Title of Invention

FIBROUS SHEET COATED WITH BIODEGRADABLE COMPOSITION AND ITS USE AS FOOD WRAP

Abstract There is disclosed an article of manufacture that is adapted for use as a food wrap that is both resistant to liquids and biodegradable, comprising a fibrous sheet comprised of tissue paper having a weight of up to 60 lb/3000 ft2, at least a portion of the fibrous sheet being coated or impregnated with a biodegradable composition that renders the fibrous sheet more resistant to liquids and that yields an article that is adapted for use as food wrap such that is is sufficiently thin and flexible so as to be easily wrapped around a food item and that possesses sufficient dead-fold that it will remain wrapped around the food item absent application of an external force, the biodegradable composition comprising at least one soft thermoplastic biodegradable polymer having a glass transition temperature less than 0°C; and at least one stiff thermoplastic biodegradable polymer having a glass transition temperature of at least 10°C.
Full Text FIBROUS SHEET COATED WITH BIODEGRADABLE COMPOSITION
AND ITS USE AS FOOD WRAP
BACKGROUND OF THE INVENTION
1. The Field of the Invention
The present inven ion relates generally to biodegradable polymers or polymer
blends and sheets manufactured therefrom. More particularly, the present invention
relates to fibrous sheets that are coated or impregnated with biodegradable polymers or
blends that render the sheets more resistant to liquids. The resulting sheets are suitable
for a number of applications, such as disposable wraps, bags, pouches or other packaging
materials.
2. The Relevant Technology
As affluence grows, so does the ability to purchase and accumulate more things.
Never before in the history of the world has there been such a large number of people
with such tremendous buying power. The ability to purchase relatively inexpensive
goods, such as books, tools, toys and food, is a luxury enjoyed by virtually all levels of
society, even those considered to be at the poorer end of the spectrum. Because a large
percentage of what is purohased is prepackaged, there has been a tremendous increase in
the amount of disposable packaging materials that are routinely discarded into the
environment as solid waste. Thus, as society becomes more affluent, it generates more
disposable trash.
Some packaging materials are only intended for a single use, such as boxes,
cartons, pouches, bags and wraps used to package items purchased from wholesale and
retail outlets. Even the advent of computers and "paperless" transactions has not
stemmed the rising tide of packaging wastes. Indeed, the onset of "e-commerce" has
spawned a great mail-order fad, thus creating a whole new market of individually
packaged and shipped items.
Moreover, the modern, fast-paced lifestyle has greatly disrupted traditional eating
routines in which people prepared their own meals and sat down as a family or group.
Instead, people grab food on the run, thus creating ever-increasing amounts of fast-food
packaging materials that are used once and then discarded. In view of the high volume of
disposable packaging materials being generated, some countries, particularly those in
Europe, have mandated either the recycling of fast food generated wastes or the use of

packaging materials which are "biodegradable" or "compostable". Environmental
activists commonly pressure companies that generate solid waste to find more
environmentally friendly alternatives. There is therefore an ever-present need to develop
biodegradable alternatives to nonbiodegradable packaging materials.
Paper, paperboard and other fibrous sheets made from natural cellulose-based
fibers are biodegradable. However, fibrous sheets tend to be porous. As a result, they do
not provide good barriers against water, oil or other liquids. When fibrous sheets are used
in applications where they will be exposed to liquids, they must generally be treated with
a liquid-resistant material, such as paraffin wax or plastic. By doing so, however, the
fibrous sheets are no longer biodegradable, but are as resistant to degradation as plastic or
paraffin wax.
In view of the foregoing, it would be an advancement in the art to provide fibrous
sheets that were resistant to liquids and that were biodegradable. In addition or
alternatively, it would be a further advancement in the packaging art to provide improved
fibrous sheets that were not only resistant to liquids, but still had good breathability and
water vapor transmission compared to conventional fibrous sheets treated with wax or
plastic.
SUMMARY OF THE INVENTION
The invention encompasses fibrous sheets that are coated or impregnated with
biodegradable polymers or polymer blends in order to yield sheets that are more resistant
to liquids (generally "treated sheets" or 'treated fibrous sheets"). The treated sheets can
be used to manufacture a wiere variety of articles of manufacture, including packaging
materials, such as wraps, bags, pouches., cartons, jugs, cups, plates, bowls, trays, platters,
lids, straws, and the like.
Exemplary fibrous sheets that may be treated with biodegradable polymers
include, but are not limited to, tissue papers, paper sheets, felts, paperboard, wovens and
nonwovens. In one aspect of the invention, fibrous sheets are coated or impregnated with
a biodegradable polymer blend comprising at least one thermoplastic biodegradable
polymer having relatively high stiffness and at least one thermoplastic biodegradable
polymer having relatively high flexibility. Thus, the present invention provides blends
that possess or demonstrate surprising syrergistic effects that are particularly well-suited
by use in treating fibrous sheets
For example, blends containing a relatively stiff BIOMAX polymer, a modified
polyethylene terephthalate (PBT) sold by DuPont, and a relatively soft or flexible

polymer ECOFLEX, an aliphaic-aromatic copolymer sold by BASF, and/or EASTAR
BIO, an aliphatic-aromatic copolymer sold by Eastman Chemical, have been shown to
have strength and elongation properties which are superior to either biopolymer taken
alone. Other stiff biopolymer:; include; BAK, a polyesteramide sold by Bayer, and
polylactic acid (PLA).
BIOMAX is characterized as having a relatively high glass transition temperature
and is highly crystalline at roo: n temperature. BIOMAX tends to be quite stiff or brittle
when formed into films or sheets. It also has poor elongation or elasticity. ECOFLEX
and EASTAR BIO, on the other hand, are characterized as having relatively low glass
transition temperatures and are relatively amorphous or noncrystalline at room
temperature, all of which contribute to the high softness, elasticity and high elongation.
Even so, various blends of BIOMAX and ECOFLEX and/or EASTAR BIO actually
exhibit higher elongation than ECOFLSX by itself, as well as higher break stress
compared to either BIOMAX or ECOFLEX by themselves.
Other polymer blends that can be used to treat fibrous sheets include, but are not
limited to, a blend of ECOFLEX, PLA and thermoplastic starch (TPS) and a blend of
BAK (a polyesteramide manufactured by Bayer Corporation) and TPS. In each case,
blending a biopolymer havirg a relatively low glass transition temperature with a
biopolymer having a relatively high glass transition temperature results in a polymer
blend that exhibits the desired characteristics of each polymer by itself. In some cases,
the blends exhibit better properties, while diminishing or minimizing the negative
properties of each biopolymer by itself.
In general, biodegradable polymers that may be characterized as being relatively
"stiff or less flexible include polymers tliat have a glass transition temperature of at least
about 10°C. Conversely, biodegradable: polymers that may be characterized as being
relatively '"soft" include polymers that have a glass transition temperature less than about
0°C. "Stiff biodegradable polymers preferably have a glass transition temperature of at
least about 15°C, more preferably at least about 25°C, and most preferably at least about
35°C. "'Soft" biodegradable polymers preferably have a glass transition temperature of
less than about -4°C, more preferably less than about-10°C, more especially preferably
less than about -20°C, and most preferably less than about -30°C. In addition, "stiff
polymers tend to be more crystalline, while "soft" polymers are generally less crystalline
and more amorphous, particularly at room temperature.

When a blend of soft and stiff biodegradable polymers is used to coat or
impregnate a fibrous sheet, the relatively stiff biodegradable polymer may have a
concentration in a range of about 20% to about 99% by weight of the blend of
biodegradable polymers exclusive of the fibrous sheet and any fillers. The stiff
biodegradable polymer preferably has a concentration of at least about 30% by weight of
the polymer blend, more preferably at least about 40% by weight of the polymer blend,
more especially preferably greater than, but not including, 50% by weight of the polymer
blend, and most preferably greater man about 55% by weight of the polymer blend.
When a blend of soft and stiff biodegradable polymers is used to coat or
impregnate a fibrous sheet, the relatively soft biodegradable polymer may have a
concentration in a range oi about 1% to about 80% by weight of the blend of
biodegradable polymers. The soft biodegradable polymer preferably has a concentration
up to about 70% by weight of the polymer blend, more preferably up to about 60% by
weight of the polymer blend, more especially preferably less than, but not including, 50%
by weight of the polymer blend, and most preferably up to about 45% by weight of the
polymer blend.
Biodegradable polymers used to treat fibrous sheets within the scope of the
present invention include, bu: are not limited to, synthetic polyesters, semi-synthetic
polyesters made by fermentation (e.g., PHB and PHBV), polyesteramides,
polycarbonates, and polyester urethanes. It is also within the scope of the invention to
optionally include a variety oi natural polymers and their derivatives, such as polymers
comprising or derived from starch, cellulose, other polysaccharides and proteins. A
single biodegradable polymer blended with an inorganic filler (e.g., silica or calcium
carbonate) may also be used to treat a fibrous sheet in order to yield a treated sheet that is
more heat resistant.
It is within the scope of the invention to incorporate inorganic and organic fillers
in order to decrease self-adhesi on, lower the cost, and increase the modulus of elasticity
(Young's modulus) of biodegradable polymers used to treat fibrous sheets as well as the
resulting sheets. Examples cf inorganic fillers include calcium carbonate, titanium
dioxide, silica, aluminum oxide talc, mica, and the like. Examples of organic fillers
include wood flour, ground seeds, cellulose particles, polymeric particles, ungelatinized
starch granules, and the like. In addition, plasticizers may be used to impart desired
softening and elongation properties.

In the case of fibrous sheets intended to be used as "wraps", such as wraps used to
enclose meats, other perishable food items, and especially fast food items (e.g.,
sandwiches, burgers and desse:t items), it may be desirable to provide wraps having good
"dead-fold" properties so that once folded, wrapped or otherwise manipulated into a
desired orientation, such wrape will tend to substantially maintain their orientation so as
to not spontaneously unfold or unwrap, as occurs with a large number of plastic sheets
and films (e.g., polyethylene). Dead-fold is a measure of the ability of a sheet or film to
retain a crease, crinkle or other bend. It is measured independently of self cling, heat
sealing, or the use of an adhesive to maintain a desired orientation.
Whereas the fibrous sheets themselves may impart or inherently possess dead-fold
properties, polymers and poiylner blends used to treat fibrous sheets may be engineered
so as to have a relatively high Young's modulus, preferably at least about 100 MPa, more
preferably at least about 150 MPa, and most preferably at least about 200 MPa. In
general, increasing the concentration of the stiff biopolymer will tend to increase the
Young's modulus and the resulting dead-fold properties. It should be understood,
however, that Young's modulus only Loosely correlates to dead-fold and does not, in
every case, serve to define or predict the dead-fold properties of a sheet or film formed
from a polymer or polymer blead.
Including particulate fillers within the polymer or polymer blend used to coat or
impregnate a fibrous sheet is another way to increase dead-fold of the resulting sheet.
When used to increase dead-feId, particulate fillers are typically included in an amount of
at least about 5% by weight of the polymer or polymer blend, preferably at least about
10% by weight, more preferably at least about 15% by weight, more especially preferably
at least about 20% by weight, and most preferably at least about 30% by weight of the
polymer or polymer blend usee to treat a. fibrous sheet.
Yet another way to increase dead-fold is to increase the surface area, or "bulk
hand feel", of treated sheets according to the invention. This may be accomplished, for
example, by disrupting the generally smooth, planar nature of the treated sheet, e.g., by
embossing, crimping, quilting or otherwise texturing the sheet so as to have regularly
spaced-apart or random hills md valleys rather than simply being a perfectly smooth,
planar sheet. A treated sheet may be textured, for example, by passing the sheet through
a pair of knurled or other embossing-type rollers. Such texturing increases the ability of a
treated sheet to take and mainain a fold, thus improving the dead-fold properties of the
sheet.

