g., the same ratio) as the pretreatment mixture used to prepare the pellets, except that in some aspects, the moisture content of the pellets is lower than the moisture content in the precursor pretreatment mixture due to drying (active or passive drying). Any amount of any component disclosed herein for pre-treating a mixture applies to the amount of the same component in the pellet.
In some aspects, the composition of the pellets is the same as the composition of the article prepared therefrom. Specifically, in some aspects, the pellets contain the same amount (e.g., and the same ratio) of the same component as in the articles prepared from the pellets. In some aspects, the pellets contain the same relative amount of each component as (e.g., the same ratio of) each component in the articles made from the pellets, except that in some aspects, the moisture content of the articles is lower than in the pellets used to make the articles due to drying (active or passive drying). Any amount of any component disclosed herein for an article is applicable to the amount of the same component in the pellet.
In some aspects, the moisture content of the pellets may be any suitable amount. In some aspects, the moisture content of the pellets is the same or substantially the same (e.g., within 5wt.% or 10 wt.%) as the moisture content of the pretreatment mixture used to shape the pellets. In some aspects, the moisture content (wt.%) of the pellet is 30, 32, 34, 35, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 55, 56, 58, or 60. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the moisture content (wt.%) is 30-55, 35-50, 28-52, at least 30, or less than 60.
In some aspects, the pellets are packaged in a package having moisture and/or air (e.g., oxygen) barrier properties. In some aspects, the pellets are not packaged in such packages. In some aspects, the pellets are transported or otherwise transported to another location where the pellets are formed into an article (e.g., by hot melt extrusion), as described elsewhere herein. In some aspects, the pellets are not transported to a separate location, but rather are formed into an article in the same location where the pellets were produced.
In some aspects, the pellets may be in any suitable form. In some aspects, the pellets are in the form of plugs, spheres, cubes, agglomerates, chips, or any combination thereof, or any other discrete shape or combination of discrete shapes that facilitates further processing of the pellets into a desired article (e.g., by hot melt extrusion in a single screw extruder with a universal screw and a tubular die, for example, when preparing the article as a straw). In some aspects, the weight of the individual pellets ranges from 0.05g to 0.2g, and the diameter of the individual pellets ranges from 1-10mm.
Hydrocolloid
The edible bio-based and/or biodegradable materials disclosed herein include one or more hydrocolloids. Hydrocolloids are polysaccharides which, when combined with water, can generally form gels. Many hydrocolloids can change their physical behavior and characteristics by adding or removing heat and can thicken and form gels at low concentrations. The hydrocolloid comprises alginate, agar, chitosan, chitin, pectin, carrageenan (e.g., kappa, iota, lambda or combinations thereof, particularly kappa-carrageenan and/or iota-carrageenan), natural gum, gelatin, starch, modified starch, pregelatinized starch, corn starch, gellan gum, guar gum, gum arabic, gum life prolonging, konjac gum, lecithin, locust bean gum Maltodextrin, methylcellulose, sodium alginate, xanthan gum, tapioca flour or any combination thereof. The hydrocolloid comprises natural gums such as gellan gum, guar gum, gum arabic, locust bean gum, konjac gum, and xanthan gum. Such a glue may act as an adhesive in the mixture herein. The hydrocolloid may be a mixture of the following hydrocolloids: such as alginate and chitosan; alginate and chitin; alginate, chitosan and chitin; kappa-carrageenan and chitosan; kappa-carrageenan and chitin; kappa-carrageenan, chitin and chitosan; kappa-carrageenan and alginate; kappa-carrageenan and iota-carrageenan; kappa-carrageenan and konjac gum; kappa-carrageenan, alginate and iota-carrageenan; kappa-carrageenan, chitosan (and/or chitin) and konjac gum; alginate and agar; agar and chitosan (and/or chitin); alginate, chitosan (and/or chitin) and agar; two different types of alginate; or two different types of alginate plus chitosan (and/or chitin) and optionally guar gum; kappa-carrageenan and two different types of alginates; kappa-carrageenan, two different types of alginate and chitosan (and/or chitin); kappa-carrageenan and high G block alginate; kappa-carrageenan, high G block alginate and chitosan (and/or chitin); kappa-carrageenan and locust bean gum; kappa-carrageenan and guar gum. In some aspects, suitable commercially available alginates include Protanal TM GP8223 (high M block high molecular weight biopolymer with viscosity of about 600-900cPs in water) (FMC biopolymer), protanal TM RF6650 (a high G block high molecular weight biopolymer having a viscosity of about 400-600cPs in water) (FMC biopolymer) or a combination thereof. In some aspects, the hydrocolloid is of biological origin, such as bacterial, animal, or plant origin (e.g., seaweed, such as kelp). In some aspects, the hydrocolloid comprises agar, carrageenan, and alginate, or a combination thereof. In some aspects, the hydrocolloid is a mixture of agar and alginate. In some aspects, the hydrocolloid is a mixture of alginate and chitosan (and/or chitin). In some aspects, the hydrocolloid is chitosan (and/or chitin) with two or more alginatesIs a mixture of (a) and (b). In some aspects, the hydrocolloid is a mixture of kappa-carrageenan and alginate. In some aspects, the hydrocolloid is a mixture of kappa-carrageenan and chitosan (and/or chitin) (e.g., low MW crustacean chitosan and/or chitin). In some aspects, the hydrocolloid is a mixture of kappa-carrageenan and chitin. In some aspects, the hydrocolloid is a mixture of kappa-carrageenan and milled chitin. In some aspects, the chitin is milled chitin. In some aspects, the milled chitin has a particle size in the range of 50 microns to 500 microns. In some aspects, the hydrocolloid is a mixture of kappa-carrageenan with chitosan and/or chitin. In some aspects, the chitosan and/or chitin is obtained from crustaceans. In some aspects, the chitosan and/or chitin is obtained from crab shells. In some aspects, the hydrocolloid is a mixture of kappa-carrageenan and konjac gum. In some aspects, the hydrocolloid is a mixture of kappa-carrageenan and iota-carrageenan. In some aspects, the hydrocolloid is a mixture of kappa-carrageenan, chitosan (e.g., low MW crustacean) and guar gum. In some aspects, the hydrocolloid is a mixture of chitosan, two or more alginates, and guar gum. In some aspects, chitosan is employed, and the chitosan is crustacean chitosan, plant-derived chitosan, synthetic chitosan, chemically modified chitosan, or a combination thereof. In some aspects, the chitosan is crustacean chitosan. In some aspects, the chitosan is a low molecular weight chitosan. In some aspects, the chitosan is a low molecular weight crustacean chitosan. As used herein, "low molecular weight chitosan" or "low MW chitosan" means chitosan having a viscosity average molecular weight of 50,000g/mol to 190,000 g/mol.
Agar, also known as agar-agar, is a natural plant counterpart of hydrocolloids and gelatin of animal origin. Agar is an odorless gelling agent derived from polysaccharides in red algae in which agar accumulates in the cell wall. In chemical terms, agar is a polymer made up of subunits of galactose. The main source of this material is gracilaria licheniformis (Gracilaria lichenoides).
Alginate is a natural polymer which is usually derived from seaweed and comprises a linear copolymer of d-mannuronic acid and 1-guluronic acid units. Structurally, alginate is a linear unbranched polymer containing covalently linked blocks of β (1-4) linked d-mannuronic acid (M block) and α (1-4) linked 1-guluronic acid (G block) residues, and may also include fractions of alternating Gu Lutang aldehyde acid and mannuronic acid (M/G block). Alginate is a heterogeneous polymer with different contents of G blocks and M blocks.
Alginates are widely found in brown seaweeds such as Ascophyllum (ascophyllum), bulgaria (durvillaea), ecklonia (ecklonia), laminaria (laminaria), cymbopogon (lesonia), phaeophyllum (macrosystems), sargassum (Sargassum) and Hortensis (turbinaria) species. In some aspects sodium alginate is used as it is widely commercially available and is the first by-product of processing alginate from seaweed sources.
Hydrocolloids, such as alginate, kappa-carrageenan, iota-carrageenan, chitosan, konjac gum, guar gum, locust bean gum or any other hydrocolloid listed herein, may be present in the presence of various multivalent cations, including divalent cations, such as Ba 2+ 、Ca 2+ 、Mg 2+ Iso-and trivalent cations, e.g. Al 3+ In the case of (2) ionic cross-linking agents are formed by cross-linking carboxylic acid groups or other electron donating groups or atoms on the hydrocolloid. Suitable crosslinking agents include any component having such multivalent cations (e.g., divalent, trivalent, tetravalent, etc.), and examples of such suitable crosslinking agents are disclosed elsewhere herein.
For pretreatment mixtures, pellets or articles herein comprising alginate, the factors responsible for hardness or flexibility of the alginate gel comprise the relative M/G ratio of the alginate and the presence of cross-links M 2+ Stoichiometry of the alginate of the cation. Higher G block content will result in a strong brittle gel, while higher M block content provides a more flexible gel. In some embodiments, and in particular for drinking straws, the alginate may comprise a high G block alginateOptionally a high G block alginate obtained by adding some high M/G block alginate, for example a high M/G block alginate with a weight ratio of 100:0 to 70:30 (high G/high M), as discussed below. The high G block alginate has a G/M ratio greater than 1:2, or greater than about 1:1, or greater than about 2:1, or greater than about 3:1. Typically, high G block alginates have a G/M ratio of about 1:2 to 4:1. Typically, high M block alginates have a G/M ratio of less than 1:2. The alginate may include a ratio of G: M/G: M of about 2:1:1 to about 4:1:1, for example about 2:1:1, or about 3:1:1 or about 4:1:1. The alginate used in the pretreatment mixture used to produce the article may be a mixture of different heterogeneous alginates. In some aspects, the high G block alginate is used in combination with the high M block alginate. In some aspects, the high G/high M weight ratio is 100:0, 95:5, 90:10, 85:15, 80:20, 75:25, 70:30, 65:35, 60:40, 55:45, or 50:50 or any range therefrom, including 100:0 to 75:25, 95:5 to 75:25, 100:0 to 60:40, 85:15 to 70:30, and the like. In some aspects, the high G/high M weight ratio may also be expressed in terms of a high M weight where 1 is set. For example, in some aspects, the weight ratio (X: 1) of high G alginate (X) to high M alginate (1) is 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the weight ratio of high G alginate to high M alginate (X: 1) is about 1:1 to about 6:1, about 2:1 to about 10:1, about 1:1 to about 20:1, about 3:1 to about 5:1, at least 3:1, less than about 20:1, or at least 4:1.
The species of seaweed that can be used as a source of alginate and the relative amounts of its M blocks, M/G blocks and G blocks comprise the relative amounts of seaweed species described in table 1:
TABLE 1
Type of seaweed | MM% | MG and GM% | GG% |
Fucoidan (Laminaia hyperborean) (stem) | 17 | 26 | 57 |
Fucoidan (leaf) | 36 | 38 | 26 |
Light black giant seaweed (Lessonia nigrescens) | 40 | 38 | 22 |
Kelp (Lessonia trabeculata) | 25 | 26 | 49 |
Arbuscular algae (Durvillaea antarctica) | 56 | 26 | 18 |
In some aspects, the pretreatment mixtures, pellets, and/or articles herein include carrageenan, specifically kappa-carrageenan. Carrageenan and its various forms (e.g., kappa, iota and lambda) are defined elsewhere herein, but typically carrageenan is a sulfated polysaccharide group comprising repeating galactose units. Carrageenan is typically derived from or extracted from red seaweed, which comprises carrageenan (Chondudrus cripus, irish moss), eucheuma (Eucheuma) and Huperzia starburst (Gigartina stellate). Carrageenan is commercially available, but can also be produced directly from sources such as seaweed by dissolution in hot (e.g., 70-100 ℃) alkaline water, filtration, pH adjustment, and then further filtration (e.g., ultrafiltration) as needed. Such methods are known in the art.
In some aspects, the pretreatment mixtures, pellets, and/or preparations herein do not comprise seaweed from Eucheuma sp, gulfweed, hornia, gracilaria, or any combination thereof.
In some aspects, the article may include any suitable amount of hydrocolloid or combination of hydrocolloids. For example, in some aspects, the article comprises a hydrocolloid 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, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 98 based on the total weight of the article. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the article comprises hydrocolloid in an amount (wt.%) of about 15 to about 98, 5 to 30, 5 to about 35, 20 to about 90, 25 to about 80, 30 to about 65, 45 to about 60, 40 to about 50, 50 to about 60, at least about 5, about 10 to about 20, less than about 25, about 8 to about 15, about 9 to about 17, or about 7 to about 13. Such amounts may refer to the single hydrocolloid present in the article, or the total amount of hydrocolloid present in the article. In addition, these amounts refer to the final product after drying (e.g., after extrusion, crosslinking, rinsing and drying, if such processes are employed).
In some aspects, the article may be prepared from a pretreatment mixture or pellet comprising any suitable amount of hydrocolloid or combination of hydrocolloids. For example, in some aspects, the pretreatment mixture or pellet includes hydrocolloid in an amount (wt.%) of 0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 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, 35, 36, 37, 38, 39, or 40, as the case may be, based on the total weight of the pretreatment mixture or pellet. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the pretreatment mixture or pellet includes hydrocolloid in an amount (wt.%) of about 5 to about 15, about 6 to about 12, about 4 to about 18, at least about 3, at least about 5, at least about 9, less than about 19, about 10 to about 13, about 10 to about 15, 0 to about 3, 0 to about 5, 0 to about 10, about 10 to about 20, about 10 to about 30, about 5 to 30, 5 to 35, about 10 to about 40, about 15 to about 30, about 15 to about 35, or about 9 to about 21. Such amounts may refer to the single hydrocolloid present in the pretreatment mixture, or the total amount of hydrocolloid present in the pretreatment mixture. In aspects in which articles are prepared from the pretreatment mixture or pellets and such articles are not subjected to a crosslinking bath and/or rinse, the pretreatment mixture, pellets, and articles are identical or substantially identical in composition (e.g., have values within 1%, 2%, 4%, 6%, 8%, or 10 wt.%), but the drying of the articles may affect the moisture content described elsewhere herein. In any event, the ratio of the components (other than water) remains the same or substantially the same (e.g., has a value within 1%, 2%, 4%, 6%, 8%, or 10 wt.%).
In some aspects, particularly when the hydrocolloid is or includes agar, chitosan, gellan gum-guar gum, xanthan gum, konjac gum, alginate, or a combination thereof, the article is prepared from a pretreatment mixture or pellet comprising: about 1.5 wt% to about 5 wt% hydrocolloid and about 80 wt% to about 98.5 wt% water, or about 85 wt% to about 98 wt% water, or about 95 wt% to about 98 wt% water (water content as described in more detail below).
In some aspects when the hydrocolloid is or includes an alginate, the article may be prepared from a pretreatment mixture or pellet that includes, based on the total weight of the pretreatment mixture or pellet, as appropriate: about 0.5wt.% to about 40wt.% of an alginate, or about 1wt.% to about 30wt.% of an alginate, or about 3wt.% to about 20wt.% of an alginate, or about 5wt.% to about 15wt.% of an alginate, or about 7wt.% to about 13wt.% of an alginate.
In some aspects when the hydrocolloid is or includes kappa-carrageenan, the article may be prepared from a pretreatment mixture or pellet comprising, based on the total weight of the pretreatment mixture or pellet, as the case may be: about 10-20wt.% kappa-carrageenan, 5-15wt.% kappa-carrageenan, 10-30wt.% kappa-carrageenan, 15-30wt.% kappa-carrageenan, 5-20wt.% kappa-carrageenan, 8-18wt.% kappa-carrageenan, 12-22wt.% kappa-carrageenan or 15-25wt.% kappa-carrageenan.
In some aspects when the hydrocolloid is or includes kappa-carrageenan (in any amount disclosed herein), the article may be prepared from a pretreatment mixture or pellet further comprising, as appropriate, based on the total weight of the pretreatment mixture or pellet: in an amount of 3-10wt.%, 0-10wt.%, 0.5-10wt.%, 5-15wt.%, 2-12wt.%, or 5-10wt.% chitosan (e.g., low MW crustacean).
In some aspects when the hydrocolloid is or includes kappa-carrageenan (in any amount disclosed herein), the article may be prepared from a pretreatment mixture or pellet further comprising, as appropriate, based on the total weight of the pretreatment mixture or pellet: the amount is 0-10wt.%, 0.5-10wt.%, 0-5wt.%, 0.5-5wt.%, 0-3wt.%, 0.5-3wt.% or 2-10wt.% of konjac gum.
In some aspects when the hydrocolloid is or includes kappa-carrageenan (in any amount disclosed herein), the article may be prepared from a pretreatment mixture or pellet further comprising, as appropriate, based on the total weight of the pretreatment mixture or pellet: the combined or individual amounts are 0-50wt.%, 1-10wt.%, 0-10wt.%, 0.5-10wt.%, 1-15wt.%, 0-5wt.%, 0.5-5wt.%, 0-3wt.%, 0.5-3wt.%, 5-15wt.%, 10-20wt.%, 3-10wt.%, or 2-10wt.% of an additional hydrocolloid (e.g., alginate, chitosan, iota-carrageenan, guar gum, konjac gum, locust bean gum, etc.).
