Note: Descriptions are shown in the official language in which they were submitted.
WO 2021/067367
PCT/US2020/053421
RE-PULPABLE THERMALLY INSULATED PAPER PRODUCTS AND METHODS OF
MAKING AND USING THE SAME
This application is being filed as a PCT International Patent Application in
the name of
Outlier Solutions LLC, a U.S. company, on 30 September 2020, designating all
countries, and
claiming priority to (i) U.S. Utility Patent Application Serial No. 16/837,129
entitled "RE-
PULPABLE INSULATED PAPER PRODUCTS AND METHODS OF MAKING AND USING
THE SAME," and filed on April 01, 2020, (ii) U.S. Utility Patent Application
Serial No. 16/590,224
entitled "RE-PULPABLE INSULATED PAPER PRODUCTS AND METHODS OF MAKING
AND USING THE SAME," and filed on October 01, 2019, and (iii) International
Patent Application
Serial No. PCT/2019/054121 entitled "RE-PULPABLE INSULATED PAPER PRODUCTS AND
METHODS OF MAKING AND USING THE SAME," and filed on October 01, 2019, the
subject
matter of all of which is hereby incorporated by reference in their entirety.
FIELD OF THE INVENTION
The present invention relates generally to insulated paper products. The
present invention
further relates to methods of making and using insulated paper products.
BACKGROUND OF THE INVENTION
Food sold in fast food restaurants is often wrapped in a low basis weight
paper product. The
wrapping paper is often treated with a coating to provide wet strength, such
as a silicone, or a
fluorocarbon, or a wax, and further is often laminated to a thin aluminum
foil. The aluminum foil
serves several purposes. First, aluminum has a low thermal emissivity, and so
the foil layer provides
thermal insulation. Second, the foil adds some resiliency to the paper when
subjected to hot moisture
and lipids, such as vegetable and animal fats, dairy products etc.
While cheap to produce, manufacture, and effective at insulating, such
laminated foil paper
products also have many disadvantages. Aluminum foil (1) is persistent in the
environment as it does
not decompose, contributing to long term landfills, (2) is frequently litter
that is unsightly and may
cause obstruction in the guts of smaller animals when ingested, (3) is not
recyclable or repulpable,
causing problems if accidentally introduced into a repulping mill, (4) does
not burn if the material is
incinerated and (5) has been linked to certain neurodegenerative diseases in
humans when ingested.
For similar reasons, some paper beverage cups are also difficult to recycle.
They are coated
with a low molecular weight polyethylene, which causes problems when
introduced into the pulp.
What is needed is a highly thermally insulating paper structure that provides
one or more of
the following benefits: (1) is non-toxic and safe for use with food, (2) is
thin and can be supplied to
restaurants in roll or sheet format, (3) insulates hot food from cooling, (4)
is recyclable by municipal
1
CA 03153211 2022-3-30 SUBSTITUTE SHEET (RULE 26)
WO 2021/067367
PCT/US2020/053421
recycling services without separation or segregation from other papers in the
waste stream, (5) is
biodegradable or biodestructable and therefore ephemeral when released into
the environment (6) is
able to maintain integrity with condensation formation after wrapping hot
food, and (7) is resistant
to the penetration of oils and fats.
SUMMARY OF THE INVENTION
The present invention is directed to insulated paper products that (1)
insulate food positioned
therein and/or surrounded thereby, (2) are biodegradable or biodestructable,
recyclable, repulpable,
and (3) can be printed and decorated, and (4) are food contact safe. The
disclosed insulated paper
products utilize a coating that acts in a similar manner to a laminated
aluminum foil. Insulating
materials included within the coating are coated onto a variety of paper
products.
The present invention is directed to paper products coated with a thermally
insulating layer.
In one exemplary embodiment, the insulated paper product of the present
invention comprises an
insulated coated paper product comprising one or more paper layers and at
least one insulating
coating.
In another exemplary embodiment, the insulated paper product of the present
invention
comprises a low basis weight paper coated on one side with a thermally
insulating coating and a
repulpable moisture and/or lipid barrier on the other side, wherein at least
one of the coatings has a
low thermal conductivity and/or a low thermal emissivity.