The surface area of a treated sheet may also be increased by incorporating
particulate fillers within the polymer or polymer blend used to coat or impregnate the
fibrous sheet in order form surface irregularities within the surface of the treated sheet.
This may be accomplished, for example, by incorporating filler particles, at least a portion
of which, have a particle size diameter equal to or greater than the thickness of the
polymer or polymer blend one or both sides of the treated sheet.
When used to wrap foods, or whenever good dead-fold properties are desired,
treated sheets according to the invention can be engineered so as to have a dead-fold of at
least about 50% (i.e., when creased using a standard dead-fold test, the sheets and films
will maintain at least about 50% of their original crease). Preferably, the treated sheets
will have a dead-fold of at least about 60%, more preferably at least about 70%, more
especially preferably at least about 80%. and most especially preferably at least about
90%. Treated fibrous sheets according to the invention can have dead-fold approaching
or equal to 100% (i.e., when folded such sheets remain folded absent the application of an
external force sufficient to reverse the fold). By way of comparison, sheets and films
made from polyethylene (e.g., for use in making sandwich or garbage bags) typically
have a dead-fold of 0%.
In some cases, it may be desirable for treated sheets according to the invention to
"breath". As set forth above, particulate fillers, both organic and inorganic, can be used
to increase the modulus of elasticity and/or dead-fold. Such fillers can also
advantageously create "cavitaton" whenever sheets or films used to coat or impregnate
fibrous sheets are stretched dufing processing. Cavitation occurs as the thermoplastic
polymer fraction is pulled in either a monoaxial or biaxial direction and the filler particles
create a discontinuity in the flim or sheet that increases in size during stretching. In
essence, a portion of the stretched polymer pulls away from the filler particles, resulting
in tiny cavities in the vicinity of the filler particles. This, in turn, results in greatly
increased breathability and vap or transmission of the sheets and films. The ability of
inorganic filler particles to create cavitation increases as the particle size diameter
approaches or exceeds the thickness of the polymer or polymer blend.
Another advantage of utilizing biodegradable polymers to treat fibrous sheets is
that biopolymers are generally able to accept and retain print much more easily than
conventionai plastics or waxes nsed to treat papers. Many plastics and waxes are highly
hydrophobic and must be surface oxidized in order to provide a chemically receptive
surface to which ink can adhere. Biodegradable polymers, on the other hand, typically


include a significant fraction of oxygen-containing moieties, such as ester, amide and/or
urethane groups, to which inks can more readily adhere.
The treated sheets according to the invention may comprise single or multiple
layers as desired. The fibrous sheets can be impregnated or coated on one or both sides,
or any portion thereof. Multiple fibrous sheets can be joined or sandwiched together with
one or more layers of biodegradable polymers, and optionally one or more auxiliary
sheets (e.g., metals foils). Fibrous sheets may be coated or impregnated by film blowing,
co-extrusion, casting, and coating techniques known in the art. In one embodiment, a
thermoplastic biodegradable composition is heated to a molten state and then spread over
a fibrous sheet using a doctor blade. In another embodiment, the thermoplastic
biodegradable composition is sprayed onto the fibrous sheet. Thermoplastic
biodegradable polymers used to treat fibrous sheets result in treated sheets that can be
heat sealed to join two ends together to form sacks, pockets, pouches, and the like. They
can be laminated onto existing sheets or substrates.
Notwithstanding the advantages of using biodegradable polymers and polymer
blends compared to polyethylene or other non-biodegradable polymers, biodegradable
polymers tend to have a n.uch lower melt flow index (MFI) compared to non-
biodegradable polymers such as polyethylene, which makes biodegradable polymers
more difficult to spread or spray onto a fibrous sheet. It may therefore be advantageous
to incorporate one or more of water, solvent, or plasticizer, and/or increase the
temperature of the biodegradable polymer or polymer blend well above its softening
temperature or range, but without burning or otherwise harming it, to increase its MFI so
as to facilitate the coating or impregnating process.
In one preferred embodiment, 4-5 lb/1000 ft2 (12-15 1b/3000 ft2) tissue paper is
treated with a biodegradable polymer blond to render it more resistant to penetration by
liquids. Of course, it is certainly within the scope of the invention to utilize any weight
paper or tissue paper, e.g., tissue paper ranging in weight from 8 lb/3000 ft2 up to 60
1b/3000 ft2. One of the benefits of coating or impregnating a fibrous sheet with a
biodegradable polymer or polymer blend, as compared to simply making a sheet or film
from the polymer blend itself, s that the: fibrous sheet core increases the thermal stability
of the resulting article of manufacture. This is beneficial in the case of wraps because
increasing the thermal stability increases their ability to be microwaved without
degrading or melting onto the food that is wrapped therein.

5 Increasing the amount of inorganic fillers within the biodegradable polymer or
polymer blend used to coat or impregnate a fibrous sheet also increases the
microwaveability of the resitting wraps. Providing biodegradable polymer wraps that are
microwaveable is an improvement over wraps made using polyethylene, which are
neither biodegradable nor microwave safe.
10 These and other advantages and features of the present invention will become
more fully apparent from the following description and appended claims, or may be
learned by the practice of the invention as set forth hereinafter.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
In order that the manner in which the above-recited and other advantages and
15 objects of the invention are obtained, a more particular description of the invention briefly
described above will be rendered by reference to a specific embodiment thereof which is
illustrated in the appended drawings. Understanding that these drawings depict only a
typical embodiment of the invention and are not therefore to be considered to be limiting
of its scope, the invention will be described and explained with additional specificity and
20 detail through the use of the accompanying drawings, in which:
Figure 1 is a plot of the percent elongation at break versus the applied strain rate
for various neat and blended polymer films;
Figure 2 is a plot o:the percent elongation of various neat polymer and blended
polymer films versus the concentration of ECOFLEX within the films at a fixed strain
25 rate of 500 mm/min.;
Figure 3 is a plot of the percent elongation of various neat polymer and blended
polymer films versus the concentration of ECOFLEX within the films at a fixed strain
rate of 1000 mm/min.;
Figure 4 is a plot of the break stress versus the applied strain rate for various neat
30 and blended polymer films;
Figure 5 is a plot of the break stress of various neat polymer and blended polymer
films versus the concentration of ECOFLEX within the films at a fixed strain rate of
500 mm/min.;
Figure 6 is a plot of the break stress of various neat polymer and blended polymer
35 films versus the concentraiion of ECOFLEX within the films at a fixed strain rate of
1000 mm/min.;
Figure 7 is a plot of the Water Vapor Permeability Coefficients (WVPC) of
various neat polymer and blended polymer films as a function of the concentration of

ECOFLEX within the films, and an estimated trend line based on the lowest measured
WVPC for a neat ECOFLEX film of 7.79 x 10-3 g.cm/m2/d/mm Hg;
Figure 8 is a plot of the Water Vapor Permeability Coefficients (WVPC) of
various neat polymer and blended polymer films as a function of the concentration of
ECOFLEX within the films, and an estimated trend line based on the highest measured
WVPC for a neat ECOFLEX film of 42 x 10-3 g.cm/m2/d/mm Hg; and
Figure 9 is a plot of the modulus of various neat polymer and blended polymer
films versus the concentration of ECOFLEX within the films.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
I. INTRODUCTION
The invention relates to fibrous sheets that are coated or impregnated with
inventive biodegradable polymers or polymer blends. The treated fibrous sheets
according to the invention are in many ways superior to conventional plastics that suffer
from their inability to degrade when discarded into the environment, that are not readily
printable absent special treatment, and that generally have poor dead-fold properties. The
treated sheets can be engineered to have improved strength, flexibility, elongation,
temperature stability, microwaveability, processability, and dead-fold.
In one aspect of the invention, a biodegradable polymer blend used to treat fibrous
sheets includes at least one biopolymer having relatively high stiffness and at least one
biopolymer having relatively nigh flexibility. When blended together, it is possible to
derive the beneficial properties from each polymer while offsetting or eliminating the
negative properties of each polymer when used separately.
In another aspect of the invention, one or more biodegradable polymers used to
coat a fibrous sheet are blended with a significant quantity of an inorganic filler in order
to greatly increase the heat stability of the resulting treated sheet. Fibrous sheets
themselves tend to have greater heat stability compared to sheets and films formed using
biodegradable polymers. Adding an inorganic filler to the biodegradable polymer or
polymer blend (e.g., in a concentration of at least about 30% by weight of the
biodegradable polymer composition used to coat or impregnate the fibrous sheet) further
increases the heat stability of treated sheets according to the invention. In the case of
wraps used to protect food, such wraps can better withstand hot foods and being
microwaved.

The treated sheets according to the invention are suitable for use as packaging
materials, such as wraps, bags, pouches, coverings, laminate coatings, cartons, jugs, cups,
plates, bowls, trays, platters, lids, straws, and the like.
Biodegradable polymers that may be used to treat fibrous sheets according to the
present invention include, but are not limited to, synthetic polyesters, naturally derived
polyesters, polyester amides, polycarbonates, and polyester urethanes, but may also
include a variety of natural polymers and their derivatives, such as polymers and
derivatives of starch, cellulose, other polysaccharides, and proteins. Particulate fillers,
both organic and inorganic, n ay be incorporated into the polymers used to treat fibrous
sheets to improve the dead-fold properties, increase bulk hand feel, create cavitation,
reduce cost, and/or decrease self-adhesion of the treated sheets. Plasticizers may be
added to impart desired softer ing and elongation properties. Treated fibrous sheets may
optionally be embossed, crimped, quilted or otherwise textured to improve bulk hand feel
and dead-fold. The biopolymers and biopolymer blends according to the invention more
readily accept and retain print compared to conventional plastics or waxed papers because
they typically include oxygen-containing moieties, such as ester, amide, or urethane
groups, to which inks can readily adhere.
The terms "sheets" and "films" are to be understood as having their customary
meanings as used in the thermoplastic and packaging arts Nevertheless, because the
distinction between what constitutes a "sheet" and what constitutes a "film" largely turns
on the thickness of the article of manufacture; the distinction is somewhat arbitrary (i.e.
some articles may constitute both sheets and films). Because the biodegradable
compositions according to tht invention can be used to manufacture a wide variety of
articles of manufacture, including articles useful to wrap, package or otherwise package
food or other solid substrates, including sheets and films having a wide variety of
thicknesses (both measured and calculated), it is not the intention of this disclosure to
precisely distinguish, in all cases, between what may arguably constitute a "sheet" versus
articles that may arguably constitute a "film". Therefore, when the present disclosure
refers to "sheets and films" and "sheets or films", the intention is to designate the entire
universe of articles of manufacture that may arguably constitute "sheets", "films" or both.
The terms "polymer b end" and "biodegradable polymer composition" includes
two or more unfilled polymers and/or one or more polymers into which one or more types
of solid fillers have been addec.

The term "microwaveable" refers to biodegradable polymer compositions and
treated sheets that can be placed together with food into a microwave oven and
microwaved so as to heat the food without the composition melting or otherwise
transferring from the treated sheet onto the food.
II. TREATED SHEETS
Treated sheets according to the invention include any fibrous sheet that has been
coated or impregnated with a biodegradable polymer blend to render the fibrous sheet
more resistant to liquids, such as water, oils or solvents. Specific examples of fibrous
sheets and biodegradable polymer blends that may be used to manufacture treated sheets
within the scope of the invention will now be discussed in greater detail.
A. Fibrous Sheets
It is within the scope of the invention to coat or impregnate various fibrous sheets
known in the art. Examples include a wide variety of tissue papers, ordinary paper,
paperboard, felts, wovens and nonwovens. In one embodiment:, the fibrous sheet
comprises a 12-15 lb/3000 fr tissue paper. Coating or impregnating 12-15 lb/3000 ft2
tissue paper yields treated sheets that ars especially suitable for use as food wraps. It will
be appreciated that it is within the scope of the invention to treat tissue papers and papers
having a wide range of possible weights, e.g., from 8 lb/3000 ft2 to 60 lb/3000 ft2.
B. Biodegradable Polymers,
Biodegradable polymers that may be used within the scope of the present
invention to coat or impregna te fibrous sheets include those which degrade through the
action of living organisms, light, air, water and combinations of the foregoing. Such
polymers include a range of synthetic polymers, such as polyesters, polyester amides,
polycarbonates and the like. Naturally-derived semi-synthetic polyesters (e.g. from
fermentation) can also be use. Biodegradation reactions are typically enzyme-catalyzed
and generally occur in the presence of moisture. Natural macromolecules containing
hydrolyzable linkages, such as protein, cellulose and starch, are generally susceptible to
biodegradation by the hydrolytic enzymes of microorganisms. A few man-made
polymers, however, are also biodegradable. The hydrophilic/hydrophobic character of
polymers greatly affects their biodegradability, with more polar polymers being more
readily biodegradable as a general rule. Other characteristics that affect polymer
biodegradability include crystallinity, chain flexibility and chain length.
Besides being able to biodegrade., it is often important for a polymer or polymer
blend to exhibit certain physical properties, such as stiffness, flexibility, water-resistance,

oil-resistance, solvent resistance, strength, elongation, temperature stability, moisture
vapor transmission, gas permeability, and/or dead-fold. The intended application of a
particular treated fibrous sheet will often dictate which properties are necessary in order
for a particular polymer, polymer blend, or treated sheet manufactured therefrom to
exhibit the desired performance criteria. When used to form treated sheets suitable for
use as packaging materials, desired performance criteria may include elongation, dead-
fold, strength, printability, imperviousness to liquids, breathability, temperature stability,
and the like.
Because of the limited number of biodegradable polymers, it is often difficult, or
even impossible, to identify one single: polymer or copolymer which meets all, or even
most, of the desired performance criteria for a given application. This is particularly true
in the area of packaging materials. Polymers that have a high glass transition temperature
(Tg) are often difficult, if not mpossible, to blow or cast into films on a mass scale. On
the other hand, polymers that nave a very low glass transition temperature typically have
relatively low softening and/or melting points, which makes them difficult to mass
produce into sheets and films without the tendency of blocking, or self adhesion.
Moreover, such sheets and films may lack adequate strength, water vapor barrier
properties, high temperature stability, and/or modulus to be suitable for certain
applications, such as in the ma mfacture of wraps or laminates coatings.
In one aspect of the ir vention, it has been discovered that compositions suitable
for coating or impregnating :ibrous sheets can be obtained by blending one or more
"stiff", or high glass transition temperature, polymers with one or more "soft", or low
glass transition temperature, polymers. In another aspect of the invention, polymers or
polymer blends can be filled with particulate fillers, and/or treated sheets or films made
therefrom can be textured, in oder to yield sheets having improved dead-fold properties.
Notwithstanding the benefits that can be derived from using a blend of stiff and
soft polymers, particularly when extruding or blowing films or sheets used to coat fibrous
sheets, it will be appreciated that there are coating methods that do not require the
formation of an extruded or blown film or sheet, such as spreading using a doctor blade or
spray coating. In such cases, it may not be necessary to use a polymer blend. It may be
desirable, however, to use water, a solvent, or plasticizer to increase the MFI to facilitate
the coating or impregnation process. It may be desirable to incorporate a significant
quantity of an inorganic fille (e.g. silica or limestone) in order to increase the heat

stability of the resulting treated sheet, In the case of a food wrap, increasing the heat
stability increases the microwaveability of the treated sheet.
1. Stiff Polymers.
Even though the use of terms such as "stiff" and "soft" polymers may be
somewhat arbitrary, such classifications are useful when determining which polymers to
blend together in order to obtain a polymer blend having the desired performance criteria.
In general, those polymers that may be characterized as being relatively "stiff', or less
flexible, typically include polymers which have a glass transition temperature of at least
about 10°C. Stiff polymers will preferably have a glass transition temperature of at least
about 15°C, more preferably at least about 25°C, and most preferably at least about
35°C. The foregoing temperatures attempt to take into consideration the fact that the
"glass transition temperature" is not always a discreet temperature but is often a range of
temperatures within which the polymer changes from being a glassy and more brittle
material to being a softer and more flexible material.
The glass transition temaperature should be distinguished from the melting point of
a polymer at or beyond which a thermoplastic polymer becomes plastic and deformable
without significant rupture. Although there is often a positive correlation between a
polymer's glass transition temperature (Tg) and its melting point (Tm), this is not strictly
the case with all polymers. In some cases the difference between Tg and Tmmay be large.
In other cases it may be relatively small. It is generally the case, however, that the
melting point of a stiffer polymer will typically be greater than the melting point of a
softer polymer.
Preferred "stiff polymlers include, but are not limited to, modified polyethylene
terephthalates (such as those manufactured by Du Pont), polyesteramides (such as those
manufactured by Bayer), polylactic acid-based polymers (such as those manufactured by
Cargill-Dow Polymers and Dianippon Ink), terpolymers based on polylactic acid,
polyglycolic acid and polyoaprolactone (such as those manufactured by Mitsui
Chemicals), polyalkylene carbonates (such as polyethylene carbonate manufactured by
PAC Polymers), and polyhydroxybutyrate (PHB).
A presently preferred stiff biopolymer includes a range of modified polyethylene
terephthalate (PET) polymers manufactured by DuPont, and sold under the trade name
BIOMAX. Various modified PET polymers of DuPont are described in greater detail in
U.S. Patent No. 5,053,482 to Tietz, U.S. Patent No. 5,097,004 to Gallagher et al., U.S.
Patent No. 5,097,005 to Tietz U.S. Patent No. 5,171,308 to Gallagher et al., U.S. Patent