In some aspects when the hydrocolloid is or includes kappa-carrageenan (in any amount disclosed herein), the article may be prepared from a pretreatment mixture or pellet further comprising, as appropriate, based on the total weight of the pretreatment mixture or pellet: the combined or individual amounts are 0-10wt.%, 0.5-10wt.%, 0-5wt.%, 0.5-5wt.%, 0-3wt.%, 0.5-3wt.%, 5-15wt.%, or 2-10wt.% filler (e.g., calcium carbonate, MCC, citrus fiber, carboxymethyl cellulose, etc.).
In some aspects when the hydrocolloid is or includes kappa-carrageenan (in any amount disclosed herein), the article may be prepared from a pretreatment mixture or pellet further comprising, as appropriate, based on the total weight of the pretreatment mixture or pellet: the combined or individual amounts are 0-10wt.%, 0.5-10wt.%, 1-8wt.%, 0-5wt.%, 0.5-5wt.%, 0-3wt.%, 0.5-3wt.%, or 2-5wt.% of an inorganic cross-linking agent (e.g., zirconium acetate, zirconium potassium carbonate, zirconium ammonium carbonate, alum, etc.).
In some aspects when the hydrocolloid is or includes kappa-carrageenan (in any amount disclosed herein), the article may be prepared from a pretreatment mixture or pellet further comprising, as appropriate, based on the total weight of the pretreatment mixture or pellet: the combined or individual amounts are 0-10wt.%, 0.5-10wt.%, 0-5wt.%, 0.5-5wt.%, 0-3wt.%, 0.5-3wt.%, 1-8wt.%, 2-5wt.%, 5-15wt.%, or 2-10wt.% of a hydrophobic additive (e.g., palm stearin, carnauba wax, zein, lignin, etc.).
When more than one hydrocolloid is employed, the amounts described herein may refer to each hydrocolloid individually, or to the total amount of hydrocolloid present in the article, pretreatment mixture, or pellet.
In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise one or more of the following: pectin, welan gum, starch, modified starch, pregelatinized starch, chitosan oligosaccharide, or any combination thereof.
In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise one or more of the following: polylactic acid (polylactic acid), chitin, chitosan, hydrolyzed chitosan, alginic acid, sodium alginate, calcium alginate, magnesium alginate, triethanolamine alginate, potassium alginate, strontium alginate, barium alginate, ammonium alginate, propylene glycol alginate, lignin, thermoplastic starch, vegetable starch, pullulan (e.g., 6- α -maltosyl branched structure, 6- α -maltotetraosyl branched structure, or a combination thereof), polyethylene, polypropylene, polyethylene glycol, polyglycolide, poly (lactide-co-glycolide), polyacrylate, polymethacrylate, poly (8-caprolactone), polyorthoesters, polyanhydrides, polylysine, polyethylenimine, carboxymethyl cellulose, acetylated carboxymethyl cellulose, gelatin, collagen, pullulan (pullulan), cold-soluble gelatin, pectin, carrageenan derivatives, kappa carrageenan, lambda carrageenan, iota gums, and derivatives, combinations and copolymers thereof. In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise a hydrocolloid that is or is derived from a starch-based leguminous seed protein.
In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise one or more of the following: n-octenyl succinic anhydride modified starch, exudative gum (acacia, ghatti), karaya (karaya), tragacanth), extractable gum (β -glucan, inulin, konjac gum, pine gum), seed gum (locust bean gum, guar gum, psyllium seed gum, quince gum, fenugreek gum, tara gum), vegetable gum (e.g., hydrolyzed vegetable gum or low viscosity hydrolyzed vegetable gum), pectin (high methoxy gum, low methoxy gum, amidated gum), microbial gum (xanthan gum, karaya gum (curdlan), pullulan, gellan gum, scleroglucan, welan gum, rhamnose gum (rhamsan)), modified cellulose (methylcellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, sodium carboxymethyl cellulose), carrageenan (iota, kappa, lambda), dextrin, dextran, hydrogenated starch hydrolysates, polydextrose, agar, gelatin (types a and B, hydrolyzed gelatin), or any combination thereof.
In some aspects, the pretreatment mixture, pellet, and/or article does not comprise insoluble alginate, e.g., insoluble alginate particles. In some aspects, the pretreatment mixture, pellet, and/or article does not comprise alginate having a molecular weight of 5,000g/mol to 350,000 g/mol. In some aspects, the pretreatment mixture and/or article does not comprise an alginate comprising one or more of calcium, strontium, barium, copper, manganese, lead, cobalt, nickel, or any combination thereof.
Water-based liquids
The water in the pretreatment mixture, pellet, or article may be supplied as pure water or a water-based liquid (e.g., an aqueous mixture or solution). According to some aspects, water may be used, such as filtered water, distilled water, purified water, spring water, mineral water, tap water, carbonated water, or any combination thereof. Additional water-based liquids that may alternatively or additionally be used include fruit juices, fruit juice concentrates, milk, syrup, tree and cactus water, alcoholic beverages, energy beverages, caffeine-containing coffee, decaffeinated coffee, soda, nut milk, coconut milk, flavored water, tea infusion, hot chocolate, cider, cold pressed fruit juices, sport drinks, coconut water, fermentation broths such as Kang Pucha (kombucha) and kvass, herbal infusions, or any combination thereof.
In some aspects, the article may include any suitable amount of water or water-based liquid. For example, in some aspects, the article comprises water in an amount (wt.%) of 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 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, 35, 36, 37, 38, 39, 40, 45, 50, 55, 60, 65, or 70 based on the total weight of the article. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the article comprises an aqueous-based liquid in an amount (wt.%) of about 35 to about 70, about 35 to about 65, about 45 to about 65, about 40 to about 55, about 40 to about 50, about 30 to about 35, about 25 to about 40, about 25 to about 35, about 27 to about 35, about 20 to about 40, less than about 50, less than about 38, or at least about 20. These amounts refer to the final article after drying of the article (e.g., after extrusion, crosslinking, rinsing and drying, if such a process is employed), however, if desired, substantial amounts of water may be removed by the drying process. For example, in some aspects, water is substantially removed from the article during dewatering, thereby providing the article with less than 10 wt% water, or less than about 5 wt% water, or less than about 1 wt% water. In some aspects, the articles are air cooled (e.g., when hot melt extrusion is employed) and/or air dried, and substantial removal of water is not achieved or desired. In such aspects, the water content or water-based liquid content of the article is the same or substantially the same as the water content or water-based liquid content of the pretreatment mixture or pellet used to make the article (e.g., within 1%, 2%, 4%, 6%, 8%, or 10wt.% of the value).
In some aspects, the pretreatment mixture or pellet may include any suitable amount of water or water-based liquid. For example, in some aspects, the pretreatment mixture or pellet includes water or a water-based liquid in an amount (wt.%) of 30, 32, 34, 35, 36, 38, 40, 42, 44, 45, 46, 48, 50, 52, 54, 55, 56, 58, 60, 62, 64, 65, 66, 68, 70, 72, 74, 75, 76, 78, 80, 82, 84, 85, 86, 88, 90, 92, 94, or 95, as the case may be, based on the total weight of the pretreatment mixture or pellet. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the pretreatment mixture includes water or a water-based liquid in an amount (wt.%) of about 40 to about 60, about 85 to about 90, at least 80, about 35 to about 75, about 35 to about 50, about 35 to about 60, about 30 to about 60, about 40 to about 90, about 44 to about 92, or less than about 80.
When more than one water-based liquid is employed, the amounts described herein may refer to each water-based liquid individually, or the total amount of water-based liquids.
In some aspects, the addition of certain components is found to improve the mechanical properties of the article formed from the pretreatment mixture or pellet and facilitate the process steps for shaping the article. In some aspects, such improved mechanical properties and/or facilitated processing step is a plasticizer; a wetting agent; plasticizers and wetting agents; filler/strength modifier; plasticizers and fillers/strength modifiers; a hydrophobic additive; plasticizers and hydrophobic additives; kappa-carrageenan; kappa-carrageenan and additional hydrocolloid; fillers/strength additives and hydrophobic additives; or any combination thereof.
Plasticizer(s)
In some aspects, the article, pellet, or pretreatment mixture includes one or more plasticizers (e.g., edible plasticizers). In some aspects, and without wishing to be bound by theory, it is believed that the plasticizer alters the texture and/or viscosity of the hydrocolloid mixture to provide one or more desirable properties, including increased ease of handling, more desirable plastic-like properties (i.e., rebound), tensile strength, young's modulus, compressive strength, etc., and also to provide a material that can be bite-through and/or chewed. In some aspects, the article, pellet, or pretreatment mixture comprises one plasticizer or a combination of two or more plasticizers. In some aspects, the plasticizer is hydrophilic or hydrophobic. In some aspects, a combination of a hydrophilic plasticizer (e.g., glycerol, sorbitol, maltitol) and a hydrophobic plasticizer (e.g., glycerol trioctanoate) is used. Without wishing to be bound by theory, it is believed that the inclusion of the hydrophobic plasticizer (and/or the hydrophobic additive described elsewhere) helps prevent leaching of the hydrophilic compound (e.g., glycerol) during the crosslinking and/or rinsing process (if such a process is employed), and also increases the water resistance and/or moisture barrier properties of the article. In some aspects, a given component, such as a plasticizer, may have additional functionality in the composition. For example, in certain compositions used in cold extrusion processes herein, hydrophilic plasticizers such as glycerol are considered to be used as solvents for seaweed-derived biopolymers (alginate or carrageenan) and function as plasticizers. Additionally, in some aspects, certain components are considered to have only a single function in the composition. For example, in certain compositions used in cold extrusion processes herein, hydrophobic plasticizers such as glyceryl trioctanoate are considered to be used only as plasticizers (e.g., not as solvents for seaweed-derived polymers such as alginate or carrageenan).
Suitable plasticizers include edible oils (e.g., as disclosed elsewhere herein), glycerin, sugar alcohols such as maltitol, sorbitol, or xylitol, microcrystalline cellulose, acacia, shellac, genipin, nanoemulsion, algae oil, coconut oil, treated shea butter, ester gums, carnauba wax, palm stearin, thermoplastic cellulose ethers (e.g., ethocell) TM ) Zein, citrate, phthalate, adipate and glyceride, including alkyl esters and fatty acid esters, or mixtures thereof. In some aspects, functionalized plasticizers (e.g., glycerol, sugar alcohols, sorbitol, maltitol, xylitol, etc.) are employed in which one or more hydroxyl groups are functionalized with alkyl groups via ether and/or ester linkages (e.g., alkylated or esterified plasticizers). Suitable groups that may be used to functionalize glycerol include alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 carbon atoms. Each of the foregoing numbers may be preceded by the word "about," "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 range or may be combined to describe multiple single points or closed ranges. For example, in some aspects, the number of carbon atoms is 5 to 10, 6 to 9, 4 to 9, at least 4, at least 6, or 8 to 12. In some aspects, suitable functionalized (e.g., hydrophobic) plasticizers include glyceryl octoate (e.g., monocaprylate, dicaprylate, trioctanoate, or any combination thereof), octylglycerol (e.g., monooctylglycerol, dioctylglycerol, trioctylglycerol, or any combination thereof), glyceryl decanoate (e.g., monocaprylate, dicaprate, tricaprate, or any combination thereof), caprylic sorbitol (e.g., monocaprylate, dicaprylate, trioctanoate, tetracaprylate, pentacaprylate, hexacaprylate, or any combination thereof), and the like. In some aspects, the hydrophobic plasticizer is or includes glyceryl tricaprylate. As used herein, when a compound is disclosed as having a given number of carbon atoms, only that number or range is desired. In other words, it is not intended that the compound includes a certain number of carbon atoms, but that the compound has a specific number of carbon atoms. For example, if a compound is disclosed as having 5 to 10 carbon atoms, a compound having 15 carbon atoms will fall outside the range of 5 to 10 carbon atoms. Even technically, a 15 carbon atom compound necessarily has 5 to 10 carbon atoms, but it is not intended that a 15 carbon atom compound fall within the range of compounds having 5 to 10 carbon atoms.
In some aspects, the article includes one or more plasticizers in any suitable amount. For example, in some aspects, the article comprises one or more plasticizers in an amount (wt.%) of 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 28, 30, 32, 34, 35, 36, 38, 40, 42, 44, 45, 46, 48, 50, 52, 54, or 55, based on the total weight of the article. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the article includes one or more plasticizers in an amount (wt.%) of about 5 to about 18, 5 to 20, 5 to 30, about 8 to about 10, about 10 to about 20, about 25 to about 45, about 30 to about 42, at least about 6, or less than about 23. When the article is prepared by a process employing a crosslinking bath and/or flushing, these processes may provide for a reduction in the amount of plasticizer in the article as compared to the amount of plasticizer in the pretreatment mixture or pellet, particularly leaching out hydrophilic plasticizers (e.g., glycerin, sugar alcohols, etc.). However, the amounts of hydrophobic plasticizers described above (if present), such as alkylated or esterified plasticizers, are generally as disclosed herein, as such hydrophobic plasticizers are less prone to leaching or more resistant to leaching during such treatment steps. In other words, if one or more hydrophobic plasticizers are employed in the pretreatment mixture or pellet, such hydrophobic plasticizers typically do not leach out during the use of the crosslinking bath and/or rinse.
In some aspects, the pretreatment mixture or pellet includes one or more plasticizers in any suitable amount. For example, in some aspects, the pretreatment mixture or pellet includes one or more plasticizers in an amount (wt.%) of 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 12, 14, 15, 16, 18, 20, 22, 24, 25, 26, 28, 30, 32, 34, 35, 36, 38, 40, 42, 44, or 45, as the case may be. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the pretreatment mixture or pellet includes one or more plasticizers in an amount (wt.%) of about 0.5 to about 2, about 0.1 to about 2, about 0.5 to about 5, about 1 to about 10, about 0.5 to about 35, about 0.5 to 40, about 1 to about 30, about 3 to about 25, about 5 to about 20, about 8 to about 20, about 0.5 to about 2, about 20 to about 35, about 0.4 to about 15, about 5 to about 20, 5 to 30, about 15 to about 40, about 22 to about 34, or at least about 15. In some aspects, the amount (wt.%) of hydrophilic plasticizer is any amount described herein, including from about 5 to about 15, from about 5 to about 20, from about 1 to about 15, from about 1 to about 20, from about 20 to about 35, from about 10 to about 25, from about 20 to about 40, from about 25 to about 40, from about 18 to about 32, from about 15 to about 40, or from about 28 to about 35. In some aspects, the amount (wt.%) of the hydrophobic plasticizer is any amount described herein, including from 0 to about 5, from 0.1 to about 5, from about 1 to about 4, from about 2 to about 4, from about 0.8 to about 1.5, from about 0.5 to about 2, at least about 0.2, from about 0.4 to about 5, from about 0.1 to about 4, or less than about 8. In some aspects, one or more hydrophilic plasticizers are used in combination with one or more hydrophobic plasticizers in any amount described herein. For example, in some aspects, one or more hydrophilic plasticizers are used in combination with one or more hydrophobic plasticizers in any amount (wt.%) disclosed herein, such as 5-15, 20-40, 25-40, 10-25, or 5-20, such as 0.5-2, 0-5, 0.1-4, 0.1-3, 0.1-2, or 0.5 to 1.5.
When more than one plasticizer is employed, the amounts described herein may refer to each plasticizer individually, or the total amount of plasticizers.
In some aspects, where the hydrocolloid provides a more rigid gel, such as an alginate and in particular a high G block alginate gel, the article may include 5% to about 70% plasticizer by weight; or 15 to about 65 weight percent plasticizer; or about 25% to about 65% by weight of plasticizer, or about 40% to about 60% by weight of plasticizer, or about 50% to about 60% by weight of plasticizer, or any other amount described herein.
In some aspects, the weight ratio of alginate to total plasticizer in the pretreatment mixture, pellet, or article is from about 1:2 to about 2:1, or from about 1:1.5 to about 1.5:1, or from about 1:1 to 1:1.5.
In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise one or more of glycerin, sorbitol, mannitol, galactitol, arabitol, erythritol, xylitol, or any combination thereof.
