WO2009103052A1 - Procédé de congélation éclair pour former des contenants biodégradables ou compostables - Google Patents

Procédé de congélation éclair pour former des contenants biodégradables ou compostables Download PDF

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Publication number
WO2009103052A1
WO2009103052A1 PCT/US2009/034216 US2009034216W WO2009103052A1 WO 2009103052 A1 WO2009103052 A1 WO 2009103052A1 US 2009034216 W US2009034216 W US 2009034216W WO 2009103052 A1 WO2009103052 A1 WO 2009103052A1
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Prior art keywords
starch
gel
mixture
homogenous
waxy
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PCT/US2009/034216
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English (en)
Inventor
Edward C. Lacy
Joe A. Bowden
Monika Reck-Glenn
Valerie J. Uschuk
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New Ice Limited
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Publication of WO2009103052A1 publication Critical patent/WO2009103052A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse

Definitions

  • the invention relates to improved methods and materials for forming biodegradable containers that can hold food products in dry, damp, or wet conditions.
  • Materials such as paper, paperboard, plastic, polystyrene, and even metals are presently used in enormous quantity in the manufacture of articles such as containers, separators, dividers, lids, tops, cans, and other packaging materials.
  • Modern processing and packaging technology allows a wide range of liquid and solid goods to be stored, packaged, and shipped in packaging materials while being protected from harmful elements, such as gases, moisture, light, microorganisms, vermin, physical shock, crushing forces, vibration, leaking, or spilling.
  • harmful elements such as gases, moisture, light, microorganisms, vermin, physical shock, crushing forces, vibration, leaking, or spilling.
  • Many of these materials are characterized as being disposable, but actually have little, if any, functional biodegradability. For many of these products, the time for degradation in the environment can span decades or even centuries.
  • Degradability is a relative term. Some products which appear to be degraded merely break apart into very small pieces. These pieces are hard to see, but can still take decades or centuries to actually break down. Other products are made from materials which undergo a more rapid breakdown than non-biodegradable products. If the speed of this degradation is such that the product will degrade within a period of less than approximately 180 days under normal environmental conditions, the product is said to be compostable. Achievement of products made of compostable materials which also meet a variety of needs, such as containers for products in a damp or wet condition, has posed a significant challenge.
  • Starch is a plentiful, inexpensive and renewable material that is found in a large variety of plant sources, such as grains, tubers, and fruits. In many cases, starch is discarded as an unwanted byproduct of food processing. Starch is readily biodegradable and does not persist in the environment for a significant period after disposal. Starch is also a nutrient, which facilitates its breakdown and elimination from the environment.
  • Starch Due to the biodegradable nature of starch, there have been many attempts to incorporate it into a variety of materials. Starch has been incorporated into multi-component compositions in various forms, including as filler and binder, as has been used as a constituent within thermoplastic polymer blends.
  • Starch can be used as a binder or glue to adhere solid constituents together to form a heterogenous mixture of different components.
  • the starch is typically dissolved or gelatinized in an appropriate solvent, such as water, so that the starch becomes a flowable material into which the other components can be dispersed. Since native starch has a melting point that approaches its decomposition temperature, it is necessary to add polar liquids or solvents to allow the starch to become molten, solvated or otherwise liquefied into a plastic state at a temperature that is safely below its decomposition temperature.
  • the starch Upon resolidification of the gelatinized starch, typically by removing enough of the water by evaporation so that the starch recrystallizes or otherwise dries out, the starch forms a solid or semi-solid binding matrix that can bind the remaining components together.
  • U.S. Patent Nos. 5,736,209 and 5,810,961, and PCT Publication No. WO 97/37842 also assigned to Khashoggi Industries, disclose methods to develop biodegradable paper and products which include a binding matrix of starch and cellulosic ether, and fibers substantially homogeneously dispersed throughout the matrix.
  • the '209 patent discloses a concentration range for the starch of about 5% to about 90% by weight of solids in the sheet, for the cellulosic ether a range from about 0.5% to about 10% by weight of solids, and for fibers a concentration range from about 3% to about 40%.
  • an inorganic mineral filler can be added. Sheets produced using this biodegradable material having a thickness less than about 1 cm and a density greater than about 0.5 g/cm are described.
  • thermoplastic starch compositions having a particulate filler (present in an amount greater than about 15% by weight of the thermoplastic starch) and, optionally, fiber reinforcement.
  • Native starch granules are made thermoplastic by mixing and heating in the presence of an appropriate plasticizer (including somewhat polar solvents such as water or glycerin) to form a starch melt.
  • the starch melt is then blended with one or more non-starch materials in order to improve the properties and reduce the cost of the resulting thermoplastic starch composition.
  • a particulate filler component is thereafter blended with the starch melt, preferably an inexpensive, naturally occurring mineral particulate filler ("inorganic filler”), included in an amount greater than about 15% by weight of the thermoplastic starch composition.
  • this reference discloses a composition comprising a thermoplastic starch melt having a water content of less than about 5% by weight while in a melted state, wherein at least one plasticizer has a vapor pressure of less than about 1 bar when in a melted state and in which a solid particulate filler phase is dispersed and included in an amount from about 5% to about 95% by weight.
  • An additional embodiment discloses dispersion of a solid particulate filler phase in an amount from about 5% to about 95% by weight of the thermoplastic starch composition and a fibrous phase in a concentration of from about 3% to about 70% by weight.
  • U.S. '341 and ' 145 teach methods for dispersing fibers within a fibrous composition comprising the steps of: (a) combining together water, fibers, and a thickening agent such that the thickening agent (such as a pregelatinized starch) and water interact together to form a fluid fraction that is characterized by a yield stress and viscosity that enables the fibers to be substantially uniformly dispersed throughout the fibrous composition as the fibers and fluid fraction are mixed together, the fibers having an average length greater than about 2 mm and an average aspect ratio greater than about 25:1; and (b) mixing together the combined thickening agent, water, and fibers in order to substantially uniformly disperse the fibers throughout the fibrous composition.
  • a thickening agent such as a pregelatinized starch
  • the thickening agent is included in an amount in a range from about 5% to about 40% by weight of the fluid fraction.
  • the inventive method involves a fluid system that is able to impart shear from a mechanical mixing apparatus down to the fiber level in order to obtain a starch-based composition having substantially uniformly dispersed fibers.
  • U.S. Patent '772 additionally discloses an inorganic filler to enhance the strength and flexibility of the articles.
  • '827 additionally discloses methods to make the article of manufacture that is developed from mixtures including fibers having an average aspect ratio greater than about 25:1.
  • WO 97/2333 disclose high aspect ratios (i.e., about 25:1 or greater) and long- length (i.e., at least about 2 mm) fibers to reinforce the structure.
  • PCT publication No. WO 97/23333 discloses articles that contain high starch contents (from about 50% to about 88% by weight ungelatinized and about 12% to about 50% by weight of gelatinized starch).
  • U.S. Publication No. US 2002/0108532 and PCT Publication No. WO 00/39213 filed by Apack AG disclose methods to produce a shaped body made of biodegradable material that shows good expansion behavior during thermoforming from 7.6 to 8.5% by weight of cellulosic fibers, from 16.1 to 17.6% by weight of native starch, from 5.4 to 6% by weight of pregelatinized starch and from 68.0 to 70.6% by weight of water.
  • the pregelatinized starch is produced by mixing between 5.4-6% starch and 94-94.6% water, heating the mixture to 68-7O 0 C, holding the mixture constant at 68-7O 0 C for 10 minutes, and cooling the pregelatinized starch to 5O 0 C.
  • German patent DE 19706642 to Apackmaschineen Gmbh discloses the production of a biodegradable article from 25-75% fibers, 13-38% starch and 13-38% water.
  • the 25-75% fibers, 13-38% starch are mixed in a dry state in a continuous process; then water is admixed continuously. The mixture is then subjected to a baking process to obtain the finished molded article, and then the molded article is coated with a biologically degradable film that is impermeable to humidity.
  • EP 0773721 Bl filed by Cooperatieve Verkoop-en Productievereniging van Aardappelmeel en Derivaten B.A. discloses a method for manufacturing a biodegradable molding suitable for containing liquid or more or less solid food or non-food products without loss of firmness or the molding.
  • the molding contains 500-1500 parts by weight of a starch product containing 5-75% by weight of a starch derivative which in comparison to native starch has a reduced swelling capacity at an increased temperature, 0.5-50 parts by weight of a thickener, 25-300 parts by weight of an inert filler, and an adhesion promoting substance are prepared with water and mixed to obtain a homogenous suspension.
  • the suspension is introduced into a baking mould and is baked to obtain a self-supporting base molding.
  • a biodegradable wax composition containing at least 50% by weight of wax components and having a melting range beginning at temperature of at least 40 degrees C.
  • U.S. Patent No. 5,849,152 teaches a process for the production of shaped bodies, in particular packaging shaped bodies, from biologically decomposable material using a viscous mass containing biologically decomposable fiber material, water and starch, which is baked with the formation of a composite of fiber material and starch in a baking mould, and a shaped body produced according to this process.
  • the use of native and pre-gelatinated or modified starch in connection with a fiber material feed stock from fibers or fiber bundles of differing lengths is said to be especially advantageous.
  • U.S. Patent No. 5,916,503 discloses a process for the manufacture of new shaped parts, preferably made from chipboards, wherein a mass formed from at least a binder and a small-particled material brought into contact with the binder is subjected to extrusion at elevated temperature and pressure. According to this process, a mass possessing a total moisture content of 6 to 25 wt. % or adjusted to the stated moisture content and made up of at least one biopolymeric preferably starch-containing binder, which converts into a melt and/or gel at extrusion temperatures and pressures, and further made up of the small-particled material, is subjected to extrusion and immediately thereafter undergoes decompression and spontaneous expansion.
