WO2005021633A2 - Composition for use in biodegradable articles and method of use - Google Patents

Composition for use in biodegradable articles and method of use Download PDF

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Publication number
WO2005021633A2
WO2005021633A2 PCT/US2004/027824 US2004027824W WO2005021633A2 WO 2005021633 A2 WO2005021633 A2 WO 2005021633A2 US 2004027824 W US2004027824 W US 2004027824W WO 2005021633 A2 WO2005021633 A2 WO 2005021633A2
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WO
WIPO (PCT)
Prior art keywords
composition
fibers
starch
range
filler material
Prior art date
Application number
PCT/US2004/027824
Other languages
French (fr)
Other versions
WO2005021633A3 (en
Inventor
Elie Helou, Jr.
David Dellinger
Original Assignee
Biosphere Industries Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Biosphere Industries Corporation filed Critical Biosphere Industries Corporation
Priority to JP2006524867A priority Critical patent/JP2007517919A/en
Priority to CN2004800244477A priority patent/CN101374900B/en
Priority to MXPA06002193A priority patent/MXPA06002193A/en
Priority to KR1020067003856A priority patent/KR101205119B1/en
Priority to EP04782322A priority patent/EP1658328A4/en
Priority to AU2004269027A priority patent/AU2004269027A1/en
Priority to CA2536311A priority patent/CA2536311C/en
Publication of WO2005021633A2 publication Critical patent/WO2005021633A2/en
Publication of WO2005021633A3 publication Critical patent/WO2005021633A3/en
Priority to HK09103356.3A priority patent/HK1127073A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02Starch; Degradation products thereof, e.g. dextrin
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • C08L101/16Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02Cellulose; Modified cellulose
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00Compositions of proteins; Compositions of derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00Compositions of proteins; Compositions of derivatives thereof
    • C08L89/005Casein

Definitions

  • the invention generally relates to a mix formulation for the production
  • proofing material such as wax or polyethylene
  • plastics one of a variety of plastics
  • polystyrene cup for example, is about 500 years, and each American disposes an
  • polystyrene is made by chemical
  • Paper and paperboard are made from wood pulp, which is a renewable
  • cooked, unmodified starch is inherently water soluble.
  • aqueous fluids or vapor are not present (e.g., dry or deep-fried items).
  • aqueous e.g., beverages, soups
  • aqueous phase e.g., thin
  • sauces, vegetables heated in water or (3) give off water vapor as they cool (e.g., rice
  • Another approach is to protect the starch from contact with aqueous fluids or vapors by applying water-resistant coatings or films to the surfaces of the food service items, essentially forming a laminated structure in which a water- sensitive core is sandwiched between layers of a biodegradable water-resistant material.
  • Many biodegradable coatings are costly to obtain and difficult to apply, thus increasing manufacturing cost and complexity and reducing the percentage of acceptable finished products.
  • Baked unmodified starch is typically quite fragile and brittle when dry, but
  • fiber is often added to the formulation to increase the flexural strength
  • inorganic mineral fillers e.g., calcium
  • wood-pulp fiber similar to the paper based articles.
  • fibrous materials from non-wood plants, and particularly from materials that are by- ⁇ products of commodities already in production.
  • biodegradable and renewable plant-based organic materials that serve the same role as
  • One embodiment of the present invention is a composition comprising
  • fibers a wax emulsion, a fiber sizing agent, and a mold release agent.
  • produced comprising water, starch, optionally insolubilizing compounds to
  • wax emulsions and/or fiber sizing agents are included in the formulation to increase water-resistance, and optionally a mold release agent to reduce adhesion between
  • Starch for use in the present embodiment may include, but is not limited
  • plant sources such as tubers, roots, seeds, and/or fruits of plants, and specific plants
  • sources may include corn, potato, tapioca, rice, or wheat or similar, or animal sources,
  • starch namely glycogen, although plant sources are most preferred. Further, the starch is
  • pregelatinized starch has a concentration in the range of about 0% to about
  • the present embodiment include, but are not limited to, aqueous solutions containing
  • modified ethandial, glyoxal-based reagents, ammonium zirconium carbonate, potassium zirconium carbonate, and polyamide-epichlorohydrine compounds are used.
  • the amount of active ingredient of the insolubilizer used is up to about 20% by weight of the starch (including both native and pregelatinized starch), and is more preferred in the range from about 0.1% to about 20% by weight of starch, depending on the cross- linking system used and the specific application.
  • Proteins and natural polymeric compounds may include, but are not
  • preparations One such preparation can be prepared in the following three steps: 1)
  • the preferred ratio of latex to casein in the preparation is between about 1 :1 to 2:1 (solids : solids), and a more preferred ratio is in a range from about 1.2:1 to
  • such proteins may include albumen, agar, gelatin, or the
  • Fiber elements are used both to control the
  • the fibrous portion of the formulation can be in a
  • Short fibers ( ⁇ 0.5 mm) serve mainly as a means to introduce readily
  • biodegradable material into the formulation i.e. filler material, that is, especially when
  • the shorter fibers may be used in conjunction with, or
  • such filler materials may include both organic and inorganic aggregates
  • silicate micaceous minerals, clay minerals, titanium dioxide, talc, etc.
  • concentration of aggregate or short fibers is in a range from about 0% to about 25%> by
  • dry weight of the formulation and more preferably in a range from about 5% to about
  • Fibers from several sources are typically included in the formulation.