In another exemplary embodiment, the insulated paper product of the present
invention
comprises a corrugated integral paper product comprising: a first linerboard
layer comprising one or
more first coated layers, a second linerboard layer comprising one or more
second coated layers, and
a fluted paper layer comprising one or more fluted paper layers or a honeycomb
layer positioned
between the first linerboard layer and the second linerboard layer, wherein
(i) the first linerboard
layer, (ii) the second linerboard layer, and (iii) the fluted paper layer or
the honeycomb layer may
each independently comprise insulating material therein or thereon.
In one desired embodiment, the insulated paper product comprises a fully
recyclable, re-
pulpable, biodegradable, biodestructable, and thermally insulating food
wrapping paper product. In
another desired embodiment, the insulated paper product comprises a fully
recyclable, re-pulpable,
biodegradable, biodestructable, and thermally insulated cardboard box
The present invention is further directed to methods of making insulated paper
products. In
one exemplary embodiment, the method of making an insulating wrapping paper
product comprises:
forming a paper sheet comprising one or more layers on a fourdrinier wire,
then coating the formed
paper layer with a coating with a low thermal conductivity and/or a low
thermal emissivity onto the
paper layer. In some exemplary embodiments, the method of making an insulating
wrapping paper
2
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
product further comprises coating the formed paper layer with a moisture
barrier and/or a grease
resistant layer at the size press, and then coating a thin layer of a coating
with a low thermal
conductivity and/or a low thermal emissivity.
In one exemplary embodiment, the method of making an insulating wrapping paper
product
comprises: forming a paper sheet comprising one or more layers, then coating
the formed paper layer
with a moisture barrier and/or a grease resistant layer on one side, and then
coating a thin layer of a
coating with a low thermal conductivity and/or a low thermal emissivity on the
opposite side.
In one exemplary embodiment, the method of making an insulating wrapping paper
product
comprises: forming a paper sheet comprising one or more layers, then coating
the formed paper layer
with a moisture barrier and/or a grease resistant layer on one side, and then
coating a thin layer of a
coating with a low thermal conductivity and/or a low thermal emissivity on the
same side.
The present invention is even further directed to methods of using insulated
paper products.
In one exemplary embodiment, the method of using an insulated paper product
comprises: insulating
an object (e.g., food, medicine, pharmaceuticals, ice, flowers, etc.) via any
one of the herein-
described insulated paper products.
These and other features and advantages of the present invention will become
apparent after
a review of the following detailed description of the disclosed embodiments
and the appended claims.
BRIEF DESCRIPTION OF THE FIGURES
The present invention is further described with reference to the appended
figure, wherein:
FIG 1 depicts a perspective view of an exemplary paper product of the present
invention;
FIGS. 2A-2C depict exemplary cross-sectional views of the exemplary paper
product shown
in FIG. 1 as viewed along line 2-2 shown in FIG. 1;
FIG. 3 depicts a perspective view of another exemplary paper product of the
present
invention;
FIGS. 4A-4C depict side views of exemplary paper products of the present
invention;
FIG, 5 depicts a perspective view of another exemplary paper product of the
present invention
(also referred to herein as "an integral paper product");
FIGS. 6A-6D depict exemplary cross-sectional views of the exemplary paper
product shown
in FIG. 5 as viewed along line 6-6 shown in FIG. 5;
FIGS. 7A-7C depict an exemplary process flow in an exemplary papermaking
process
suitable for use in forming the exemplary paper products of the present
invention,
FIG, 8 depicts a side view of another paper product forming process step
suitable for forming
an exemplary paper product of the present invention;
3
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
FIGS. 9A-9C depict exemplary storage containers comprising any one of the
exemplary
insulated paper products of the present invention;
FIG. 9D depicts an exemplary cross-sectional view of the wall structure of the
exemplary hot
beverage cup shown in FIG. 9C;
FIGS. 10-13A depict additional exemplary storage containers comprising any one
of the
exemplary insulated paper products of the present invention;