  • DE 19751234 discloses biologically degradable foamed molded articles of a fiber/starch material.
  • Starch is provided in an amount of 8 to 26%, further hydro- colloids in an amount from 5 to 15%, and a foaming means in an amount of up to 3%, whereby a foam means acts at approximately 80 to 140C, so that the volume of the mass becomes larger in such a manner by expansion of the water vapor and the sets free gas from the foam means thereby filling in the figuration cavity.
  • the invention is applied to producing shaped elements, in particular for packaging uses.
  • EP 0524920 describes new shaped elements for construction, insulation and packaging purposes on the basis of biogenic, biologically degradable materials including starch or a starch-containing material, characterized in that it is formed by a plurality of performs connected to each other at least in places by a plurality of contact points with a structure- providing base matrix comprising a multiplicity small dimensioned voids, bubbles or pores on the basis of at least one melt solidified or gelled after exposure to an elevated temperature, elevated humidity, elevated pressure and/or mechanically stress or a gel of at least one starch or one starch-containing material thus obtained.
  • U.S. Patent Nos. 6,878,199 and U.S. 7,083,673 disclose method and materials for forming biodegradable containers that can hold food products in dry, damp or wet conditions and provides the biodegradable containers prepared according to the disclosed process.
  • the containers are produced through the use of a pre-gelled starch suspension that is said to be unique in its ability to form hydrated gels and to maintain this gel structure in the presence of many other types of materials and at low temperatures.
  • biodegradable and compostable materials for packaging, the resulting substances are not ideal.
  • the currently available materials either cannot successfully be used to package materials, particularly those that are wet, or do not effectively degrade under normal environmental conditions.
  • Biodegradable or compostable materials of this sort which are lightweight and flexible, are also highly desired.
  • the present invention provides improved methods for batch processing or continuous processing of materials for use in the formation of biodegradable containers that can hold food products in dry, damp, or wet conditions.
  • the present invention provides novel formulations that result in improved properties of the biodegradable containers, such as but not limited to, increased flexibility and strength.
  • the present invention is a process for forming a biodegradable material involving
  • pre-gel comprising at least one or more starches, and optionally, one or more of cellulose pulps or powders, and one or more plant derived oils, such that the pre-gel is maintained at temperatures between about 0-60 0 C, preferably about 0-40 0 C;
  • the present invention is a "flash-gel" process for forming a biodegradable material involving: (i) forming a pre-gelled starch suspension, the "pre-gel,” by first pre-heating and maintaining water at temperatures between 65-80 0 C, preferably between 65-75°C, adding a cellulose pulp or powder, followed by addition of at least one or more starches, and optionally, one or more plant derived oils;
  • the flash gel method while useful for batch preparation, allows for faster and more efficient production of the moldable homogenous compositions using continuous batch preparation. For example, a typical batch preparation that requires adding the components of the pre-gel to water and then heating until a pre-gel forms can take 30 minutes to 1 hour, or more to prepare the final moldable homogenous composition. In contrast, the flash gel method allows for formation of a pre-gel in 30 to 120 seconds and production of a moldable homogenous composition within 10 to 15 minutes.
  • the pre-gel comprises 3-10%, preferably 3, 5, 7.5, or 10% starch by weight of the pre-gel, and 90-97% water by weight of the pre-gel.
  • the pre-gel comprises 2-15% starch by weight of the pre-gel
  • the pre-gel comprises 5-15%, preferably 10% starch by weight of the pre-gel, 5-10% paper pulp, preferably 5.9-8.0%, by weight of the pre-gel, and an amount of water sufficient to equal 100% of the total weight of the pre-gel.
  • the pre-gel comprises 5-15% starch, preferably 8.2%, by weight of the pre-gel, 5-10% wood fibers or wood flour, preferably 9.2%, by weight of the pre-gel, and an amount of water sufficient to equal 100% of the total weight of the pre-gel.
  • the starch of the pre-gel is a waxy potato starch.
  • Waxy starches include starches containing at least about 85% by weight amylopectin, preferably about 90% by weight amylopectin, more preferably about 95% by weight amylopectin, even more preferably about 100% amylopectin (i.e., amylose-free).
  • the starch is a native pea starch.
  • the pre-gel further comprises 0.01-2.0% of a plant derived oil by weight of the pre-gel.
  • the plant-derived oil is soy oil.
  • the homogenous mixture comprises a native or waxy corn or potato starch. In another embodiment the homogenous mixture comprises a waxy potato starch and a native corn starch. In yet another embodiment the homogenous mixture comprises a native potato starch, a native corn starch and a tapioca starch. In another embodiment the homogenous mixture comprises a native potato starch, a native tapioca starch, and a modified tapioca starch. In yet another embodiment, the homogenous mixture comprises native potato and tapioca starch.
  • the homogenous mixture comprises one or more starches selected from native corn, native potato, waxy potato, native tapioca, and modified tapioca, and diatomaceous earth.
  • the homogenous mixture comprises a native tapioca starch and/or a modified tapioca starch and diatomaceous earth.
  • the diatomaceous earth is in an amount of 30-60% by weight of the homogenous moldable composition. In yet another embodiment, the diatomaceous earth is in an amount of 50% by weight of the homogenous moldable composition.
  • wood fibers or wood flour can be included in the dry or damp homogenous mixture.
  • the wood fibers and wood flour have an aspect ratio of about 1 :2 and 1 :8.
  • the homogenous mixture may optionally include fillers such as, but not limited to, bentonite clay, gypsum, calcium sulfate, limestone and fly ash.
  • biodegradable or compostable materials formed according to the process of the present invention can be coated or filmed, either before, during or after any of the molding processes.
  • the materials are coated or filmed by applying a heated biodegradable film, wherein the temperature of the biodegradable or compostable material is approximately the melt point of the biodegradable film, as described in co-pending U.S. Patent Application No. 11/605,169.
  • sheet refers to any substantially flat, corrugated, curved, bent, or textured sheet made using the methods described herein.
  • the sheets can also include organic coatings, printing, other sheets laminated thereto.
  • the sheets within the scope of the present invention can have greatly varying thicknesses depending on the particular applications for which the sheets are intended.
  • the sheets can be as thin as about 0.001 mm or as thick as 1 cm or greater where strength, durability, and or bulk are important considerations.
  • films are not inherently different from the term "sheet” except that "film” normally denotes a very thin sheet. Films are often formed by processes that are different from how sheets are normally formed, such as by film blowing rather than sheet calendering. In general, films will be defined as sheet-like articles having thicknesses as low as about 1 micron and up to about 1 mm.
  • molded article shall refer to articles that are shaped directly or indirectly from starch compositions using any molding method known in the art.
  • injection molding shall refer to articles that are made in classic injection machines such as, but not limited to, the Arburg Model 42 Allrounder.
  • injection molding the dough is injected directly into a heated mold at temperatures between 176 0 C and 21O 0 C, preferably between 196 0 C and 218 0 C, more preferably between 198 0 C and 21O 0 C.
  • the dough is injected into a heated mold via a plunger type system rather that a runner type system.
  • container as used in this specification and the appended claims is intended to include any article, receptacle, or vessel utilized for storing, dispensing, packaging, portioning, or shipping various types of products or objects (including, but not limited to, food and beverage products).
  • Specific examples of such containers include, among others, boxes, cups, "clam shells,” jars, bottles, plates, bowls, trays, cartons, cases, crates, cereal boxes, frozen food boxes, milk cartons, bags, sacks, carriers for beverage containers, dishes, egg cartons, lids, straws, envelopes, or other types of holders.
  • containment products used in conjunction with containers are also intended to be included within the definition "container”.
  • Such articles include, for example, lids, liners, straws, partitions, wrappers, cushioning materials, utensils, and any other product used in packaging, storing, shipping, portioning, serving, or dispensing an object within a container.
  • dry or damp refers to a solid composition that can be dry, or can be moist or wetted, generally with water, although other solvents may be used.
  • the amount of liquid in the composition is not sufficient to act as a carrier between particles in the composition.
  • homogeneous mixture refers to mixtures of solid particulates or of solids in a liquid carrier which are substantially uniform in composition on a macroscopic scale. It will be appreciated that mixtures of different types of solid particles or of solids in a liquid carrier are not homogeneous when viewed on a microscopic scale, i.e., at the particle size level.
  • the term “native starch” refers to a starch that has been derived from its natural source, wherein the natural source has not been genetically or chemically modified to increase its amylopectin content.
  • modified starch refers to a starch that has been derivatized or modified by typical processes known in the art such as, e.g. esterification, etherification, oxidation, acid hydrolysis, cross-linking, and enzyme conversion.
  • Typical modified starches include esters, such as the acetate and the half-esters of dicarboxylic acids/anhydrides, particularly the alkenylsuccinic acids/anhydrides; ethers, such as the hydroxyethyl and hydroxypropyl starches; oxidized starches, such as those oxidized with hypochlorite; starches reacted with cross-linking agents, such as phosphorus oxychloride, epichlorohydrin, hydrophobic cationic epoxides, and phosphate derivatives prepared by reaction with sodium or potassium orthophosphate or tripolyphosphate, and combinations thereof.
  • Modified starches also include seagel, long-chain alkylstarches, dextrins, amine starches, and dialdehyde starches.
  • Starches used in forming the pre-gelled starch suspension used in the method of the invention desirably possess the following properties: the ability to form hydrated gels and to maintain this gel structure in the presence of many types of other materials; and the ability to melt into plastic-like materials at low temperatures, for example, between 0-60 0 C, preferably between 0-40 0 C, and in the presence of a wide range of materials and in moist environments and to exhibit high binding strengths and produce an open cell structure for both insulation and cross linking of components.