  • the long to very long fibers or fiber composites typically come from lightly processed
  • Fibrous material in the form of ground nut shells may also serve as an organic, biodegradable fibers that are particularly water-resistant especially when treated with an optional fiber sizing agent.
  • these other sources of fiber suitable as structural elements in starch-based food service articles are readily available. Some of these are from fast- growing plants that can be broadly characterized as grasses or reeds, such as kenaf and
  • fiber is also widely available as a by-product of agricultural production.
  • Stalks, stems, and husks from cereal grains, for example, are a ready source of fibrous
  • grass species is extremely cheap and, as a by-product, has essentially no additional
  • the materials have an average fiber length that is less than about 2 mm and an average aspect ratio that is in the range of about 5:1 to 25 : 1.
  • aqueous emulsion usually made of paraffin or microcrystalline wax; it sometimes contains rosin. It is usually prepared by means of emulsifying agents and mechanical agitation.
  • the emulsion may be either acid- or alkali-stable, depending on the emulsifying agent employed.
  • the wax emulsion may be made from natural waxes, for example, animal, vegetable or mineral, or synthetic waxes, for example, ethylenic polymers and poly ethyl esters, chlorinated naphthalenes, or hydrocarbon type waxes, depending on the particular application and desired
  • present formulation include emulsified paraffin wax and emulsified polycrystalline
  • Emulsifying systems include both soap-based and lignosulfonate-based types.
  • the fiber sizing agent can be any suitable fiber sizing agent such that the
  • agent forms a coating (or interphase) on the fiber surface to serve one or more of the
  • adhesion promoter (coupling agent)
  • adhesion promoter to protect the surface of the fibers
  • formulation include aklylketene dimer emulsions, alkenyl succinic anhydrides,
  • aqueous dispersions of styrene acrylate copolymer, and alkylated melamine are examples of styrene acrylate copolymer, and alkylated melamine.
  • a mold release agent or abherent is provided to reduce adhesion
  • magnesium stearate magnesium stearate, talc, fats or oils or similar or a combination of any of the
  • the containers may be fashioned
  • any portion of the container will preferably vary
  • thickness of the containers may also vary across the cross section of the container.
  • such as a coating and or sealant may be applied to containers fashioned from the mix
  • Said biodegradable material may be applied such that it permeates the
  • Said materials when applied as a coating may partially or
  • a further embodiment of the invention is a method to produce a
  • a further method according to the present invention comprises the steps of providing a mold apparatus having a cavity in the shape of a desired final product and a gap or gaps for venting vapor from the mold apparatus produced during heating or baking, heating or baking the mold apparatus, adding a mixture that is liquid or semi-liquid to the cavity of the mold apparatus prior to closing the mold apparatus and closing the mold apparatus, wherein as vapor or steam is produced in the cavity during heating or baking, the mixture is pushed by vapor or steam pressure to completely fill
  • skin forms on the outer surface of the mixture, the skin being permeable or semi-
  • gap is of sufficient size - i.e., small enough - that the skin formed on the surface of the
  • cookie dough, or ice cream cone batter starch-based mixtures comprised of starch and
  • baking procedures such as heating temperature and time will vary depending on

Abstract

The present invention relates to a composition for use in making a starch-based food or beverage container, the formulation allowing the container to be water resistant for a usable amount of time without the need for coatings or similar. An embodiment of the formulation comprising water, native and pregelatinized starch, an insolubilizing compound, proteins or natural polymeric compounds, fibers, a wax emulsion, and a fiber-sizing agent.

Description

TITLE OF THE INVENTION
COMPOSITION FOR USE IN BIODEGRADABLE ARTICLES AND
METHOD OF USE
CROSS-REFERENCE TO RELATED APPLICATIONS ] This application claims priority to U.S. Provisional Applications Serial 0/498,396, filed August 27, 2003.
Background of the Invention
Field of the Invention
[0002] The invention generally relates to a mix formulation for the production
of biodegradable goods and methods for use of said formulations. Background
[0003] Conventional disposable food service items are commonly made from
paper or paperboard (commonly coated or impregnated with a polymeric water-
proofing material such as wax or polyethylene), or one of a variety of plastics
(polystyrene is the most common). These materials have good to excellent resistance
to moisture, can be made insulating (foamed polystyrene or "Styrofoam"), and are
inexpensive and durable. The industrial production methods used to produce
disposable packaging from these materials are mature; these items can be produced
quickly and relatively cheaply in great quantities.
[0004] There is, however, a growing recognition that the environmental costs of
using these "cheap" materials may be quite high. The expected lifetime of a
polystyrene cup, for example, is about 500 years, and each American disposes an
average of about 100 cups per year. Further, polystyrene is made by chemical
processing of benzene and ethyl ene, both byproducts of the petroleum industry, and
thus both non-renewable resources. Although the environmental record of the
petroleum industry has improved greatly since the mid-twentieth century, extraction and processing of petroleum for fuel and chemical production remain recognized
environmental problems.
[0005] Paper and paperboard are made from wood pulp, which is a renewable
material. The regeneration time, however, for wood fiber - the time required to grow
a tree - is substantial, and the chemical processing needed to produce white fibers has
been recognized to be detrimental to the environment. The use of unbleached and
recycled fibers helps alleviate these environmentally detrimental activities, but the use
of slow-growing trees as a fiber source when many agricultural byproduct sources are
available is in itself questionable.