Wetting agent
In some aspects, one or more wetting agents are employed in the article, pellet, or pretreatment mixture. Suitable wetting agents include, for example, hydroxides (e.g., aluminum hydroxide, calcium hydroxide, hydrates thereof, or any combination thereof), sulfates (e.g., calcium sulfate, magnesium bisulfate, sodium sulfate, sodium bisulfate, alum (e.g., KAl (SO) 4 ) 2 ) A hydrate thereof, aluminum sulfate, or a hydrate thereof, or any combination thereof), a chloride (e.g., calcium chloride, potassium chloride, magnesium chloride, a hydrate thereof, or any combination thereof), a carbonate (e.g., calcium carbonate, potassium carbonate, magnesium carbonate, zirconium potassium carbonate (e.g., zirmel available from Luxfer MEL technologies company (Luxfer MEL Technologies)) TM 1000 A) or a mixture thereof, an oxide (e.g., calcium oxide, magnesium oxide, aluminum oxide, a hydrate thereof, or any combination thereof), an aluminate (e.g., calcium aluminate, a hydrate thereof, or any combination thereof), a silicate (e.g., calcium silicate, potassium silicate, lithium silicate, magnesium silicate, a hydrate thereof, or any combination thereof), an acetate (e.g., sodium acetate, potassium acetate, zirconium acetate, a hydrate thereof, or any combination thereof), a silica, pentasodium triphosphate, sepiolite, silica gel, silica, a zeolite, any hydrate thereof, or any combination thereof.
In some aspects, suitable wetting agents include, for example, salts selected from the group consisting of: hydroxides (e.g., aluminum hydroxide, calcium hydroxide, hydrates thereof, or any combination thereof), sulfates (e.g., calcium sulfate, magnesium bisulfate, sodium sulfate, sodium bisulfate, alum (e.g., KAl (SO) 4 ) 2 ) A hydrate thereof, or any combination thereof), a chloride (e.g., calcium chloride, magnesium chloride, a hydrate thereof, or any combination thereof), a carbonate (e.g., calcium carbonate, potassium carbonate, magnesium carbonate, potassium zirconium carbonate, a hydrate thereof, or any combination thereof), an aluminate (e.g., calcium aluminate, a hydrate thereof, or any combination thereof), a silicate (e.g., calcium silicate, potassium silicate, lithium silicate, magnesium silicate, or a combination thereof)Hydrates or any combination thereof), acetates (e.g., sodium acetate, potassium acetate, zirconium acetate, hydrates thereof, or any combination thereof), pentasodium triphosphate, any hydrate thereof, or any combination thereof.
In some aspects, the wetting agent is or includes aluminum hydroxide or a hydrate thereof. In some aspects, the wetting agent is or includes aluminum hydroxide monohydrate or aluminum hydroxide monohydrate. In some aspects, the aluminum hydroxide or hydrate thereof is derived from bauxite. The aluminum hydroxide or a hydrate thereof may comprise aluminum trihydrate. In some aspects, without wishing to be bound by theory, wetting agents are used to prevent or reduce swelling of the article upon contact with water-based liquids, and/or to increase the flexibility of the article. It has surprisingly been found that articles made from a pretreatment mixture comprising a wetting agent such as aluminum hydroxide or a hydrate thereof prevent or reduce swelling of the article when placed in contact with an aqueous based liquid and/or improve mechanical properties of the article such as flexibility, compressive strength, tensile strength, young's modulus or any combination thereof.
In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise aluminum hydroxide, bentonite, calcium sulfate, calcium chloride, calcium carbonate, calcium oxide, calcium hydroxide, calcium aluminate, calcium silicate, potassium carbonate, silica, lithium silicate, magnesium sulfate, magnesium carbonate, magnesium chloride, magnesium bisulfate, magnesium silicate, sodium sulfate, sodium acetate, sodium bisulfate, pentasodium triphosphate, sepiolite, silica gel (silicic acid gel), silica, zeolite, or any combination thereof.
In some aspects, the article includes one or more wetting agents in any suitable amount. For example, in some aspects, the article comprises one or more wetting agents in an amount (wt.%) of 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.2, 3.4, 3.6, 3.8, 4.2, 4.4, 4.6, 4.8, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, or 15, based on the total weight of the article. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the article includes one or more wetting agents in an amount (wt.%) of from about 0.1 to about 10, from about 0.5 to about 10, from 0 to about 5, from 0.1 to 5, from about 1 to about 5, at least about 1.5, less than about 12, or from about 1.1 to about 4.5.
In some aspects, the pretreatment mixture or pellet includes one or more wetting agents in any suitable amount. For example, in some aspects, the pretreatment mixture includes one or more amounts (wt.%) of a wetting agent of 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.2, 3.4, 3.6, 3.8, 4.2, 4.4, 4.6, 4.8, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, or 12 based on the total weight of the pretreatment mixture. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the pretreatment mixture includes one or more wetting agents in an amount (wt.%) of about 0.1 to about 8, 0 to about 5, 0.1 to 5, about 0.5 to about 7, about 1 to about 5, at least about 1.5, less than about 12, about 1.1 to about 4.5, or about 1.8 to about 3.
When more than one wetting agent is employed, the amounts described herein may refer to each wetting agent individually, or the total amount of wetting agents.
Filler/strength modifier
In some aspects, the article, pellet, or pretreatment mixture may include a filler. In some aspects, the filler may replay a strength modifier (e.g., an impact strength modifier). Suitable fillers/strength modifiers may be organic or inorganic and may comprise, for example, starch (e.g., corn starch), microcrystalline cellulose (MCC), guar gum, carboxymethyl cellulose, citrus fiber, mineral salts, calcium carbonate (or hydrates thereof), or any combination thereof. In addition, suitable fillers also include any wetting agent disclosed elsewhere herein, such as salts or compounds that are hydroxides, sulfates, chlorides, carbonates, oxides, aluminates, silicates, acetates, silica, pentasodium triphosphate, sepiolite, silica, zeolite, or any hydrate thereof, or any combination thereof; or the salt or compound is a salt of an alkali metal, alkaline earth metal, aluminum, or any combination thereof.
In some aspects, such fillers may be disclosed elsewhere herein as having a different function, such as guar gum or starch as a hydrocolloid; MCC as a plasticizer or reinforcing fiber; or calcium carbonate as a wetting agent; however, such disclosure merely indicates that certain components may have different or multiple functions in the article, pellet, and/or pretreatment mixture.
In some aspects, the pretreatment mixture, pellet, or article may include any suitable amount of filler. For example, in some aspects, the pretreatment mixture, pellet, or article includes a filler or combination of fillers in an amount (wt.%) of 0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, or 15, as the case may be, based on the total weight of the pretreatment mixture, pellet, and/or article. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the pretreatment mixture, pellet, or article comprises a filler or combination of fillers in an amount (wt.%) of about 1 to about 10, 5 to 15, 4.5 to 12, 3 to 11, 6 to 14, at least 3, at least 5, or less than 12. In general, when the pretreatment mixture is formed into pellets, or when the pretreatment mixture or pellets are formed into articles, the amount of filler is not changed except that the moisture content may be changed as described elsewhere herein, particularly where drying is employed.
Hydrophobic additives
In some aspects, the article, pellet, or pretreatment mixture may include a hydrophobic additive. Suitable hydrophobic additives include, for example, palm stearin, carnauba wax, zein, lignin, or any combination thereof. In addition, suitable hydrophobic additives also include any of the hydrophobic plasticizers, edible oils, and/or coatings disclosed elsewhere herein. Without wishing to be bound by theory, it is believed that the inclusion of a hydrophobic additive in the pretreatment mixture, pellet, and/or article improves resistance to moisture absorption and/or improves moisture barrier properties, for example, by increasing the hydrophobicity of the article and/or pellet.
In some aspects, the article, pellet, or pretreatment mixture includes any suitable amount of the hydrophobic additive. For example, in some aspects, the pretreatment mixture, pellet, or article comprises a hydrophobic additive or combination of hydrophobic additives 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, or 20, as the case may be, based on the total weight of the pretreatment mixture, pellet, and/or article. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the pretreatment mixture, pellet, and/or article comprises a hydrophobic additive or combination of hydrophobic additives in an amount (wt.%) of 0 to about 10, about 1 to about 15, 0 to 5, 1 to 5, 0 to 3, 1 to 3, 5 to 10, 3 to 11, 5 to 10, about 5 to about 10, about 5 to 15, 6 to 14, at least 3, at least 5, or less than 12. In general, when the pretreatment mixture is formed into pellets, or when the pretreatment mixture or pellets are formed into articles, the amount of hydrophobic additive is not changed except that the moisture content may be changed as described elsewhere herein, particularly where drying is employed.
Additional ingredients
In some aspects, the articles, pellets, and pretreatment mixtures further include one or more additional ingredients, such as flavors, colorants, fragrances, acids, actives, or any combination thereof, as described in more detail elsewhere herein. These additional ingredients are typically present in the pretreatment mixture, pellets, and/or articles herein in amounts or combinations such that their presence or combined presence does not affect the mechanical properties of the shaped articles.
In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise fibrous material embedded in a hydrocolloid matrix. In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise hydrated fibrous material embedded in a hydrocolloid matrix. The fibrous material may comprise particulate cellulosic fibers such as recycled paper, corn stover, cotton batting, sawdust, and the like. In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise a clot or extruded fiber of a water insoluble biopolymer. In some aspects, the pretreatment mixtures, pellets, and/or the absence of fibers herein, such as wood pulp fibers, cotton batting, or combinations thereof. In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise natural fibers, such as wood fibers, cereal fibers, husk fibers, grass fibers, corn flour, cellulose fibers, cellulose flakes, or any combination thereof. In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise cellulose, water-soluble cellulose, or mechanical pulp. In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise lipids, dried fats, or lipids derived from dried fats.
In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise polyphenols, tea polyphenols, gluconate, calcium gluconate, tartaric acid, or any combination thereof.
In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise a protein gum comprising gluten (or gelatin protein), collagen, albumin, gelatin, cartilage gum, agar-agar, xanthan gum, or any combination thereof. In some aspects, the pretreatment mixture, pellet, and/or article herein does not comprise a protein. In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise one or more of the following: milk proteins (whole milk proteins, sodium caseinate, calcium caseinate, whey proteins, albumin, lactoglobulin), seed proteins (from soy, sunflower, cottonseed, peanut), cereal proteins (wheat, corn, oats, rice), fractionated proteins, hydrolyzed proteins, or any combination thereof. In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise protein isolates, such as protein isolates from soybeans, gluten, or a combination thereof.
In some aspects, the pretreatment mixture, pellet, and/or article herein does not comprise a nonionic polysaccharide. In some aspects, the pretreatment mixtures and/or articles herein do not comprise one or more of the following: pullulan, pullulan derivatives, inulin, guar gum, cellulose, konjac gum, agar, agarose, curdlan gum, hydroxypropyl methylcellulose, hydroxyethyl cellulose, methylcellulose, hydroxypropyl cellulose, hydroxypropyl guar gum, cellulose acetate, cellulose aldehyde, carboxymethyl starch, hydroxypropyl starch, hydroxyethyl starch, starch acetate, starch aldehyde, or any combination thereof. In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise one or more of the following: carboxymethyl cellulose, xanthan gum, acacia gum, xanthan gum, locust bean gum, tara gum, carboxymethyl starch, cationic starch, gelatin, gellan gum, pectin, and carrageenan.
In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise flour, such as rice flour, gluten meal, or combinations thereof. In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise tubers, such as tubers from potatoes, tapioca, sweet potato, or any combination thereof.
In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise juice, e.g., from rubber, copaiba fat, damascena, jelutong gum, or any combination thereof. In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise polyethylene glycol. In some aspects, the pretreatment mixture, pellet, and/or article does not comprise one or more cellulose esters, such as cellulose acetate or polylactic acid.
Sugar and/or non-sugar sweetener
In some aspects, the articles, pellets, and/or pretreatment mixtures include a sugar or non-sugar sweetener, such as sugar, honey, agave honey, a low-calorie sweetener, a zero-calorie sweetener, or any combination thereof. In some aspects, the sweetener is a natural agent derived from biological sources and particularly from plant sources. In some aspects, the sweetener may include one or more of stevia, erythritol, lo Han Guo, and the like, or any combination thereof. In some aspects, the sweetener may alternatively or additionally include sugar substitutes such as maltitol, lactitol, mannitol, xylitol, or sorbitol. Any single sweetener or combination of sweeteners may be used in the pretreatment mixture, pellet, article, or coated on or impregnated into the article and/or pellet. When employed, the sweetener may be used in any suitable amount to provide the desired level of sweetness. In some aspects, the pretreatment mixtures, pellets, and/or articles herein are not low or sugar-free. In some aspects, the pretreatment mixture or article herein does not comprise sugar, honey, or other sweetener.
Edible oil
In some aspects, the article, pretreatment mixture, and/or pellet comprises one or more edible oils. In some aspects, the edible oil is derived from a plant or plant source. In some aspects, the edible oil comprises one or more of vegetable glycerin, palm oil, and the like. In some aspects, the edible oil comprises an essential oil.
In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not comprise a lubricant, such as vegetable oil, canola oil, olive oil, and poppy seed oil, lecithin, acetyl triethyl citrate, sucrose esters, lactones, lactams, synthetic triglycerides, or any combination thereof.
In some aspects, the article comprises any suitable amount of edible oil or combination of edible oils. For example, in some aspects, the article comprises edible oil or a combination of edible oils in an amount (wt.%) of 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or 10 based on the total weight of the article. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the article comprises edible oil or a combination of edible oils in an amount (wt.%) of from about 1 to about 10, from about 2 to about 5, or from about 1 to about 7.
In some aspects, the pretreatment mixture or pellet comprises any suitable amount of edible oil or combination of edible oils. For example, in some aspects, the pretreatment mixture or pellet comprises an edible oil or combination of edible oils in an amount (wt.%) of 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, or 5, as the case may be, based on the total weight of the pretreatment mixture or pellet. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the pretreatment mixture or pellet includes edible oil or a combination of edible oils in an amount (wt.%) of from about 0.05 to about 3, from about 0.1 to about 1, at least 0.3, less than about 5, or from about 0.45 to about 1.8.
Flavoring agent and essence
In some aspects, the article, pellet, or pretreatment mixture includes one or more flavoring agents, one or more fragrances, or any combination thereof. Flavoring agents and essences suitable for the present disclosure may be derived from natural sources such as plants, herbs, spices, and the like. The various flavors and/or fragrances may include, but are not limited to, grapefruit, cherry, green tea, vanilla, chocolate, raspberry, strawberry, cranberry, passion fruit, apple, blueberry, papaya, lemon, lime, champagne, grape, banana, watermelon, honey, peach, orange, kiwi, pomegranate, plum, coconut, grapefruit, etc., or any combination thereof. The flavoring agent may also comprise one or more edible flowers such as rose water, damascus rose, jasmine, lavender, and the like. Representative examples of flavoring agents are available from Abelei (Abelei), the Tec Team (The Tec Team), virginia Del (Virginia Dare), cyriliisia (Silesia), kami flavor company (Carmi color), fruit D 'Or (Fruit D' Or), united states Fruit flavor company (American Fruit Flavors), rakewood Organic, and Kemanx flavor company (Comax Flavors), and are present at about 0.1% to about 10% by weight. In some aspects, no flavoring or essence is employed.
Coloring agent
In some aspects, the article, pellet, or pretreatment mixture includes one or more colorants (sometimes referred to herein as colorants). The colorant may be added as an optional ingredient in the pretreatment mixture, may be applied to the article as an edible coating, or may be injected into the article or pellet. In some aspects, the colorant is derived from a plant source and is present in the article, pellet, or pretreatment mixture in an amount of about 0.1 wt.% to about 10 wt.% or about 0.1 wt.% to about 0.3 wt.%. Representative colorants are available from DDW Color House, food ingredient solutions (Food Ingredient Solutions), GNT (GNT), natural Flavors (Natural colors Inc.), sunchemical (Sunchemical), fireDots (FireDots), and Senxin food coloring (Sensient Food Colors). Depending on the colorant or colorants selected, the article (e.g., edible article) may be translucent, opaque, or transparent. In some aspects, the colorant is a pigment, e.g., cyan, red, blue, yellow, green, violet, or any other desired color, which may 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 a self-assembled polymer flake ranging in color from violet to red and provided in powder form. In some aspects, the article, pellet, or pretreatment mixture does not contain any colorants. Colorants may be applied to provide a specific appearance, such as striped, color block spliced, fading from one color to another, color change throughout, tie-dyeing, marble swirls, or any combination thereof.
Active ingredient
In some aspects, the article, pellet, or pretreatment mixture includes one or more active ingredients. Suitable active ingredients include vitamins, minerals, phytonutrients (e.g., carotenoids, flavonoids, resveratrol and thioglucosides), antioxidants, fibers, fatty acids such as omega-3 fatty acids, such as caffeine and PureEnergy TM (caffeine pterostilbene co-crystal) and the like, amino acids, polypeptides, proteins (plant and insect based, i.e., cricket, etc.), hemp oil, CBD oil, hemp, THC, plant-based charcoal for detoxification, brain tonic such as lion mane and cordyceps, nootropic agents such as hyperzine-a, acetal choline, DHA, GABA, phosphatidylserine, L-Thyanine, jatropha curcas, agaricus, collagen and collagen peptides, plant products, plant extracts, or any combination of any of the active ingredients listed herein. In some aspects, the active ingredient comprises any plant-derived material that is safe for human consumption, including herbal extracts, plant extracts, and the like, such as centella asiatica (Gotu Kola), cola Nut (Kola Nut), bacopa Manieri, ginseng, ginkgo biloba, schisandra chinensis, wolfberry, turmeric, ginger, terpenes, and aromatic isolates (alpha-pinene, myrcene, and the like), or any combination thereof. Other materials such as prebiotics, probiotics, etc. may also be used as active ingredients.