  • the gel property holds other components in suspension until the product can be molded and to hold the moisture levels constant within the mixture until and during molding.
  • the second property is evident in the transition in the mold of the gel structure into a drier and dried form that will then melt into the binding plastic-like product within the confines of the mold.
  • This complex three dimensional cross linked structure provides a backbone for the product, exhibiting both strength and insulation properties.
  • Starch is produced in many plants, and many starches may be used (e.g., corn, waxy corn, wheat, sorghum, rice, and waxy rice), which can be used in the flour and cracked state.
  • starches include tubers (potato), roots (tapioca (i.e., cassava and maniac), sweet potato, and arrowroot), and the pith of the sago palm.
  • Suitable starches can also be selected from the following: ahipa, apio (arracacha), arrowhead (arrowroot, Chinese potato, jicama), baddo, bitter casava, Brazilian arrowroot, casava (yucca), Chinese artichoke (crosne), Japanese artichoke (chorogi), Chinese water chestnut, coco, cocoyam, dasheen, eddo, elephant's ear, girasole, goo, Japanese potato, Jerusalem artichoke (sunroot, girasole), lilly root, ling gaw, malanga (tanier), plantain, sweet potato, mandioca, manioc, Mexican potato, Mexican yam bean, old cocoyam, saa got, sato-imo, seego
  • Starch is typically considered a natural carbohydrate chain comprising polymerized glucose molecules in an alpha-(l,4) linkage.
  • Starch contains a mixture of two molecules amylose and amylopectin. Both consist of polymers of ⁇ -D-glucose units in the 4Cl conformation. In the amylose molecule, these are linked -(I — ⁇ 4)-, with the ring oxygen atoms all on the same side, whereas in amylopectin molecule about one residue in every twenty or so is also linked -(I — >6)- forming branch-points. Starches vary from one another in several ways, including amylose: amylopectin ratio, structure of amylose and amylopectin molecules, granual size and shape and other variations.
  • the relative proportions of amylose to amylopectin depend on the source of the starch. See J-Y. Li and A-I. Yeh, Relationships between thermal, rheological characteristics and swelling power for various starches, J. Food Engineering 50 (2001) 141-148. (b) N. Singh, J. Singh, L. Kaur, N. Singh Sodhi and B. Singh Gill, Morphological, thermal and rheological properties of starches from different botanical sources, Food Chem. 81 (2003) 219-231. This ratio varies not only among the different types of starch, but among the many plant varieties within a type. In the native form, most starches contain 18% to 28% wt.% amylose.
  • the commercially most important starch types (maize starch, potato starch, wheat starch and tapioca starch) contain 15 to 30 wt. % amylose.
  • Native, non-waxy potatoes are typically about 20-25 wt. % amylose.
  • Native pea starches contain amylose at higher levels above 30 and as high as 70%.
  • Wildy starch is a term used to describe starches with high amylopectin ratios.
  • the term “waxy” is often used to describe starch or flour containing at least about 85% by weight amylopectin, and more preferably, about 90 % by weight amylopectin, and even more preferably, about 95% by weigh amylopectin, and most preferably about 99% by weight amylopectin.
  • Certain waxy starches are 100% amylopectin or, put another way, amylose-free.
  • GBSS granule-bound starch synthase I
  • amylose The enzyme granule-bound starch synthase I (GBSS) is exclusively responsible for the synthesis of amylose (Shure M, Wessler S, Federoff N. Molecular identification and isolation of the waxy locus in maize. Cell. 1983;35:225-233; Hovenkamp-Hermelink JHM, Jacobsen E, Ponstein AS, Visser RGF, Vos-Scheperkeuter GH, Bijmolt EW, de Vries JN, Witholt B, Feenstra WJ. Isolation of an amylose-free starch mutant of potato (Solanum tuberosum L.). Theor Appl Genet. 1987;75 :217-2211; Hseih J-S.
  • starch granules nearly completely consist of amylopectin. Calculated as weight percent on dry substance, these starch granules contain more than 95%, and usually more than 98% amylopectin. The amylose content of these cereal starch granules is thus less than 5%, and usually less than 2%.
  • Legume sources often contain high levels of amylase.
  • Native pea starches contain amylose at higher levels above 30% and as high as 70%.
  • Rice with a high percentage of amylopectin has grains that become sticky and tend to disintegrate upon cooking.
  • Sticky or glutinous rice consists essentially of starch that is pure amylopectin.
  • Non-waxy sorghum is approximately 70% amylopectin and 30% amylose.
  • Waxy sorghum contains approximately 100% amylopectin.
  • Wheat starch is normally 75% amylopectin and 25% amylose.
  • Three genes encode GBSS in hexaploid wheat. Naturally occurring mutations (null alleles) resulting in the loss of one or more GBSS isoforms have been identified. The presence of one or two GBSS null alleles results in the production of starch with reduced amylose content. Reduced amylose wheats have been termed "partial waxy'. Wheats with three GBSS null alleles produce essentially amylose-free, or waxy, starch. See Waxy wheats: Origin, properties, and prospects Graybosch RA. In: Trends in Food Science & Technology, 1998, 9(4):135-142.
  • amylopectin In contrast to the situation of cereals, root and tuber varieties of which the starch granules nearly exclusively consist of amylopectin are not known in nature.
  • potato starch granules isolated from potato tubers usually contain about 20-25% amylose and 75-80% amylopectin (wt. % on dry substance).
  • the elimination of these genes can be realized by recessive modification or genetic modification of potato plant material.
  • An example thereof is the amylose-free mutant of the potato of which the starch substantially only contains amylopectin through a recessive mutation in the GBSS gene. This mutation technique is described in, inter alia, J. H. M.
  • Elimination or inhibition of the expression of the GBSS gene in the potato is also possible by using so-called antisense inhibition.
  • This genetic modification of the potato is described in R. G. F. Visser et al., "Inhibition of the expression of the gene for granule-bound starch synthase in potato by antisense constructs", MoI. Gen. Genet., (1991), 225:289-296. See U.S. Patent No. 6,784,338 and US Patent No. 5,824,798.
  • ElianeTM (Avebe Group, the Netherlands) is a high amylopectin potato produced by physical processing and natural breeding techniques which is sold in a variety of formulations, including ElianeTM100.
  • amylopectin-potato starch and tapioca amylopectin- starch differ from those of the waxy cereal starches.
  • Amylopectin-potato starch has a much lower content of lipids and proteins than the waxy cereal starches. Problems regarding odor and foaming, which, because of the lipids and/or proteins, may occur when using waxy cereal starch products (native and modified), do not occur or occur to a much lesser degree when using corresponding amylopectin-potato starch products.
  • amylopectin-potato starch contains chemically bound phosphate groups.
  • amylopectin-potato starch products in a dissolved state have a distinct polyelectrolyte character.
  • a few varieties of natural "partial waxy” wheat have been identified in which one or two of the iso-enzymes are inactive or missing. Starches derived from this wheat are also called “partial waxy”. The concentration in amylose in these "partial waxy” starches is low and variable, but it is not zero, and in some cases the content of amylose remains almost unchanged by a compensation phenomenon.
  • starches come from the structure of amylose and amylopectin molecules.
  • the length of the amylose molecules in a starch can also vary.
  • amylopectin the length and number of branches on the molecule are also variable.
  • Additional starch variations include granual size and shape.
  • Starch is found in nature in the form of granules which are easily liberated from plant materials in known processes. The starch is found tightly and radially packed into dehydrated granules (about one water per glucose) with origin-specific shape and size. Sizes ranging from 3 microns to over 100 microns. Representative granual sizes: maize (2-30 ⁇ m), wheat (-45 ⁇ m) and potato (5-100 ⁇ m). For some starches the granule size is polymodal, meaning the granules can be grouped into more than one size range. Granule shape also can be diverse.
  • Granule shapes include symmetrical spheres, asymmetrical spheres, symmetrical disks and asymmetrical disks. Some granules exhibit their shape smoothly, while others are polyhedrons with a faceted surface. The size distribution determines its swelling functionality with granules being generally either larger and lenticular (lens-like, A-starch) or smaller and spherical (B-starch) with less swelling power. Granules contain 'blocklets' of amylopectin containing both crystalline (-30%) and amorphous areas. As they absorb water, they swell, lose crystallinity and leach amylose. The higher the amylose content, the lower is the swelling power and the smaller is the gel strength for the same starch concentration.
  • Starch in the native state is completely insoluble.
  • starch granules are insoluble in cold water; however, if the outer membrane has been broken by, e.g., by grinding, the granules can swell in cold water to form a gel.
  • the intact granules are treated with warm water, the granules swell and a portion of the soluble starch diffuses through the granule wall to form a paste.
  • hot water the granules swell to such an extent that they burst, resulting in gelation of the mixture.
  • the exact temperature at which a starch swells and gelates depends on the type of starch.
  • the sources of starch for pre-gels according to the present invention are high amylopectin-content starches.
  • the starch or flour contains at least about 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 or 100% by weight amylopectin.
  • the starch or flour contains at least about 90% by weight amylopectin.
  • the starch or flour contains at least 95% by weight amylopectin.
  • the starch or flour contains about 99% by weight amylopectin.
  • the starch or flour contains about 100% amylopectin.
  • the starch component of the pre-gel may include any known starch material.
  • the starch can be selected from natural starch, chemically and/or physically modified starch, biotechnologically produced and/or genetically modified starch and mixtures thereof.
  • the starch is a waxy starch.
  • the waxy starch is a waxy tuber, such as a waxy potato.
  • the waxy starch is a waxy root, such as a waxy tapioca or waxy cassava.
  • Other waxy starches suitable for use in the present invention include waxy wheat, waxy pea, waxy yam, waxy arrowroot, waxy manihot and waxy sweet potato.