[0006] The pressure to use biodegradable disposable packaging materials has
been steadily increasing in the last decade. As recently as March, 2003, Taiwan
outlawed the use of polystyrene foam in disposable packaging. China's major cities
(e.g., Beijing and Shanghai) have also outlawed the use of polystyrene foam in
disposable packaging. [0007] To address the environmental concerns about conventional disposable
food container products, one approach in the art has been the manufacture of starch-
based disposable food service items such as trays, plates, and bowls. Starch-based
packaging used in the art, however, currently has several drawbacks, the most
important being that the containers are susceptible to water. [0008] Specifically, cooked, unmodified starch is inherently water soluble.
Because all of the starch-based biodegradable food service items currently being manufactured are formed in heated molds, much or all of the starch in these items is
cooked, and the products thus formed are very sensitive to moisture. When exposed to
water, other aqueous fluids, or significant amounts of water vapor, these items become
very soft, losing form-stability and becoming susceptible to puncture by cutlery (e.g.,
knives and forks).
[0009] Manufacturers currently address the problem of the moisture-
susceptibility of starch-based food-service items in two ways, either by not using the
products in aqueous environments or by applying a coating to the product. One
approach is to avoid the problem simply by marketing their food service items for uses
in which aqueous fluids or vapor are not present (e.g., dry or deep-fried items). This
approach greatly limits the potential markets for these items, since many food products
either (1) are aqueous (e.g., beverages, soups), (2) include an aqueous phase (e.g., thin
sauces, vegetables heated in water) or (3) give off water vapor as they cool (e.g., rice
and other starchy foods, hot sandwiches, etc.) [0010] Another approach is to protect the starch from contact with aqueous fluids or vapors by applying water-resistant coatings or films to the surfaces of the food service items, essentially forming a laminated structure in which a water- sensitive core is sandwiched between layers of a biodegradable water-resistant material. Many biodegradable coatings, however, are costly to obtain and difficult to apply, thus increasing manufacturing cost and complexity and reducing the percentage of acceptable finished products. [0011] Further, in the current art, the mechanical properties of the matrix
material (mainly starch) are critical to the performance of starch-based food service
articles. Baked unmodified starch is typically quite fragile and brittle when dry, but
relatively soft and pliable when the starch contains 5% to 10% moisture. In current
practice, fiber is often added to the formulation to increase the flexural strength and
fracture energy of starch-based items, especially during the period immediately after
demolding, when the moisture content of the starch is very low. Even with the
addition of significant amounts (10% or more) of fiber, however, starch-based articles
are commonly very brittle immediately after demolding or when stored for extended
periods in dry environments (heated buildings in winter, air conditioned buildings in
summer, desert environments any time of year). Brittle failure of starch-based articles
thus continues to present problems during the manufacturing process (especially
before coatings or laminated films are applied) and when the articles are used in dry
environments. [0012] Moreover, in the current art, inorganic mineral fillers (e.g., calcium
carbonate, silica, calcium sulfate, calcium sulfate hydrate, magnesium silicate,
micaceous minerals, clay minerals, titanium dioxide, etc.) are often included in
formulations used to produce starch-based biodegradable food service articles. These fillers are not, however, biodegradable. Marketing claims made for products using these materials as fillers point out that the materials are natural, renewable, and environmentally benign. However, there are inherent environmental costs associated with the mining (or synthesis) and processing of all inorganic filler materials. [0013] Finally, in the current art, the most commonly used fiber in starch-based
food service articles is wood-pulp fiber (similar to the paper based articles). As the
main source material for the paper industry, it is readily available, is consistent in
quality and material properties, and has the main properties needed to serve as
structural elements in the finished food service articles. The use, however, of slow-
growing trees as a fiber source when many agricultural byproduct sources are
available is, as set forth above, in itself questionable.
[0014] Accordingly, there is a need for an improved system for producing
water-resistant, biodegradable disposable items that can serve the full range of uses to
which containers, boxes, plates, trays, and bowls are usually put, but which avoids the
cost and complexity of film lamination or spray coating systems.
[0015] There is also a need for a means to enhance the mechanical properties of
the matrix material in starch-based food service articles, in order (a) to ease handling
requirements during manufacture and (b) to enhance usability in dry environments. [0016] There is also a need for an improvement in the current art that will
replace mineral fillers with fully biodegradable and renewable plant-based organic
materials that serve the same role as traditional mineral fillers. Even greater benefit is available if the filler material is currently produced as a byproduct of the production of another agricultural material. [0017] There is also a need for methods and formulations that incorporate
fibrous materials from non-wood plants, and particularly from materials that are by- \ products of commodities already in production.
Summary of the Invention
[0018] It is an object of the present invention to provide an improved system for
producing water-resistant, biodegradable disposable items that can serve the full range
of uses to which containers, boxes, plates, trays, and bowls are usually put, but which
avoids the cost and complexity of film lamination or spray coating systems.
[0019] It is another object of the present invention to provide improved the
mechanical properties of matrix material in starch-based food service articles, in order
(a) to ease handling requirements during manufacture and (b) to enhance usability in
dry environments.
[0020] It is another object of the present invention to provide fully
biodegradable and renewable plant-based organic materials that serve the same role as
traditional mineral fillers in starch-based food containers.