No. 5,219,646, to Gallagher e;. al., and U.S. Patent No. 5,295,985 to Romesser et al. For
purposes of disclosing "stiff polymers, the foregoing patents are disclosed herein by
reference.
In general, the modified PET polymers of DuPont may be characterized as
comprising alternating units of a terephthalate constituent and an aliphatic constituent,
with the aliphatic constituent comprising a statistical distribution of two or more different
aliphatic units derived from two or more different diols, such as ethylene glycol,
diethylene glycol, triethylene oxide, polyethylene glycol, lower alkane diols, both
branched and unbranched, and derivatives of the foregoing. A portion of the aliphatic
units may also be derived from an aliphatic diacid, such as adipic acid. In addition, a
fraction of the phenylene groups within the repeating terephthalate units may be
sulfonated and neutralized with an alkali metal or alkaline earth metal base. Both the
aliphatic portion of the modified PET polymer as well as the statistically significant
quantity of sulfonated terephtlhalate units contribute significantly to the biodegradability
of the BIOMAX polymer.
Some BIOMAX gradf s of polymers have a melting point of 200-208°C and a
glass transition temperature of 40-60°C. BIOMAX 6926 is one such grade. It is a
relatively strong and stiff polymer that, when blended with a softer polymer, yields a
mixture that can readily be formed into sheets and films. In addition, or in the alternative,
one or more particulate fillers may be included in order to impart desired properties
described more fully herein.
In general, modified polyethylene terephthalates that would be expected to have
properties suitable for use as a "stiff biodegradable polymer consist essentially of
recurring structural units havin g the following general formula:
—[—C(O)—R- -C(O)—OGO—]a—[-C(O)-Q—O—] —
wherein up to about 40 mole % of R is selected from the group consisting of a
chemical bond and one or more divalent, non-aromatic, C1-C10 hydrocarbylene radicals,
and the remainder of R is at lee st about 85% mole % p-phenylene radical,
wherein G includes from 0 to about 30 mole % of a polyethylene ether radical
selected from the group consisting of:
—(CH2)2—O—(CH2)2— and — (CH2)2—O—(CH2)2—O—(CH2)2—
and the remainder of G is selected from the group consisting of polyalkylene ether
radicals of molecular weight at least about 250 (number average), and —(CH2)2—,

—(CH2)3—, and —(CH2)4— radicals,
wherein Q is derived from a hydroxy acid of the formula:
HO[—C(O)—Q—D—]xH
wherein x is an integer and such, hydroxy acids have a melting point at least 5°C.
below their decomposition temperature, and Q is selected from the group consisting of a
chemical bond and hydrocarbylene radicals —(CH2)n—, where n is an integer from 1 to
5, — C(R1)H—, and —C(R1)HOH2—. wherein R' is selected from the group consisting of
—CH3 and —CH2CH3, and wherein "d" and "b" are mole fractions of the polymer, and
the mole fraction "a" may be 0.6 to 1 and, correspondingly, mole fraction ub" may be 0 to
0.4, and wherein about 0.1 to about 15 mole %, preferably about 0.1 to about 2.5 mole %,
of the polymer contains alkali metal or alkaline earth metal sulfo groups, especially about
1.5 to about 2 mole % of such groups.
Another stiff biopolyrner that may be used in manufacturing polymer blends
according to the present invention includes polylactic acid (PLA). Polylactic acid
typically has a glass transition temperature of about 59°C. and a melting point of about
178°C PLA has low elongaton and is quite hard. It is a strong thermoplastic material
that can be injection molded, extruded, cast, thermoformed, or used as spun or melt-
blown fibers to produce nonwc ven goods.
Polymers based on or including PLA first found commercial application as
medical sutures in 1970. Higli polymers of lactic acid (Mn=50,000-l 10,000) are strong
thermoplastics that can be fabricated into useful products that can be broken down by
common soil bacteria. Potential applications of PLA include paper coatings for
packaging (food and beverage cartons), plastic foam for fast foods, microwavable
containers, and other consume r products such as disposable diapers or yard waste bags.
PLA can be a homopolymer or it may be copolymerized with glycolides, lactones or other
monomers. One particularly attractive feature of PLA-based polymers is that they are
derived from renewable agricu rural products.
Because lactic acid is difficult to polymerize directly to high polymers in a single
step on a commercial scale, most companies employ a two-step process. Lactic acid is
first oligomerized to a linean chain with a molecular weight of less than 3000 by
removing water. The oligome is then depolymerized to lactide, which is a cyclic dimer
consisting of two condensed lactic acid molecules. This six-member ring is purified and


subjected to ring opening polymerization to produce polylactic acid with a molecular
weight of 50,000-110,-000.
Because lactic acid has an asymmetric carbon atom, it exists in several isomeric
forms. The lactic acid most commonly sold commercially contains equal parts of L-(+)-
lactic acid and D-(-)-Iactic acid and is therefore optically inactive, with no rotatoiy power.
The racemic mixture is called DL-lactic acid.
Another stiff polymer fiat may be used within the inventive polymer blends is
known as CPLA, which is a derivative ofPLA and is sold by Dianippon Ink. Two classes
of CPLA are sold and are refeired to as "CPLA hard" and "CPLA soft", both of which
comprise "stiff polymers", as that term has been defined herein. CPLA hard has a glass
transition temperature of 60°C, while CPLA soft has a glass transition temperature of
5 PC.
Bayer corporation manufactures polyesteramides sold under the name BAK.
Polyester amides manufactured by Bayer are described more fully in U.S. Patent No.
5,644,020 to Timmermann et al For purposes of disclosing biodegradable polymers, at
least some of which constitute "stiff' polymers, the foregoing patent is incorporated
herein by reference. One form of BAK is prepared from adipic acid, 1,4-butanediol, and
6-aminocaproic acid. BAK 1(H5, a polyesteramide having an Mn of 22,700 and an Mw of
69,700 and which contains aromatic constituents, has a melting point of 125°C. BAK
2195 has a melting point of 175°C. Although the glass transition temperatures of BAK
1095 and BAK 2195 are difficult to measure, because BAK appears to behave like a stiff
polymer in the sense that improved properties may be obtained by blending BAK with a
soft polymer, the inventors believe that the glass transition temperature of BAK polymers
is essentially at least about 10 0C. For purposes of understanding the meaning and scope
of the specification and clains, polyestsr amides such as BAK, as well as others that
behave like BAK and can be ised as a "stiff' polymer, shall be deemed to have a glass
temperature of at least about 10°C.
Mitsui Chemicals, Inc. manufactures a terpolymer that includes units derived from
polylactide, polyglycolide and polycaprolactone that have been condensed together.
Thus, this polymer is an aliph itic polymer and may be characterized as a PLA/PGA/PCL
terpolymer. Three grade of :his polymer are available, H100J, S100 and T100. The
H100J grade PLA/PGA/PCL terpolymer has been analyzed to have a glass transition
temperatures of 74°C. and a rr elting point of 173°C.

PAC Polymers Inc. manufactures polyethylene carbonate (PEC) having a glass
transition temperature range of 10-28°C. PEC is a "stiff' polymer for purposes of the
present invention.
Polyhydroxybutyrates (FHBs) can act as either a stiff or soft polymer depending
on their molecular weight, whetlier they li£.ve been modified using chain extenders and/or
branching agents, whether the;' have been copolymerized with another polymer, and
depending on the other constituents with it. the overall thermoplastic composition. In this
sense, PHBs are unique amon;; biopolymers and may be of special interest for use in
making wraps, laminate coatings, packaging materials, and the like.
As discussed more fully below, native or dried gelatinized starch can be used as
particulate fillers in order to ircrease the dead-fold properties of sheets and films made
from a particular polymer or polymer blend. However, to the extent that starches become
thermoplastic but retain a substantially portion of their crystallinity, such starches may act
as "stiff, rather than "soft", pc lymers.
2. Soft Polymers.
In general, those biopolymers that may be characterized as being "soft", or less
rigid, typically include polymers which have a glass transition temperature of less than
about 0°C. Soft biopolymers within the scope of the invention will typically have a glass
transition temperature of less than about 0°C, preferably less than about -4Q(O, more
preferably less than about -100C, more especially preferably less than about -20°C, and
most preferably less than about -30°C. The foregoing temperatures attempt to take into
consideration the fact that the "glass transition temperatures" of "soft" polymers are not
always discreet temperatures but often comprise a range of temperatures.
Preferred "soft" biopolymers within the scope of the present invention include, but
are not limited to, aliphatic-aromatic copolyesters (such as those manufactured by BASF
and Eastman Chemical), aliphatic polyesters which include repeating units having at least
5 carbon atoms, e.g., polyhydroxyvalerate, polyhydroxybutyrate-hydroxyvalerate
copolymer and polycaprolactone (such as those manufactured by Daicel Chemical,
Monsanto, Solvay, and Union Carbide), and succinate-based aliphatic polymers, e.g.,
polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), and polyethylene
succinate (PES) (such as those manufactured by Showa High Polymer).
U.S. Patent Nos. 5,817,721, 5,863,991, 5,880,220, 5,889,135, 5,936,045,
6,018,004, 6,046,248, 6,111,(58, 6,114,042, 6,201,034, 6,258,924, 6,297,347, 6,303,677,
6,353,084, all to Warzelhan et. al., and assigned to BASF, disclose a range of aliphatic-

aromatic copolyesters within the scope of the invention, as do U.S. Patent No. 6,103,058
to Yamamoto et ai. and U.S. Patent No. (5,120,895 to Kowitz et al. Similarly, U.S. Patent
Nos. 5,292,783., 5,446,079, 6,559,171.. 5,580,911, 5,599,858 and 5,900,322, all to
Buchanan et al. and assigned tc Eastman Chemical, as well as U.S. Patent Nos. 6,020,393
and 6,922,829 to Khemani, also assigned to Eastman Chemical, disclose aliphatic-
aromatic copolyesters within the scope of the invention. For purposes of disclosing "soft"
polymers, the foregoing patents are incoiporated herein by reference.
A preferred "soft" polymer that may be used in the manufacture of polymer
blends includes aliphatic-aromatic copolyesters manufactured by BASF and sold under
the trade name ECOFLEX. The aliphatic-aromatic copolyesters manufactured by BASF
comprise a statistical copolyester derived from 1,4-butanedioi, adipic acid, and
dimethyiterephthalate (DMT). In some cases, a diisocyanate is used as a chain
iengthener. Branching agents may also be used to yield branched, rather than linear,
copolymers.
Copolyxnerization of aliphatic monomers, such as diols and diacids, with aromatic
monomers, such as diols and diacids (e.g., terephthalic acid or diester derivatives such as
DMT), is one way to improve the performance properties of aliphatic polyesters.
However, questions have been raised within the industry regarding the complete
biodegradability of aliphatic-atomatic copolyesters because aromatic copolyesters such as
PET are known to be resistant to microbial attack. Nevertheless, researchers have
discovered that aliphatic-aromatic copolyesters are indeed biodegradable and that the
biodegradability of these copolyesters is related to the length of the aromatic sequence.
Block copolyesters with relatively long Exomatic sequences are less rapidly degraded by
microorganisms compared to random copolyesters having more interrupted aromatic
sequences. Film thickness is also a factor, with thicker films degrading more slowly due
to their reduced surface to volume ratio than thinner films, al] things being equal. The
polymer presently sold under the name ECOFLEX S BX 7000 by BASF has a glass
transition temperature of-33°C. and a melting range of 105-115oC.
Another "soft" aliphatic-aromatic copolyester is manufactured by Eastman
Chemical Company and is sald under the trade name EASTAR. BIO. The aliphatic-
aromatic copolyester manufadured by Eastman is a random copolymer derived from 1,4-
butanediol, adipic acid, and dimethyiterephthalate (DMT). One particular grade of
EASTAR BIO, known as EASTAR BIO 14766, has a glass transition temperature of
-33°C and a melting point oi 112°C. I: has a tensile strength at break in the machine