  • the starch used to form the pre-gel is a waxy potato starch.
  • a potato plant variety are the variety Apriori or Apropect, or varieties derived thereof.
  • the high amylopectin content starch used to form the pre-gel may be the produced by any means, including but without limitations, physical means of separation, classical plant breeding or genetic engineering of the plant source.
  • the high amylopectin content starch is produced by physical means of separation or classical plant breeding.
  • the high amylopectin starch is ElianeTM, and more particularly Eliane 100TM.
  • the high amylopectin content starch is a genetically modified potato, such as AmfloraTM.
  • the source of starch for pre-gels according to the present invention may include starch mixtures of waxy and non-waxy (native) starches.
  • the starch mixture includes a first waxy starch and a second, non-waxy (native) starch wherein the non- waxy starch contains less than about 85% by weight amylopectin, and more preferably, lower than about 84, 83, 82, 81, 80, 79, 78, 77, 76, 75, 74, 73, 72, 71, 70, 69, 68, 67, 66, 65, 64, 63, 62, 61, 59, 58, 57, 56, 54, 53, 52, 51, or 50% by weight amylopectin.
  • the starch mixture includes 100% amylopectin potato starch (amylose-free) and non-waxy potato starch (e.g., 80% amylopectin starch).
  • the starch mixture may contain the same or different botanical source of starch.
  • a starch mixture may include (i) waxy potato starch and non-waxy potato starch; (ii) waxy potato starch and non-waxy corn starch; or (iii) waxy potato starch and non-waxy tapioca starch.
  • Starches suitable for combination include without limitation potato, tapioca, yam, cassava, corn, rice, wheat and barley starch.
  • Starch mixtures of waxy or non-waxy starches in proportions between about 0% and 99 % can be used to form the pre-gel.
  • the waxy starch represents about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99% of the starch mixture.
  • a potato starch mixture is used to form the pre-gel which includes a high amylopectin content potato starch (e.g., Eliane 100TM) and a non-waxy potato starch, i.e., about 80% amylopectin.
  • the starch mixture includes about 5, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99% of the waxy potato starch (e.g., Eliane 100TM).
  • the starch mixture is 50% waxy potato starch (e.g., Eliane 100TM) and 50% non-waxy potato starch.
  • a potato starch and cellulose fiber or cellulose flour mixture is used to form the pre-gel which includes a high amylopectin content potato starch (e.g. Eliane 100TM).
  • the source of starch is not a waxy corn or waxy rice.
  • a low amylopectin starch can be used.
  • An example is, native pea starch which contains amylose levels between 30 and 70%.
  • the pre-gel can optionally contain cellulose pulps or cellulose powders and certain plant derived oils.
  • Cellulose pulps that may be used in the pre-gel can be produced by any method known in the art.
  • Cellulose pulp production is a process that utilizes mainly arboreal species from specialized cultivations.
  • wood typically reduced to dimensions of about 30-40 mm and a thickness of about 5-7 mm, is treated at high temperature and pressure with suitable mixes of chemical reagents that selectively attack lignin and hemicellulose macromolecules, rendering them soluble.
  • Pulps coming from this first treatment commonly called “cooking” are called “raw pulps”; they still contain partly modified lignin and are more or less Havana-brown colored.
  • Raw pulps can be submitted to further chemical-physical treatments suitable to eliminate almost entire lignin molecules and colored molecules in general; this second operation is commonly referred to as "bleaching".
  • rapid growth capitaous plants are mainly used, which, with the help of chemical substances (alkali or acids), in condition of high pressure and temperature, are selectively delignified to obtain pulps containing cellulose and other components of lignocellulose.
  • chemical substances alkali or acids
  • pulps are then submitted to mechanical and chemical-physical treatments, in order to complete the removal of lignin and hemicellulose residual components, and utilized thereafter for paper production.
  • Any of form of cellulose pulp can be used in the packaging materials described herein.
  • Cellulose pulps or powders for this invention can be derived from any of the wood fibers described herein. Aspect ratios for cellulose pulps are less than about 1 :10, preferably less than 1 :9, and more preferably less than about 1.8. In a particular embodiment, the aspect ratio for the cellulose pulp or powder is about 1 :8.
  • Virgin cellulose pulp can be provided, e.g., as large blocks of compressed pulp and is derived from managed forests. Alternatively, virgin cellulose pulp can be obtained as loose pulps.
  • Representative, non-limiting examples of cellulose pulps or powders include, e.g., ArbocelTM 1000, IFCl 178 or similar cellulose products.
  • Wood represents one source of cellulose pulp. Other suitable sources of cellulose pulp are known and include, e.g., cotton, flax, and hemp, sugarcane, bagasse, etc.
  • oils such as but not limited to, soy, canola, peanut, or palm oil may be added to the pre-gelled suspensions.
  • the plant derive oil functions as a water repellant.
  • the pre-gelled starch suspension is produced from approximately 3-10%, preferably, 3, 5, 7.5 or 10%, waxy starch by weight of the pre-gel and 90-97% water by weight of the pre-gel such that the pre-gelled suspension is maintained at low temperatures.
  • the pre-gelled starch solution can be maintained at all temperatures above freezing, O 0 C.
  • the pre-gelled starch solution can be maintained for greater that 24 hours, up to a few days, if stored refrigerated, for example, between 3-15 0 C.
  • a pre-gelled paper starch suspension is produced from approximately 5-15%, preferably 10%, waxy starch (by weight of the pre-gel), preferably a waxy potato starch; 5-10% cellulose fiber or powder (by weight of the pre-gel), preferably 5.9-8%, more preferably, 7.3-7.5, 6.5-6.7, or 5.9-6.1%; and an amount of water sufficient to equal 100% of the total weight of the pre-gel such that the pre-gelled suspension is maintained at low temperatures.
  • the pre-gelled paper starch solution can be maintained at all temperatures above freezing, O 0 C.
  • the pre-gelled paper starch solution can be maintained for greater that 24 hours, up to a few days, if stored refrigerated, for example, between 3-15 0 C.
  • a pre-gelled paper starch suspension is produced from approximately 5-15%, preferably 10%, waxy starch by weight of the pre-gel (by weight of the pre-gel); 5-10% paper pulp (by weight of the pre-gel), preferably 5.9-8%, more preferably, 7.3-7.5, 6.5-6.7, or 5.9-6.1%; and an amount of water sufficient to equal 100% of the total weight of the pre-gel such that the pre-gelled suspension is maintained at low temperatures.
  • the pre-gelled paper starch solution can be maintained at all temperatures above freezing, O 0 C.
  • the pre-gelled paper starch solution can be maintained for greater that 24 hours, up to a few days, if stored refrigerated, for example, between 3-15 0 C.
  • a pre-gelled fiber starch suspension is produced from approximately 5-15%, preferably 8.2%, waxy starch (by weight of the pre-gel), 5-10% wood fibers or wood flour (by weight of pre-gel) preferably 9.2%, and a percentage of water sufficient to equal 100% of the total weight of the pre-gel, such that the water is pre-heated to a range of 65-75 0 C, prior to addition of the waxy starch and wood fibers or wood flour.
  • virgin cellulose pulp is added to the pre-gel in an amount from about 5-10% by weight. In a particular embodiment, virgin cellulose pulp is 5, 6, 7, 8, or 9% by weight of the pre-gel. In a preferred embodiment, virgin cellulose pulp is 5% by weight of the pre-gel.
  • recycled cellulose pulp is added to the pre-gel is an amount from about 5-10% by weight. In a particular embodiment, recycled cellulose pulp is 5, 6, 7, 8 or 9% by weight of the pre-gel. In a preferred embodiment, recycled cellulose pulp is 5% by weight of the pre-gel.
  • plant derived oils are added to the pre-gel in an amount from 0.01 to 2.0 % by weight of the pre-gel.
  • soy oil is add in amount of 0.7% by weight of the pre-gel.
  • the pre-gelled starch may be prepared by mixing the starch with water at about ambient temperature (approximately 25 0 C).
  • the gel is formed by slowly heating the water- starch mixture with constant agitation until a gel forms. Continued heating will slowly degrade the gel, so the process should be stopped as soon as an appropriate level of gelation is achieved.
  • Gels can be used cold. The gel is stable for a few days if refrigerated. For storage a biocide can be added, preferably at a concentration of about 10 to about 500 ppm.
  • the pre-gelled starch may be prepared using a "flash gel" method that allows for preparation of a pre-gel that, while useable in batch preparation, makes continuous preparation of the homogenous moldable compositions possible. Continuous preparation in turn allows for easier scale-up of production as well as increases in the speed and efficiency with which the final moldable homogenous compositions can be prepared.
  • the pre-gel is formed by first pre-heating the water to a range of 65-85 0 C followed by addition of cellulose pulps or powders. In one embodiment, the water is heated to 70-80 0 C. In another embodiment, the water is pre-heated to 72 0 C.
  • the mixing of the cellulose fibers or powders results in heat reduction of the water to temperatures in the range of 55-75 0 C.
  • the waxy starch and any additional components plant derived oils, etc
  • the flash-gel method results in a pre- gel that forms within 30-120 seconds.
  • gelling of the starch materials takes place at about 62-63 0 C.
  • a typical batch process that requires adding the ingredients at ambient temperature followed by heating until a gel forms can take up to 30 minutes to 1 hour, or longer to prepare the final moldable homogenous composition.
  • the flash-gel method allows for preparation of a final moldable homogenous compositions within 10 to 15 minutes.
  • a continuous mixer that may be used in preparation of the homogenous moldable compositions by the flash-gel method is the ReadCo LLC 2" paddle mixer (Readco Kurimoto, LLC, York, PA).
  • Water can be removed before processing by using starch that has been pre-dried so as to remove at least a portion of the natural water content.