[0021] It is another object of the present invention to provide methods and formulations that incorporate fibrous materials from non-wood plants, and particularly from materials that are by-products of commodities already in production.
[0022] These and other aspects of the present invention which may become obvious to those skilled in the art through the following description of the invention are achieved by a formulation used in making starch-based goods and a method fur use
of said formulation.
[0023] One embodiment of the present invention is a composition comprising
water, starch, a insolubilizing compound, a protein or natural polymeric compound,
fibers, a wax emulsion, a fiber sizing agent, and a mold release agent.
Detailed Description of the Invention
[0024] In order to fully understand the manner in which the above-recited
details and other advantages and objects according to the invention are obtained, a
more detailed description of the invention will be rendered by reference to specific
embodiments thereof.
[0025] A formulation according to the present invention from which water-
resistant packaging items (boxes, containers, plates, trays, bowls, and cups) can be
produced is provided comprising water, starch, optionally insolubilizing compounds to
reduce the moisture susceptibility of the starch portion of the baked food service items,
optionally proteins and natural polymeric compounds to reduce the brittleness of the
articles produced for use in dry environments and to prevent breakage immediately
after forming when the items are typically dry, optionally several natural fibrous
materials used in combination both as structural elements (at several size scales) in the
baked items and as inexpensive organic replacements for inorganic fillers, optionally
wax emulsions and/or fiber sizing agents are included in the formulation to increase water-resistance, and optionally a mold release agent to reduce adhesion between
baked parts and the mold system.
[0026] Starch for use in the present embodiment may include, but is not limited
to, plant sources such as tubers, roots, seeds, and/or fruits of plants, and specific plants
sources may include corn, potato, tapioca, rice, or wheat or similar, or animal sources,
namely glycogen, although plant sources are most preferred. Further, the starch is
preferably provided as a combination of both pregelatinized and native starches.
Preferably, pregelatinized starch has a concentration in the range of about 0% to about
30% by weight of total starch in the formulation, and more preferably 5% to 20%, and
most preferably 7% to 15%.
[0027] Insolubilizing compounds (or cross-linking agents) have been used in
the paper industry in the preparation of water-resistant coatings on paper to increase
printability and decrease susceptibility to moisture. Insolublizers that may be used in
the present embodiment include, but are not limited to, aqueous solutions containing
modified ethandial, glyoxal-based reagents, ammonium zirconium carbonate, potassium zirconium carbonate, and polyamide-epichlorohydrine compounds. The amount of active ingredient of the insolubilizer used is up to about 20% by weight of the starch (including both native and pregelatinized starch), and is more preferred in the range from about 0.1% to about 20% by weight of starch, depending on the cross- linking system used and the specific application. [0028] It has been found that in some cases in order to maximize the
effectiveness of the insolubilizer used, it is necessary to adjust the pH of the
formulation before adding the insolubilizing compound. It has also been found that
depending upon the specific mix formulation some insolubilizer compounds react with
the mix at low temperatures causing the mix to become too thick prior to molding. In
such cases an insolubilizer with the desired properties should be selected.
[0029] Proteins and natural polymeric compounds may include, but are not
limited to preparations made from casein and natural uncured latex or similar such
preparations. One such preparation can be prepared in the following three steps: 1)
cooking a solution of casein in water (about 10% casein by weight) as per usual
manufacturer's recommendations (generally, hydrating the casein by soaking, then
gradually raising the temperature and pH of the solution to 180°F and pH=9 to 9.5,
then holding the solution at 180°F for 15 minutes); 2) cooling the preparation to room
temperature; and 3) and adding the latex in an amount sufficient and blending
thoroughly. The preferred ratio of latex to casein in the preparation is between about 1 :1 to 2:1 (solids : solids), and a more preferred ratio is in a range from about 1.2:1 to
about 1.8:1, and a most preferred ration is about 1.48: 1. The ratio of casein to latex,
however, may be adjusted according to the specific needs of the containers to be
produced. [0030] Moreover, other proteins may also be used in combination with the
casein and latex preparation or separately to improve the water-resistant properties of the containers. For example, such proteins may include albumen, agar, gelatin, or the
like.
[0031] Several natural fibrous materials may be used in combination both as
structural elements (at several size scales) in the baked items and/or as inexpensive
organic replacements for inorganic fillers. Fiber elements are used both to control the
molding characteristics of the wet batter and to enhance the structural stability of the
finished food service articles. Although there is a continuum of fiber lengths and fiber
aspect ratios used in the formulation, the fibrous portion of the formulation can be in a
general sense separated into three classes (based on fiber length) that serve different
functions. Long or very long (4 to 25 mm or longer) fibers or composite fiber
elements are used to form a meshwork that helps prevent defects from forming in the
batter as it expands in the mold. Medium-length fibers (0.5 to 5 mm) also help control
the flow characteristics of the wet batter, and serve to increase the toughness of the
finished food service articles, preventing fracture during handling and during normal
use. Short fibers (<0.5 mm) serve mainly as a means to introduce readily
biodegradable material into the formulation, i.e. filler material, that is, especially when
treated with standard sizing agents, much more water-resistant than the starch-based matrix that contains them. (All types of fiber provide this functionality, but the presence of the medium, long, and very long fibers are required for the molding, handling and usage characteristics they provide, whereas the short fiber elements are present primarily for the contribution to water-resistance that they make.) [0032] Optionally, the shorter fibers may be used in conjunction with, or
replaced by other filler materials imparting the same advantages as the shorter fibers.