Suitable vitamins include vitamin A, B complexes (e.g., B-1, B-2, B-6, and B-12), vitamin C, vitamin D, vitamin E, and vitamin K, niacin, acidic vitamins such as pantothenic acid and folic acid, and biotin, or minerals including calcium, iron, zinc, magnesium, iodine, copper, phosphorus, manganese, potassium, chromium, molybdenum, selenium, nickel, tin, silicon, vanadium, and boron, or any combination of any of the vitamins disclosed herein.
For example, suitable specific actives include caffeine, beta-glucan, isoflavones, lignans, lycopene, garlicins, thioglucosides, limonoids, polyphenols, catechins (e.g., epigallocatechin-3-gallate, epigallocatechin, epicatechin-3-gallate, epicatechin), phenols, omega fatty acids comprising EPA and DHA, conjugated linoleic acid, capsicum, ginseng, echinacea, cola, passion fruit, jojohn's grass (st. John's wort), mahuang/guarana, slips, and chamomile, or any combination thereof.
Natural preservative
In some aspects, the article, pellet, or pretreatment mixture includes one or more preservatives (e.g., natural preservatives). In some aspects, the preservative includes 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, sour salts, or any combination thereof. In some aspects, any combination of preservatives may be employed.
Coating layer
In some aspects, the article or pellet includes a coating, e.g., a coating for enhancing water repellency, extending shelf life (e.g., acting 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 tackiness 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, beech fruit oil, castor oil, cottonseed oil, groundnut oil, hazelnut oil, olive oil, palm kernel oil, peanut oil, nut oil, poppy oil, blackcurrant seed oil, linseed oil, amaranth oil, almond oil, raisin seed oil, rapeseed oil, rice bran oil, safflower oil, sesame oil, sunflower seed oil, star palm oil, soybean oil, almond oil, brazil nut oil (brazil nut oil), cashew oil, macadamia nut oil, mongolian nut oil, pine nut oil, pistachio oil, walnut oil, or any combination thereof; short, medium or long chain triglycerides, monoglycerides, diglycerides, or any combination thereof; sugar coating of a candy shop; acetylated monoglycerides; waxes such as beeswax, soybean wax, rice bran wax, shellac, etc.; or any combination of any of the coating materials or coating components listed herein. In some aspects, the coating or coating composition includes 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 by way of a coating solution that includes a coating component (e.g., the coating component is or includes any of the coatings or coating materials described herein). For example, in some aspects, the coating solution includes a coating component (e.g., an oil, an edible wax, a combination of an edible wax, or a combination of one or more oils and one or more edible waxes) 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 based on the total weight of the coating solution. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the coating solution includes coating components 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 includes 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 molded and dried or extruded and dried. In some aspects, a coating (e.g., a coating solution) is applied to the article during the drying process. In some aspects, the coating (e.g., coating solution) is applied by spraying, immersing, dipping, brushing, edible ink-jet printing, coextrusion, or any combination thereof, or is otherwise applied to the inner and/or outer surfaces of the article. In some aspects, coating the article or pellet may be performed as known in the art to coat the article (e.g., straw) with any known coating agent, such as the coating agents/materials/components described herein. In some aspects, the process comprises applying a coating to the pellets, optionally by spraying, immersing, dipping, brushing, edible inkjet printing, coextrusion, or any combination thereof, wherein the coating comprises an oil coating, a wax coating, a sugar coating of a confectionery store, or any combination thereof, or any other coating disclosed herein.
In some aspects, the coated article has any suitable contact angle when measured using a version of Rame-Hart 90 CA using dropoimage 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 word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open 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, the article may have such a static contact angle when any suitable coating disclosed herein is present on the article, including, for example, beeswax, a combination of beeswax and carnauba wax, oil, a confectionery coating, soy wax, or the like, or any combination thereof.
In some aspects, the pellets and/or articles herein do not comprise a coating, e.g., a coating comprising rubber.
Crosslinking
In some aspects, one or more components of the article, pellet, or pretreatment mixture may be crosslinked. In some aspects, the hydrocolloid or other components in the article, the pretreatment mixture, and/or the pellet are crosslinked by adding a crosslinking agent (e.g., an inorganic crosslinking agent) to the pretreatment mixture. In some aspects, the article or pellet is crosslinked by immersing in a crosslinking bath after molding, extruding, or otherwise shaping the pellet or article. In some aspects, crosslinking provides end products (e.g., pellets or articles) having improved properties, such as hardness, tensile strength, and water resistance, as compared to non-crosslinked pellets or articles. In some aspects, suitable cross-linking agents are non-toxic and/or may be substantially removed from the pellet or article, for example, by rinsing, evaporation, or other suitable methods. In some aspects, the cross-linking agent does not affect the ability of the article to contain or otherwise contact a potable liquid or food product.
In some aspects, the cross-linking agent comprises a metal cation, particularly when the hydrocolloid is alginate, chitosan, guar gum, carrageenan (e.g., kappa-carrageenan and/or iota-carrageenan), pectin, konjac gum, or any combination thereof. In some aspects, the crosslinking agent is added to the pre-treatment mixture containing the hydrocolloid prior to shaping (e.g., by molding, casting, extrusion, or any combination thereof) into its final shape (e.g., pellet or article) so long as the reaction with the crosslinking agent does not interfere with subsequent shaping. In some aspects, the cross-linking agent is applied to the pellet or article after the pellet or article has been processed into its final shape. In such aspects in which the cross-linking agent is applied after shaping the pellet or article, the solution of the cross-linking agent may be applied to the shaped pellet or article by brushing, dipping, spraying, or any combination thereof, the solution of the cross-linking agent onto one or more of the surfaces of the pellet or article. In some aspects, the pellets or articles are immersed in a solution of the cross-linking agent, followed by a subsequent optional rinse.
In some aspects, the pellet or article can be crosslinked by exposing a hydrocolloid (e.g., alginate, chitosan, guar gum, or a combination thereof) to a multivalent metal cation, such as a metal cation having a 2+ or 3+ charge. In some aspects, suitable metal cations for crosslinking the hydrocolloid comprise Ba 2+ 、Ca 2+ 、Mg 2+ 、Al 3+ Or any combination thereof. In some casesIn aspects, the counter ion of the metal cation can be any acceptable non-toxic anion, such as a halide (e.g., chloride, bromide, fluoride, iodide, or any combination thereof), an organic anion such as acetate or carboxylate, or any combination of anions. In some aspects, the metal cations are applied to the article in the form of an aqueous solution of a metal salt. In some aspects, the metal salt solution is applied to the article by spraying, brushing, dipping, immersing, or the like, or any combination thereof. In some aspects, the metal salt solution is maintained in contact with the article for a sufficient period of time to allow sufficient diffusion of the metal cations into the pellet or article and provide for cross-linking of the hydrocolloid (e.g., alginate and/or kappa-carrageenan). In some aspects, the concentration of the metal salt in the aqueous solution ranges from 2 wt.% to saturation, from about 5wt.% to about 15 wt.%, from about 5wt.% to about 40wt.%, or from about 20wt.% to about 40wt.%, based on the total weight of the aqueous solution.
Suitable crosslinking agents that may be included in the pretreatment mixture or that may be used in the crosslinking bath include, for example, inorganic crosslinking agents. Suitable inorganic crosslinking agents include, for example, zirconium acetate, potassium zirconium carbonate (e.g., zirmel TM 1000 Ammonium zirconium carbonate (e.g., bacote available from Luxfer MEL technologies Inc.) TM ) Alum (e.g., KAl (SO) 4 ) 2 ) Calcium chloride, or any combination thereof. In addition, suitable inorganic cross-linking agents also include any of the wetting agents disclosed elsewhere herein.
In some aspects, such inorganic cross-linking agents may be disclosed elsewhere herein as having a different function, such as zirconium acetate as a wetting agent; however, such disclosure merely indicates that certain components may have different or multiple functions in the article, pellet, and/or pretreatment mixture.
In some aspects, the inorganic cross-linking agent is added to and mixed with the other components of the pretreatment mixture to form the pretreatment mixture, pellets, and articles, and is thus generally evenly distributed throughout the pretreatment mixture, pellets, and articles. Such inorganic crosslinkers typically contain ions that act to ionically crosslink at least some of the various other components present in the composition, such as the hydrocolloid, filler, and/or plasticizer, by electrostatic interactions.
In some aspects, the pretreatment mixture, pellet, and/or article includes any suitable amount of a crosslinking agent (e.g., an inorganic crosslinking agent). For example, in some aspects, the pretreatment mixture, pellet, and/or article comprises a crosslinker or combination of crosslinkers 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, or 20, as the case may be, based on the total weight of the pretreatment mixture, pellet, and/or article. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the pretreatment mixture, pellet, and/or article comprises a crosslinker or combination of crosslinkers in an amount (wt.%) of 0 to about 10, about 1 to about 10, 0 to 5, 1 to 5, 0 to 3, 1 to 3, 5 to 10, 3 to 11, 5 to 10, about 5 to about 10, about 5 to 15, 6 to 14, at least 3, at least 5, or less than 12.
In some aspects, the pretreatment mixtures, pellets, and/or articles herein do not include a cross-linking agent, such as caramel color, wood fume concentrate, furfural, dialdehydes, dicarboxylic acids, dicarboxylic anhydrides, di-or triisocyanates, di-or tri-epoxides, polysaccharide aldehydes, or any combination thereof.
In some aspects, the article or pellet is immersed in the crosslinking bath at a temperature of about 20 ℃ to about 70 ℃, or about 25 ℃ to about 60 ℃, or about 40 ℃ to about 55 ℃ for a period of about 1 minute to about 10 minutes, or about 3 minutes to about 8 minutes. In some aspects, after crosslinking, the article or pellet may be rinsed to remove excess crosslinking agent. For example, in some aspects, the rinsing is performed at a temperature of about 20 ℃ to about 70 ℃, or about 25 ℃ to about 60 ℃, or about 40 ℃ to about 55 ℃ for a period of about 1 minute to about 10 minutes, or about 3 minutes to about 8 minutes, or about 3 minutes to about 6 minutes.
In some aspects, a crosslinking bath is not employed. In some aspects, a crosslinking bath is not employed and an inorganic crosslinking agent is included in the pretreatment mixture, pellet, and/or article. In some aspects, no rinsing step is employed. In some aspects, the crosslinking bath is not employed, and no rinsing step is employed. In some aspects, the organic crosslinking agent is included in the pretreatment mixture, pellet, and/or article, and no rinse step is employed. In such aspects, the compositions of the pretreatment mixture, pellets, and articles are the same or substantially similar (e.g., within 1wt.%, within 5wt.%, within 8wt.%, or within 10 wt.%) without employing a crosslinking bath and/or a rinse step.
In some aspects, the pretreatment mixture, pellets produced therefrom, or articles produced therefrom (e.g., articles produced from the pretreatment mixture or pellets) comprise any suitable combination of components. The article, pellet, or pretreatment mixture may include any of the amounts of any of the components described elsewhere herein. The specific combinations described below represent only a few examples of suitable combinations, but are not intended to be limiting, as it is expressly contemplated that the components described elsewhere herein can be combined in any manner and in any amount.
In some aspects, the pretreatment mixture or pellet comprises about 5-40wt.% of one or more hydrocolloids (e.g., 5-15wt.% alginate, 0.5-10wt.% chitosan with 0.5-10wt.% guar gum), 20-35wt.% hydrophilic plasticizer (e.g., glycerin), 0.5-2wt.% hydrophobic plasticizer (e.g., glyceryl tricaprylate), 0.5-10wt.% wetting agent (e.g., aluminum hydroxide or a hydrate thereof), 40-60wt.% water, and optional ingredients (e.g., colorants, flavors, etc.).
In some aspects, the article comprises about 5-70wt.% hydrocolloid (e.g., 8-20wt.% alginate, 2-10wt.% chitosan with 2-10wt.% guar gum), 30-45wt.% hydrophilic plasticizer (e.g., glycerin), 1.5-3.5wt.% hydrophobic plasticizer (e.g., glyceryl tricaprylate), 1-10wt.% wetting agent (e.g., aluminum hydroxide or a hydrate thereof), 20-40wt.% water, and optional ingredients (e.g., colorants, flavors, etc.).
In some aspects, the pretreatment mixture or pellet comprises 15-35wt.% of one or more hydrocolloids (e.g., 10-20wt.% kappa-carrageenan with 5-15wt.% chitosan), 5-15wt.% hydrophilic plasticizers (e.g., glycerin), 0.5-2wt.% hydrophobic plasticizers (e.g., glyceryl trioctanoate), 5-10wt.% fillers (e.g., calcium carbonate or hydrates thereof), 40-60wt.% water, and optional ingredients (e.g., colorants, flavors, etc.).
Ratio of the components
Any amount of any component or combination of components disclosed herein can be readily converted to a weight ratio relative to the amount of any other component or combination of components disclosed herein. For example, in some aspects, the amount of any component or combination of components is expressed as a weight ratio relative to the total amount of hydrocolloid present, or vice versa, or the amount of any component or combination of components is expressed as a weight ratio relative to the total amount of alginate present, or vice versa, or the amount of kappa-carrageenan is expressed as a weight ratio relative to the total amount of any component or combination of components.
For example, in the pretreatment mixture, X (total alginate) to 1 (total plasticizer) may be included in a suitable weight ratio according to the amount of total alginate to total plasticizer calculated for these components as disclosed elsewhere herein, where X is 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, or 0.8. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, suitable weight ratios of total alginate (X) to total plasticizer (1) include cases where X is from about 0.07 to about 0.8, from about 0.08 to about 0.75, from about 0.2 to about 0.5, from about 0.3 to about 0.45, or at least about 0.3.
For example, in the pretreatment mixture, X (total alginate) to 1 (hydrophilic plasticizer) may be included in a suitable weight ratio according to the amount of these components calculated as disclosed elsewhere herein, where X is 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, or 0.8. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, suitable weight ratios of total alginate (X) to hydrophilic plasticizer (1) include cases where X is from about 0.1 to about 0.8, from about 0.15 to about 0.75, from about 0.2 to about 0.5, from about 0.3 to about 0.45, at least about 0.35, or less than about 0.6.
For example, in a pretreatment mixture or article, X (total alginate) to 1 (hydrophobic plasticizer), where X is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, or 35, may be included in a suitable weight ratio of total alginate to hydrophobic plasticizer based on the amount of these components disclosed elsewhere herein. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, suitable weight ratios of total alginate (X) to hydrophobic plasticizer (1) include cases where X is from about 1 to about 35, from about 1 to about 10, from about 2 to about 9, from about 3 to about 12, at least about 5, or less than about 15.
For example, in the pretreatment mixture or article, X (total alginate) to 1 (chitosan) may be included in a suitable weight ratio according to the amount of these components as disclosed elsewhere herein, wherein X is 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, or 35. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, suitable weight ratios of total alginate (X) to chitosan (1) include cases where X is from about 0.1 to about 30, from about 1 to about 10, from about 1 to about 8, from about 3 to about 7, at least about 2, or less than about 20.
For example, in a pretreatment mixture or article, X (total alginate) to 1 (wetting agent) may be included in a suitable weight ratio according to the amount of total alginate to wetting agent calculated for these components as disclosed elsewhere herein, where X is 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, or 35. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, suitable weight ratios of total alginate (X) to wetting agent (1) include cases where X is from about 0.1 to about 30, from about 1 to about 10, from about 1 to about 8, from about 3 to about 7, from about 4 to about 12, at least about 3, or less than about 10.
For example, in a pretreatment mixture or article, X (total hydrocolloid) to 1 (wetting agent) may be included in a suitable weight ratio based on the calculated amounts of these components as disclosed elsewhere herein, where X is 0.1, 0.2, 0.4, 0.5, 0.6, 0.8, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 35, 40, 45, 50, 55, 60, 65, 70, or 75. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, suitable weight ratios of total hydrocolloid (X) to wetting agent (1) include cases where X is from about 0.1 to about 75, from about 1 to about 20, from about 6 to about 25, from about 3 to about 15, from about 4 to about 12, at least about 7, from about 5 to about 15, or less than about 18.
For example, in a pretreatment mixture or article, X (total hydrocolloid) to 1 (hydrophobic plasticizer) may be included in a suitable weight ratio according to the amount of total hydrocolloid to hydrophobic plasticizer calculated for these components as disclosed elsewhere herein, where X is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 35, 40, 45, 50, 55, 60, 65, 70, or 75. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, suitable weight ratios of total hydrocolloid (X) to hydrophobic plasticizer (1) include cases where X is from about 1 to about 75, from about 1 to about 20, from about 6 to about 25, from about 3 to about 15, from about 4 to about 12, at least about 7, or less than about 18.