  • water can removed during processing by degassing or venting the molten mixture, such as by means of an extruder equipped with venting or degassing means.
  • Native starch can also initially be blended with a small quantity of water and glycerin in order to form starch melts that are subjected to a degassing procedure prior to cooling and solidification in order to remove substantially all of the water therefrom.
  • dry or damp materials can be added (such as dry starches and optionally, fibers, flour, pulp, diatomaceous earth, lubricants, foaming agents, etc.) to produce the final moldable mixture.
  • the dry or damp materials can be pre-mixed before addition to the pre-gel, to increase the homogeneity of the final product and increase the structural integrity of the final molded product.
  • the amount of pre-gel added to the final mixture is in the range of about 7-60% by weight of the homogenous moldable composition.
  • the pre-gel is about at least 7%, 8%, 9%, 10%, 11%, 12%, 16%, 16.3%, 25%, 33%, 42%, 47%, 54%, 50%, 52%, 55%, 56%, 60% or 60.4% by weight of the homogenous moldable composition.
  • the dry or damp materials are generally pre-mixed into a homogeneous mixture before being added to the pre-gel.
  • the dry or damp materials can be mixed to form a homogeneous mixture using any suitable means, such as, for example, a Kitchen Aid® Commercial Mixer.
  • a dry or damp starch binder component is a dry or damp starch binder component.
  • This starch can be corn or other dry starch (for example potato or tapioca).
  • the starch is a waxy potato starch or other starch identified above in the section entitled "Pre-Gelled Starch Suspensions.”
  • Pre-gelatinized starch-based binders can also be added to the moldable mixture.
  • Pregelatinized starch-based binders are starches that have previously been gelated, dried, and ground back into a powder. Since pre-gelatinized starch-based binders gelate in cold water, such starch-based binders can be added to the moldable mixture to increase the mixture viscosity prior to being heated. The increased viscosity prevents settling and helps produce thicker cell walls.
  • This starch component can be pre-gelled in a manner similar to that describes above.
  • the second starch component can be pre-gelled in a mixture of between about 1 and 15% starch (for example 15% corn starch) and 85-99% water.
  • the preferred amount to be added is in the range of 55-65% by weight of the homogenous moldable composition, most preferably about 57% or about 65%.
  • the concentration of the native or waxy starch binder within the moldable mixtures of the present invention are preferably in a range from about 5% to about 60% by weight of the homogenous moldable composition, more preferably in a range from about 15% to about 30%, and most preferably about at least 6%, 20%, 21%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, or 34% by weight of the homogenous moldable composition.
  • combinations of different starches can be employed to more carefully control the viscosity of the mixture throughout a range of temperatures, as well as to affect the structural properties of the final hardened article.
  • the mixture can consist of a mixture of dry or damp corn and potato starch (16-44% of corn and potato starch by weight of the homogenous moldable composition), such that the corn starch comprises between about 13-30%, preferably between about 13-18% or 28-30%, and the potato starch comprises between about 3-14%, preferably approximately 11-14% or 3-5% of the final homogenous moldable composition.
  • Preferred starches include waxy starches, such as waxy potato starch, or other suitable waxy tuber and root starches, as discussed above. Starch mixtures may also be utilized including, without limitation, waxy potato starch and corn starch (non-waxy).
  • the dry or damp homogenous mixture added to the pre-gel includes waxy potato starch.
  • the dry or damp homogenous mixture added to the pre-gel includes waxy potato starch, native tapioca starch and corn starch (non-waxy).
  • the homogenous mixture comprises native corn starch, native tapioca starch and modified tapioca starch.
  • the damp or dry homogenous mixture added to the pre-gel includes a waxy starch selected from the group including, without limitation, waxy potato, waxy tapioca, waxy wheat, waxy yam, waxy sweet potato and waxy arrowroot.
  • diatomaceous earth can be used to replace substantial amounts of one or more starches in the homogenous mixture.
  • the replacement of starch with diatomaceous earth results in unexpected improvements in the properties of the products made from the homogenous moldable compositions, such as but not limited to, increases in flexibility and strength.
  • diatomaceous earth is used to replace at least 50%, at least 75%, or 100% of one or more starches of the homogenous mixture.
  • the diatomaceous earth is ground, washed, dried and passed through a #40 sieve. Powders passing smaller sieves (#80 to #200) may also be used.
  • the diatomaceous earth will pass a #100 sieve and be retained on a #200 sieve.
  • the size of the diatomaceous earth is, between 20 and 75 microns. In another embodiment the size of the diatomaceous earth is between 30 and 60 microns. In yet another embodiment, the diatomaceous earth is between 40 and 50 microns.
  • the diatomaceous earth is a fluxed calcined diatomaceous earth.
  • a non-limiting example of fluxed calcined diatomaceous earth is Celite® (World Minerals, Santa Barbara, CA).
  • the amount of diatomaceous used is in the range of 1-60% by weight of the homogenous moldable composition. In another embodiment, the amount of diatomaceous earth used is in the range of 30-60% by weight of the homogenous moldable composition. In yet another embodiment, the amount of diatomaceous earth used is 50% by weight of the homogenous moldable compositions.
  • additional fibers can be employed as part of the dry/damp material added to the pre-gelled starch, or as part of the pre-gel itself. Larger particles are considered to be fibers.
  • fibers refers to fine, thin objects restricted in their length, the length being greater than the width. They can be present as individual fibers or as fiber bundles. Such fibers can be produced in a manner known to those skilled in the art. Preferred fibers have a low length to diameter ratio and produce materials of excellent strength and light weight.
  • the fibers used in the invention will have an aspect ration of about between 1 :2 and 1 :10; 1 :2 and 1 :9; 1 :2 and 1 :8; 1 :2 and 1 :7; 1 :2 and 1 :6; 1 :2 and 1 :5; 1 :2 and 1 :4; 1 :2 and 1 :3; 1 :2 and 1 :2; or 1 :2 and 1 :9.9.
  • the fibers used are preferably organic, and most preferably cellulose-based materials, which are chemically similar to starches in that they comprise polymerized glucose molecules.
  • Cellulosic fibers refers to fibers of any type which contain cellulose or consist of cellulose. Plant fibers preferred here are those of differing lengths typically in the range from
  • 600 micron to 3000 micron principally from hemp, cotton, plant leaves, sisal, abaca, bagasse, wood (both hard wood or soft wood, examples of which include southern hardwood and southern pine, respectively), or stems, or inorganic fibers made from glass, graphite, silica, ceramic, or metal materials.
  • the cellulosic fibers include wood fibers and wood flour.
  • Wood flour and fibers are very much like rough tooth picks that have small barb like structures coming out from the main fiber to participate in the cross linkage process with the cooling starch melt. This property adds both strength and water resistance to the surface produced within the mold.
  • the rapid grinding process to produce flour or short fibers by- passes the expensive and polluting processes that are used to manufacture pulp and paper.
  • the wood flour can be a resinous wood flour.
  • the wood flour is softwood flour, which contains relatively large amounts of resin.
  • softwood is used industrially on a large scale, such as in the building trade, with the consequence that an abundance of wood flour from, for instance, saw mills, is available at a low price.
  • Wood flours can be graded based on the mesh size the flour. In general, wood flour having a mesh size of 20 - 100 is suitable, and an aspect ratio or 1 :8 or 1 :9, or 1 :10 or less.
  • wood fibers or flour comprise about at least about 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, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 or 50 by weight of the homogenous moldable composition.
  • the dry or damp homogenous mixture may also include additional ingredients such as mold release agents/lubricants, foaming agents, and/or citric acid.
  • Suitable lubricants include, but are not limited to, magnesium, calcium, or sodium stearate or oleates and similar lubricants.
  • the mold release agent is present in an amount between about 0.1% and 0.5% by weight of the homogenous moldable composition.
  • a representative, non- limiting foaming agent is CT1480 (Clariant, Charlotte, NC).
  • the foaming agent is present in an amount between about 0.01 and 0.1%, preferably, about 0.025% by weight of the homogenous moldable composition.
  • citric acid is added to the homogenous mixture in an amount between about 0.001 to about 0.010% by weight of the homogenous moldable composition.
  • the amount of paper pulp can be increased to 50%, or 30-50%, by weight of the final mixture, and the amount of wood flour or fiber can be decreased to 0%.
  • additional fibers e.g., wood fibers or wood flour
  • wood fibers or wood flour are not employed as part of the dry/damp material added to the pre-gelled starch.
  • the homogenous mixture can also include one or more optional additional materials depending on desired characteristics of the final product.
  • Fillers can be included for a stronger product. Suitable fillers include but are not limited to clays such as bentonite, amorphous raw products such as gypsum (calcium sulfate dehydrate) and calcium sulfate, minerals such as limestone and man made materials such as fly ash. These natural earth fillers are able to take part in the cross linking and binding that occurs during the molding process.
  • useful fillers include perlite, vermiculite, sand, gravel, rock, limestone, sandstone, glass beads, aerogel, xerogels, seagel, mica, clay, synthetic clay, alumina, silica, fused silica, tabular alumina, kaolin, microspheres, hollow glass spheres, porous ceramic spheres, calcium carbonate, calcium aluminate, lightweight polymers, xonotlite (a crystalline calcium silicate gel), lightweight expanded clays, hydrated or unhydrated hydraulic cement particles, pumice, exfoliated rock, and other geologic materials. Partially hydrated and hydrated cement, as well as silica fume, have a high surface area and give excellent benefits such as high initial cohesiveness of the freshly formed article.
  • discarded inorganically filled materials such as discarded containers or other articles of the present invention can be employed as aggregate fillers and strengtheners. It will also be appreciated that the containers and other articles of the present invention can be easily and effectively recycled by simply adding them to fresh moldable mixtures as an aggregate filler.