For example, such filler materials may include both organic and inorganic aggregates
such as calcium carbonate, silica, calcium sulfate, calcium sulfate hydrate, magnesium
silicate, micaceous minerals, clay minerals, titanium dioxide, talc, etc. The preferred
concentration of aggregate or short fibers is in a range from about 0% to about 25%> by
dry weight of the formulation, and more preferably in a range from about 5% to about
20% by total dry weight of the formulation, and most preferably in a range from about
10% to about 20%) dry weight of the formulation.
[0033] Fibers from several sources are typically included in the formulation.
Relatively high quality fibers from grass or reed species provide the mid-length fibers
that contribute most to the structural stability and resilience if the finished articles.
The long to very long fibers or fiber composites typically come from lightly processed
agricultural byproducts, e.g. stalk or husk materials that have been chopped, ground,
or milled to an appropriate size. Under appropriate processing conditions (e.g.,
hammer milling), these materials can also provide a considerable amount of the very short fiber that serves to replace starch and add water resistance to the finished article.
Fibrous material in the form of ground nut shells (or other very hard, lignin-rich plant materials) may also serve as an organic, biodegradable fibers that are particularly water-resistant especially when treated with an optional fiber sizing agent.
[0034] Moreover, these other sources of fiber suitable as structural elements in starch-based food service articles are readily available. Some of these are from fast- growing plants that can be broadly characterized as grasses or reeds, such as kenaf and
bamboo, which provide fiber with smaller associated environmental costs than taking
fiber from trees. A growing segment of the fiber industry is based on the use of fiber
from these plants. In many cases the quality and consistency of fibers taken from
these plants (after processing) is as good as that provided by the wood pulp industry.
In addition, fiber is also widely available as a by-product of agricultural production.
Stalks, stems, and husks from cereal grains, for example, are a ready source of fibrous
material that, while not as high in quality as the fiber taken from wood or the better
grass species, is extremely cheap and, as a by-product, has essentially no additional
environmental cost (beyond whatever environmental costs are associated with the
production of the main crop).
[0035] The fibrous materials included in the formulations described here vary
greatly in both fiber length and fiber aspect ratio. Overall, however, it is preferred that
the materials have an average fiber length that is less than about 2 mm and an average aspect ratio that is in the range of about 5:1 to 25 : 1.
[0036] The preferred wax emulsions in the formulation used to increase water-
resistance is a stable aqueous emulsion usually made of paraffin or microcrystalline wax; it sometimes contains rosin. It is usually prepared by means of emulsifying agents and mechanical agitation. The emulsion may be either acid- or alkali-stable, depending on the emulsifying agent employed. The wax emulsion may be made from natural waxes, for example, animal, vegetable or mineral, or synthetic waxes, for example, ethylenic polymers and poly ethyl esters, chlorinated naphthalenes, or hydrocarbon type waxes, depending on the particular application and desired
properties for the final product. Examples of wax emulsions suitable for use in the
present formulation include emulsified paraffin wax and emulsified polycrystalline
wax. Emulsifying systems include both soap-based and lignosulfonate-based types.
[0037] The fiber sizing agent can be any suitable fiber sizing agent such that the
agent forms a coating (or interphase) on the fiber surface to serve one or more of the
following: as adhesion promoter (coupling agent); to protect the surface of the fibers
from damage; as an aid in handling; to add strength or stiffness to the fibers; or to
reduce absorbency. Examples of fiber sizing agents suitable for use in the present
formulation include aklylketene dimer emulsions, alkenyl succinic anhydrides,
aqueous dispersions of styrene acrylate copolymer, and alkylated melamine.
[0038] A mold release agent or abherent, is provided to reduce adhesion
between baked parts and the mold system. Examples of specific mold release agents
that are suitable for use in the present formulation include, but are not limited to
magnesium stearate, talc, fats or oils or similar or a combination of any of the
foregoing.
[0039] Containers fashioned from a mix formulation according to the present
invention can be of varying shape and thickness depending upon the desired use for,
and properties of, the final container. For example, the containers may be fashioned
into open containers such as plates, cups, or bowls, clamshell containers, or any other
useful configuration known in the art. [0040] Further, the thickness of any portion of the container will preferably vary
in the range from about 0.5 mm to about 3.2 mm, and more preferably from about 1.5
mm to about 3.0 mm, and most preferably from about 1.6 mm to about 2.5 mm. The
thickness of the containers may also vary across the cross section of the container.
[0041] In another embodiment of the present invention a biodegradable material
such as a coating and or sealant may be applied to containers fashioned from the mix
formulation. Said biodegradable material may be applied such that it permeates the
outer and or inner surface of the container improving water and heat resistant
properties of the container. Said materials when applied as a coating, may partially or
completely permeate the container matrix or a combination of a forming a coating and
partially or completely permeating the container matrix.
[0042] A further embodiment of the invention is a method to produce a
container or other article for use with food or beverage containers. Said method
comprises providing the mix formulation set forth above; heating said mix in a mold of desired shape to form a container of a corresponding desired shape.