FIG. 13B depicts a close-up cross-sectional view of the wall structure of the
exemplary
shipping container shown in FIG. 13A;
FIG. 14 depicts an exemplary cross-sectional view of a wall structure of an
exemplary
shipping container;
FIGS. 15-17 depict views of another apparatus that may be used to determine
the relative
emissivity of paper samples and/or insulating materials;
FIG. 18 depicts a view of another apparatus that may be used to determine the
relative
emissivity of paper samples and/or insulating materials;
FIG. 19A and 19B depict views of an apparatus that may be used to determine
the rate of heat
transfer of paper samples and/or insulating materials with FIG. 19A depicts a
cut-away view of
modifications to an expanded polystyrene cooler including dimensions, as well
as positioning of the
window through the cooler wall. FIG. 19B depicts a cross sectional view of the
test apparatus;
FIG. 20 depicts a corrugated structure of the present invention with one side
coated; and
FIG. 21 depicts single faced corrugate paper hot beverage cup sleeves
including the net and
cross section.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to insulated paper products comprising
fibers 11 (e.g., wood
pulp fibers 11) and insulating material 12. Although shown in all figures,
each paper layer 10
comprises fibers 11 (e.g., wood pulp fibers 11) with or without other paper
layer additives including,
but not limited to, an insulating material 12. Some definitions of fibers,
paper, and packaging, as
well as product specification and fiber sources, are provided below.
As used herein, the term "paper" is used to identify a type of non-woven
material in which
fibers are randomly oriented in all directions. Fibers principally made from
cellulose are poured as
a slurry on a mesh screen. As the paper is formed, the fibers come into
contact with each other, and
physically bond with neighboring fibers via a variety of interactions,
including hydrogen bonding.
The fibers originally come from plants including trees, although synthetic and
mineral fibers, or other
types of fibers, may optionally be included. Often, the paper also contains
recycled fiber. Wood
may be sourced from direct harvesting of trees from forest land, or from
lumber industry byproducts
4
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
(such as sawdust).
Paper fibers may include the fibrous portions from many parts, including
softwoods (such as
those plants with needles instead of leaves, for example, loblolly pine) and
hardwoods. Other plants
that yield useful paper fibers include but are not limited to bamboo, sugar
cane, wheat straw, reed
grass, mischanthus grass, coconut fiber, hemp fiber, cotton fiber, jute, palm,
reeds, and papyrus.
Cellulose fibers in many plants are bound together with lignin.
In the case of virgin (non-recycled) fiber, much of the lignin is removed
during the pulping
process. Recycled paper may include fibers from corrugated, fiber board,
writing paper, pressboard,
card, newspaper, tissue paper, specialty papers, linerboard, containerboard,
boxboard, PE-lined
paperboard, carton material, cup stock, or foodboard.
When made from trees, the pulping process involves methods to separate the
individual
cellulosic fibers into a slurry, as well as remove some or all of the lignin.
Pulping methods may
include a) thermomechanical pulping, which involves the use of steam and sheer
forces generated
between a spinning and a stationary plate, b) chemical pulping, which uses
strong chemicals to break
down the pulp by dissolving the lignin, and/or c) the semi-chem process, which
uses a combination
of mechanical and chemical methods. Most often, fluted medium board (e.g.,
fluted medium board
23) is made using semi-chem process pulp and/or recycled paper fiber. Other
types of pulp include
solid bleached sulfate pulp, chipboard, and lu-aft.
Paper (and paper layer 10), as used herein, may broadly include any material
that includes
15% or more cellulose fibers (discussed further below). Other additives,
including insulating
material 12, other particles/additives/components that impart grease resistant
and/or water resistant,
as well as other particles/additives/components to impart strength. Non-paper
(and non-paper layer
30) is anything containing less than 15% of cellulose fibers (discussed
further below).
As used herein, the term insulating material, such as insulating material 12,
is used to
described inorganic or organic materials that provide some degree of
insulation. The term insulating
material, as in insulating material 12, does not include air alone or any
other gas alone, although air
and/or another gas could be trapped within one or more inorganic or organic
insulating material 12.