  • Hydraulic cement can also be added in either its hydrated or unhydrated form. Both clay and gypsum can be important aggregate materials because they are readily available, relatively inexpensive, workable, form easily, and can also provide a degree of binding and strength if added in high enough amounts (for example in the case of gypsum hemihydrate). Because gypsum hemihydrate can react with the water within the moldable mixture, it can be employed as a means for holding water internally within the molded article.
  • the inorganic materials are added in an amount from up to approximately 5%, 0-4%, 0-13%, 2-13% or 0-15% by weight of the weight of the final composition.
  • concentration ranges are difficult to calculate.
  • bentonite clay a preferred range is from about 2.5-4% of the weight of the final mixture.
  • the additional agents can be pre-dissolved or can be added dry.
  • a preferred clay slurry is 20% bentonite clay in water.
  • cellulose-based thickening agents can be added, which can include a wide variety of cellulosic ethers, such as methylhydroxyethylcellulose, hydroxymethylethylcellulose, carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxyethylpropylcellulose, hydroxypropylmethylcellulose, and the like.
  • Other natural polysaccharide-based thickening agents include, for example, alginic acid, phycocolloids, agar, gum arabic, guar gum, locust bean gum, gum karaya, xanthan gum, and gum tragacanth.
  • Suitable protein-based thickening agents include, for example, Zein®.
  • Suitable synthetic organic thickening agents include, for example, polyvinyl pyrrolidone, polyethylene glycol, polyvinyl alcohol, polyvinylmethyl ether, polyacrylic acids, polyacrylic acid salts, polyvinyl acrylic acids, polyvinyl acrylic acid salts, polyacrylamides, ethylene oxide polymers, polylactic acid, and latex.
  • Latex is a broad category that includes a variety of polymerizable substances formed in a water emulsion. An example is styrene-butadiene copolymer.
  • Additional copolymers include: vinyl acetate, acrylate copolymers, butadiene copolymers with styrene and acetonitrile, methylacrylates, vinyl chloride, acrylamide, fluorinated ethylenes.
  • Hydrophilic monomers can be selected from the following group: N-(2- hydroxypropyl)methacrylamide, N-isopropyl acrylamide, N,N-diethylacryl-amide, N- ethylmethacrylamide, 2-hydroxyethyl methacrylate, acrylic acid 2-(2-hydroxyethoxy)ethyl methacrylate, methacrylic acid, and others, and can be used for the preparation of hydro lyrically degradable polymeric gels.
  • Suitable hydrophobic monomers can be selected from the 2-acetoxyethyl methacrylate group of monomers comprising dimethylamino ethyl methacrylate, n-butyl methacrylate, tert-butylacrylamide, n-butyl acrylate, methyl methacrylate, and hexyl acrylate.
  • the polymerization can be carried out in solvents, e.g. in dimethylsulfoxide, dimethylformamide, water, alcohols as methanol and ethanol, using common initiators of the radical polymerization.
  • the hydrophilic gels are stable in an acidic environment at pH 1-5. Under neutral or weak alkaline conditions at pH above 6,5, the gels degrade. The gels mentioned above are nontoxic as well as the products of their biodegradation.
  • co-polymers include: aliphatic polyester, polycaprolactone, poly-3- hydroxybutyric acid, poly-3-hydroxyvaleric acid, polygly colic acid, copolymers of gly colic acid and lactic acid, and polylactide, PVS, SAN, ABS, phenoxy, polycarbonate, nitrocellulose, polyvinylidene chloride, a styrene/allyl alcohol copolymer, polyethylene, polypropylene, natural rubber, a sytrene/butadiene elastomer and block copolymer, polyvinylacetate, polybutadiene, ethylene/propylene rubber, starch, and thermoplastic segmented polyurethane, homopolymers or copolymers of polyesters, polyorthoesters, polylactides, polyglycolides, polycaprolactones, polyhydroxybutyrates, polyhydroxyvalerates, porno acids, pseudopolyamino acids, polyamides and polyanhydr
  • Additional polymers that can be added include: citrates, diethyl citrate (DEC), triethyl citrate (TEC), acetyl triethyl citrate (ATEC), tributyl citrate (TBC), acetyl tributyl citrate (ATBC), phthalates such as dimethyl phthalate (DMP), diethyl phthalate (DEP), triethyl phthalate (TEP), dibutyl phthalate (DBP), dioctyl phthalate, glycol ethers such as ethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether (TranscutolTM), propylene glycol monotertiary butyl ether, dipropylene glycol monomethyl ether, n-methyl pyrrolidone, 2 pyrrolidone (2-PyrrolTM), propylene glycol, gly
  • Plasticizers also include: phthalates, glycol ethers, n-methyl pyrrolidone, 2 pyrrolidone, propylene gycol, glycerol, glyceryl dioleate, ethyl oleate, benzylbenzoate, glycofurol sorbitol, sucrose acetate isobutyrate, butyryltri-n-hexyl-citrate, acetyltri-n-hexyl citrate, sebacates, dipropylene glycol methyl ether acetate (DPM acetate), propylene carbonate, propylene glycol laurate, propylene glycol caprylate/caprate, caprylic/capric triglyceride, gamma butyrolactone, polyethylene glycols (PECs), vegetable
  • the homogenous mixture does not include a thickening agent.
  • Baking powder and other materials such as leavening agents, which release gases, (e.g., sodium or calcium bicarbonates or carbonates) can be included in the compositions of the invention to elevate the number of open cells in the final structure by introducing a source of carbon dioxide gas which is released in the mold.
  • gases e.g., sodium or calcium bicarbonates or carbonates
  • Glycerol, microcrystalline wax, fatty alcohols and other similar organic molecules can be added as a mold release agent, and to produce a smoother surface on the finished product.
  • agents that can be added, either as plasticizers or as mold releasing agents are ethylene glycol, propylene glycol, glycerin, 1,3 -propanediol, 1 ,2-butandiol, 1,3-butandiol, 1 ,4-butanediol, 1,5-pentandiol, 1,5-bexandiol, 1 ,6-hexandiol, 1,2,6-hexantriol, 1,3,5- hexantriol,neopentylglycol, sorbitol acetate, sorbitol diacetate, sorbitol monoethoxylate, sorbitol diethoxylate, sorbitol hexaethoxylate, sorbitol dipropoxylate, arrunosorbitol, trihydroxy
  • derivatives include ethers, thiethers, inorganic and organic esters, acetals, oxidation products, amides, and aniines. These agents can be added from 0-10%, preferably 3-4% (w/w).
  • a consideration of the inventive mixture should be that the composition preferably contains at least 75%, more preferably at least 95% of natural or organic-derived materials by weight of the homogenous moldable composition.
  • the starch, and optionally, wood flour mixture, with any included additives, is added to the pre-gelled starch and mixed (for example with a Kitchen Aid® Commercial Mixer, a Hobart mixer, or a ReadCo 2" paddle mixer) until a homogeneous moldable mixture is generated.
  • the mixture can be as thick as peanut butter or as thin as a pancake batter. Varying amounts of additional water can by added to facilitate different types of molding, since the form of the pre-molded [green] product is dependent on the mold, heating rate and drying/melt time. If the product is to be molded by classic injection methods the material is thinner, if the material is molded on the equipment described below the mixture is thicker.
  • the material can also be rolled into green sheets and molded, extruded and made into dry pellets for other processes.
  • the means of production for the product could be created from any of several possible process approaches. One specific methodology is described below, but this description is intended only to describe one possible means of production, and shall not be construed in any way to represent a limitation to the outlined approach. While the compression molding process detailed herein is useful, other types of compression molding, injection molding, extrusion, casting, pneumatic shaping, vacuum molding, etc can be used.
  • One embodiment involves a means of production incorporating moving upper and lower continuous track assemblies each with an upper and lower substantially elongated horizontal section, and with a curved portion of track joining the upper and lower horizontal section for each of the upper and lower tracks.
  • each of the track assemblies is a linked belt made from any material or combination of materials that allows the belt or belt assembly to be in constant or intermittent motion about the tracks.
  • the track assemblies are located vertically such that the upper portion of the lower track and the lower portion of the upper track are in close proximity such that the belts of each track move at a synchronized speed and in a common direction.
  • the male mold portion is mounted to the belt following the upper track
  • the female portion of the mold is mounted to the belt following the lower track, with the tracks synchronized in a fashion that causes the mold halves to join and close as they merge between the upper and lower tracks.
  • the material to be processed is deposited into the female mold half prior to the mold haves closing, or is injected into the mold after it has been closed.
  • the track and belt assemblies hold the mold halves together during drying by any of a number of, or combination of, methods including without limitation spring force, pneumatic force, or mechanical compression. Other forcing methods are possible.
  • One possible arrangement of the curved end of the tracks aligns them such that the lower tracks' upper horizontal section are located to start before the upper tracks' lower horizontal section to allow the female mold half on the upper section of the lower track to assume a substantially horizontal orientation prior to the male mold half attached to upper track, thereby allowing the female mold half to receive deposited material before it engages the corresponding male mold half merging from the upper track and belt assembly.
  • removable cavity inserts and or multiple cavities in the molds heating of the molds or product to speed drying by electric, microwave, hot gas, friction, ultrasonic, or any other means: on the fly cleaning of the molds, on the fly coating of product with any of a number of coating agents.
  • the moldable mixture is positioned within a heated mold cavity.
  • the heated mold cavity can comprise many different embodiments, including molds typically used in conventional injection molding processes and die-press molds brought together after placing the inorganically filled mixture into the female mold.
  • the moldable mixture is placed inside a heated female mold. Thereafter, a heated male mold is complementarily mated with the heated female mold, thereby positioning the mixture between the molds. As the mixture is heated, the starch-based binder gelates, increasing the viscosity of the mixture.