direction of 19 MPa, an elongation at break of 600%, and a tensile modulus of elasticity
of 97 MPa (tangent). It has an Blmendorf tsar strength of 282 g.
Polycaprolactone (PCL) is a biodegradable aliphatic polyester having a relatively
low melting point and a very to v glass transition temperature. It is so named because it is
formed by polymerizing -caprolactone. The glass transition temperature of PCL is
-60°C. and the melting point is only 60°C. Because of this PCL and other similar
aliphatic polyesters with low melting points are difficult to process by conventional
techniques such as film blowing and blow molding. Films made from PCL are tacky as
extruded and have low melt strength over 130°C. Also, the slow crystallization of this
polymer causes the properties to change over time. Blending PCL with other polymers
improves the processability of PCL. One common PCL is TONE, manufactured by
Union Carbide. Other manufactures of PCL include Daicel Chemical, Ltd. and Solvay.
Though the use of PCL is certainly within the scope of the invention, it is currently a less
preferred soft biopolymer that aliphatic-aromatic polyesters, which give overall better
performance.
e-Caprolactone is a seven member ring compound that is characterized by its
reactivity. Cleavage usually takes placs at the carbonyl group. e-Caprolactone is
typically made from cyclohexanone by a peroxidation process. PCL is a polyester made
by polymerizing e-caprolactone. Higher molecular weight PCL may be prepared under
the influence of a wide variey of catalysts, such as aluminum alkyls, organometallic
compositions, such as Group I;, IIa, IIb, or IIIa metal alkyls, Grignard reagents, Group II
metal dialkyls, calcium or other metal amides or alkyl amides, reaction products of
alkaline earth hexamoniates, alkaline oxides and acetonitrile, aluminum trialkoxides,
alkaline earth aluminum or boron hydrides, alkaline metal or alkaline earth hydrides or
alkaline metals alone. PCL is typically prepared by initiation with an aliphatic diol (HO-
R-OH), which forms a terminal end group.
Another "soft" aliphatic polyester that may be used in manufacturing the inventive
polymer blends is polyhydroxybutyrate-hydroxyvalerate copolymer (PHBV), which is
manufactured using a microbial-induced fermentation process. One such PHBV
copolyester, manufactured by the Monsanto Company, has a glass transition temperature
of about 0°C. and a melting point of about 170°C. If possible, PHBV copolyesters should
be formulated and/or modified so as have a glass transition temperature less than about
-5°C.

In the fermentation process used to manufacture PHBV, a single bacterium
species converts corn and potato feed stocks into a copolymer of polyhydroxybutyrate
and hydroxyvalerate constituent;. By manipulating the feed stocks, the proportions of the
two polymer segments can be varied to make different grades of material. All grades are
moisture resistant while still being fully biodegradable. The world producers of PHBV
are Monsanto, with its BIOPOL., product, and METABOLIX, with its various grades of
polyhydroxy-alkanqates (PHAs). Polyhydroxyvalerate (PHV) is also an example of a
"soft" polymer.
As set forth above, polyhydroxybutyrates (PHBs) can act as either a stiff or soft
polymer depending on their molecular weight, whether they have been modified using
chain extenders and/or branch ,ng agents, whether they have been copolymerized with
another polymer, and depending on the other constituents within the overall thermoplastic
composition. In this sense, PFIBs are unique among biopolymers and may be of special
interest for use in making wrap laminate coatings, packaging materials, and the like.
Another class of "soft" aliphatic polyesters are based on repeating succinate units
such as polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), and
polyethylene succinate (PBS). Each of these succmate-based aliphatic polyesters are
manufactured by Showa High Polymer, Ltd. and are sold under the trade name
BIONELLE. PBS (Bionolle 001) has a glass transition temperature of-30°C. and a
melting point of 114°C. PBSA (Bionolle 3001) has a glass transition temperature of
-35°C. and a melting point of 95°C. PES (Bionolle 6000) has a glass transition
temperature of ~4°C. and a melting point of 102° .
The target applications for BIONOLLE include films, sheets, filaments, foam-
molded products and foam-expanded products. BIONOLLE is biodegradable in compost,
in moist soil, in water with act vated sludge, and in sea water. PBSA degrades rapidly in
a compost environment, so it s similar to cellulose, whereas PBS degrades less rapidly
and is similar to newspaper in terms of biodegradation.
BIONOLLE is manufactured according to a patented two-step process of
preparing succinate aliphatic polyesters with high molecular weights and useful physical
properties. In a first step, a low molecular weight hydroxy-terminated aliphatic polyester
prepolymer is made from a glycol and an aliphatic dicarboxylic acid. This
polymerization is catalyzed by a titanium catalyst such as tetraisopropyltitanate,
tetraisopropoxy titanium, dibutoxydiacetoacetoxy titanium, or tetrabutyltitanate. In the

second step, a high molecular weidght polyester is made by reacting a diisocyanate, such
as hexamethylene diisocyante (HMDI) with a polyester prepolymer.
Showa manufactures PBS by first reacting 1,4-butanediol with succinic acid in a
condensation reaction to form a p repolymer and then reacting the prepolymer with HMDI
as a chain extender.
PBSA copolymer is manufactured by first condensing 1,4-butanediol, succinic
acid and adipic acid to form a prepolymer and then reacting the prepolymer with HMDI
as a chain extender.
PES homopolymer is pre oared by reacting ethylene glycol and succinic acid and
using HMDI or diphenylmethane diisocyanate as a chain extender.
Succinate-based aliphatic polyesters are also manufactured by Mitsui Toatsu,
Nippon Shokubai, Cheil Synthetics, Eastman Chemical, and Sunkyon Industries.
Finally, although starch, such as modified starch or starch that has been
gelatinized with water and subsequently dried, is known to have a high glass transition
temperature (i.e., 70-85°C.) and be very crystalline at room temperature, certain forms of
starch in which the crystallinity 1 as been greatly reduced or destroyed altogether can have
very low glass transition temperatures and may, in fact, constitute "soft" biodegradable
polymers within the scope of the invention. As discussed more fully below, native or
dried gelatinized starch can be u; ;ed as particulate fillers in order to increase the dead-fold
properties of sheets and films made from a particular polymer or polymer blend.
Moreover, to the extent that starches become thermoplastic but retain a substantially
portion of their crystallinity, such starches may act as "stiff, rather than "soft", polymers.
Nevertheless, there exists a range of thermoplastic starch polymers that can behave as
"soft" polymers.
For example, U.S. Paten: No. 5,362,777 to Tomka is a landmark patent and was
the first attempt to manufactun what is known as thermoplastically processable starch
(TPS). TPS is characterized a: a thermoplastic starch polymer formed by mixing and
heating native or modified stareh in the presence of an appropriate high boiling plasticizer
(such as glycerin and sorbitol) in a manner such that the starch has little or no
crystallinity, a low glass transition temperature, and very low water (less than 5%,
preferably less than about 1% bv weight while in a melted state after venting and prior to
conditioning). When blended with appropriate hydrophobic polymers, such as the stiff
polymers disclosed herein, e.g., polyesteramides such as BAK, TPS can have a glass
transition temperature as low as -60°C, and typically below about -20°C.

Although it is within the : cope of the invention to include thermoplastic polymers
based on starch that include plas icizers such as glycerine, sorbitol, propylene glycol and
the like, it is preferable, when manufacturing packaging materials that will come into
contact with food products, to ut lize therraoplastic starch polymers that are made without
the use of such plasticizers, which can potentially diffuse into food. Preferred
thermoplastic starch polymers for use in making food wraps may advantageously utilize
the natural water content of naive starch granules to initially break down the granular
structure and melt the native starch. Thereafter, the melted starch can be blended with
one or more synthetic biopolyners, and the mixture dried by venting, in order to yield a
final polymer blend. Where is desired to make food wraps or other sheets or films
intended to contact food using a thermoplastic starch polymer made with a high boiling
liquid plasticizer, it will be preferable to limit the quantity of such thermoplastic starch
polymers to less than 10% by weight of the polymer mixture, exclusive of any solid
fillers.
C. OTHER COMPONENTS
There are a number of optional components which may be included within the
biodegradable polymer blends in order to impart desired properties. These include, but
are not limited to, plasticizers. lubricants., fillers, natural polymers and nonbiodegradable
polymers.
1. Plasticizers and Lubricants.
Plasticizers and lubncants may optionally be added in order to improve
processing, such as extrusion film blowing, spreading or spraying, or final mechanical
properties, particularly of polymer blends that are relatively stiff. A stiffer polymer blend
may be dictated by other performancs criteria, such as high temperature stability,
strength, lower elongation, higher dead-fold, resistance to "blocking" during and after
processing, and the like. In such cases, a plasticizer may allow the polymer blend to
satisfy certain processing and/or performance criteria.
In the case where a biodegradable polymer or polymer blend is spread or sprayed
onto a fibrous sheet, it may be advantageous to use a plasticizer to increase the melt flow
index (MFI) of the molten polymer or polymer blend. Increasing the MFI of a molten
polymer or polymer blend facilitates high speed coating. In general, when certain
biodegradable polymers are heated to above their softening point, they have an MFI
between about 2-10 g/10 mia. Increasing the MFI preferably to at least about 40 g/10
min., more preferably to at least about 70 g/10 min., and most preferably to at least about

100 g/10 min. greatly facilitates spreading or spraying a molten biodegradable polymer
blend.
Suitable plasticizers wthin the scope of the invention, particularly when
incorporated into a polymer blend that is intended to be used in the manufacture of wraps
and other packaging materials that will come into contact with food, will preferably be
safe if consumed, at least in smaller quantities.
Exemplary plasticizers that may be used in accordance with the present invention
include, but are not limited to, soybean oil, caster oil, TWEEN 20, TWEEN 40, TWEEN
60, TWEEN 80, TWEEN 85, sorbitan monolaurate, sorbitan monooleate, sorbitan
monopalmitate, sorbitan trioleat s, sorbitan monostearate, PEG, derivatives of PEG, N,N-
ethylene bis-stearamide, N,N-ethylene bis-oleamide, polymeric plasticizers such as
poly(l,6-hexamethylene adipate), and other compatible low molecular weight polymers.
Examples of lubricants include salts of fatty acids, an example of which is
magnesium stearate.
Volatile plasticizers that can be removed during or after the coating process, such
as water or volatile solvents, may be used to facilitate high speed coating. Examples of
volatile solvents that may be used, preferably by recovering and reusing such solvents,
include, but are not limited to, chloroform, methylene chloride, other chlorinated
hydrocarbons, ethyl alcohol, sopropyl alcohol, other alcohols, acetone, methyl ethyl
ketone, other ketones, and the like.
It has been found, for e cample, that including 200 ppm water increases the MFI of
a molten biodegradable polymer composition from 4 g/10 min. to about 40 g/10 min.
Whereas many of the biodegrmdable polymers described herein are "hydrophobic" in the
sense that they do not dissolve or degrade when exposed to water at room temperature,
they do contain polar moieties that greatly increase the affinity of such polymers for water
while heated to a molten state Thus, it is possible to blend some amount of water within
molten a biodegradable polyner that would otherwise be hydrophobic when cooled to
room temperature.
2. Solid Fillers.
Particulate fillers may optionally be added for a number of reasons, including but
not limited to, increasing the Young's modulus, dead-fold properties, rigidity,
breathability, thermal stability, microwaveability, and insulating ability, and for
decreasing the cost and tendency of the polymer blend to "block" or self-adhere during
processing. Other fillers, like fibers having a high aspect ratio, may increase the strength,

fracture energy and dead-fold properties of the sheets and films according to the
invention. In general, fillers within the scope of the invention will generally fall within
three classes or categories: (1) inorganic paniculate fillers, (2) fibers and (3) organic
fillers.
a. Inorganic Particulate Fillers
The terms "particle" or' particulate filler" should be broadly interpreted to include
filler particles having any of a variety of different shapes and aspect ratios. In general,
"particles" are those solids having an aspect ratio (i.e., the ratio of length to thickness) of
less than about 10:1. Solids heving an aspect ratio greater than about 10:1 may be better
understood as "fibers", as that tsrm will be defined and discussed hereinbelow.
Virtually any known filler, whether inert or reactive, can be incorporated into the
biodegradable polymer blends. In general, adding an inorganic filler will tend to reduce
the cost of the resulting polymer blend. If a relatively small amount of inorganic filler is
used, the effects on the properties of the final composition are minimized, while adding a
relatively large amount of inorganic filler will increase those effects. In those cases
where adding the inorganic filler will tend to detract from a critical physical parameter,
such as tensile strength or flexibility, only so much of the filler should be added in order
to reduce the cost of the res uiting composition, while retaining adequate mechanical
properties required by the in;ended use. However, in those cases where adding the
inorganic filler will improve one or more desired physical properties of a given
application, such as stiffness, compressive strength, dead-fold, heat resistance,
microwaveability, insulating ability, and/or breathability, it may be desirable to increase
the quantity of added filler in order to provide this desired property while also proving
greatly decreased cost.
It will be appreciated 1 hat one of ordinary skill in the art, using a microstructural
engineering approach, can self ct the types and amount of the various inorganic fillers that
may be included within the pc lymer blend in order to engineer a final material having the
desired properties while taking advantage of the cost-reducing properties of adding the
inorganic filler.
In general, in order to maximize the quantity of inorganic filler while minimizing
the deleterious mechanical effects of adding the filler as much as possible, it may be
advantageous to select filler p articles in a manner that decreases the specific surface area
of the particles. The specifie surface area is defined as the ratio of the total particle
surface area versus the total particle volume. One way to decrease the specific surface