Paper products 10/100760, comprising fibers 11 (e.g., wood pulp fibers 11) and
insulating
material 12, can either be made flat (e.g., insulated paper products 100/100')
using a screen to make
flat materials, or alternatively be molded, vacuum formed, or thermoformed
from a pulp suspension
to form essentially three-dimensional (non-flat) objects (e.g., molded or
otherwise formed containers
60 shown in FIGS. 9A-13B). Such three-dimensional paper products include
certain packaging, for
instance, egg crates and egg cartons, packaging that protects the corners of
products shipped in the
mail, biodegradable compost containers, biodegradable plant pots, disposable
urinals and bed pans
used in hospitals, disposable cat little boxes, and the like. Additives,
including insulating material
5
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
12, may be included within and/or on the paper products 10/100760 to impart
thermal insulation
properties, strength under moist or wet conditions, impart water repellency or
waterproofing, impart
grease absorption resistance, increase strength, improve the color, improve
printability, or other
aesthetic aspects.
Additives, including insulating material 12, may be added to the paper pulp
prior to casting
on the paper wire or otherwise molding the pulp with additives into a product
10/100760.
Alternatively, additives, including insulating material 12, may be added at
the size press, or after the
steam can dryers. Additives, including insulating material 12, can also be
added to a clay coating
(e.g., coating 30) often applied to liner board (e.g., liner board 21/22) to
make clay coated kraftback,
or clay coated newsback.
Paper packaging (e.g., containers 60 shown in FIGS. 9A-13B), formed from the
insulated
paper products 100/100'/100" of the present invention, may include a wide
variety of formats,
including: regular slotted container (RSC), overlap slotted container, full
overlap slotted container,
special center slotted container, Bag-in-Box, center special overlap slotted
container, center special
full-overlap slotted container, snap- or 1-2-3-bottom box with tuck top, snap-
or 1-2-3-bottom box
with RSC top, Full Bottom File Box, Hamper Style, Ft. Wayne Bottom or Anderson
Lock Bottom,
Bellows Style top and Bottom Container, Integral Divider Container, RSC with
Internal Divider or
Self Divider Box, Full-telescope Design-style Box, Full-telescope Half-slotted
Box, Partial-
Telescope Design-style Box, Partial-telescope half-slotted box, Design-Style
Box with cover, Half-
slotted Box with cover, Octagonal Double Cover Container, Double cover box,
Interlocking Double-
Cover box, double-thickness score-line box, one-piece folder, two-piece
folder, three-piece folder,
Liver panel folder, one piece folder with air cell/end buffers (used to
protect e.g. books), wrap-around
blank, tuck folder, one piece telescope, double-slide box, number 2 or 3 bliss
box, recessed end box,
self-erecting box, pre-glued auto bottom with RSC top flaps, four corner tray,
self-erecting six-corner
tray, flange box, Arthur lock bottom, valentine lock container, reverse
valentine lock container.
Medium board used in the insulated paper products 100/1007100" of the present
invention
may be fluted with flutes of different dimensions. See, for example, exemplary
fluted medium board
23 shown in FIGS. 6A-6D). The Fiber Box Handbook defines flutes and flute
dimensions as: A, B,
C, E, F, G, K, N, as well as R/S/T/D. The liner and medium papers may also be
tested and rated by
different burst grade: 125-350 SW, 23-55 ECT, 200-600 DW, 42-82 ECT DW, 700-
1300 TW, 67-
112 ECT TW. The carton or box (e.g., box 61) may then be folded into the
following industry known
styles: reverse tuck, snap lock, automatic bottom, straight tuck, tuck top
snaplock bottom, tuck top
automatic bottom, seal end, beers, mailing envelopes, folder, and simplex.
As discussed herein, the insulated paper products of the present invention may
comprise a
single paper layer with insulating material dispersed therein or coated
thereon, or may comprise two
6
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
or more paper layers in combination with insulating material, wherein the
insulating material is
within one or more of the paper layers of the insulated paper product and/or
is present as a component
within the insulated paper product (e.g., as a separate layer from the paper
layers and/or as a filler
within a layer or component of the insulated paper product). See, for example,
exemplary insulated
paper products 100/100'/100" in FIGS. 1-6D.