  • the mixture increases in volume within the heated molds cavity as a result of the formation of gas bubbles from the evaporating solvent, which are initially trapped within the viscous matrix.
  • a temperature between 195-225 0 C, preferably 200 0 C is used for baking for a time period of 60-90 seconds, preferably 75 seconds. Temperatures can vary based on the article bring manufactured, for example, 200 0 C. is preferred for the rapid production of thin-walled articles, such as cups. Thicker articles require a longer time to remove the solvent and are preferably heated at lower temperatures to reduce the propensity of burning the starch-based binder and fiber. Leaving the articles within the locked molds too long can also result in cracking or deformation of the articles.
  • the temperature of the mold can also effect the surface texture of the molds. Once the outside skin is formed, the solvent remaining within the interior section of the mixture escapes by passing through minute openings in the outside skin and then traveling between the skin and the mold surface to the vent holes. If one mold is hotter than the other, the laws of thermodynamics would predict, and it has been empirically found, that the steam will tend to travel to the cooler mold. As a result, the surface of the article against the hotter mold will have a smoother and more uniform surface than the surface against the cooler mold.
  • article can be produced from the processes and compositions of the present invention.
  • article and article of manufacture as used herein are intended to include all goods that can be formed using the disclosed process.
  • coatings can be applied to the surface of a substantially dried article for any desired purpose, such as to make the article more waterproof, grease and food product proof, more flexible, or to give it a glossier surface.
  • Coatings can be used to alter the surface characteristics including sealing and protecting the article made therefrom. Coatings can provide protection against moisture, base, acid, grease, and organic solvents. They can provide a smoother, glossier, or scuff-resistant surface, they can help reinforce the article and coatings can also provide reflective, electrically conductive or insulative properties. Water resistance can be achieved through the use of a water resistant layer applied on one or both sides of the product. There are many currently available coatings that can be used to coat this product.
  • Zein® a biodegradable material isolated from corn
  • poly lactic acid [PLA] a polymer of lactic acid from fermentation feed stock
  • polyhydroxyalkanoates [PHA] from microbial fermentation
  • bacterial cellulose a polymer of lactic acid from fermentation feed stock
  • PHA polyhydroxyalkanoates
  • Appropriate organic coatings include edible oils, melamine, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyacrylates, polyamides, hydroxypropylmethyl- cellulose, polyethylene glycol, acrylics, polyurethane, polyethylene, polylactic acid, Biopol TM (a polyhydroxybutyrate-hydroxyvalerate copolymer), starches, soybean protein, polyethylene, and synthetic polymers including biodegradable polymers, waxes (such as beeswax or petroleum based wax), elastomers, edible oils, fatty alcohols, phospholipids and other high molecular weight biochemicals, and mixtures or derivatives thereof.
  • Biopol® is manufactured by ICI in the United Kingdom.
  • Elastomer, plastic, or paper coatings can aid in preserving the integrity of the article.
  • Appropriate inorganic coatings include sodium silicate, calcium carbonate, aluminum oxide, silicon oxide, kaolin, clay, ceramic and mixtures thereof.
  • the inorganic coatings can also be mixed with one or more of the organic coatings set forth above. Coatings based upon materials such as soybean oil or Methocel®. (available from Dow Chemical), either alone or in combination with polyethylene glycol, can be applied to the surface in order to permanently soften the article or a hinge area within the article.
  • the coating can be applied either during the forming process or after the article is formed.
  • the coating can be formed during the forming process by adding a coating material that has approximately the same melting temperature as the peak temperature of the mixture. As the mixture is heated, the coating material melts and moves with the vaporized solvent to the surface of the article where it coats the surface.
  • the coatings can be applied to the shaped articles using any coating means known in the art of manufacturing paper, paperboard plastic, polystyrene, sheet metal, or other packaging materials, including blade, puddle, air-knife, printing, Dahlgren, gravure, and powder coating. Coatings can also be applied by spraying the article with any of the coating materials listed below or by dipping the article into a vat containing an appropriate coating material. These materials can be applied either as a thin film or can be sprayed/dipped onto the product.
  • the apparatus used for coating will depend on the shape of the article. For example, cups will usually be coated differently than flat plates. Bonding processes for application of thin films of water-resistant material are known in the art.
  • the second method of improving the water resistance of the product is to add one or more biodegradable materials to the material either before molding or as part of the molding process. In each of these cases the basic composition of the product will remain fairly constant.
  • a waterproof coating is desirable for articles intended to be in contact with water.
  • the preferred coatings are non-aqueous and have a low polarity.
  • Appropriate coatings include paraffin (synthetic wax); shellac; xylene-formaldehyde resins condensed with 4,4'- isopropylidenediphenolepichlorohydrin epoxy resins; drying oils; reconstituted oils from triglycerides or fatty acids from the drying oils to form esters with various glycols (butylene gylcol, ethylene glycol), sorbitol, and trimethylol ethane or propane; synthetic drying oils including polybutadiene resin; natural fossil resins including copal (tropical tree resins, fossil and modern), damar, elemi, gilsonite (a black, shiny asphaltitc, soluble in turpentine), glycol ester of damar, copal, elemi, and
  • Biopol® is manufactured by ICI in the United Kingdom.
  • Appropriate inorganic coatings include sodium silicate, calcium carbonate, aluminum oxide, silicon oxide, kaolin, day, ceramic and mixtures thereof.
  • the inorganic coatings can also be mixed with one or more of the organic coatings set forth above.
  • the coating material will preferably include an FDA-approved coating.
  • An example of a particularly useful coating is sodium silicate, which is acid resistant.
  • Resistance to acidity is important, for example, where the article is a container exposed to foods or drinks having a high acid content, such as soft drinks or juices. It is generally unnecessary to protect the article from basic substances, but increased resistance to basic substances can be provided by an appropriate polymer or wax coating, such as those used to coat paper containers.
  • Polymeric coatings such as polyethylene are useful in forming generally thin layers having low density. Low density polyethylene is especially useful in creating containers which are liquid-tight and even pressure -tight to a certain extent. Polymeric coatings can also be utilized as an adhesive when heat sealed.
  • Aluminum oxide and silicon oxide are useful coatings, particularly as a barrier to oxygen and moisture.
  • the coatings can be applied to the article by any means known in the art, including the use of a high energy electron beam evaporation process, chemical plasma deposition and sputtering.
  • Another method of forming an aluminum oxide or silicon oxide coating involves treating article with an aqueous solution having an appropriate pH level to cause the formation of aluminum oxide or silicon oxide on the article due to the composition of the article.
  • Waxes and wax blends particularly petroleum and synthetic waxes, provide a barrier to moisture, oxygen, and some organic liquids, such as grease or oils. They also allow an article such as a container to be heat sealed. Petroleum waxes are a particularly useful group of waxes in food and beverage packaging and include paraffin waxes and microcrystalline waxes.
  • the coating it can be preferable for the coating to be elastomeric or deformable. Some coatings can also be used to strengthen places where the articles are severely bent. In such cases, a pliable, possibly elastomeric, coating can be preferred.
  • starch compositions of the present invention can themselves be used as coating materials in order to form a synergistic composite with, or otherwise improve the properties of, any number of other materials.
  • Such disparate materials such as paper, paperboard, molded starch-bound articles such as starch- based foams, metals, plastics, concrete, plaster, ceramics, and the like can be coated with starch composition.
  • print or other indicia such as trademarks, product information, container specifications, or logos
  • print or other indicia such as trademarks, product information, container specifications, or logos
  • This can be accomplished using any conventional printing means or processes known in the art of printing paper or cardboard products, including planographic, relief, intaglio, porous, and impactless printing.
  • Conventional printers include offset, Van Dam, laser, direct transfer contact, and thermographic printers.
  • any manual or mechanical means can be used.
  • the amount of paper pulp can be increased to 50%, or 30-50%, by weight of the final mixture, and the amount of wood flour or fiber can be decreased to 0%.
  • wood flour/fiber and/or paper pulp When using a vacuum to form a film around the molded article, increasing the levels of wood flour/fiber and/or paper pulp can facilitate the vacuuming process.
  • wood flour/fiber and/or paper pulp levels can be increased to 30, 40 or 50% by weight of the final mixture.
  • the articles of the present invention can be, in one embodiment, coated according to the methods and utilizing the coating compositions as described in U.S. Patent Application No. 11/605,169, which describes methods for filming biodegradable or compostable containers by applying a heated film to a heated biodegradable or compostable container, wherein the temperature of the container is approximately the temperature of the biodegradable film.
  • Containers suitable for holding dry materials can be used to hold dried fruit, or raw nuts such as almonds.
  • Containers suitable for holding damp materials can be used to hold fresh mushrooms or tomatoes (for example in groups of 4 or 6) and should be able to perform this function for a period of at least about two to three weeks since normal packing to use time is about 14 days.
  • Damp food packing can also be used with a hot fast food item such as French fries or hamburger, in which case the container needs to last for only a short time, for example about one hour after addition of the damp food. Damp food packing could also be used, in combination with an adsorbent pad, to package raw meat.
  • the container needs to withstand exposure to the meat for a period of seven days or longer and desirably can stand at least one cycle of freeze and thaw. If possible this package should be able to withstand a microwave signal.
  • the containers of the invention will suitably have the ability to hold a hot liquid, such as a bowl of soup, a cup of coffee or other food item for a period of time sufficient to allow consumption before cooling, for example within one hour of purchase.
  • a hot liquid such as a bowl of soup, a cup of coffee or other food item for a period of time sufficient to allow consumption before cooling, for example within one hour of purchase.
  • Such containers can also be used to hold a dry product that will be re-hydrated with hot water such as the soup-in-a-cup products.