For example, in the pretreatment mixture, X (total hydrocolloid) to 1 (hydrophilic plasticizer) may be included in a suitable weight ratio according to the amount of these components as disclosed elsewhere herein, where X is 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, or 5. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, a suitable weight ratio of total hydrocolloid (X) to hydrophilic plasticizer (1) comprises a case where X is from about 0.1 to about 5, from about 0.1 to about 2, from about 0.2 to about 1, from about 0.3 to about 3, from about 0.44 to about 0.95, at least about 0.5, or less than about 3.
For example, in a pretreatment mixture or article, X (total hydrocolloid) to 1 (total plasticizer) may be included in a suitable weight ratio according to the amount of total hydrocolloid to total plasticizer as disclosed elsewhere herein, where X is 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, or 5. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, suitable weight ratios of total hydrocolloid (X) to total plasticizer (1) include cases where X is from about 0.1 to about 5, from about 0.1 to about 2, from about 0.2 to about 1, from about 0.3 to about 3, from about 0.44 to about 0.95, at least about 0.5, or less than about 3.
For example, in a pre-treatment mixture, pellet or article, a suitable weight ratio of kappa-carrageenan (X) to total plasticizer (1) that may be calculated from the amounts of these components disclosed elsewhere herein comprises X (kappa-carrageenan) to 1 (total plasticizer), wherein X is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.8, 5, 5.2, 5.4, 5.6, 5.8, 6, 6.2, 6.4, 6.8, 7, 7.2, 7.4, 7.6, 7.8 or 8. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, suitable weight ratios of kappa-carrageenan to (X) to total plasticizer (1) include cases where X is about 0.1 to 8, 1 to 6, 0.1 to 0.8, 0.1 to 0.6, 0.3 to 0.8, 0.3 to 3, 0.3 to 2, 0.3 to 1, 0.6 to 6, 0.6 to 5, 0.6 to 4, 0.6 to 3, or 0.8 to 4.
For example, in a pretreatment mixture, pellet or article, a suitable weight ratio of kappa-carrageenan (X) to hydrophilic plasticizer (1) that may be calculated from the amounts of these components disclosed elsewhere herein comprises X (kappa-carrageenan) to 1 (hydrophilic plasticizer), wherein X is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.8, 5, 5.2, 5.4, 5.6, 5.8, 6, 6.2, 6.4, 6.8, 7, 7.2, 7.4, 7.6, 7.8 or 8. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, suitable weight ratios of kappa-carrageenan (X) to hydrophilic plasticizer (1) include cases where X is about 0.6 to 4, 0.7 to 4, 0.6 to 2, 0.1 to 5, 0.5 to 2.4, 1 to 2, 1 to 3, or 0.8 to 1.6.
For example, in a pretreatment mixture, pellet or article, a suitable weight ratio of kappa-carrageenan (X) to hydrophobic plasticizer (1) that may be calculated based on the amounts of these components disclosed elsewhere herein comprises X (kappa-carrageenan) to 1 (hydrophobic plasticizer), where X is 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, or 50. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, suitable weight ratios of kappa-carrageenan (X) to hydrophobic plasticizer (1) include cases where X is about 5 to 40, 2 to 10, 4.5 to 20, 10 to 30, 14 to 26, about 40, 34 to 44, or 4 to 8.
For example, in a pre-treatment mixture, pellet or article, a suitable weight ratio of kappa-carrageenan (X) to total filler (1) that may be calculated from the amounts of these components disclosed elsewhere herein comprises X (kappa-carrageenan) to 1 (total filler), wherein X is 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4, 5.6, 5.8, 6.2, 6.4, 6.6, 6.8, 7, 7.2, 7.8, 8, 8.2, 8.4, 8.6, 8.8, 9.2, 9.4, 9.9.10 or 9.10. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, suitable weight ratios of kappa-carrageenan (X) to total filler (1) include cases where X is about 0.8 to 5, 1 to 4, 1 to 3, 1.2 to 4.4, 0.6 to 3, 0.9 to 4.1, 2 to 3, about 2, 2 to 2.6, or 1.8 to 2.8.
For example, in a pre-treatment mixture, pellet or article, a suitable weight ratio of kappa-carrageenan (X) to total other hydrocolloid (1) that may be calculated from the amounts of these components disclosed elsewhere herein comprises X (kappa-carrageenan) to 1 (total other hydrocolloid), wherein X is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4, 5.6, 5.8, 6.2, 6.4, 6.8, 7, 7.2, 7.4, 7.6, 7.8 or 8. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, suitable weight ratios of kappa-carrageenan (X) to total other hydrocolloids (1) include cases where X is about 0.6 to 4, 0.7 to 4, 0.6 to 2, 0.1 to 5, 0.5 to 2.4, 1 to 2, 1 to 3, or 0.8 to 1.6.
Procedure
In some aspects, the article is prepared, for example, by molding, casting, extruding (e.g., hot melt extrusion), or any combination thereof, a pretreated mixture or pellet comprising one or more hydrocolloids, one or more plasticizers, one or more wetting agents, a water-based liquid, and optional ingredients. In some aspects, the article is prepared, for example, by molding, casting, extruding (e.g., hot melt extrusion), or any combination thereof, a pretreated mixture or pellet comprising one or more hydrocolloids, one or more plasticizers, one or more fillers, a water-based liquid, and optional ingredients. In some aspects, the pellets are prepared, for example, by molding, casting, extruding (e.g., hot melt extrusion), or any combination thereof, a pretreatment mixture comprising one or more hydrocolloids, one or more plasticizers, one or more wetting agents, a water-based liquid, and optional ingredients. In some aspects, the pellets are prepared, for example, by molding, casting, extruding (e.g., hot melt extrusion), or any combination thereof, a pretreatment mixture comprising one or more hydrocolloids, one or more plasticizers, one or more fillers, a water-based liquid, and optional ingredients.
In some aspects, the article or pellet is prepared according to the steps provided below:
for heat activated hydrocolloid, the pretreatment mixture was prepared as follows: (a) Adding one or more hydrocolloids to water and/or a water-based liquid to provide a mixture; (b) Heating the mixture comprising the hydrocolloid to activate the hydrocolloid; (c) Optionally concentrating the heated mixture by evaporating water; (d) the mixture may be cooled to a precasting temperature; (e) Optionally, additional ingredients are added to the water or the water-based liquid before adding the hydrocolloid and/or before thermally activating the hydrocolloid and/or after cooling the mixture to a precasting temperature to provide the pretreatment mixture. Such a pre-treatment mixture may be compounded into pellets using, for example, a hot melt extruder, if desired.
In some aspects, the pretreatment mixture is prepared as follows: (a) Adding one or more hydrocolloids, one or more plasticizers, and one or more wetting agents and/or fillers to water and/or water-based liquids to provide a mixture; (b) Optional ingredients, including colorants, flavors, etc., may be added before or after the addition of the hydrocolloid; (c) The mixture may be cooled to a pretreatment temperature to provide the pretreated mixture.
In some aspects, the article may be prepared from a pretreatment mixture or pellet comprising a hydrocolloid and other ingredients by: (i) Shaping the shape of the article by introducing the pre-treated mixture of the hydrocolloid or the pellet into a mould comprising an inner form and an outer form; (ii) allowing the hydrocolloid to set; (iii) removing the external form; (iv) Dehydrating the article while maintaining the article on the interior form; (v) removing the internal form; (vi) optionally coating the article; (vii) Optionally, after one or more of steps (iii), (iv) or (v), applying a solution comprising a cross-linking agent to one or more surfaces of the article.
In some aspects, the article is prepared from a pretreatment mixture or pellet comprising a hydrocolloid and other ingredients by: (i) Extruding (e.g., hot melt extrusion) the preconditioning mixture or the pellets; (ii) Optionally applying a solution comprising a cross-linking agent to one or more surfaces of the article; (iii) optionally performing a rinse; and (iii) optionally drying, dehydrating or air cooling the article.
In some aspects, a method for making an article is disclosed, the method comprising: combining at least one hydrocolloid, at least one plasticizer, at least one wetting agent and/or filler, water, and optionally at least one colorant to prepare a pretreatment mixture; shaping the pre-treatment mixture into a shape (e.g., pellet or article); optionally, immersing the shape in a crosslinking bath to shape the crosslinked shape; optionally, rinsing the crosslinked shape to remove excess crosslinking agent; and optionally drying the crosslinked shape to shape the shape (e.g., article or pellet), optionally shaping the shape on a mandrel; wherein the at least one hydrocolloid, the at least one plasticizer, the at least one wetting agent and/or the filler, the water and the optional colorant are as defined elsewhere herein.
In some aspects, certain compositions are more suitable for certain processing steps, such as cold extrusion, hot melt extrusion, crosslinking baths, and/or whether a pre-mixing step is employed prior to extrusion. For example, in some aspects, cold extrusion is generally applicable to a pretreatment mixture comprising alginate as the predominant hydrocolloid (not comprising water) in combination with chitin and/or chitosan, and is generally mixed to prepare the pretreatment mixture prior to addition to an extruder for cold extrusion. In addition, articles prepared by cold extrusion are also typically immersed in a crosslinking bath.
In contrast, in some aspects, hot extrusion is generally applicable to a preconditioning mixture that includes carrageenan (e.g., kappa-carrageenan) as the primary hydrocolloid (without water) in combination with chitin and/or chitosan, and generally does not require mixing prior to addition to the extruder to prepare the preconditioning mixture (i.e., mixing directly in the extruder, e.g., a screw extruder, for hot melt extrusion). In some aspects, when alginate is the primary hydrocolloid, such mixtures are not suitable for hot melt extrusion. Furthermore, articles prepared by hot melt extrusion are generally not required, but may optionally comprise immersion in a crosslinking bath. Reference is also made to fig. 2 for a flow chart depicting an aspect of a hot melt extrusion process for preparing an exemplary article (e.g., a straw).
In some aspects, two hydrocolloids (e.g., one or more of alginate and chitosan/chitin, or kappa-carrageenan and alginate) are mixed together in the form of a powder and the powder mixture is added to one or more plasticizers (e.g., glycerol and glycerol tricaprylate) and then a wetting agent (e.g., aluminum hydroxide or a hydrate thereof) and/or a filler (e.g., calcium carbonate) are added. In some aspects, such mixtures are mixed, then water is added to make a dough that is thermally blended, and then optionally cooled to below 50 ℃, additional optional ingredients (e.g., flavor, color, or both) may also be added before or after the optional cooling step. In some aspects, such pre-treatment mixtures are then extruded (e.g., hot or cold) into pellets or articles, optionally crosslinked, optionally rinsed, and optionally dried.
In some aspects, extruding includes tube extruding, e.g., to shape the straw. In some aspects, the extrusion is on a mandrel. When extruded onto a mandrel, the extruded composition may optionally be dehydrated while still on the mandrel, before the article is released from the mandrel.
In some aspects, the hydrocolloid is added to water and/or a water-based liquid to provide a pre-treatment mixture comprising from about 1% to about 6% hydrocolloid, and preferably from 1% to 5% hydrocolloid (e.g., for a heat activated hydrocolloid such as agar), wherein the mixture is optionally stirred with heating. When heating is performed, the heating is typically performed until the mixture reaches a temperature of about 80 ℃ to about 100 ℃. In some aspects, the mixture may be heated to reach boiling. In some aspects, the temperature may be maintained for a time sufficient to activate the hydrocolloid, for example, for a time of from about 1 minute to about one hour, or from about 5 minutes to about 45 minutes, or from about 10 minutes to about 30 minutes.
In some aspects, the article (e.g., straw) is prepared by a continuous hot melt extrusion process. In some aspects, the preconditioning mixture is prepared into an article (e.g., a straw) by a continuous hot melt extrusion process. In some aspects, the pretreatment mixture is compounded into pellets using hot melt extrusion (e.g., using a twin screw extruder). In some aspects, the pellets are prepared into articles (e.g., pipettes) by a continuous hot melt extrusion process. In some aspects, the pre-treatment mixture is first compounded into pellets using a hot melt extruder (e.g., twin screw) and then the pellets are prepared into articles (e.g., straws) by a continuous hot melt extrusion process, such as using a single screw extruder. In some aspects, pellet molding using an extruder (e.g., a twin screw extruder) is a cold extrusion process.
In some aspects, compounding the pre-treatment mixture into pellets employs a twin screw hot melt extruder having a temperature (c) of 70, 75, 80, 85, 90, 95, 99, or 100. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the temperature (°c) is 85 to 100, 85 to 99, 75 to 95, 70 to 100, 70 to 99, 75 to 99, 80 to 100, 80 to 95, or 80 to 99.
In some aspects, compounding the preconditioning mixture into pellets employs a twin screw hot melt extruder having a screw speed (rpm) of 150, 175, 200, 225, 250, 275, 300, 325, or 350. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, the screw speed (rpm) is 200 to 300, 175 to 325, about 175 to about 350, at least 200, at least 225, less than 350, or 225 to 275.
In some aspects, compounding the pretreatment mixture into a pellet employs a feed weight ratio of solids (X) to liquids (1), wherein X is 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2. Each of the foregoing numbers may be preceded by the word "about," "at least about," "less than" or "less than about," and any of the foregoing numbers may be used individually to describe a single point or open range or may be used in combination to describe multiple single points or closed ranges. For example, in some aspects, a feed weight ratio of solids (X) to liquids (1) may be employed, where X is about 1, about 1 to 2, 0.25 to 1, 0.2 to 1.2, 0.5 to 1, or 0.6 to 0.8.
In some aspects, compounding the pretreatment mixture into a pellet employs any suitable combination of parameters, including a temperature of about 85 ℃ to about 100 ℃, a screw speed of about 200rpm to about 300rpm, and a solids to liquid feed weight ratio of 0.25:1 to 1:1.
In some aspects, the preparation of an article (e.g., a straw) from the pre-treatment mixture or pellet employs any suitable process. For example, in some aspects, the process includes extrusion. In some aspects, articles (e.g., pipettes) are prepared from the pre-treated mixture or pellets using a single screw extruder with a universal screw. In some aspects, articles (e.g., pipettes) are prepared from the pre-treated mixture or pellets using a single screw extruder with a universal screw and a tubular die.
In some aspects, articles (e.g., straws) are prepared from the preconditioning mixture or pellets by a process that includes hot melt extrusion and employs a single screw extruder having a universal screw with a compression ratio of about 2:1, about 2.5:1, about 3:1, about 3.5:1, or about 4:1. In some aspects, an article (e.g., a straw) is prepared from the pre-treated mixture or pellet by employing a single screw extruder having a common screw and a tubular die at a temperature (deg.c) of 70 to 100, 70 to 99, 70 to 95, 75 to 100, 75 to 99, 75 to 95, 80 to 100, 80 to 99, or 80 to 95. In some aspects, an article (e.g., a straw) is prepared from the pre-treated mixture or pellet by using a screw speed (rpm) of 5 to 60, 5 to 55, 5 to 50, 5 to 45, 10 to 60, 10 to 55, 10 to 50, 15 to 60, 15 to 55, 15 to 50, or 15 to 45 using a single screw extruder with a universal screw. In some aspects, when preparing an article (e.g., a straw) from the pre-treatment mixture or pellet, any combination of treatment parameters, such as any combination of compression ratio, temperature, and screw speed, may be employed. For example, in some aspects, the preconditioning mixture or pellets are extruded into articles (e.g., pipettes) using a 3:1 compression ratio universal screw and a tubular die at a temperature of 75 ℃ to 95 ℃ and at a screw speed of 5rpm to 50 rpm.
In some aspects, an article (e.g., a straw) obtained during hot melt extrusion (e.g., from a pre-treatment mixture or pellet) is cooled (e.g., air cooled) and cut to a desired length. Such final articles contain moisture in an amount (wt.%) of about 20 to about 40, about 15 to about 35, about 20 to about 35, about 25 to about 35, or about 15 to about 30. In some aspects, the pretreatment mixture or pellet contains moisture in an amount (wt.%) of about 35 to about 50, about 35 to about 55, about 30 to about 50, about 30 to about 55, about 30 to about 45, about 35 to about 45, or about 30 to about 40. As described elsewhere herein, such articles do not require a crosslinking bath and/or rinse such that the amount of components in the article is the same or substantially the same as the amount of components in the pretreatment mixture and/or pellet, but the moisture content may vary slightly (e.g., 35-50wt.% in the pretreatment mixture or pellet, as compared to 25-35wt.% in the article), such that the composition of the components in the article may be recalculated accordingly, taking into account such moisture differences.