[0043] A further method according to the present invention comprises the steps of providing a mold apparatus having a cavity in the shape of a desired final product and a gap or gaps for venting vapor from the mold apparatus produced during heating or baking, heating or baking the mold apparatus, adding a mixture that is liquid or semi-liquid to the cavity of the mold apparatus prior to closing the mold apparatus and closing the mold apparatus, wherein as vapor or steam is produced in the cavity during heating or baking, the mixture is pushed by vapor or steam pressure to completely fill
the cavity, and upon sufficient contact of the mixture to the heated mold apparatus a
skin forms on the outer surface of the mixture, the skin being permeable or semi-
permeable to the vapor or steam and the skin and gap being such that, in combination,
they allow escape of steam or vapor from the cavity to the exterior of the mold
apparatus but do not allow any significant amount of the mixture to escape. Any
significant amount of mixture as referred to herein is any amount the loss of which
would cause any one of the aforementioned drawbacks found in the prior art in a
meaningful amount, such as waste of raw materials, waste of energy needed to heat
additional mixture, additional processes to remove excess material to form the final
product and clogging of the gap or gaps
[0044] The vapor escapes while the mixture is retained in the cavity because the
gap is of sufficient size - i.e., small enough - that the skin formed on the surface of the
mixture from contact of the mixture with the heated mold surface, when under
sufficient pressure from the steam or vapor produced during heating or baking of the
mixture, allows the steam or vapor to escape through the skin and then through the gap
to the exterior of the mold apparatus without rupture of the skin. Because the skin is
not permeable to the mixture, which may still be liquid or semi-liquid prior to the completion of heating or baking, the mixture cannot escape from the cavity of the mold apparatus.
[0045] The aforementioned method according to the present invention allows for venting of the vapors produced during baking without significant loss of mixture and the associated drawbacks of said loss outlined above such as waste of raw
materials, waste of energy needed to heat additional mixture, additional processes to
remove excess material to form the final product and clogging of the gap or gaps.
[0046] The aforementioned method according to the present invention may be
used to manufacture both edible baked goods and other baked products such as starch-
based materials for use as food containers and the like. Mixtures for use in said
method are typically water-based and include mixtures as described herein. One
skilled in the art, however, will recognize that the mixtures need not be water-based,
such as alcohol-based mixtures or other non-water-based mixtures. Specific examples
of mixtures that may be used said method should be readily apparent to one skilled in
the art and include, but are not limited to, common baking mixtures such as waffle,
cookie dough, or ice cream cone batter, starch-based mixtures comprised of starch and
water and mixtures comprising composite materials mixed with resins that form skins
which are still permeable to the gases produced during heating or baking. Further,
specific baking procedures such as heating temperature and time will vary depending
upon the specific mixture to be heated or baked and should be apparent to one skilled
in the art.
[0047] Although the invention has been described with respect to specific embodiments and examples, it will be readily appreciated by those skilled in the art
that modifications and adaptations of the invention are possible without deviation from the spirit and scope of the invention. Accordingly, the scope of the present invention is limited only by the following claims.

Claims

CLAIMSWhat is claimed is:
1. A composition for use in making biodegradable food service containers comprising: water; starch; fibers; a wax emulsion; and a fiber sizing agent.
2. The composition of claim 1 wherein the starch comprises preglatinized and native starch.
3. The composition of claim 2 wherein the pregelatinized starch is in a range from more than 0% to less than 30% by weight of the total starch in the composition.
4. The composition of claim 2 wherein the pregelatinized starch is in a range from more than 5% to less than 20%) by weight of the itotal starch in the composition.
5. The composition of claim 2 wherein the pregelatinized starch is in a range from more than 7% to less than 15% by weight of the total starch in the composition.
6. The composition of claim 1 further comprising an insolubilizing
compound.
7. The composition of claim 6 wherein the insolubilizing compound
comprises an aqueous solution containing modified ethandial, glyoxal-
based reagents, ammonium zirconium carbonate, potassium zirconium
carbonate or polyamide-epichlorohydrine compounds.
8. The composition of claim 7 wherein the insolubilizing compound
is in a concentration less than 20% by weight of total starch in the
composition.
9. The composition of claim 7 wherein the insolubilizing compound
is in a concentration in a range from about 0.1% to about 20% by weight
of the total starch in the composition.
10. The composition of claim 1 further comprising a protein or
natural polymeric compound.
11. The composition of claim 10 wherein the protein or natural
polymeric compound comprises casein and latex.
12. The composition of claim 11 wherein the latex is natural uncured latex.
13. The composition of claim 11 wherein the ratio of latex solids to casein solids is in a range between about 1 to 1 and about 2 to 1.
14. The composition of claim 11 wherein the ratio of latex solids to
casein solids is in a range between about 1.2 to 1 and about 1.8 to 1.
15. The composition of claim 11 wherein the ratio of latex solids to
casein solids is about 1.45 to 1.
16. The composition of claim 1 further comprising a protein to
improve the water resistant properties of the composition.
17. The composition of claim 16 wherein said protein to improve the
water resistant properties of the composition further comprises albumen,
agar, or gelatin.
18. The composition of claim 1 wherein the fibers comprise long,
medium, and short fibers.
19. The composition of claim 18 wherein the fibers comprise natural
fibrous materials.
20. The composition of claim 19 wherein the fibers have an average
fiber length less than about 2 mm.
21. The composition of claim 20 wherein the fibers have an average aspect ratio in the range of 5 : 1 to 25 : 1.
22. The composition of claim 1 comprising filler material.
23. The composition of claim 22 wherein the filler material is
organic.