area is to select particles that ha ve a more uniform surface geometry. The more jagged
and irregular the particle surface geometry, the greater will be the ratio of surface area to
volume of that particle. Another way to decrease the specific surface area is to increase
the particle size. In view of the advantages of decreasing the specific surface area of the
inorganic filler, it will be preferable to include inorganic filler particles having a specific
surface area in a range fiom about 0.1 m2/g to about 400 m2/g, more preferably in range
from about 0.15 m2/g to about 50 m2/g, and most preferably in a range from about 0.2
m2/g to about 2 m2/g.
Related to decreased specific surface area in improving the rheology and final
strength properties of the polymer blends of the present invention is the concept of
particle packing. Particle packing techniques allow for a reduction in "wasted" interstitial
space between particles while maintaining adequate particle lubrication and, hence,
mixture rheology, within the melted polymer blend, while also allowing for more efficient
use of the thermoplastic phase as a binder in the final hardened polymer blends of the
present invention. Simply stated, particle packing is the process of selecting one or more
ranges of particle sizes in order that the spaces between larger particles are substantially
occupied by a selected group c f smaller particles.
In order to optimize the packing density of the inorganic filler particles,
differently sized particles having sizes ranging from as small as about 0.01 micron to as
large as about 2 mm may be used. Of course, the thickness and other physical parameters
of the desired article to be manufactured from any given polymer blend may often dictate
the upper particle size limit, in general, the particle packing will be increased whenever
any given set of particles is m.xed with another set of particles having an average particle
size (i.e., width and/or length) that is at least about 2 times bigger or smaller than the
average particle size of the f rst group of particles. The particle packing density for a
two-particle system will be rr aximized whenever the size ratio of a given set of particles
is from about 3-10 times the size of another set of particles. Similarly, three or more
different sets of particles may be used to further increase the particle packing density.
The degree of packing; density that will be "optimal" will depend on a number of
factors including, but not imited to, the types and concentrations of the various
components within both the thermoplastic phase and the solid filler phase, the shaping
method that will be employed, and the desired mechanical and other performance
properties of the final articles to be manufactured from a given polymer blend. One of
ordinary skill in the art will be able to determine the optimal level of particle packing that

will optimize the packing density through routine testing. A more detailed discussion of
particle packing techniques can be found in U.S. Patent No. 5,527,387 to Andersen et al.
For purposes of disclosing particle packing techniques that may be useful in maximizing
or optimizing particle packing density, the foregoing patent is incorporated herein by
reference.
In those cases where it is desired to take advantage of the improved properties of
rheology and binding efficiency utilizing particle packing techniques, it will be preferable
to include inorganic filler part c[es having a natural particle packing density in a range
from about 0.55 to about 0.95, more preferably in range from about 0.6 to about 0.9, and
most preferably in a range from about 0.7 to about 0.85.
Examples of useful inorganic fillers that may be included within the
biodegradable polymer blends include such disparate materials as sand, gravel, crushed
rock, bauxite, granite, limestone, sandstone, glass beads, aerogels, xerogels, mica, clay,
alumina, silica, kaolin, micrcspheres, hollow glass spheres, porous ceramic spheres,
gypsum dihydrate, insoluble salts, calcium carbonate, magnesium carbonate, calcium
hydroxide, calcium aluminate, magnesium carbonate, titanium dioxide, talc, ceramic
materials, pozzolanic materials, salts, zirconium compounds, xonotlite (a crystalline
calcium silicate gel), lightweight expanded clays, perlite, vermiculite, hydrated or
unhydrated hydraulic cement particles, pumice, zeolites, exfoliated rock, ores, minerals,
and other geologic materials. A wide variety of other inorganic fillers may be added to
the polymer blends, including materials such as metals and metal alloys (e.g., stainless
steel, iron, and copper), balls or hollow spherical materials (such as glass, polymers, and
metals), filings, pellets, flakes and powders (such as mierosilica).
The particle size or range of particle sizes of the inorganic fillers will depend on
the wall thickness of the film sheet, or other article that is to be manufactured from the
polymer blend. In general, the larger the wall thickness, the larger will be the acceptable
particle size. In most cases, it will be preferable to maximize the particle size within the
acceptable range of particle sizes for a. given application in order to reduce the cost and
specific surface area of the inorganic filler. For films that are intended to have a
substantial amount of flexibility, tensile: strength, bending endurance and relatively low
dead-fold and breathability (e.g., plastic bags) the particle size diameter of the inorganic
filler will preferably be less than about 20% of the wall thickness of the film. For
example, for a film or sheet having a thickness of 40 microns, it may be preferable for the
inorganic filler particles to have a particle size diameter of about 8 microns or less.

On the other hand, it may be desirable in some cases for at least a portion of the
filler particles to have a larger particle size diameter, such as a diameter that is equal to or
greater than the thickness of the polymeric sheet or film. Utilizing filler particles whose
diameters equal or exceed the th chiess of the polymeric sheet or film disrupts the surface
of the sheet or film and increases the surface area, which can advantageously increase the
bulk-hand-feel and/or dead-folo. properties of the sheet or film. In the case where the
sheets or films are mono or biaxial stretched, the use of larger filler particles (e.g., larger
than 20% of the wall thickness of the film) creates definitive discontinuities that yield
sheets and films having a high degree of cavitation. Cavitation results in sheets having a
touch and feel that more closely resembles the touch and feel of paper. In addition, it
greatly increases the breathabilty and waiter vapor transmission of the sheets and films.
The amount of particulate filler added to a polymer blend will depend on a variety
of factors, including the quantiy and identities of the other added components, as well as
the specific surface area, packing density, and/or size distribution of the filler particles
themselves. Accordingly, the concentration of particulate filler within the polymer blends
may be included in a broad range from a:; low as 0% by volume to as high as about 90%
by volume of the polymer blend. Because of the variations in density of the various
inorganic fillers than can be used, it may be more correct in some instances to express the
concentration of the in organ c filler in terms of weight percent rather than volume
percent. In view of this, the inorganic filler components can be included within a broad
range from as low as 0% by veight to as high as 95% by weight of the polymer blend,
preferably in a range from about 5% to about 90% by weight.
In those cases where is desired for the properties of the thermoplastic phase to
predominate due to the required performance criteria of the articles being manufactured,
the inorganic filler will prefeiably be included in an amount in a range from about 5% to
about 50% by volume of polymer blend. On the other hand, where it is desired to create
highly inorganically filled systems, the inorganic filler will preferably be included in an
amount in a range from about 50% to about 90% by volume.
In light of these competing objectives, the actual preferred quantity of inorganic
filler may vary widely. In general terms, however, in order to appreciably decrease the
cost of the resulting polymer blend and/or to impart increased dead-fold, heat-resistance,
insulation ability, and/or microwaveability, the inorganic filler component will typically
be included in an amount of at least about 10% by weight of the overall composition,
preferably at least about 15% by weight, more preferably at least about 20% by weight,

more especially preferably at least about 30% by weight, and most preferably at least
about 35% by weight of the ove: all composition.
b. Discrete Fibers
In addition to the fibrous sheet being treated, discrete fibers can optionally be used
in order to improve the physical properties of the polymer blends. Like the
aforementioned fillers, fibers will typically constitute a solid phase that is separate and
distinct from the thermoplastic phase. However, because of the shape of fibers, i.e., by
having an aspect ratio greater than at least about 10:1, they are better able to impart
strength and toughness than particulate fillers. As used in the specification and the
appended claims, the terms "fioers" and "fibrous material" include both inorganic fibers
and organic fibers. Fibers may be added to the moldable mixture to increase the
flexibility, ductility, bendability, cohesion, elongation ability, deflection ability,
toughness, dead-fold, and fraclure energy, as well as the flexural and tensile strengths of
the resulting sheets and articles.
Fibers that may be incorporated into the polymer blends include naturally
occurring organic fibers, such as cellulosic fibers extracted from wood, plant leaves, and
plant stems. In addition, inorganic fibers made from glass, graphite, silica, ceramic, rock
wool, or metal materials may also be used. Preferred fibers include cotton, wood fibers
(both hardwood or softwood :fibers, examples of which include southern hardwood and
southern pine), flax, abaca, sisal, ramie, hemp, and bagasse because they readily
decompose under normal conditions. Even recycled paper fibers can be used in many
cases and are extremely inexpensive and plentiful.
The fibers used in making the sheets and other articles of the present invention
preferably have a high length to width ratio (or "aspect ratio") because longer, narrower
fibers can impart more strength to the pclymer blend while adding significantly less bulk
and mass to the matrix than thicker fibers. The fibers will have an aspect ratio of at least
about 10:1, preferably greater than about 25:1, more preferably greater than about 50:1,
and most preferably greater than about 100:1.
The amount of fibers added to the polymer blends will vary depending upon the
desired properties of the finished article of manufacture, with tensile strength, toughness,
flexibility, and cost being the principle criteria for determining the amount of fiber to be
added in any mix design. Accordingly, the concentration of fibers within the polymer
blends of the present invention can be ncluded in a broad range from 0% to about 90%
by weight of the polymer blend. If included at all, fibers will preferably be included in an

amount in a range from about 1% to about 80% by weight of the polymer blend, more
preferably in a range from about 3% to about 50% by weight, and most preferably in a
range from about 5% to about 30% by weight of the polymer blend.
c. Organic Fillers
The polymer blends may also include a wide range of organic fillers. Depending
on the melting points of the polymer blend and organic filler being added, the organic
filler may remain as a discrete particle and constitute a solid phase separate from the
thermoplastic phase, or it may partially or wholly melt and become partially or wholly
associated with the thermoplastic phase.
Organic fillers may cofnprise a wide variety of natural occurring organic fillers
such as, for example, seagel, cork, seeds, gelatins, wood flour, saw dust, milled polymeric
materials, agar-based materials, native starch granules, pregelatinized and dried starch,
expandable particles, and the like. Organic fillers may also include one or more synthetic
polymers of which there is vietually endless variety. Because of the diverse nature of
organic fillers, there will not generally be a preferred concentration range for the optional
organic filler component.
Organic fillers can partially or wholly take the place of inorganic fillers. In some
cases, organic fillers can be seslected that will impart the same properties as inorganic
fillers, such as to increase dee d-fold, the: bulk hand feel, breathability and water vapor
transmission. When included at all, the organic filler component will typically be
included in an amount of at least about 5% by weight of the overall composition,
preferably at least about 10% by weight, more preferably at least about 20% by weight,
and more especially preferably at least a.bout 30% by weight, and most preferably at least
about 35% by weight of the overall composition.
3. Natural Polymers,
In addition to thermoplastic starch or starch particles, other natural polymers that
may be used within the polyner blends comprise or are derivatives of cellulose, other
polysaccharides, polysaccharicle gums and proteins.
Examples of starches and starch derivatives include, but are not limited to,
modified starches, cationic ani anionic starches, and starch esters such as starch acetate,
starch hydroxyethyl ether, alkyl starches, dextrins, amine starches, phosphates starches,
and dialdehyde starches.
Examples of derivatives of cellulose include, but are not limited to, cellulosic
esters (e.g., cellulose formate, cellulose acetate, cellulose diacetate, cellulose propionate,

cellulose butyrate, cellulose valerate, mixed esters, and mixtures thereof) and ceilulosic
ethers (e.g.', methylhydroxyethy cellulose, hydroxymethylethylcellulose, carboxymethyl-
cellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxyethylpropyl-
cellulose, and mixtures thereof).
Other polysaccharide-based polymers that can be incorporated into the polymer
blends of the invention include alginic acid, alginates, phycocolloids, agar, gum arabic,
guar gum, acacia gum, carragsenan gum, furcellaran gum, ghatti gum, psyllium gum,
quince gum, tamarind gum, locust bean gum, gum karaya, xanthan gum, and gum
tragacanth, and mixtures or derivatives thereof.
Suitable protein-based polymers include, for example, Zein® (a prolamine derived
from com), collagen (extracted from animal connective tissue and bones) and derivatives
thereof such as gelatin and glue, casein (the principle protein in cow milk), sunflower
protein, egg protein, soybean protein, vegetable gelatins, gluten and mixtures or
derivatives thereof.
4. Non Biodegradable Polymers.
Although polymer blends preferably include biodegradable polymers, it is
certainly within the scope of the invention to include one or more polymers which are not
biodegradable. If the nonbioc egradable polymer generally comprises a disperse phase
rather than the dominant continuous phase, polymer blends that include a
nonbiodegradable polymer will nevertheless be biodegradable, at least in part. When
degraded, the polymer blend may leave behind a nonbiodegradable residue that
nevertheless is superior to the waste left behind by sheets and films that are entirely made
of nonbiodegradable polymers.
Examples of common nonbiodegradable polymers suitable for forming sheets and
films include, but are not Unrated to, polyethylene, polypropylene, polybutylene, PET,
PETG, PETE, polyvinyl chloride, PVDC, polystyrene, polyamides, nylon,
polycarbonates, polysulfides, polysulfones, copolymers including one or more of the
foregoing, and the like.
D. Polymer Blends.
1. Concenpration Ranges of Biodegradable Polymers.
The concentrations of the various components within the polymer blends used to
treat fibrous sheets will depend on a number of factors, including the desired physical and
mechanical properties of the treated sheet, the performance criteria of articles to be

manufactured from a treated sheet, the processing equipment used to manufacture and
convert the blends and treated sheets into the desired article of manufacture, and the
particular components within the blends. One of ordinary skill in the art will be able, in
light of the specific examples and other teachings disclosed herein, to select and optimize
the concentrations of the various components through routine testing.
In view of the wide variety of polymer blends within the scope of the invention, as
well as the wide variety of different properties that may be engineered within the blends,
the hard and soft polymers may be included within widely varying concentration ranges.
In those cases where the polymer blend or composition includes a blend of stiff and soft
biodegradable polymers, the one or more stiff biodegradable polymers within the
inventive blends may have a c oncentration in a range from about 20% to about 99% by
weight of the biodegradable polymers exclusive of the fibrous sheet and any fillers,
preferably a concentration of at least about 30% by weight of the polymer blend, more
preferably at least about 40% by weight of the polymer blend, more especially preferably
greater than, but not including 50% by weight of the polymer blend, and most preferably
at least about 55% by weight of the polymer blend.
Similarly, when a blend of stiff and soft polymers is employed, the soft polymers
may have a concentration in a range from about 1% to about 80% by weight of the
biodegradable polymers exclusive of the fibrous sheet and any fillers, preferably a
concentration up to about 70 % by weight of the polymer blend, more preferably up to
about 60% by weight of the polymer blend, more especially preferably less than, but not
including, 50% by weight of he polymer blend, and most preferably up to about 45% by
weight of the polymer blend.
The foregoing concernrations are measured in terms of the blend of hard and soft
polymers exclusive of any optional components that may be added, as described and
identified above.
2. Properties of Polymer Blends and Treated Sheets.
The polymer blends may be engineered to have a variety of desired properties as
described herein. The properties of the final treated fibrous sheet will depend on a
number of factors, including mix design of the polymer blend, processing conditions,
post-formation processing, poduct size,, particularly thickness, and the like. In the case
of treated sheets intended to be used as "wraps", such as wraps used to enclose meats,
other perishable food items, and especially fast food items (e.g., sandwiches, burgers and
dessert items), it will generally be desirable to provide treated sheets having good "dead-