In some aspects, during the preparation of the pretreatment mixture, pellets, and/or articles, water may be lost by evaporation (e.g., by cooking/boiling and/or by natural or forced drying). For example, if heat is applied, e.g., to activate the hydrocolloid, water may evaporate from the mixture, thereby concentrating the hydrocolloid. Thus, the water content by weight of the heated hydrocolloid mixture may be less than the water content of the initial hydrocolloid mixture by weight. In some embodiments, up to about 35wt.%, or up to about 30wt.%, or up to about 25wt.% of the original water is lost by evaporation. In some aspects, about 5wt.% to about 30wt.%, about 5wt.% to about 33wt.%, about 10wt.% to about 25wt.%, or about 15wt.% to about 25wt.% of the initial water is lost.
In some aspects, if the hydrocolloid solution is activated at high temperature, and particularly if the hydrocolloid solution is activated by boiling, the resulting hydrocolloid solution can be cooled to a pre-forming (e.g., molding, extrusion, etc.) temperature prior to shaping the article or pellet. In such aspects, the temperature of the hydrocolloid mixture prior to formation of the article or pellet can be cooled to a temperature of about 60 ℃ to about 90 ℃, or about 75 ℃ to about 85 ℃, or about 20 ℃ to about 50 ℃.
In some aspects, and particularly for pretreatment mixtures comprising alginate as a hydrocolloid, the pretreatment mixture may be cooled prior to shaping, e.g., shaping by molding, casting, extrusion, or any combination thereof. The pretreatment mixture may be cooled to a temperature of about 0 ℃ to about 10 ℃. The pretreatment mixture may be cooled and used immediately, or may remain in a cooled form for about 30 minutes to about 48 hours or more prior to molding.
In some aspects, additional ingredients of the article or pellet may be added to the hydrocolloid mixture at any point during the process for preparing the pretreatment mixture. Additional ingredients are added to the water or water-based liquid prior to addition of the hydrocolloid and/or prior to thermal activation of the hydrocolloid and/or after the mixture is cooled to the precasting temperature to provide the final pretreatment mixture. In some aspects, where ingredients that can degrade upon exposure to high temperatures (e.g., exposure to boiling water during hydrocolloid activation), such ingredients are typically added to the hydrocolloid mixture after thermal activation but prior to shaping of the article or pellet.
In some aspects, after preparing the pretreatment mixture with all desired ingredients, the pretreatment mixture can be shaped into various shapes for the article or pellet by extrusion (e.g., hot melt extrusion), molding, casting, or any combination thereof. In some aspects, the article may be molded, for example, using a polycarbonate or food grade silicone mold. In some aspects, the mold may include at least one, and at most three or more individual portions. In some aspects, the mold will include at least one internal form that defines the shape of the internal portion of the article. In some aspects, the mold includes one or more external forms that define the shape of the outer surface of the article. In some aspects, other materials and molding processes may be used to prepare the article or pellet.
In some aspects, the article is allowed to solidify (cure) in the mold. After the article has set, the outer form of the mold is removed. In some aspects, it is preferable not to remove the article from the internal form prior to subsequent dehydration of the article to avoid deformation of the article shape. In some aspects, the mold is pretreated with a release agent to facilitate removal of the mold form from the article. In some aspects, the mold release agent comprises one or more vegetable oils.
In some aspects, the article is dehydrated while still in an internal form so as to maintain the size and shape of the article during dehydration. Dewatering helps to enhance the structural integrity of the article by removing excess water to make the material more durable. Dewatering is typically applied to the article after the material has been molded and the outer mold form has been removed. In some aspects, after the outer mold form is removed from the article, the article in the inner mold form is placed on a metal tray and moved into a dehydrator to remove excess moisture.
In some aspects, the dehydrator is a commercial dehydrator, a convection oven, a vacuum dehydrator, or the like, or any combination thereof. In some aspects, the temperature of the dehydration is from about 35 ℃ to about 70 ℃, or from about 40 ℃ to about 60 ℃. In some aspects, the article may be held in the dehydrator for a period of time ranging from about one hour to about twenty-four hours until the article has the proper texture, moisture content, or combination thereof.
In some aspects, the clean water loss of the article relative to the pretreatment mixture or pellet is nearly 100% of the water. In some aspects, the water loss due to dehydration is 96 wt% relative to the article. In some aspects, the water loss of the article due to dehydration may be from about 80% to about 95% by weight relative to the article, or from about 85% to about 95% by weight relative to the article. In some aspects, for an alginate-based product, the water loss due to dehydration may be from 90 wt% to about 99.99 wt%.
In some aspects, the final dehydrated product may have a moisture content of from about 35% to about 70%, or any amount described elsewhere herein. In some aspects, the moisture content of the final article is from about 20 wt% to about 35 wt%, from about 35 wt% to about 65 wt%, or from about 45 wt% to about 65 wt% or from about 40 wt% to about 55 wt%. In other embodiments, the moisture content is from about 40 wt% to about 50 wt%. In some aspects, such as for an alginate-based product or a kappa-carrageenan-based product, the final water content may be about 0 wt% to 4 wt%.
In some aspects, water removal during dewatering may be monitored to ensure that a desired final moisture content is achieved. In some aspects, the weight of the product may be monitored to determine the moisture content of the product during and/or after dewatering.
In some aspects, the wall thickness of the dehydrated article may be from about 0.1mm to about 3mm. For articles such as cups, the wall thickness may be from about 0.5mm to about 3mm or from about 0.7mm to about 2mm. For drinking straws, the wall thickness may be about 0.1mm to about 0.8mm, about 0.1mm to about 0.6mm, about 0.3mm to about 0.6mm, about 0.4mm to about 0.6mm, about 0.2mm to about 0.5mm, about 0.2mm to about 0.4mm, or about 0.5mm. The wall thickness is selected based on the identity and intended use of the article.
In some aspects, after the article is dehydrated, the article may be coated to enhance water repellency, provide flavor, a specific color, and/or provide a smooth finish to the final product. The article may be coated as described elsewhere herein, for example with a wax-based edible coating. In some aspects, the article may be coated with an edible coating for imparting gloss, a gloss finish to the article, for reducing tackiness, or a combination thereof. In some aspects, the coating increases the shelf life of the article to 6 months, 8 months, 10 months, 12 months, 14 months, 16 months, 18 months, 20 months, 22 months, or 24 months without refrigeration. In some aspects, the coating is applied by any conventional method, including spraying, painting, rolling, dipping, or co-extrusion, or the like, or any combination thereof.
In some aspects, the coating is applied to the article by a spray process. In some aspects, the article may be placed on a spinning surface and a coating spray applied to the outer surface of the container while the article is spinning. In some aspects, the inner surface is coated by spraying. In some aspects, the coated article is dried, for example, with a fan for up to twenty-four hours, although shorter or longer periods of time may be employed if desired. In some aspects, the coating increases the total weight of the article by about 0.1 grams to about 2 grams, or about 0.2 grams to about 1.2 grams. In some aspects, the edible coating facilitates use of the article to contain or contact a hot liquid, such as coffee, tea, soup, hot chocolate, and other beverages, having a temperature in the range of 0 ℃ to 10 ℃. In some aspects, the edible coating may enable the article to maintain or contact a liquid at about 71 ℃ for about one hour, or about 2 hours, or 3 hours or more. In some aspects, the coating is present at a thickness of about 0.5mm to about 3mm or about 1 mm.
In some aspects, the pretreatment mixture or pellet may be shaped into articles having different shapes as described elsewhere herein. For example, in some aspects, the article is in the form of a cup adapted to hold a beverage or other liquid (hot or cold). In some aspects, the cup is edible and contains low viscosity liquids, such as water, juice, milk, alcoholic beverages, coffee, tea, sports beverages, soda and other beverages, for an extended period of time without degradation, preferably over an hour or more.
In some aspects, the processing steps are performed with one or more automated steps that do not involve manual manipulation by a human worker. For example, in some aspects, the process includes mixing the components, shaping (e.g., extruding), immersing the shaped article into a crosslinking bath, rinsing the crosslinked article, and drying the rinsed crosslinked article, wherein one or more of such steps are performed in an automated manner. For example, in some aspects, the process comprises a fully automated process whereby the components are mixed, extruded, optionally crosslinked, optionally rinsed, and dried without human intervention or manipulation. However, automation may be used for specific steps (if desired), or not used at all (as needed).
In some aspects, the hydrocolloids in the pretreatment mixtures, pellets, and articles herein do not foam. In some aspects, the pretreatment mixture herein is not aerated. In some aspects, the articles or pellets herein are not prepared by a process that includes immersing or immersing the seaweed in water and cutting the immersed/immersed seaweed into pieces (e.g., less than 1 cm). In some aspects, the process for producing an article (e.g., a straw) or pellet from the pretreatment mixture does not comprise rolling the article (e.g., straw) or pellet from the pretreatment mixture comprising rice flour, wheat gluten, or a combination thereof. In some aspects, the pretreatment mixture, pellet, and/or article is not produced using a process of extruding alginate into a coagulation bath of chitosan. In some aspects, the pretreatment mixture and/or article is not produced using a process that extrudes chitosan into the coagulation bath of alginate.
In certain aspects, the addition of one or more hydrophobic additives to the pretreatment mixtures and pellets herein may improve the processability of such compositions, particularly when processed by extrusion. In particular, the addition of such additives may improve the flowability of such compositions during processing, in particular during processing by extrusion. More specifically, the addition of fatty acid salts and fatty acid esters or mixtures thereof, such as stearates, palm stearates and mixtures thereof, may improve the flowability of such compositions, particularly during extrusion. Such hydrophobic additives may act, for example, as mold release agents in the treatment of such compositions herein. In certain aspects, such additives may be included in the pretreatment mixtures and pellets herein in an amount ranging from 0.5wt.% to 10 wt.%. In various aspects, such additives may be included in the compositions herein in an amount ranging from 1wt.% to 10wt.%, or 2wt.% to 8wt.%, or 3wt.% to 7 wt.%.
In certain aspects, one or more amphiphilic compounds, such as one or more phospholipids (e.g., lecithin or phosphatidylcholine) or a combination of phospholipids (e.g., soybean phospholipids) may be included in the pretreatment mixtures and pellets herein, particularly in pretreatment mixtures and pellets containing carrageenan and/or alginate. In certain aspects, such compounds may be present in the compositions herein in an amount ranging from 1-10wt.% or 4wt.% to 8 wt.%.
In certain aspects, the compositions herein (pretreatment mixtures) may comprise a combination of kappa-carrageenan and one or more of iota-carrageenan, alginate or chitosan. In aspects, the compositions herein may comprise from 10wt.% to 15wt.% of such a combination.
In certain aspects, the compositions (pretreatment mixtures) herein may comprise MCC, CMC, cellulose fibers, or mixtures thereof. In aspects, the compositions herein may comprise 1.5wt.% to 3wt.% or 2wt.% to 3wt.% of MCC, CMC, cellulose fibers, or mixtures thereof.
In certain aspects, the compositions herein (pretreatment mixtures) may comprise glycerol or a combination of glycerol and glycerol trioctanoate, wherein the glycerol is present in an amount ranging from 15wt.% to 40wt.% or 20wt.% to 35wt.% and the glycerol trioctanoate, if present, is present in an amount ranging from 0.5wt.% to 2.5 wt.%.
In certain aspects, the compositions herein (pretreatment mixtures) may comprise glycerol or a combination of glycerol and glycerol trioctanoate, wherein the glycerol is present in an amount ranging from 5wt.% to 10wt.%, and the glycerol trioctanoate, if present, is present in an amount ranging from 0.5wt.% to 2.5 wt.%.
In certain aspects, certain natural gums or mixtures thereof may be included in the compositions (pretreatment mixtures) herein. In various aspects, natural gums are typically included in the range of 0.5 wt% to 3 wt%, or 1 wt% to 3 wt%, or 1.5 wt% to 3 wt%. The natural gums comprise, inter alia, guar gum, konjac gum, locust bean gum or mixtures thereof.
In certain aspects, the compositions (pretreatment mixtures) herein may comprise a combination of kappa-carrageenan with one or more of iota-carrageenan, alginate or chitosan and further combinations with MCC, CMC, cellulose fibers or mixtures thereof. In aspects, the compositions herein may comprise a combination of 10 to 15wt.% of kappa-carrageenan and one or more of iota-carrageenan, alginate or chitosan and 1.5 to 3wt.% or 2 to 3wt.% of MCC, CMC, cellulose fibers or mixtures thereof and a combination of glycerol or glycerol and tricaprylin, wherein the glycerol is present in an amount ranging from 15 to 40wt.% or 20 to 35wt.% and the tricaprylin, if present, is present in an amount ranging from 0.5 to 2.5 wt.%.
In certain aspects, the compositions (pretreatment mixtures) herein may comprise a combination of kappa-carrageenan with one or more of iota-carrageenan, RF6650 or chitosan and further comprise MCC, CMC, cellulose fibers or mixtures thereof and further comprise glycerol or a combination of glycerol and tricaprylin. In aspects, the compositions herein may comprise a combination of 10 to 15wt.% of one or more of kappa-carrageenan and iota-carrageenan, RF6650 or chitosan and 1.5 to 3wt.% or 2 to 3wt.% of MCC, CMC, cellulose fibers or mixtures thereof and further glycerol or a combination of glycerol and glycerol tricaprylate, wherein the glycerol is present in an amount ranging from 5 to 10wt.% and the glycerol tricaprylate (if present) is present in an amount ranging from 0.5 to 2.5 wt.%.
In certain aspects, the compositions (pretreatment mixtures) herein may comprise a combination of kappa-carrageenan with one or more of iota-carrageenan, alginate or chitosan and further combinations with MCC, CMC, cellulose fibers or mixtures thereof and further combinations with one or more natural gums. In certain aspects, the compositions herein may comprise a combination of 10wt.% to 15wt.% of kappa-carrageenan and one or more of iota-carrageenan, alginate or chitosan, 1.5wt.% to 3wt.% or 2wt.% to 3wt.% of MCC, CMC, cellulose fibers or mixtures thereof, and typically in the range of 0.5wt.% to 3wt.%, or 1 wt.% to 3wt.%, or 1.5wt.% to 3wt.% of natural gums. In aspects, the compositions herein may comprise 10 to 15wt.% of a combination of one or more of kappa-carrageenan, RF6650 or chitosan, 1.5 to 3wt.% or 2 to 3wt.% of MCC, CMC, cellulose fibers or mixtures thereof, natural gums typically in the range of 0.5 to 3wt.%, or 1.5 to 3wt.%, or a combination of glycerol or glycerol and glycerol trioctanoate, wherein the glycerol is present in an amount in the range of 15 to 40wt.% or 20 to 35wt.%, and the glycerol trioctanoate (if present) is present in an amount in the range of 0.5 to 2.5 wt.%. In aspects, the compositions herein may comprise 10 to 15wt.% of a combination of one or more of kappa-carrageenan, RF6650 or chitosan, 1.5 to 3wt.% or 2 to 3wt.% of MCC, CMC, cellulose fibers or mixtures thereof, natural gums typically in the range of 0.5 to 3wt.%, or 1.5 to 3wt.%, or a combination of glycerol or glycerol and glycerol trioctanoate, wherein the glycerol is present in an amount in the range of 5 to 10wt.%, and the glycerol trioctanoate (if present) is present in an amount in the range of 0.5 to 2.5 wt.%.
In certain aspects, the compositions herein (pretreatment mixtures) comprising a combination of kappa-carrageenan and one or more of iota-carrageenan, alginate or chitosan, and further combinations with MCC, CMC, cellulose fibers or mixtures thereof, may further comprise one or more wetting agents, such as salts (e.g., KCl or MgSO) in an amount in the range of 0.5 to 10wt.%, or 0.8 to 8wt.%, or 1 to 5wt.% 4 ). In aspects, the compositions herein comprise a combination of kappa-carrageenan and one or more of iota-carrageenan, alginate or chitosan, MCC, CMC, cellulose fibers or mixtures thereof, and a wetting agent, such as a salt (e.g., KCl or MgSO) in an amount in the range of 0.5 to 10wt.%, or 0.8 to 8wt.%, or 1 to 5wt.% 4 ) And glycerol or a combination of glycerol and glycerol trioctanoate, wherein glycerol is present in an amount ranging from 15wt.% to 40wt.% or 20wt.% to 35wt.% and glycerol trioctanoate (if present) is present in an amount ranging from 0.5wt.% to 2.5 wt.%.
In certain aspects, compositions herein (pretreatment mixtures) containing a combination of kappa-carrageenan with one or more of iota-carrageenan, alginate or chitosan, and further combinations with MCC, CMC, cellulose fibers or mixtures thereof, may To further contain one or more wetting agents, such as salts (e.g., KCl or MgSO) in an amount ranging from 0.5 to 10wt.%, or 0.8 to 8wt.%, or 1 to 5wt.% 4 ). In aspects, the compositions herein comprise a combination of kappa-carrageenan and one or more of iota-carrageenan, alginate or chitosan, MCC, CMC, cellulose fibers or mixtures thereof, and a wetting agent, such as a salt (e.g., KCl or MgSO) in an amount in the range of 0.5 to 10wt.%, or 0.8 to 8wt.%, or 1 to 5wt.% 4 ) And glycerol or a combination of glycerol and glycerol trioctanoate, wherein glycerol is present in an amount ranging from 5wt.% to 10wt.% and glycerol trioctanoate (if present) is present in an amount ranging from 0.5wt.% to 2.5 wt.%.