24. The composition of claim 22 wherein the filler material
comprises calcium carbonate, silica, calcium sulfate hydrate, magnesium
silicate, micaceuous minerals, clay minerals, titanium dioxide or talc.
25. The composition of claim 22 wherein the filler material and/or
short fibers having a combined concentration less than 25% by dry
weight of the composition.
26. The composition of claim 22 wherein the filler material and/or
short fibers have a combined concentration less than 20% and greater
than 5% by dry weight of the composition.
27. The composition of claim 22 wherein the filler material and/or
short fibers have a combined concentration less than 20% and greater
than 10% by dry weight of the composition.
28. The composition of claim 1 wherein the fibers comprise fibers from fast growing plants.
29. The composition of claim 1 wherein the composition comprises fibers available as the by product of agricultural production.
30. The composition of claim 1 wherein the wax emulsion comprises paraffin or microcrystalline wax.
31. The composition of claim 30 wherein the wax emulsion
comprises rosin.
32. The composition of claim 1 wherein the wax emulsion comprises
natural wax.
33. The composition of claim 1 wherein the wax emulsion comprises
hydrocarbon wax.
34. The composition of claim 1 wherein the fiber sizing agent forms a
coating on at least a portion of the surface of at least a portion of the
fibers to serve as an adhesion promoter, to protect the surface of the
fibers from damage, as an aid in handling, to add strength or stiffness to
the fiber, or to reduce absorbency.
35. The composition of claim 34 wherein the fiber sizing agent
comprises alkylketene dimer emulsion, alkenyl succinic anhydride,
styrene acrylate copolymer or alkylated melamine.
36. The composition of claim 1 further comprising a mold release
agent.
37. The composition of claim 36 wherein the mold release agent comprises magnesium strearate, talc, fats or oils.
38. The composition of claim 1 further comprising a coating.
39. The composition of claim 38 wherein the coating partially
permeates the matrix of the composition.
40. A composition for use in making biodegradable containers
comprising:
water;
starch;
an insolubilizing compound;
a protein or natural polymeric compound;
fibers;
a wax emulsion;
a fiber sizing agent; and
a mold release agent.
41. The composition of claim 40 wherein the starch comprises
preglatinized and native starch.
42. The composition of claim 41 wherein the pregelatinized starch is in a range from more than 0% to less than 30% by weight of the total starch in the composition.
43. The composition of claim 41 wherein the pregelatinized starch is in a range from more than 5% to less than 20%> by weight of the total starch in the composition.
44. The composition of claim 41 wherein the pregelatinized starch is
in a range from more than 7% to less than 15% by weight of the total
starch in the composition.
45. The composition of claim 40 wherein the insolubilizing
compound comprises an aqueous solution containing modified ethandial,
glyoxal-based reagents, ammonium zirconium carbonate, potassium
zirconium carbonate or polyamide-epichlorohydrine compounds.
46. The composition of claim 45 wherein the insolubilizing
compound is in a concentration less than 20% by weight of total starch
in the composition.
47. The composition of claim 45 wherein the insolubilizing
compound is in a concentration in a range from about 0.1% to about
20% by weight of the total starch in the composition.
48. The composition of claim 40 wherein the protein or natural
polymeric compound comprises casein and latex.
49. The composition of claim 48 wherein the latex is natural uncured latex.
50. The composition of claim 48 wherein the ratio of latex solids to casein solids is in a range between about 1 to 1 and about 2 to 1.
51. The composition of claim 48 wherein the ratio of latex solids to
casein solids is in a range between about 1.2 to 1 and about 1.8 to 1.
52. The composition of claim 48 wherein the ratio of latex solids to
casein solids is about 1.45 to 1.
53. The composition of claim 40 further comprising a protein to
improve the water resistant properties of the composition
54. The composition of claim 53 wherein said protein to improve the
water resistant properties of the composition comprises albumen, agar,
or gelatin.
55. The composition of claim 40 wherein the fibers comprise long,
medium, and short fibers.
56. The composition of claim 55 wherein the fibers comprise natural
fibrous materials.
57. The composition of claim 56 wherein the fibers have an average
fiber length less than about 2 mm.
58. The composition of claim 57 wherein the fibers have an average aspect ratio in the range of 5 : 1 to 25 : 1.
59. The composition of claim 40 comprising filler material.
60. The composition of claim 59 wherein the filler material is
organic.
61. The composition of claim 59 wherein the filler material
comprises calcium carbonate, silica, calcium sulfate hydrate, magnesium
silicate, micaceuous minerals, clay minerals, titanium dioxide or talc.
62. The composition of claim 59 wherein the filler material and/or
short fibers have a combined concentration less than 25% by dry weight
of the composition.
63. The composition of claim 59 wherein the filler material and/or
short fibers have a combined concentration less than 20% and greater
than 5% by dry weight of the composition.
64. The composition of claim 59 wherein the filler material and/or
short fibers have a combined concentration less than 20% and greater
than 10% by dry weight of the composition.
65. The composition of claim 40 wherein the fibers comprise fibers
from fast growing plants.
66. The composition of claim 40 wherein the composition comprises fibers available as the by product of agricultural production.
67. The composition of claim 40 wherein the wax emulsion comprises paraffin or microcrystalline wax.
68. The composition of claim 67 wherein the wax emulsion
comprises rosin.