  • the container should be capable of holding its contents, whether stationary or in movement or handling, while maintaining its structural integrity and that of the materials contained therein or thereon. This does not mean that the container is required to withstand strong or even minimal external forces. In fact, it can be desirable in some cases for a particular container to be extremely fragile or perishable.
  • the container should, however, be capable of performing the function for which it was intended. The necessary properties can always be designed into the material and structure of the container beforehand.
  • the container should also be capable of containing its goods and maintaining its integrity for a sufficient period of time to satisfy its intended use. It will be appreciated that, under certain circumstances, the container can seal the contents from the external environments, and in other circumstances can merely hold or retain the contents.
  • tainer or “containers” as used herein, are intended to include any receptacle or vessel utilized for, e.g., packaging, storing, shipping, serving, portioning, or dispensing various types of products or objects (including both solids and liquids), whether such use is intended to be for a short-term or a long-term duration of time.
  • Containment products used in conjunction with the containers are also intended to be included within the term “containers.”
  • Such products include, for example, lids, straws, interior packaging, such as partitions, liners, anchor pads, corner braces, corner protectors, clearance pads, hinged sheets, trays, funnels, cushioning materials, and other object used in packaging, storing, shipping, portioning, serving, or dispensing an object within a container.
  • the containers within the purview of the present invention can or can not be classified as being disposable. In some cases, where a stronger, more durable construction is required, the container might be capable of repeated use. On the other hand, the container might be manufactured in such a way so as to be economical for it to be used only once and then discarded.
  • the present containers have a composition such that they can be readily discarded or thrown away in conventional waste landfill areas as an environmentally neutral material.
  • the articles within the scope of the present invention can have greatly varying thicknesses depending on the particular application for which the article is intended. They can be as thin as about 1 mm for uses such as in a cup. In contrast, they can be as thick as needed where strength, durability, and or bulk are important considerations. For example, the article can be up to about 10 cm thick or more to act as a specialized packing container or cooler. The preferred thickness for most articles is in a range from about 1.5 mm to about 1 cm, with about 2 mm to about 6 mm preferred.
  • the present invention can produce a variety of articles, including plates, cups, cartons, and other types of containers and articles having mechanical properties substantially similar or even superior to their counterparts made from conventional materials, such as paper, polystyrene foam, plastic, metal and glass.
  • inventive articles can also be made at a fraction of the cost of their conventional counterparts. The minimal cost is a result of the relatively inexpensive aggregate which typically comprises a large percentage of the mixture and the minimum processing energy required.
  • the method of the present invention provides basic methodologies which can be utilized with little modification and a basic material from which product items can be produced by tailoring of the additives and additional processing steps employed.
  • the composition preferably contains at least 75%, at least 85% or at least 95% or more of natural or organic-derived materials by weight of the homogenous moldable composition.
  • thermoplastic starch compositions according to the present invention, as well as articles therefrom.
  • the examples include various mix designs, as well as various processes for manufacturing thermoplastic starch compositions, including sheets, films, pellets, containers, and other articles of manufacture.
  • Example 1 is preferably used for flatter trays.
  • Example 2 is preferably used for deeper trays that require high edge strength.
  • homogenous mixture Add homogenous mixture to the pre-gelled paper potato starch, mix with a dough hook mixer on low speed. This mixture is stable and can be cooled or refrigerated, but not frozen.
  • Example 3 is preferably used for trays that need to be over wrapped or edge sealed.
  • Example 4 Place mixture into mold (about 50-55 g) and bake at 195-225°C (ideal 215°C) for 60-90 seconds (ideal 75°C).
  • Example 4 is preferably used for deeper trays or salad/soup type bowls requiring high edge strength.
  • Example 6 [20% cornstarch using powdered cellulose formula 1] 1. Form a pregelled cellulose paper- waxy potato starch suspension.
  • Step 1 The water is introduced into the preheated [to 68 deg C] mixer such as a Kitchen Aid Classic fitted with the paddle blade in a stainless steel bowl.
  • the fiber is quickly added with mixing [setting # I].
  • the gelling starch is added.
  • the gel will form within 60 seconds.
  • Step 2 Now add the mold release and the foaming agent [pre blended], with mixing at setting #1.
  • the balance of the starch is added slowly until the mixture is homogenous. Continue mixing for an additional four minutes. At this time the dough will be smooth and slightly sticky.
  • the mixed dough is transferred into a sealed transport container and product produced.
  • amylopectin [Eliane 100 starch, Avebe Veendam, Holland]
  • Step 1 The water is introduced into the preheated [to 65 deg C] mixer such as a Kitchen Aid Classic fitted with the paddle blade in a stainless steel bowl.
  • the fiber is quickly added with mixing [setting # I].
  • the gelling starch is added. The gel will form within 60 seconds. Continue mixing for an additional 120 seconds.
  • Step 2 Now add the mold release and the foaming agent [pre blended], with mixing at setting #1. The balance of the starches are added [pre blended] slowly until the mixture is homogenous. Continue mixing for an additional four minutes. At this time the dough will be smooth and slightly sticky. The mixed dough is transferred into a sealed transport container and product produced.
  • Example 10 flash gel preparation of a large batch of dough made from 100% amylopectin starch
  • amylopectin Eliane 100 starch, Avebe Veendam, Holland
  • Step 1 The water is introduced into the preheated [to 68 deg C] large capacity mixer such as a Varimixer Bear AR40 [A/S Wodscow & Co of Denmark] fitted with a twin fin paddle blade and scraper in a stainless steel bowl.
  • the fiber is quickly added with mixing [setting # 1.5].
  • the gelling starch is added. The gel will form in 60 seconds. Continue mixing for an additional 120 seconds.
  • Step 2 Now add the mold release and the foaming agent [pre blended], with mixing at setting #1.5. The balance of the starch is added slowly until the mixture is homogenous.
  • Example 11 [flesh gel preparation of a large batch of dough made from amylopectin starch and corn starch]
  • amylopectin Eliane 100 starch, Avebe Veendam, Holland
  • Step 1 The water is introduced into the preheated [to 65 deg C] mixer such as a Varimixer Bear AR40 [A/S Wodscow & Co of Denmark] fitted with a twin fin paddle blade and scraper in a stainless steel bowl.
  • the fiber is quickly added with mixing [setting # 1.5].
  • the gelling starch is added. The gel will form within 60 seconds. Continue mixing for an additional 120 seconds.
  • Step 2 Now add the mold release and the foaming agent [pre blended], with mixing at setting #1.5. The balance of the starches are added [pre blended] slowly until the mixture is homogenous. Continue mixing for an additional four minutes. At this time the dough will be smooth and slightly sticky. The mixed dough is transferred into a sealed transport container and product produced.
  • Example 12 [High % Tapioca starch]
  • Example 12 is preferably used for flatter trays with good flexibility and moderate crush strength.
  • Example 13 is preferably used for flatter trays with high flexibility and moderate crush strength.
  • Example 14 is preferably used for flatter trays with high flexibility and moderate crush strength with a smooth finish.
  • Example 15 is preferably used for flatter trays with high flexibility and moderate crush strength with a smooth finish.
  • Example 16 is preferably used for flatter trays with high flexibility and moderate crush strength with a smooth more water repellant finish.
  • Example 17 is preferably used for flatter trays which are highly flexible and dense exhibiting a very smooth finish.
  • Example 18 is preferably used for flatter trays which have high crush strength, good flexibility and a smooth finish.
  • the flour When the flour is well dispersed add gelling starch and mix for 1-3 min. The final temperature will be 64-66 deg C. Alternatively, the wood flour and gelling starch are dispersed into warm water. The mixing bowl is heated. The RPM of the mixer is set at the first setting (KitchenAid®). The heating continues until the temp reaches 65 0 C. At this time, the mixture is a homogeneous gel suspension. Once gelled, the gel may be used hot, cooled or refrigerated (but not frozen) until used.
  • the temperature of the produced dough is between 50 and 55 0 C and is ready for molding or direct injection.
  • the rate of dough produced is 340 +/- 5 kg/hour.
  • the scaled-up batch process can be achieved using, for example, the Hobart 140 quart mixer which can mix up to 300 kg of dough per hour using the flash-gel method.
  • Tables 1 and 2 list formulations prepared for patch processing using the Hobart 140 quart mixer. Table 1 (Pre-Gel).
  • Test one is a break test for a tray clamped at 2/3 of its length and pressed down with the Admet Model 5600 Universal Tester until the tray fails.
  • the computer calculates the peak load (in lbs) to break the tray, the amount of stress required to break the tray (in PSI) and the amount of deflection before breakage (in inches deflected).
  • the Peak Stress is indicative of strength and Deflection in indicative of flexibility.
  • Test two is a break test for a tray supported upside down. A 2 inch disk is pressed down on the bottom of the upside down tray by the Admet Model 5600 Universal Tester until the tray bottom fails. The computer calculates the peak load (in lbs) to break the tray, the amount of stress required to break the tray (in PSI) and the amount of deflection before breakage (in inches deflected). The Peak Stress is indicative of strength and Deflection in indicative of flexibility.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

L’invention concerne un procédé et des matériaux améliorés pour former des contenants biodégradables ayant une flexibilité et une résistance mécanique accrues qui peuvent contenir des produits alimentaires dans des conditions sèches, moites ou humides et former des contenants biodégradables préparés selon le procédé révélé. Les contenants sont produits en utilisant une suspension d’amidon prégélifiée qui est unique dans sa capacité à former des gels hydratés et à maintenir cette structure de gel en présence de nombreux autres types de matériaux à de basses températures.
PCT/US2009/034216 2008-02-15 2009-02-16 Procédé de congélation éclair pour former des contenants biodégradables ou compostables WO2009103052A1 (fr)

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US2915208P 2008-02-15 2008-02-15
US61/029,152 2008-02-15
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