In certain aspects, the compositions (pretreatment mixtures) herein containing a combination of kappa-carrageenan with one or more of iota-carrageenan, RF6650 or chitosan and further combinations with MCC, CMC, cellulose fibers or mixtures thereof may further contain one or more fillers, such as salt CaCO present in an amount ranging from 1 to 10wt.% or 2 to 6wt.% 3 . In aspects, the compositions herein containing a combination of kappa-carrageenan and one or more of iota-carrageenan, RF6650 or chitosan and further combinations with MCC, CMC, cellulose fibers or mixtures thereof may further contain one or more fillers, such as CaCO present in an amount ranging from 1wt.% to 10wt.% or 2wt.% to 6wt.% 3 . In aspects, the kappa-carrageenan-containing compositions herein are combined with one or more of iota-carrageenan, RF6650 or chitosan and further combined with MCC, CMC, cellulose fibers or mixtures thereof and one or more fillers, such as CaCO present in an amount ranging from 1wt.% to 10wt.% or 2wt.% to 6wt.% 3 The composition of (c) may further contain glycerin or a combination of glycerin and glyceryl trioctanoate, wherein glycerin is present in an amount ranging from 15wt.% to 40wt.% or 20wt.% to 35wt.% and glyceryl trioctanoate (if present) is present in an amount ranging from 0.5wt.% to 2.5 wt.%.
In certain aspects, the compositions herein comprise kappa-carrageenan and iota-carrageenan, RF6650 orThe composition (pretreatment mixture) with the optional combination of one or more of the chitosan and further combination of MCC, CMC, cellulose fibers or mixtures thereof may further contain one or more fillers, such as CaCO present in an amount ranging from 1wt.% to 10wt.% or 2wt.% to 6wt.% 3 . In aspects, the compositions herein containing an optional combination of kappa-carrageenan and one or more of iota-carrageenan, alginate or chitosan and one or more of MCC, CMC, cellulose fibers or mixtures thereof may further contain one or more fillers, such as CaCO present in an amount ranging from 1wt.% to 10wt.% or 2wt.% to 6wt.% 3 . In aspects, the optional combination of kappa-carrageenan and one or more of iota-carrageenan, alginate or chitosan and further combination with one or more of MCC, CMC, cellulose fibers or mixtures thereof and one or more fillers, such as CaCO present in an amount ranging from 1wt.% to 10wt.% or 2wt.% to 6wt.% 3 The composition of (c) may further contain glycerin or a combination of glycerin and glyceryl trioctanoate, wherein glycerin is present in an amount ranging from 5wt.% to 10wt.%, and glyceryl trioctanoate (if present) is present in an amount ranging from 0.5wt.% to 2.5 wt.%.
In certain aspects for directly producing an article, particularly a straw, by directly treating a pretreatment mixture using a twin screw extruder, the pretreatment mixture composition may contain an optional combination of kappa-carrageenan and one or more of iota-carrageenan, alginate, or chitosan, one or more of MCC, CMC, or cellulose fibers, one or more fillers (such as CaCO 3 ) Glycerin or a combination of glycerin and glyceryl trioctoate, optionally a humectant, and optionally a natural gum. In aspects, for such direct generation of an article, the composition may contain: an optional combination of kappa-carrageenan and one or more of iota-carrageenan, alginate or chitosan, wherein the total amount of these components ranges from 10wt.% to 15wt.% or from 12wt.% to 14wt.%; one or more of MCC, CMC or cellulose fibers, wherein the total amount of these components is 1.5wt.% to 3wt.% or 2wt.% to 3wt.%; one or more fillers, wherein the total amount of fillers is 1w t.%to 5wt.% or 2wt.% to 4wt.%; and glycerol or a combination of glycerol and glycerol trioctanoate, wherein glycerol is present in an amount ranging from 5wt.% to 10wt.% and glycerol trioctanoate (if present) is present in an amount ranging from 0.5wt.% to 2.5 wt.%.
In the foregoing aspect of the composition (pretreatment mixture) comprising an optional combination of kappa-carrageenan and one or more of iota-carrageenan, alginate or chitosan and further combinations with MCC, CMC, cellulose fibers or mixtures thereof, the ratio of liquid to solids for treatment in the twin screw extruder ranges from 40:60 to 80:20, or 50:50 to 70:30, or 50:50, 60:40 or 70:30. In the foregoing aspect of the composition, the liquid may be water.
FIG. 1 depicts carbon dioxide generated when a single straw was prepared from plastic (1.47 g), paper (4.11 g) and polylactic acid (PLA) (4.57 g). Fig. 1 also shows that the techniques disclosed herein for preparing the compositions and articles of the present disclosure have a net inventory of 1.39g per straw produced when using a formulation that includes an alginate as the major component (excluding water).
FIG. 2 is a flow chart illustrating an exemplary method of the present disclosure for shaping an exemplary article. The flow chart illustrates a method for preparing a straw by an extrusion process. The liquid (2) and solid (4) inputs (components) of the preconditioning mixture are introduced into a twin screw extruder (TSE, 5). The liquid and solid components are shown as being added separately to the TSE, but may alternatively be pre-mixed (5) prior to introduction into the TSE. In some aspects, the liquid and solid components are extruded through a tube die (7 a) to shape a straw (8 a) of selected diameter and thickness. In some aspects, liquid and solid components are introduced into the TSE (5) and then passed through a wire drawing die and pellet cutter (9) to form pellets (10). In some aspects, pellet molding using TSE is a hot melt extrusion process. In some aspects, the pellets are introduced into a single screw extruder (SSE, 11) and then extruded through a tube die (7 b) to shape a straw of selected diameter and wall thickness. In some aspects, the pellets are extruded using hot melt extrusion.
The invention may be further understood by the following non-limiting examples.
Examples
Example 1:this example compares the characteristics of two pipettes of the present invention with pipettes made of plastic and paper.
The results of comparing several characteristics of the two straws of the present invention with respect to straws made of plastic and paper are shown in table 2. The characteristics were measured as described elsewhere herein. The straw No. 1 of the present invention contains alginate, a wetting agent and a plasticizer as main components, and the straw No. 2 of the present invention contains kappa-carrageenan, a filler and a plasticizer. Both of these inventive pipettes are generally prepared as described herein. Both plastic pipettes and paper pipettes are commercially available.
TABLE 2
N/D: is not determined
N/A: is not suitable for
a. Axial, 1000N apply force
b. Paper straw for coloring
Example 2:this example compares the composition of the pretreatment mixture to the expected composition of the article produced by the process comprising crosslinking, rinsing and drying, taking into account the amount of hydrophilic plasticizer and water present in the article as a result of the treatment step. The results are shown in table 3.
TABLE 3 Table 3
Component (A) | Pretreatment mixture (wt.%) | Article (wt.) |
Hydrophilic plasticizers | 20-35 | 15-25 |
Hydrophobic plasticizer | 0.5-2 | 1-4 |
Alginate | 5-15 | 10-30 |
Chitosan | 0.5-10 | 1-20 |
Other hydrocolloids | 0.5-10 | 1-20 |
Wetting agent | 0.5-10 | 1-20 |
Coloring agent (aqueous solution) | 0.1-0.3 | 0.2-0.6 |
Deionized water | 40-60 | 30-40 |
As shown in table 3, the water content of the final article was reduced by drying, the hydrophilic plasticizer content was reduced by about two thirds, and the balance was approximately doubled. The amount of the article was calculated by assuming that the amount (g) of hydrophilic plasticizer was reduced by about one third (which has been experimentally verified), and that the amount of water was set at about 30-40wt.%, and the remaining weight percentages were recalculated based on these set amounts. A similar calculation can be made if the amount of water in the article is set to a different amount, such as 20 wt.%.
Example 3: the present example compares the composition of the pretreatment mixture (or pellet) to the expected composition of an article (prepared from the pretreatment mixture or pellet) or pellet (prepared from the pretreatment mixture) produced by a process that does not include crosslinking and/or flushing. Elimination of such crosslinking and/or flushing steps can result in articles or pellets from which no hydrophilic components (e.g., hydrophilic plasticizers) leach. The results are shown in table 4.
TABLE 4 Table 4
As shown in table 4, the water content of the final product was reduced from 42wt.% to 30wt.% due to drying (whether active or passive). While the absolute number of the other components does not change (as any component leaches out or otherwise is removed), a decrease in the water content results in a relative increase in the amount of the other components. Generally, a decrease in water content of about 12wt.% will result in an increase in the weight percent of the other components by a factor of about 1.2. The amount of the article or pellet is calculated by assuming that the amount of water (g) is reduced from 42wt.% to 30wt.%, and then the remaining weight percentages are recalculated based on this set amount. Similar calculations can be made for any other water content.
Example 4:this example compares straws produced using different pretreatment mixtures or pellets that include various components.
The straw is produced using the methods described herein using a pretreatment mixture or pellet within the general scope disclosed herein. The bendability and compressibility were evaluated empirically. The flexibility of the straw was evaluated by bending the straw three times in the middle and compressing it at the ends. The suction tube pieces were immersed in water at Room Temperature (RT) and the weight change after 1 hour was recorded to conduct the swelling experiment. The classification is as follows: "crisp": the straw breaks into sharp fragments when bent or compressed; "rupture": the straw breaks upon bending/compression, but does not break up (i.e., crumble); "rigidity": some cracks were generated during bending/compression without cracking; "flexible": the suction pipe is bent in the middle; "compressible": the straw may be compressed/squeezed without breaking. The results are shown in Table 5.
TABLE 5
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* Chitosan: low molecular weight crustacean
Example 5:this example shows that straws made from pre-treated mixtures or pellets comprising specific wetting agents, which contain alginate as the main component (excluding water), produce a brittle straw that breaks upon bending.
Specifically, the straw is produced from a pretreatment mixture comprising the general amounts of hydrocolloid (alginate as the main component), plasticizer, humectant and water disclosed elsewhere herein, wherein the humectant is Ludox TM LS colloidal silicon (DuPont), hydrotalcite or magnesium sulfate. In testing the straw for bendability and compressibility as described in example 4When the straw breaks. This suggests that certain wetting agents do not produce pipettes having the desired mechanical properties in pipettes containing alginate as the main component (excluding water).
Example 6: this example compares pipettes produced using different pretreatment mixtures comprising various components. The pretreatment composition is treated with a twin screw hot melt extruder at a temperature of 85-100 ℃ and at a screw speed of 200-300rpm at a liquid to solid feed such as indicated to form pellets.
Suction tubes were created using pellets within the general scope disclosed herein. Suction tubes were produced on a 1.5 "single screw hot melt extruder (93 ℃ to 107 ℃, universal screw, 3:1 compression ratio); based on ASTM D882-12 (2012), the breaking force (psi) of the article was measured using a universal tester (34 SC-1, instron company, noowood, ma, usa) equipped with a 1kN load cell and an initial gap of 25 mm. The elongation at break (%) of the article was measured using a universal tester (34-SC-1, instron company, noowood, ma) equipped with a 1kN load cell and an initial gap of 25 mm. Elongation at break is determined according to the following formula: the%= (final gauge length-initial gauge length)/initial gauge length x 100.
To evaluate the water absorption spectrum (swelling ratio), the pipettes were weighed before and after immersing 2 inch pipette samples in DI water for 1 hour at RT. The swelling ratio (wt.%) was estimated according to the formula [ (Wf-Wo)/Wo ] ×100, where Wf is the weight of the sample after 1 hour immersion in room temperature DI water and Wo is the weight of the sample before this immersion. The results are shown in Table 6, where the listed characteristics represent characteristics of the composition ranges in the table entries. In general, increased breaking force and increased elongation at break produce an article of increased mechanical strength. The compositions in table 6 other than the composition of item 8 were generally used to prepare pipettes.
TABLE 6
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Example 7: this example demonstrates a process for coating an article (e.g., drinking straw) with a wax-based coating, and a comparison of the properties of the coated article with an uncoated article.
In this example, a pipette from example 6, item 15 was used.
A wax solution was prepared by first melting the wax (2-30 g) and then slowly adding 50g of acetone. The wax solution was further stirred with heating to form a homogeneous solution (wax particles not visible). To this homogeneous solution 50g of water were added with vigorous stirring to achieve a 1:1 ratio by weight relative to acetone. In solutions using both carnauba wax and beeswax, a ratio of 1:1 by weight relative to wax is used. The amount of wax employed in the coating solution is shown in table 7.
The 2 inch long straw was immersed in the coating solution where it was immersed for about 5 seconds. The soaked pipette is removed from the coating solution and slowly rotated on its axis while air dried to ensure that the coating on the pipette is uniform and does not drip off the sides. The dried coated pipettes were weighed and then the absorption test was performed by immersing in a room temperature water bath and recording the weight change after 1 hour. The swelling ratio is the percentage increase in the weight of the straw due to the absorption of water. Static contact angles were measured using the Rame-Hart 90 CA version with dropoimage software and using water as the liquid. The results are reported in table 7.
TABLE 7
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* Solvent: water acetone (by weight, 1:1)
Statement regarding incorporation by reference and alteration
All references, e.g., patent documents, including issued or issued patents or equivalents, patent application publications, and non-patent documents or other sources, throughout this application are hereby incorporated by reference in their entirety as if individually incorporated by reference to the extent that each reference is not at least partially inconsistent with the disclosure in this application (e.g., partially inconsistent references are incorporated by reference except for the partially inconsistent portions of the references).
The terms and expressions which have been employed herein are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is 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, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims. The specific embodiments provided herein are examples of useful embodiments of the invention, and it will be apparent to those skilled in the art that the invention may be practiced with numerous variations of the apparatus, apparatus assemblies, method steps set forth in the present specification. As will be apparent to those skilled in the art, the methods and apparatus useful in the methods of the present invention may comprise a wide variety of optional compositions as well as processing elements and steps.
As used herein and in the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a cell" includes a plurality of such cells and equivalents thereof known to those skilled in the art. Also, the terms "a" (or "an"), "one or more" and "at least one" can be used interchangeably herein. It should also be noted that the terms "comprising," "including," and "having" are used interchangeably. The expression "any of claims XX-YY (of any of claimsXX-YY) according to claims (where XX and YY refer to claim numbers) is intended to provide multiple dependent claims in alternative form and in some embodiments is interchangeable with the expression" any of claims XX-YY according to claims (as in any one ofclaims XX-YY) ".
When substituent groups are disclosed herein, it is to be understood that all individual members of the group and all subgroups of the group, including any isomers, enantiomers, and diastereomers of the group members, are individually disclosed. When a Markush (Markush) group or other grouping is used herein, all individual members of the group, as well as all possible combinations and subcombinations of the group, are intended to be individually included in the present disclosure. When a compound is described herein such that a particular isomer, enantiomer or diastereomer of the compound is not specified, for example in a formula or chemical name, the description is intended to encompass each isomer and enantiomer of the compound described alone or in any combination. Moreover, unless otherwise indicated, all isotopic variations of the compounds disclosed herein are intended to be encompassed within the present disclosure. For example, it should be understood that any one or more hydrogens in the disclosed molecules may be replaced with deuterium or tritium. Isotopic variants of a molecule are typically useful as standards in molecular assays and in chemical and biological studies related to the molecule or its use. Methods for making such isotopic variants are known in the art. The specific names of the compounds are intended to be exemplary, as it is known that one of ordinary skill in the art may name the same compounds differently.
Certain molecules disclosed herein may contain one or more ionizable groups [ groups from which protons may be removed (e.g., -COOH) or added (e.g., amine) or may undergo nitrile (e.g., amine) ]. All possible ionic forms of such molecules and salts thereof are intended to be individually encompassed by the disclosure herein. Regarding salts of the compounds herein, one of ordinary skill in the art can select from a variety of available counterions that are suitable for use in preparing the salts of the invention for a given application. In particular applications, the selection of a given anion or cation to prepare a salt may increase or decrease the solubility of the salt.
Unless otherwise indicated, each device, system, formulation, combination of components or methods described or illustrated herein may be used to practice the invention.
Whenever a range is given in the specification, such as a temperature range, a time range or a composition or concentration range, all intermediate ranges and subranges and all individual values included within the given range are intended to be included in the present disclosure. It is to 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.
All patents and publications mentioned in the specification are indicative of the levels of those skilled in the art to which the invention pertains. The references cited herein are incorporated by reference herein in their entirety to indicate the prior art by the date of their disclosure or filing and it is intended that this information may be employed herein, if necessary, to exclude specific embodiments in the prior art. For example, where the composition of matter is claimed, it is to be understood that compounds known and available in the art prior to applicants' invention, including the references cited herein provide compounds capable of disclosure, are not intended to be included in the composition of matter claimed herein.