69. The composition of claim 40 wherein the wax emulsion
comprises natural wax.
70. The composition of claim 40 wherein the wax emulsion
comprises hydrocarbon wax.
71. The composition of claim 40 wherein the fiber sizing agent forms
a coating on at least a portion of the surface of at least a portion of the
fibers to serve as an adhesion promoter, to protect the surface of the
fibers from damage, as an aid in handling, to add strength or stiffness to
the fiber, or to reduce absorbency.
72. The composition of claim 40 wherein the fiber sizing agent
comprises alkylketene dimer emulsion, alkenyl succinic anhydride,
styrene acrylate copolymer or alkylated melamine.
73. The composition of claim 40 wherein the mold release agent
comprises magnesium strearate, talc, fats or oils.
74. A composition for use in making biodegradable containers
comprising:
water; starch comprising preglatinized and native starch wherein the pregelatinized starch is in a range from more than 0% to less than 30%
by weight of the total starch in the composition;
an insolubilizing compound comprising an aqueous solution containing
modified ethandial, glyoxal-based reagents, ammonium zirconium
carbonate, potassium zirconium carbonate or polyamide-
epichlorohydrine compounds;
natural fibers; and
a fiber sizing agent forming a coating on the surface of at least a portion
of the fibers.
75. The composition of claim 74 wherein the pregelatinized starch is
in a range from more than 5% to less than 20% by weight of the total starch in the composition.
76. The composition of claim 74 wherein the pregelatinized starch is in a range from more than 7% to less than 15% by weight of the total starch in the composition.
77. The composition of claim 74 wherein the insolubilizing compound is in a concentration less than 20% by weight of starch in the composition.
78. The composition of claim 74 wherein the insolubilizing compound is in a concentration in a range from about 0.1% to about
20% by weight of the total starch in the composition.
79. The composition of claim 74 further comprising a protein or
natural polymeric compound wherein the protein or natural polymeric
compound comprises casein and latex.
80. The composition of claim 79 wherein the latex is natural uncured
latex.
81. The composition of claim 80 wherein the ratio of latex solids to
casein solids is in a range between about 1 to 1 and about 2 to 1.
82. The composition of claim 80 wherein the ratio of latex solids to
casein solids is in a range between about 1.2 to 1 and about 1.8 to 1.
83. The composition of claim 80 wherein the ratio of latex solids to
casein solids is about 1.45 to 1.
84. The composition of claim 74 further comprising a wax emulsion.
85. The composition of claim 84 wherein the wax emulsion comprises paraffin or microcrystalline wax.
86. The composition of claim 84 wherein the wax emulsion comprises rosin.
87. The composition of claim 84 wherein the wax emulsion comprises natural wax.
88. The composition of claim 84 wherein the wax emulsion
comprises hydrocarbon wax.
89. The composition of claim 74 wherein the fibers comprise long,
medium, and short fibers.
90. The composition of claim 74 wherein the fibers have an average
fiber length less than about 2 mm.
91. The composition of claim 90 wherein the fibers have an average
aspect ratio in the range of 5 : 1 to 25 : 1.
92. The composition of claim 74 further comprising a mold release
agent comprising magnesium strearate, talc, fats or oils.
93. The composition of claim 74 wherein the fiber sizing agent
comprises alkylketene dimer emulsion, alkenyl succinic anhydride,
styrene acrylate copolymer or alkylated melamine..
94. The composition of claim 74 further comprising filler material.
95. The composition of claim 94 wherein the filler material is
organic.
96. The composition of claim 94 wherein the filler material comprises calcium carbonate, silica, calcium sulfate hydrate, magnesium silicate, micaceuous minerals, clay minerals, titanium dioxide or talc.
97. The composition of claim 94 wherein filler material and/or short
fibers have a combined concentration less than 25% by dry weight of the
composition.
98. The composition of claim 94 wherein the filler material and/or
short fibers have a combined concentration less than 20%> and greater
than 5% by dry weight of the composition.
99. The composition of claim 94 wherein filler material and/or short
fibers have a combined concentration less than 20% and greater than
10% by dry weight of the composition.
PCT/US2004/027824 2003-08-27 2004-08-26 Composition for use in biodegradable articles and method of use WO2005021633A2 (en)

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MXPA06002193A MXPA06002193A (en) 2003-08-27 2004-08-26 Composition for use in biodegradable articles and method of use.
KR1020067003856A KR101205119B1 (en) 2003-08-27 2004-08-26 Composition for use in biodegradable articles and method of use
EP04782322A EP1658328A4 (en) 2003-08-27 2004-08-26 Composition for use in biodegradable articles and method of use
AU2004269027A AU2004269027A1 (en) 2003-08-27 2004-08-26 Composition for use in biodegradable articles and method of use
CA2536311A CA2536311C (en) 2003-08-27 2004-08-26 Composition for use in biodegradable articles and method of use
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JP2007517919A (en) 2007-07-05
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US7553363B2 (en) 2009-06-30
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AU2004269027A1 (en) 2005-03-10
CA2536311C (en) 2013-11-12
KR101205119B1 (en) 2012-11-26
WO2005021633A3 (en) 2008-10-30
EP1658328A2 (en) 2006-05-24
TW200513214A (en) 2005-04-16
US20050089606A1 (en) 2005-04-28
KR20060119888A (en) 2006-11-24
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