fold" properties so that once folied, wrapped or otherwise manipulated into a desired
orientation, such wraps will tend to maintain their orientation so as to not spontaneously
unfold or unwrap, as which occurs with a large number of plastic sheets and films (e.g.,
polyethylene).
In order to improve the dead-fold properties of treated sheets biodegradable
polymers may be selected which yield blends having a relatively high Young's modulus,
preferably at least about 100 MPa, more preferably at least about 150 MPa, and most
preferably at least about 200 MPa. In general, increasing the concentration of the stiff
biodegradable polymer will tend to increase the Young's modulus. The Young's
modulus may also be increased by loading the polymer blends with one or more fillers,
such as particulate or fibrous fillers, as described above.
In addition to, or instead of, increasing the Young's modulus to improve dead-
fold, the treated sheets may be optionally processed to increase the "bulk hand feel" of a
sheet, which is done by disrupt ng the generally planar nature of the sheet. This can be
done, for example, by embossing, crimping, quilting or otherwise texturing the sheet so as
to have regularly spaced-apart or random hills and valleys rather than simply a smooth,
planar sheet. This may be done, for exsimple, by passing the sheet through a pair of
knurled or other embossing-type rollers. Such texturing increases the ability of a sheet to
take and maintain a fold, crinkle, creases; or other bend, thus improving the dead-fold
properties of the sheet.
Another way to increase the surface area of the treated sheets according to the
invention so as to increase their bulk hand feel aod/or dead-fold is to include particulate
fillers in which at least a porticn of the particles have a particle size diameter that equals
or exceeds the thickness of the polymer coating. In this way, treated sheets can be
manufactured that have dead-fold approaching or equaling 100%, which exceeds the
dead-fold properties of virtually all conventional paper or plastic wraps and sheets
currently on the market. An example of a conventional sheet or wrap having 100% dead-
fold is aluminum or other meta i foils.
Other properties that may be desirable when manufacturing food wraps are beat
resistance, microwaveability, ;nd insulation ability. Increasing the amount of inorganic
filler within the polymer blend or composition used to coat or impregnate a fibrous sheet
tends to increase the heat resistance, microwaveability, and insulation ability of the
treated fibrous sheets. It has teen found, for example, that a soft biodegradabJe polymer
can be blended with an inorganic filler, such as ground or precipitated silica, to yield

abiodegradable polymer composition that includes at least about 30% by weight of the
inorganic filler. Adding at least about 30% by weight inorganic filler to a soft
biodegradable polymer yields a treated fibrous sheet that does not break down when
placed in a microwave oven.
The use of fillers, coupled with specific processing techniques, can also be used to
create "cavitation". Cavitatior. occurs as the thermoplastic polymer fraction is pulled in
either a monoaxial or biaxial direction and the filler particles create a discontinuity in the
film or sheet that increases in size during stretching. During stretching, a portion of the
stretched polymer pulls away from the filler particles, resulting in tiny cavities in the
vicinity of the filler particles. This, in turn, results in greatly increased breathabiliry and
vapor transmission of the sheets and fibms. It also results in films or sheets having a
touch and feel that much more closely resembles the touch and feel of paper, as
contrasted with conventional plastic sheets and films. The result is a sheet, film or wrap
that can be used for applications that are presently performed or satisfied using paper
products (i.e., wraps, tissues, printed materials, etc.)
Treated sheets accordirg to the invention can have any desired thickness. Treated
sheets suitable for wrapping, inclosing or otherwise covering food items or other solid
substrates will typically have a measured thickness between about 0.0003" and about
0.01" (about 7.5-250 microns , and a calculated thickness between about 0.00015" and
about 0.005" (about 4-125 mic-ons).
The measured thickness will typically be between 10-100% larger than the
calculated thickness when the sheets and films are made from compositions that have a
relatively high concentration of particulate filler particles, which can protrude from the
surface of the treated sheet. This phenomenon is especially pronounced when significant
quantities of filler particles having a particle size diameter that is larger than the thickness
of the polymer matrix are used.
Treated sheets suitable for use as wraps will preferably have a measured thickness
in a range from about 0.0004' to about 0.005" (about 10 to about 125 microns), more
preferably in a range from about 0.0005" to about 0.003" (about 12 to about 75 microns),
and most preferably in a range from about 0.001" to about 0.002" (about 25 to about 50
microns). On the other hand, ireated sheets suitable for use as wraps will preferably have
a calculated thickness in a range from about 0.0002" to about 0.003" (about 5 to about 75
microns), more preferably in a range from about 0.0003" to about 0.002" (about 7.5 to

about 50 microns), and most preferably in a range from about 0.0005" to about 0.0015"
(about 12 to about 40 microns),
The difference betweet the calculated and measured thickness tends to increase
with increasing filler content and also with increasing particle size. Conversely, the
difference between the calculated and measured thickness tends to decrease with
decreasing filler content and also with decreasing particle size. Treated sheets that
include no fillers, or lower quantities of fillers having a particle size diameter that is
substantially lower than the thickness of the polymer matrix, will have a measured
thickness that is similar or equal to the calculated thickness.
Another important property of the biodegradable blends is that when such blends
are used to coat or impregnate fibrous sheets, the treated sheets are readily printable
without further processing. 1 hus, another advantage of utilizing the inventive polymer
blends in the manufacture of wraps is that such blends are generally able to accept and
retain print much more easily than conventional plastics or waxed papers. Many plastics
and waxes are highly hydropliobic and must be surface oxidized in order to provide a
chemically receptive surfacero which ink can adhere. Biodegradable polymers, on the
other hand, typically include oxygen-containing moieties, such as ester or amide groups,
to which inks can readily adhe re.
3. Measuring Dead-Fold
The term "dead-fold" refers to the tendency of a sheet to maintain a crease,
crinkle, fold or other bend. The dead-fold properties of a sheet can be accurately
measured using a standard tesi known in the art. This test provides the ability to compare
and contrast the dead-fold properties of various sheets. The following equipment is
useful in performing the standard dead-fold test: (1) a semicircular protractor, divided
along a 1" diameter semicircle; (2) a weight consisting of a smooth-faced metal block that
is 0.75" ± 0.05" by 1.25" ± 0.05" and of such a thickness so as to weigh 50 g± 0.05 g; (3)
a 1" x 4" template for cutting test specimens; (4) a timer or stopwatch capable of timing to
1 second; (5) a utility knife or other cutting tool; and (6) a humidity chamber.
The first step is preparation of an appropriately sized sample. In the case where a
sheet has different properties in the machine direction compared to the cross-machine
direction it may be useful to measure and average the dead-fold properties in both
directions. The standard sample specimen is a 1" x 4" strip of the sheet to be tested.

The second step is a conditioning step in order to ensure uniformity of test
conditions. The specimens are conditioned by placing them in a humidity chamber at 23
C and 50% relative humidity fir a minimum of 24 hours.
The third step is the actual dead-fold test of each conditioned test strip. The
specimen is removed from the 1aumidity chamber and its weight recorded. A light mark is
made 1" from one end of the test strip. The test strip is then placed on a flat surface and
bent over at the mark but without creasing the strip. Next, the weight is placed squarely
and gently over the bend with two thirds (or 0.5") of the weight overlapping the specimen
so that a crease is formed, and with one third or (0.25") of the weight overhanging the
crease. The edges of the weight parallel to the strip should project evenly (about 0.125")
beyond each side of the strip. The weight is allowed to rest on the specimen for 10
seconds. Then it is removed. After exactly 30 seconds, the angle formed by the crease is
measured.
The foregoing process i s repeated using the other side of the strip and using as
many additional strips as will give a statistically accurate measure of the dead-fold
properties of a given sheet or film. The average angle A is then input into the following
formula to determine the percenrage dead-fold C for a given sample:
C = 100*(180-A)/180
If the angle A is 0° (i.e. where the crease is maintained so that no spring back is
observed), the sample has 100% dead-fold (C = 100*(180-0)/180 = 100%). At the other
extreme, if the angle A is 180° (i.e., where the sample springs all the way back so that the
sample is essentially flat, the simple has 0% dead-fold (C = 100*(180-180)/180 = 0%).
In the middle, a sample that sp: ings back half way so as to form a right angle has 50%
dead-fold (C = 100*(180-90)/18) = 50%).
When used to wrap foods, or whenever good dead-fold properties are desired,
treated sheets according to the vention can be manufactured so as to have a dead-fold of
at least about 50%. Preferably, reated sheets will have a dead-fold of at least about 60%,
more preferably at least about 20%, more especially preferably at least about 80%, and
most preferably at least about 90%. Treated sheets according to the invention have been
developed that have a dead-fold approaching or equal to 100%. By way of comparison,
sheets and films made from polyethylene (e.g., for use in making sandwich or garbage
bags) typically have a dead-fold of 0%. Standard paper wraps commonly used in the fast
food industry typically have a dead-fold between about 40-80%. Thus, treated sheets
according to the invention can be manufactured so as to have dead-fold properties that

meet or exceed those of standard paper wraps, and which are many times greater than
conventional plastic films and sheets, often orders of magnitude greater.
III. METHODS OF MANUFACTURING POLYMER BLENDS AND FIBROUS
SHEETS
It is within the scope of the invention to employ any manufacturing apparatus
known in the art of manufacturing thermoplastic compositions to form the polymer and
any coating apparatus to coat or impregnate fibrous sheets with the polymer blends.
Examples of suitable mixing apparatus that can be used to form polymer blends according
include a twin-shafted kneader with meshing screws having kneading blocks sold by the
Buss Company, a BRABENDER mixer, a THEYSOHN TSK 045 compounder, which is
a twin-shaft extruder with shafts rotating in the same direction and which has multiple
heating and processing zones, a BUSS KO Kneader having a heatable auger screw, a
BAKER-PERKINS MPC/V-30 double and single auger extruder, single or twin auger
OMC extruders, a Model EPV 60/56D extruder, a BATTAGGION ME100 direct-current
slow mixer, a HAAKE Reomex extruder, a COLLIN Blown Film Extruder, a
BATTENFELD-GLOUCESTER Blown Film Extruder, and a BLACK-CLAWSON Cast
Film Extruder.
Many of the foregoing mixers are also extruders, which makes them suitable for
extruding films or sheets from the polymer blends, which can then be laminated together
with a fibrous sheet. Alternativey, polymer blends can be made using transfer-line-
injection technology where resin manufacturers can inject the various minor components
of these blends into the main poly components during manufacture. One of ordinary skill
in the art will be able to select and optimize an appropriate manufacturing apparatus
according to the desired article to be manufactured. Once a thermoplastic melt has been
formed using any of the above-mentioned mixers, or any other appropriate mixing and
melting apparatus known in the thermoplastic art, virtually any molding, extrusion,
shaping or coating apparatus known in the thermoplastic molding or processing art can be
used to produce finished articles of manufacture comprising fibrous sheets that have been
coated or impregnated with a polymer blend to render the sheets more resistant to
penetration by liquids.
In a preferred embodiment for manufacturing sheets and films from the polymer
blends, which can then be laminated together with fibrous sheets, the sheets and films can
be manufactured using a compounding twin screw extruder to prepare the blends, and a
blown film or cast film line to make he films and sheets. Blown films and sheets tend to

have similar, if not identical, styrength and other performance properties in the biaxial
direction due to how they are processed (i.e., they are extruded as a tube and then
expanded in all directions by bl
owing air within the confines of the tube, causing it to
expand like a balloon). Cast films or sheet:;, on the other hand, unless subjected to biaxial
stretching, will be substantially stronger (e.g. will have substantially greater tensile
strength) in the machine direction and will be substantially more tear resistant in the
cross-machine direction. When extruding a thermoplastic material, the polymer
molecules tend to be oriented in the machine direction. Machine direction orientation is
further increased if the extruded sheet or film is passed through a nip to decrease the sheet
or film thickness in the machine direction.
The treated sheets according to the invention may be coated or impregnated on
one or both sides as desired. The / may be formed by laminating a fibrous sheet with one
or more sheets or films, co-extruding a sheet or film of a polymer blend with a fibrous
sheet, dipping, spreading (e.g., using a doctor blade), spraying, and the like. Because a
portion of the treated sheets are thermoplastic, the sheets can be post-treated by heat
sealing to join two ends together to form sacks, pockets, pouches, and the like. They can
be laminated onto existing sheets or substrates.
Monoaxial or biaxial stretching of slieets and films used to coat a surface of a
fibrous sheet can be used to create cavitation. To create cavitation, a particulate filler is
included that yields discontinuities as the sheet or film is stretched while still in a
thermoplastic condition. Cavitation increases: the breathability and vapor transmission of
the sheets and films. It also results in films or sheets having a touch and feel that much
more closely resembles the touch and feel of paper compared to conventional
thermoplastic sheets and films.
When employing certain coating or impregnating techniques, such as spreading or
spraying a biodegradable polymer composition onto a fibrous sheet, it may be
advantageous to increase the MFI of the molten polymer composition. This allows the
molten polymer composition to flow more readily so as to coat or impregnate the fibrous
sheet. Preferably, the molten polyrner composition has an MFI of at least about 40 g/10
min., more preferably at least about 70 g/10 min., and most preferably at least about 100
g/10min.
As discussed above, the MFI can, depending on the biodegradable polymer or
polymer blend, be increased to a desired level by heating it to a higher temperature. In
some cases, however, heating a polymer to temperature that might theoretically decrease

the MFI to an acceptable level might, instead, scorch, burn or otherwise damage the
polymer composition. In such cases it may be desirable to add a plasticizer to the
polymer composition. The plast icizer might be a volatile or non-volatile plasticizer, as
discussed above.
According to one embodiment, water is added to increase the MFI of the molten
polymer composition. Adding 2(0 ppm water to a polymer composition has been found
to increase the MFI from 4 g/10 min. to 40 g/10 min. Based on this, one of ordinary skill
can adjust the water concentration as desired to raise or lower the MFI to a predetermined
level.
In the case of a spray coating method, one or more volatile solvents, such as
alcohols, ketones, or chlorinated hydrocarbons, can be used to raise the MFI of the molten
polymer composition. During or a fter the coating process, as the volatile solvent is driven
off by evaporation, the solvent is a dvantageously recovered and reused for both economic
and environmental reasons.
IV. EXAMPLES
The following examples are presented in order to more specifically teach
compositions and process conditio is for forming biodegradable polymer blends, as well
as treated fibrous sheets therefrom. The examples include various mix designs of the
inventive biodegradable polymer blends as well various processes for manufacturing the
blends and then forming polymeric sheets and films therefrom.
EXAMPLES 1-3
Biodegradable polymer films were manufactured from biodegradable polymer
blends having the following mix designs, with the concentrations being expressed in
terms of weight percent of the entire polymer blend:

The foregoing polymer bleids were blended and blown into films at Gemini
Plastics, located in Maywood, California, using DuPont supplied BIOMAX 6926 (both
new and old lots), a silica master bach in BIOMAX 6926 base resin supplied by DuPont,
and ECOFLEX-F resin obtained fro: n BASF. The films were blown using a Gemini film
blowing extruder (L/D 24/1) equipped with a 2 inch barrier mixing screw containing a

Maddock shear mixing tip, and a 4 inch diameter annular die with a die gap of 0.032-
0.035".
Even though a typical quantity of silica antiblock was used (i.e., 0.16%),
significant blocking of the film was obseived for the film made using the mix design of
Example 3 (i.e. 20% ECOFLEX); however, there was no observed blocking of the 5 and
10% ECOFLEX blends of Examples 1 and 2. For purposes of comparison, films of neat
ECOFLEX and BIOMAX were manufactured. The neat ECOFLEX films were
manufactured using BASF ECOI LEX-F resin and a 30% talc master batch in the same
resin. The neat BIOMAX film: (new and old) included 0.16% SiO2, while the neat
ECOFLEX films included 4 5% talc;. The mechanical properties of the
BIOMAX/ECOFLEX blend films and the control BIOMAX and neat ECOFLEX-F films
were measured under ambient conditions. The data generated is show graphically in
Charts 1-8 depicted in Figures 1-8. respectively.
Chart 1, depicted in Figure 1, is a plot of the strain rate versus percent elongation
at break for the various films tested. At 500 mm/min. strain rate, both new and old
BIOMAX films displayed poor elongation. The neat ECOFLEX films and all of the films
made from the BIOMAX-ECOFLEX blends had significantly better elongations than the
neat BIOMAX films at all of the strain rates studied. On the other hand, the 20%
ECOFLEX blend of Example 3 exhibited equal or better elongation compared to the neat
ECOFLEX films at lower strain rates, ever though these films included nearly 80%
BIOMAX, which was shown to have very poor elongation.
Chart 2, depicted in Figure 2, is a plot of percent elongation versus percentage of
ECOFLEX in the BIOMAX/ECO]'LEX blends measured at a fixed strain rate of 500
mm/min. As represented by Chat 2, there was a nearly linear improvement in the
percent elongation as the concentration of ECOFLEX was increased. Moreover, the 20%
ECOFLEX blend of Example 3 had an elongation as good as the neat ECOFLEX films.
Chart 3, depicted in Figure 3, similarly plots the percent elongation versus the
percentage of ECOFLEX in the BIOMAX/ECOFLEX blends measured at a fixed strain
rate of 1000 mm/min. Again, a dramatic improvement in the elongation of the
BIOMAX/ECOFLEX blend was seen as the concentration of ECOFLEX reached 10 and
20%, respectively, although the tren 1 was not as clear as the data in Chart 2, measured at
a fixed strain rate of 500 mm/min.
Chart 4, depicted in Figure 4, is a plot of the strain rate versus break stress of the
various films. Again, neat ECOFLEX and all of the BIOMAX/ECOFLEX blends had

significantly better break stress than the neat BIOMAX films at all of the strain rates
studied. Moreover, the BIOMAK/ECOFLEX blends had significantly better break stress
than the neat ECOFLEX films at all strain rates, thus showing that the
BIOMAX/ECOFLEX blends are all stronger in tensile strength than either of neat
BIOMAX or ECOFLEX.
Chart 5, depicted in Figure 5, is a plot of the break stress versus percent
ECOFLEX in the BIOMAX/ECOFLEX blends of Examples 1-3 measured at a fixed
strain rate of 500 mm/min. Once again, a. nearly linear increase in break stress was
observed as the concentration of ECOFLEX was increased. Moreover, the 20% blend of
Example 3 exhibited the surprising and unexpected result of having nearly twice the
break stress as the neat ECOFLEX film, and nearly three times the break stress as the neat
BIOMAX film.
Chart 6, depicted in Figure 6, is a plot of the break stress versus percent
ECOFLEX in the BIOMAX/ECC FLEX blends of Examples 1-3 measured at a fixed
strain rate of 1000 mm/min. At this strain rate, the 10% ECOFLEX blend of Example 2
had the highest break stress, with a maximum peak stress of 72 MPa.
Charts 7 and 8, depicted in Figures 7 and 8, respectively, plot the water vapor
permeability coefficient (WVPC) of the various films as a function of the concentration
of ECOFLEX within the films. In Chart 7, the estimated trend line is based on a WVPC
of 7.79 x 10"3 g cm/m2/d/mm Hg, which is the lowest measured WVPC for a neat
ECOFLEX film. In Chart 8, the esimated trend line is alternatively based on a WVPC of
42 x 10"3 g cm/m2/d/mm Hg, which is the highest measured WVPC for a neat ECOFLEX
film. The data in Charts 7 and 8 irdicate that the water vapor barrier properties of the 5
and 10% ECOFLEX blends of Examples 1 and 2 were essentially the same as that of the
neat BIOMAX film. The WVPC data for all samples were measured by the standard
procedures described in the Test Method ASTM F 1249-90.
Chart 9, depicted in Figure 9, is a plot of the modulus of various films as a
function of the concentration of ECOFLEX within the films. Surprisingly, the modulus
of blends containing BIOMAX ard ECOFLEX are significantly higher than of neat
BIOMAX and ECOFLEX. Becaust one of the uses of the films manufactured according
to the present invention is as a wrab having good dead-fold properties, and because the
degree of dead-fold is believed to be related to the modulus of a film, blends of BIOMAX
and ECOFLEX appear to have superior dead-fold properties over each of the neat

BIOMAX and ECOFLEX films, with the 5% and 10% blends exhibiting the highest
modulus.
The foregoing films are used to laminate at least one side of a fibrous sheet, such
as a tissue paper, more particularly a 12-15 lb/3000 ft2 tissue paper, to yield a treated
sheet. The treated sheet can be used as a food packaging wrap that resists penetration by
water and oils found in food.
EXAMPLES 4-5
Films were manufactured from biodegradable polymer blends having the
following mix designs, with the concentrations being expressed in terms of weight
. percent of the entire polymer blends:

The films were blown usir.g a Gemini film blowing extruder (L/D 24/1) equipped
with a 2 inch barrier mixing screw containing a Maddock shear mixing tip, and a 4 inch
diameter annular die with a die g;.p of 0.032-0.035". The film of Example 5 had better
dead-fold properties than the film of Example 4, which might be attributable to the higher
concentration of talc within the blend used in Example 5.
The foregoing films are used to laminate at least one side of a fibrous sheet, such
as a tissue paper, more particulary a 12-15 lb/3000 ft2 tissue paper, to yield a treated
sheet. The treated sheet can be used as a food packaging wrap that resist penetration by
water and oils found in food.
EXAMPLE 6
A film was manufactured from a biodegradable polymer blend having the
following mix design, with the concentration being expressed in terms of weight percent
of the entire polymer blend:
ECOFLBX-F 20%
Thermoplastic Starch 50%
Polylactic Acid 15%
Inorganic Filler 15%
The Thermoplastic Starch was obtained from Biotec Biologische
Natuverpackungen GmbH & Co., KG ("Biotes"), located in Emmerich, Germany. The
polylactic acid was obtained from Cargill-Dow Polymers, LLC, located in Midland,

Michigan, USA. The inorganic filler was calcium carbonate obtained from OMYA,
division Pluess-Staufer AG, located in Oftringen, Switzerland.
The foregoing blend was manufactured and blown into films using a proprietary
extrusion line thermoplastic statch extrusion/film blowing apparatus manufactured and
assembled specifically for Biote<. in particular the extrusion blowing apparatus was> manufactured by Dr. Collin GmbH, located in Ebersberg, Germany. A detailed
description of an extrusion/film blowing apparatus similar to the one used by Biotec is set
forth in U.S. Patent No. 5,525,281 to Lorcks et al. U.S. Patent No. 6,136,097 to Lorcks et
al. discloses processes for manufacturing intermediate thermoplastic starch-containing
granulates that can be further processed to make films and sheets. For purposes of
disclosure, the foregoing patents are incorporated herein by reference.
The film had a modulus of 215.65 MPa. Thus, it had excellent dead-fold
properties as a result of the inclus on of the inorganic filler and the polylactic acid, which
is a generally stiff, crystalline polrmer at room temperature. As set forth above, PLA has
a glass transition temperature between 50-60°C. The ECOFLEX and thermoplastic starch
(TPS) both acted as soft, low glass transition temperature polymers. The TPS, when
blended with additional polymers and at very low water, has a glass transition
temperature approaching -60°C. The ECOFLEX and TPS thus assisted the blowability
and flexibility of the blend. The TPS also increased the natural polymer content, thus
making the film more biodegradable.
The foregoing film is used :o laminate: at least one side of a fibrous sheet, such as
a tissue paper, more particularly a 12-15 lb/3000 ft2 tissue paper, to yield a treated sheet.
The treated sheet can be used as a food packaging wrap that resists penetration by water
and oils found in food.
EXAMPLE 7
A film was manufactured from a biodegradable polymer blend having the
following mix design, with the concentration being expressed in terms of weight percent
of the entire polymer blend:
Thermoplastic Starcl 30%
BAK1095 60%
Inorganic Filler 10%
The thermoplastic starch wa,; obtained from Biotec. The BAK 1095 was obtained
from Bayer AG, located in Köln, Germany, and was an aliphatic-aromatic

polyesteramide. The inorganic filler was calcium carbonate obtained from OMYA,
division Piuess-Staufer AG, loc ated in Oftringen, Switzerland.
The foregoing blend was manufactured and blown into films using the proprietary
thermoplastic starch extrusion/1 Urn blowing apparatus described in Example 6. The film
had excellent dead-fold propert.es as a result of the inclusion of the inorganic filler and
the BAK 1095, which is a some what stiff, crystalline polymer at room temperature even
though it is classified as "film gade". As set forth above, BAK 1095 behaves as if it has
a glass transition temperature of at least .10°C. Because the glass transition temperature
of BAK 1095 is relatively low compared to PLA, considerably more BAK could be
included without destroying the film-blow;ing properties and flexibility of the resulting
film. The TPS acted as the soft, low glass transition temperature polymer, and further
assisted the blowability and flexibility of the blend. It also increased the natural polymer
content, thus making the film more biodegradable.
The foregoing film is usec to laminate at least one side of a fibrous sheet, such as
a tissue paper, more particularly a 12-15 lb/3000 ft2 tissue paper, to yield a treated sheet.
The treated sheet can be used as a food packaging wrap that resists penetration by water
and oils found in food.
EXAMPLES 8-12
Films were manufactureo from biodegradable polymer blends having the
following mix designs, with the coocentrations being expressed in term of weight percent
of the entire polymer blend:

The tale was supplied by luzenac, located in Englewood, Colorado, having a
particle size of 3.8 microns. The titanium dioxide was supplied by Kerr-McGee
Chemical, LLC, located in Oklahoma City, Oklahoma, grade TRONOX 470, having a
particle size of 0.17 micron. The calcium carbonate was supplied by Omnia, located in
Lucerne Valley, California, particle size of 2 microns. The foregoing blends were

manufactured on a Werner Pfeiderer ZSK twin-screw extruder, and blown into sheets
using a Gemini film blowing extruder (L/D 24/1) equipped with a 2 inch barrier mixing
screw containing a Maddock shear mixing tip, and a 4 inch diameter die. All of the films
had excellent dead-fold properties. The polymer blends of Examples 10-12 were also
extruded into sheets using a sing.e screw extruder and a 14 inch flat cast-film die, and the
usual nip-rolls and film take-up assembly normal to such a system. All of these films also
had excellent dead-fold properties.
The foregoing films are used to laminate at least one side of a fibrous sheet, such
as a tissue paper, more particularly a 12-15 lb/3000 ft2 tissue paper, to yield a treated
sheet. The treated sheet can be used as a food packaging wrap that resists penetration by
water and oils found in food.
Examples 13-61
Blown and cast films and sheets were manufactured from biodegradable polymer
blends having the following mix designs, with the concentrations being expressed in term
of weight percent of the entire polymer blend:






92%, 92%, 91%, 100%, 100%, 100%, 100% and 100%, respectively. Although films
made from the other compositiors were net tested for dead-fold, they would be expected
to have relatively high dead-fold compared to conventional biopolymers (i.e., at least
about 80%). The water vapor transmission rate for films made using the compositions of
Examples 36, 38, 41 and 43 were 91.94, 9132, 98.29 and 80.31 g/m2/day, respectively.
The composition of Example 60 was processed and blown into a film using a
BATTENFELD-GLOUCESTER Blown Film Extruder. A film made from this
composition was found to have a vater vapor transmission rate of 42.48 g/m2/day.
The composition of Examp e 61 was processed and blown into various films using
both a BATTENFELD-GLOUCESTER Blown Film Extruder and a BLACK-CLAWSON
Cast Film Extruder. The film formed using the BATTENFELD-GLOUCESTER Blown
Film Extruder apparatus was tested and found to have a dead-fold of 100%. Two
different thicknesses of films were formed using the BLACK-CLAWSON Cast Film
Extruder, one having a thickness of 1.3 mils (0.0013") and another having a thickness of
1.8 mils (0.0018"). Both had a distinctive machine direction orientation because they
were cast, rather than blown, films. The 1.3 mil film had a dead-fold of 99%, and the 1.8
mil film had adead-foldof 100%.
The foregoing films and sheets are used to laminate at least one side of a fibrous
sheet, such as a tissue paper, more particularly a 12-15 lb/3000 ft2 tissue paper, to yield a
treated film or sheet. The treated film or sheet can be used as a food packaging wrap that
resists penetration by water and oils found in food.
EXAMPLE 62
Any of the foregoing biodegradable polymer blends is used to coat or impregnate
at least one side of a fibrous sheet. The polymer blend is heated, mixed or otherwise
processed into a thermoplastic melt and then spread over a surface of a fibrous sheet
using a doctor blade. The fibrous sheet is moved while the doctor blade remains
stationary. Alternatively, the polymer blend is sprayed onto the fibrous sheet using spray-
coating techniques known in the art.
EXAMPLE 63
Any of the foregoing b, odegradable polymer blends is modified by adding silica
or replacing some or all of the calcium carbonate with silica. The modified composition
is used to coat or impregnate at least one side of a fibrous sheet. The polymer blend is
heated, mixed or otherwise processed into a thermoplastic melt and then spread over a
surface of a fibrous sheet usin£ a doctor blade. The fibrous sheet is moved while the
doctor blade remains stationary Alternatively, the polymer blend is sprayed onto the
fibrous sheet using spray-coating techniques known in the art.
Any of the foregoing compositions is modified by removing at least a portion of
the particulate filler and then usiag the modified biodegradable composition to coat one
or both sides of a fibrous sheet.
The present invention may be embodied in other specific forms without departing
from its spirit or essential characteristics. The described embodiments are to be
considered in all respects only is illustraiive and not restrictive. The scope of the
invention is, therefore, indicated by the appended claims rather than by the foregoing
description. All changes which cc me within the meaning and range of equivalency of the
claims are to be embraced within their scope.

WE CLAIM:
1. An article of manufacture that is adapted foe use as a food wrap that is both
resistant to liquids and biodegradable, comprising :
a fibrous sheet comprised of tissue paper having a weight of up to 60 lb/3000 ft2,
at feast a portion of the fibrous sheet being coated or impregnated with a
biodegradable composition that renders the fibrous sheet more resistant to liquids and that
yields an article that is adapted for use as food wrap such that is is sufficiently thin and
flexible so as to be easily wrapped armnd a food item and that possesses sufficient dead-
fold that it will remain wrapped around the food item absent application of an external
force, the biodegradable composition comprising :
at least one soft thermoplastk biodegradable polymer having a glass transition
temperature less than 0°C; and
at least one stiff thermoplastic biodegradable polymer having a glass transition
temperature of at least 10QC.
2. An article of manufacture as c aimed in claim 1, wherein the stiff thermoplastic
biodegradable polymer comprises a modified polyethylene terephthalate in which a
portion of the terephthalate groups are substituted with at least one aliphatic diacid.
3. An article of manufacture as claimed in claim 1, wherein the stiff thermoplastic
biodegradable polymer comprises at least one of a polyesteramide, a polyhydroxybutyrate
having a glass transition temperature of at least l0oC, a terpolymer including units
formed from glycolide, lactide and e-caprolactons, or a polyesteramide formed from at
least one diacid, at least one diol, and al least one ammo acid.
4. An article of manufacture as claimed in claim 1, wherein the stiff thermoplastic
biodegradable polymer comprises at least one of a poly lactic acid or a poly lactic acid
derivative.

5. An article of manufacture as claimed in claim 1, wherein the soft thermoplastic
biodegradable polymer comprises a; least one of an aliphatic polyester including units
formed from at least one of a lactide or a hydroxyacid having at least 4 carbon atoms, a
polyester including units formed from succinic acid and an aliphatic diol, and at least one
aliphatic diol, polycarporlactone, polyhydroxybutyrate-hydroxyvalerate copolymer,
polybutylene succinate, polybutyldne succinate adipate, polyethylene succinate, or
thermoplastic starch.
6. An article of manufacture as claimed in claim 1, wherein the soft thermoplastic
biodegradable polymer comprises at least one of an aliphatic-aromatic copolyester
including units formed from an aliphatic diol, an aliphatic diacid and an aromatic diacid
or an aliphatic-aromatic copolyester including units formed from adipic acid, dialkyl
terephthaalate, and at least one aliphatic diol.
7. An article of manufacture as claimed in claim 1, wherein the stiff thermoplastic
biodegradable polymer has a concentration in a range of 20% to 99% by weight of the
biodegradable composition.
8. An article of manufacture as claimed in claim 1, wherein the stiff thermoplastic
biodegradable polymer has a concentration in a range of at least 40% by weight of the
biodegradable composition.
9. An article of manufacture as claimed in claim 1, wherein the stiff thermoplastic
biodegradable polymer has a concentration greater than 50% by weight of the
biodegradable composition.
10. An article of manufacture as claimed in claim 1, wherein the stiff thermoplastic
biodegradable polymer has a glass transition temperature of at least 15°C.
11. An article of manufacture as claimed in claim 1, wherein the stiff thermoplastic
biodegradable polymer has a glass transition temperature of at least 25°C.

12. An article of manufacture as claimed in claim 1, wherein the stiff thermoplastic
biodegradable polymer has a glass transition temperature of at least 35oC.
13. An article of manufacture as claimed in claim 1, wherein the soft thermoplastic
biodegradable polymer has a concentration up to 70% by weight of the biodegradable
composition.
14. An article of manufacture as claimed in claim 1, wherein the stiff thermoplastic
biodegradable polymer has a concent-ation less than 50% by weight of the biodegradable
composition.
15. An article of manufacture as claimed in claim 1, wherein the stiff thermoplastic
biodegradable polymer has a concentration up to 45% by weight of the biodegradable
composition.
16. An article of manufacture as claimed in claim 1, wherein the soft thermoplastic
biodegradable polymer has a glass transition temperature less than -4°C.
17. An article of manufacture as c laimed in claim 1, wherein the soft thermoplastic
biodegradable polymer has a glass transition temperature less than -10°C.
18. An article of manufacture as claimed in claim 1, wherein the soft thermoplastic
biodegradable polymer has a glass transition temperature less than -20°C.
19. An article of manufacture as claimed in claim 1, wherein the soft thermoplastic
biodegradable polymer has a glass transition temperature less than -30°C.
20. An article of manufacture as claimed in claim 1, wherein the biodegradable
composition has at least one paniculate filler, such as herein described.
21. An article of manufacture as chimed in claim 20, wherein the paniculate filler is
added in an amount so as to render the article of manufacture microwaveable.

22. An article of manufacture as claimed in claim 20, wherein the particulate filler has
a concentration of at least 10% by weight of the biodegradable composition.
23. An article of manufacture as claimed in claim 20, wherein the particulate filler has
a concentration of at least 20% by weight of the biodegradable composition.

24. An article of manufacture as claimed in claim 20, wherein the particulate filler has
a concentration of at least 30% by we ght of the biodegradable composition.
25. An article of manufacture as claimed in claim 20, wherein the particulate filler
comprises at least one of silica, calciun carbonate, clay, talc, mica, alumina, or ceramic.
26. An article of manufacture as claimed in claim 1, wherein the biodegradable
composition comprises a film or sheei that has been laminated to at least one side of the
fibrous sheet.

27. An article of manufacture as claimed in claim 1, wherein the fibrous sheet
comprises tissue paper, paper or paperboard.
28. An article of manufacture as claimed in claim 1, wherein the fibrous sheet
comprises 8-60 lb/3000 ft2 in weight of tissue paper prior to being coated or impregnated
with biodegradable composition.
29. An article of manufacture as claimed in claim 1, wherein the fibrous sheet
comprises 12-15 lb/3000 ft2 in weight of tissue paper prior to being coated or impregnated
with biodegradable composition.
30. A method of rendering a fibrous sheet more resistant to liquids, comprising:
providing a fibrous sheet comprised of tissue paper having a weight of up to 60
lb/3000 ft2; and

coating or impregnating the fibrous sheet with a biodegradable composition in
order to render the fibrous sheet more resistant to liquids and yield an article that is
adapted for use as a food wrap such that it is sufficiently thin and flexible so as to be
easily wrapped around a food item and that possesses sufficient dead-fold that it will
remain wrapped around the food item without application of an external force, the
thermoplastic biodegradable composition comprising :
at least one soft thermoplastic biodegradable polymer having a glass transition
temperature less than 0°C; and
at least one stiff thermoplasti.; biodegradable polymer having a glass transition
temperature of at least 10°C.
31. A method as claimed in claim 30, which involves :
heaving the thermoplastic biodegradable composition so as to form a
thermoplastic melt comprising an initially flowable composition;
applying the thermoplastic meln to at least one side of the fibrous sheet so as to
coat or impregnate the fibrous sheet; and
allowing the thermoplastic melt to harden.
32. A method as claimed in claim 3 1, wherein the thermoplastic melt is applied to the
at least one side of the fibrous sheet using a doctor blade or by spraying.
33. A method as claimed in claim 32, wherein the thermoplastic melt has a melt flow
index of at least 40 g/10 min.
34. A method as claimed in claim 32, wherein the thermoplastic melt has a melt flow
index of at least 70 g/10 min.

35. A method as claimed in claim 32, wherein the thermoplastic melt has a melt flow
index of at least 100 g/10 min.
36. A method as claimed in claim 30, which involves :
heating the thermoplastic biolegradable composition so as to form a thermoplastic
melt comprising an initially flowable composition;
forming a sheet or film from (he thermoplastic melt; and
laminating the sheet or film to at least one side of the fibrous sheet.
37. A method as claimed in claim 36, wherein the sheet or film is formed by at least
one of casting, extrusion or blowing.
38. A method as claimed in claim 37, wherein the sheet or film is laminated to the
fibrous sheet by co-extrusion.
39. A method as claimed in claim 30, wherein the fibrous sheet comprises 8-60
lb/3000 ft2 in weight of tissue paper.
40. A method as claimed in claim 39, wherein the fibrous sheet comprises 12-15
lb/3000 ft2 in weight of tissue paper.

There is disclosed an article of manufacture that is adapted for use as a food wrap
that is both resistant to liquids and biodegradable, comprising a fibrous sheet comprised
of tissue paper having a weight of up to 60 lb/3000 ft2, at least a portion of the fibrous
sheet being coated or impregnated with a biodegradable composition that renders the
fibrous sheet more resistant to liquids and that yields an article that is adapted for use as
food wrap such that is is sufficiently thin and flexible so as to be easily wrapped around a
food item and that possesses sufficient dead-fold that it will remain wrapped around the
food item absent application of an external force, the biodegradable composition
comprising at least one soft thermoplastic biodegradable polymer having a glass
transition temperature less than 0°C; and at least one stiff thermoplastic biodegradable
polymer having a glass transition temperature of at least 10°C.

Documents:

2643-KOLNP-2005-CORRESPONDENCE.pdf

2643-KOLNP-2005-FORM 27.pdf

2643-kolnp-2005-granted-abstract.pdf

2643-kolnp-2005-granted-assignment.pdf

2643-kolnp-2005-granted-claims.pdf

2643-kolnp-2005-granted-correspondence.pdf

2643-kolnp-2005-granted-description (complete).pdf

2643-kolnp-2005-granted-drawings.pdf

2643-kolnp-2005-granted-examination report.pdf

2643-kolnp-2005-granted-form 1.pdf

2643-kolnp-2005-granted-form 18.pdf

2643-kolnp-2005-granted-form 3.pdf

2643-kolnp-2005-granted-form 5.pdf

2643-kolnp-2005-granted-gpa.pdf

2643-kolnp-2005-granted-reply to examination report.pdf

2643-kolnp-2005-granted-specification.pdf


Patent Number 230330
Indian Patent Application Number 2643/KOLNP/2005
PG Journal Number 09/2009
Publication Date 27-Feb-2009
Grant Date 25-Feb-2009
Date of Filing 20-Dec-2005
Name of Patentee BIOTEC BIOLOGISCHE NATURVERPACKUNGEN GMBH & CO. KG
Applicant Address WERNER-HEINSENBERG-STR. 32, 46446 EMMERICH
Inventors:
# Inventor's Name Inventor's Address
1 HODSON SIMON K 910 ESTRELLA DRIVE, SANTA BARBARA, CA 93110
PCT International Classification Number B32B 27/04
PCT International Application Number PCT/IB2004/002164
PCT International Filing date 2004-06-02
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10/453,318 2003-06-03 U.S.A.