As used herein, "comprising" is synonymous with "including," "containing," or "characterized by," and is inclusive or open-ended, and does not exclude additional, unrecited elements or method steps. As used herein, "consisting of" excludes any element, step, or ingredient not indicated in the claim elements. As used herein, "consisting essentially of" does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claims. With respect to the pretreatment mixture herein, "consisting essentially of" does not exclude components present in amounts that do not affect the mechanical properties of the article formed therefrom or the processability of the article formed from the pretreatment mixture. With respect to the articles herein, "consisting essentially of" does not exclude components present in amounts that do not adversely affect the desired mechanical and physical properties of the article, in particular flexibility, shelf life, neutral taste and smell, and swelling rate in aqueous solution, wt.%. In each instance herein, any of the terms "comprising," "consisting essentially of," and "consisting of," can be replaced with any of the other two terms. The invention illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein.
Those of ordinary skill in the art will appreciate that starting materials, biological materials, reagents, synthetic methods, purification methods, analytical methods, assay methods, and biological methods other than those specifically exemplified may be used to practice the present invention without resort to undue experimentation. All art-known functional equivalents of any such materials and methods are intended to be included in the present invention. The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Accordingly, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims.
Claims (78)
1. An article, pellet, or pretreatment mixture comprising:
a. at least one kind of hydrocolloid which is used for the treatment of the skin,
b. at least one of the plasticizers is used in the composition,
c. at least one wetting agent, at least one filler, or any combination thereof, and
d. and (3) water.
2. The article, pellet, or pretreatment mixture of claim 1, comprising:
a. at least one kind of hydrocolloid which is used for the treatment of the skin,
b. at least one of the plasticizers is used in the composition,
c. at least one wetting agent, and
d. and (3) water.
3. The article, pellet, or pretreatment mixture of claim 2, which does not comprise a filler.
4. The article, pellet, or pretreatment mixture of claim 1, comprising:
a. at least one kind of hydrocolloid which is used for the treatment of the skin,
b. at least one of the plasticizers is used in the composition,
c. at least one filler, and
d. and (3) water.
5. The article, pellet, or pretreatment mixture of claim 4, which does not comprise a wetting agent.
6. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one hydrocolloid is derived from a biological source.
7. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one hydrocolloid comprises alginate, agar, chitin, chitosan, pectin, carrageenan (e.g., kappa, iota, lambda, or any combination thereof), gelatin, corn starch, natural gums, gellan gum, guar gum, gum arabic, gum life, konjac gum, lecithin, locust bean gum, maltodextrin, methylcellulose, sodium alginate, xanthan gum, tapioca flour, or any combination thereof.
8. The article, pellet, or pretreatment mixture of any one of the preceding claims, wherein the at least one hydrocolloid comprises an alginate and chitosan.
9. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one hydrocolloid comprises a high G block alginate and a high M block alginate.
10. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one hydrocolloid comprises, as the case may be, based on the total weight of the article, pellet, or pretreatment mixture:
a. an alginate in an amount of 5 to 30 wt%,
b. chitosan and/or chitin in an amount of 0.5 to 10wt.%, and
c. guar in an amount of 0.5wt.% to 10 wt.%.
11. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one hydrocolloid comprises carrageenan.
12. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one hydrocolloid comprises kappa-carrageenan.
13. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one hydrocolloid comprises a combination of carrageenan and at least one of alginate, chitin, or chitosan.
14. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one hydrocolloid comprises, as the case may be, based on the total weight of the article, pellet, or pretreatment mixture:
a. kappa-carrageenan in an amount of 10 to 20wt.%, and
b. chitin and/or chitosan in a total amount of 5 to 15 wt.%.
15. An article, pellet or pretreatment mixture of any of the preceding claims, wherein the at least one hydrocolloid comprises chitosan, optionally the chitosan comprises crustacean chitosan, and optionally the crustacean chitosan comprises low molecular weight crustacean chitosan.
16. The article, pellet, or pretreatment mixture of any one of the preceding claims, wherein the at least one hydrocolloid comprises chitin, optionally the chitin comprises milled chitosan, and optionally the chitin comprises low molecular weight crustacean chitin.
17. The article, pellet or pretreatment mixture of any of the preceding claims, comprising a total amount of hydrocolloid of 1 to 40wt.% as the case may be, based on the total weight of the article, pellet or pretreatment mixture.
18. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one plasticizer comprises glycerin, sugar alcohol, microcrystalline cellulose, acacia, shellac, genipin, nanoemulsion, algae oilCoconut oil, treated shea butter, ester gum, carnauba wax, palm stearin, thermoplastic cellulose ether (e.g., ethocell) TM ) Zein, citrate, phthalate, adipate, fatty acid or any alkylated or esterified form thereof or any combination thereof.
19. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one plasticizer comprises glycerin.
20. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one plasticizer comprises a combination of:
a. Hydrophilic plasticizers
b. A hydrophobic plasticizer.
21. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one plasticizer comprises a combination of:
a. glycerol and/or sugar alcohol
b. Alkylated or esterified glycerol or alkylated or esterified sugar alcohols.
22. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one plasticizer comprises a combination of:
a. glycerol
b. An esterified or alkylated glycerol, wherein the esterified or alkylated glycerol has 4 to 15 carbon atoms in the ester group or alkyl group.
23. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the total amount of the at least one plasticizer is from 5wt.% to 40wt.%.
24. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one plasticizer comprises a hydrophilic plasticizer in an amount of 15wt.% to 40wt.% and a hydrophobic plasticizer in an amount of 0.5wt.% to 10 wt.%.
25. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one plasticizer comprises a hydrophilic plasticizer in an amount of 5wt.% to 15wt.% and a hydrophobic plasticizer in an amount of 0.5wt.% to 5 wt.%.
26. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one filler is present and comprises a starch (e.g., corn starch), microcrystalline cellulose (MCC), guar gum, carboxymethyl cellulose, citrus fiber, mineral salt, calcium carbonate, or a hydrate thereof, a salt or compound that is a hydroxide, sulfate, chloride, carbonate, oxide, aluminate, silicate, acetate, silica (silica), pentasodium triphosphate, sepiolite, silica (silica dioxide), zeolite, or any hydrate thereof, or any combination thereof.
27. The article, pellet or pretreatment mixture of any of the preceding claims, wherein the at least one wetting agent is present and comprises a salt or compound that is a hydroxide, sulfate, chloride, carbonate, oxide, aluminate, silicate, acetate, silica (silica), pentasodium triphosphate, sepiolite, silica (silica dioxide), zeolite, or any hydrate thereof, or any combination thereof.
28. The article, pellet, or pretreatment mixture of claim 27, wherein the salt or the compound is an alkali metal, alkaline earth metal, calcium, aluminum salt, or any combination thereof.
29. The article, granulate of claim 27A charge or pretreatment mixture, wherein the hydroxide comprises aluminum hydroxide, calcium hydroxide, or a hydrate thereof; the sulfate includes calcium sulfate, magnesium bisulfate, sodium sulfate, sodium bisulfate, alum (e.g., KAl (SO) 4 ) 2 ) Or a hydrate thereof; the chloride comprises calcium chloride, magnesium chloride or a hydrate thereof; the carbonate includes calcium carbonate, potassium carbonate, magnesium carbonate, zirconium potassium carbonate (e.g., zirmel TM 1000 Or a hydrate thereof; the oxide comprises calcium oxide, magnesium oxide, aluminum oxide or hydrate thereof; the aluminate comprises calcium aluminate or a hydrate thereof; the silicate comprises calcium silicate, potassium silicate, lithium silicate, magnesium silicate or a hydrate thereof; or the acetate salt comprises sodium acetate, potassium acetate, zirconium acetate or a hydrate thereof; or any combination thereof.
30. The article, pellet, or pretreatment mixture of any of the preceding claims, further comprising a colorant, a flavoring, or a combination thereof.
31. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one wetting agent is present and comprises a hydroxide salt or hydrate thereof.
32. The article, pellet, or pretreatment mixture of claim 31, wherein the hydroxide is a salt of an alkali metal, alkaline earth metal, or aluminum.
33. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one wetting agent is present in an amount of from 0.5wt.% to 10wt.% as the case may be, based on the total weight of the article, pellet, or pretreatment mixture.
34. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the water is present in an amount of 20wt.% to 70 wt.%.
35. The article, pellet, or pretreatment mixture of any of the preceding claims, comprising a total hydrocolloid to wetting agent weight ratio of from 5:1 to 15:1.
36. The article, pellet, or pretreatment mixture of any of the preceding claims, comprising a weight ratio of total hydrocolloid to total plasticizer of from 0.1:1 to 5:1.
37. The article, pellet, or pretreatment mixture of any of the preceding claims, comprising a weight ratio of total hydrocolloid to hydrophobic plasticizer of from 1:1 to 20:1.
38. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one hydrocolloid comprises at least one alginate, and wherein the article, the pellet, or the pretreatment mixture comprises a weight ratio of total alginate to total plasticizer of from 0.07:1 to 0.8:1.
39. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one hydrocolloid comprises at least one alginate, and wherein the article, the pellet, or the pretreatment mixture comprises a weight ratio of total alginate to hydrophobic plasticizer of from 1:1 to 10:1.
40. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one hydrocolloid comprises at least one alginate, and wherein the article, the pellet, or the pretreatment mixture comprises a weight ratio of total alginate to chitosan of from 1:1 to 10:1.
41. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one hydrocolloid comprises at least one alginate, and wherein the article, the pellet, or the pretreatment mixture comprises a weight ratio of total alginate to wetting agent of from 1:1 to 10:1.
42. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one filler is present and comprises calcium carbonate or a hydrate thereof.
43. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one filler is present in an amount of 5wt.% to 15wt.% as the case may be, based on the total weight of the article, pellet, or pretreatment mixture.
44. The article, pellet, or pretreatment mixture of any of the preceding claims, further comprising at least one inorganic crosslinking agent.
45. The article, pellet, or pretreatment mixture of claim 44, wherein the at least one inorganic crosslinking agent is present in an amount of 1wt.% to 10wt.% as the case may be, based on the total weight of the article, pellet, or pretreatment mixture.
46. The article, pellet, or pretreatment mixture of claim 44 or claim 45, wherein the at least one inorganic crosslinking agent comprises zirconium acetate, potassium zirconium carbonate (e.g., zirmel TM 1000 Ammonium zirconium carbonate (e.g., bacote available from Luxfer MEL technologies Inc.) TM ) Alum (e.g., KAl (SO) 4 ) 2 ) Calcium chloride, or any combination thereof.
47. The article, pellet, or pretreatment mixture of any of the preceding claims, further comprising at least one hydrophobic additive.
48. The article, pellet, or pretreatment mixture of claim 47, wherein the at least one hydrophobic additive is present in an amount of 1wt.% to 15wt.% as the case may be, based on the total weight of the article, pellet, or pretreatment mixture.
49. The article, pellet, or pretreatment mixture of claim 47 or claim 48, wherein the at least one hydrophobic additive comprises palm stearin, carnauba wax, zein, lignin, a hydrophobic plasticizer, an edible oil, a coating, or any combination thereof.
50. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one hydrocolloid comprises kappa-carrageenan, and the article, pellet, or pretreatment mixture comprises a weight ratio of kappa-carrageenan to total plasticizer of from 0.5:1 to 4:1.
51. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one hydrocolloid comprises kappa-carrageenan, and the article, pellet, or pretreatment mixture comprises a weight ratio of kappa-carrageenan to hydrophilic plasticizer of from 0.6:1 to 4:1.
52. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one hydrocolloid comprises kappa-carrageenan, and the article, pellet, or pretreatment mixture comprises a weight ratio of kappa-carrageenan to hydrophobic plasticizer of from 5:1 to 40:1.
53. The article, pellet, or pretreatment mixture of any of the preceding claims, wherein the at least one hydrocolloid comprises kappa-carrageenan, and the article, pellet, or pretreatment mixture comprises a weight ratio of kappa-carrageenan to total filler of from 1:1 to 4:1.
54. The article, pellet or pretreatment mixture of any of the preceding claims, wherein the at least one hydrocolloid comprises kappa-carrageenan and the weight ratio of kappa-carrageenan to total other hydrocolloids of the article, the pellet or the pretreatment mixture is from 0.6:1 to 4:1.
55. A method for preparing an article, the method comprising:
a. combining (i) at least one hydrocolloid, (ii) at least one plasticizer, (iii) at least one wetting agent, filler, or combination thereof, (iv) water, and (v) optionally at least one colorant, to produce a pretreatment mixture; and
b. Optionally, compounding the pretreatment mixture into a pellet;
c. shaping the pre-treatment mixture or the pellets into a shape;
d. optionally, immersing the shape in a crosslinking bath to shape the crosslinked shape;
e. optionally, rinsing the crosslinked shape to remove excess crosslinking agent; and
f. drying the crosslinked shape to shape the article, optionally shaping the article on a mandrel, wherein the at least one hydrocolloid, the at least one plasticizer and the at least one wetting agent or filler, or a combination thereof, is as defined in any one of the preceding claims.
56. The method of claim 55, wherein the at least one hydrocolloid comprises carrageenan and at least one of chitosan and chitin.
57. The method of claim 55, wherein the shaping comprises molding, extrusion, casting, or any combination thereof.
58. The method of claim 56 or claim 57, wherein said shaping comprises hot melt extrusion.
59. The method of claim 58, wherein the hot melt extruding comprises a single screw extruder utilizing a universal screw with a 3:1 compression ratio and a tubular die at a temperature of 75 ℃ to 95 ℃ and at a screw speed of 5rpm to 50 rpm.
60. The method of any one of claims 55-59, wherein the method is a continuous hot melt extrusion process.
61. The method of any one of claims 55 to 60, wherein the compounding is performed.
62. The method of any one of claims 55-61, further comprising applying a coating or optionally an edible coating to the article.
63. The method of claim 62, wherein the applying comprises spraying, dipping, brushing, edible inkjet printing, co-extrusion, or any combination thereof.
64. The method of claim 62, wherein the applying comprises immersing the article in a solution of a coating component in a solvent.
65. The article or pellet of claim 62, wherein the coating or the edible coating comprises an oil coating, a wax coating, a sugar coating of a confectionary, or a combination thereof.
66. The article or pellet of claim 62, wherein the coating or the edible coating comprises the wax coating and the wax coating comprises beeswax, carnauba wax, soy wax, rice bran wax, shellac, or a combination thereof.
67. The article of any one of the preceding claims, exhibiting a tensile strength of from 10MPa to 30MPa.
68. The article of any one of the preceding claims, exhibiting a young's modulus of 50MPa to 250MPa.
69. The article of any one of the preceding claims, exhibiting a compressive strength of from 10MPa to 25MPa.
70. The article of any one of the preceding claims, exhibiting a swelling ratio in room temperature water of from 0% to 50%.
71. The article of any one of the preceding claims, exhibiting a swelling ratio in a cold non-alcoholic beverage of 0% to 40%.
72. The article of any one of the preceding claims, exhibiting a swelling ratio in a cold alcoholic beverage of 0% to 50%.
73. The article of any one of the preceding claims, exhibiting a swelling rate in a cold carbonated beverage of from 0% to 50%.
74. A method for preparing pellets, the method comprising:
a. combining (i) at least one hydrocolloid, (ii) at least one plasticizer, (iii) at least one wetting agent, filler, or combination thereof, (iv) water, and (v) optionally at least one colorant, to produce a pretreatment mixture; and
b. compounding the pre-treatment mixture into pellets, wherein the at least one hydrocolloid, the at least one plasticizer and the at least one filler or wetting agent are as defined in any of the preceding claims.
75. The method of claim 74, wherein the compounding comprises extrusion with a twin screw hot melt extruder at a temperature of 85 ℃ to 100 ℃, at a screw speed of 200-300rpm, and at a feed weight ratio of solids to liquid of 0.25:1 to 1:1.
76. The method of any one of claims 55-75, wherein the at least one hydrocolloid comprises alginate and chitosan.
77. The method of any one of claims 55-75, wherein the at least one hydrocolloid is a combination of carrageenan and chitin and/or chitosan.
78. The method of claim 77, wherein the carrageenan comprises kappa-carrageenan.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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US63/213,887 | 2021-06-23 | ||
US202163243358P | 2021-09-13 | 2021-09-13 | |
US63/243,358 | 2021-09-13 | ||
PCT/US2022/033527 WO2022271496A1 (en) | 2021-06-23 | 2022-06-15 | Bio-based, biodegradable compositions and articles made therefrom |
Publications (1)
Publication Number | Publication Date |
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CN117715537A true CN117715537A (en) | 2024-03-15 |
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CN202280050113.5A Pending CN117715537A (en) | 2021-06-23 | 2022-06-15 | Bio-based biodegradable compositions and articles made therefrom |
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CN (1) | CN117715537A (en) |
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2022
- 2022-06-15 CN CN202280050113.5A patent/CN117715537A/en active Pending
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