The insulated paper products of the present invention may further comprise one
or additional
layers other than the one or more paper layers and possible layers of
insulating material. Suitable
additional layers may include, but are not limited to, a coating that provides
reduced emissivity of
the insulated paper product, a coating that provides a desired color and/or
surface texture for the
insulated paper product, and a coating that provide enhanced water-repellency
(e.g., waterproofing
properties) to the insulated paper product. See, for example, exemplary
insulated paper products
100/100'/100" in FIGS. 6A-6D.
In exemplary insulated paper product 100/1007100" shown in FIG. 6A, a
corrugated
cardboard structure 100/100'/100" comprises two liner boards 21/22 bonded to a
fluted medium
board 23. One (or both) of the liner boards 21/22 may be coated (e.g., clay
coated) with coating
layer 30 for aesthetics. The fluted medium 23 may have a range of flute
dimensions, which are
classified by the industry as A-flute through F-Flute. Each liner board 21/22
may be made from one
ply of paper 10/100', or it may comprise two or more plies 10/100'. Other
types of board that could
be used in combination with the above-described insulated paper products
100/100'/100" discussed
above: pressboard ¨ pressed fiber board; honeycomb board ¨ e.g., two liner
boards 21/22 with a
honeycomb spacer in between.
In exemplary insulated paper product 100/100'/100" shown in FIG. 6B, a
corrugated
cardboard structure 100/100'/100" comprises two liner boards 21/22 bonded to a
fluted medium
board 23, and demonstrates several opportunities for incorporation of
insulating additives 12 into the
structure of corrugated cardboard 100/100'/100". First, insulating additives
12 have been added to
the furnish of the fluted medium 23. Second, the flutes have been further
isolated from heat transfer
via conduction by incorporating insulating additives 12 into the starch
adhesive 40 that bonds each
flute (e.g., of fluted medium 23) to the liner boards 21/22. Third, the liner
board 21 is coated with
insulating additives 12 via a coating 30. Fourth, to slow radiative heat
transfer, a low emissivity
coating 30 is overcoated on the outside of the corrugated cardboard structure
100/100'/100" (e.g., a
box 61). Such a coating 30 will reflect vs. absorb radiative heat and infra-
red radiation.
In exemplary insulated paper product 100/100'/100" shown in FIG. 6C, another
corrugated
cardboard structure 100/100'/100" comprises two liner boards 21/22 bonded to a
fluted medium
board 23, and again demonstrates several opportunities for incorporation of
insulating additives 12
into the corrugated cardboard structure 100/100'/100". First, insulating
additives 12 have been added
7
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
to the furnish of the fluted medium board 23, however, in such a way that the
insulating material 12
has preferentially segregated to one face (e.g., the upper face as shown) of
the medium fluted board
23 over the other (e.g., the lower face as shown). Second, the flutes (of the
medium fluted board 23)
have been further isolated from heat transfer via conduction by incorporating
insulating additives 12
into the starch adhesive 40 that bonds each flute of the medium fluted board
23 to the liner boards
21/22. Third, another coating 310 containing insulating additives 12 has been
incorporated in the
valleys 231 of the flutes. Fourth, one of the liner boards 21/22 contains
insulating additives 12
distributed in a non-uniform manner (e.g., such as in first liner board 21 as
shown). Fifth, to slow
radiative heat transfer, a low emissivity coating 30 is overcoated on the
outside faces of both liner
boards 21/22. Such a coating 30 will reflect vs. absorb radiative heat and
infra-red radiation.
Emissivity relates to both a surface's ability to absorb and radiate heat.
Thus, a low emissivity coating
will also show reduced heat loss through radiative cooling.
In exemplary insulated paper product 100/1007100" shown in FIG. 6D, another
corrugated
cardboard structure 100/1007100" comprises two liner boards 21/22 bonded to a
fluted medium
board 23, and again demonstrates several opportunities for incorporation of
insulating additives 12
into the insulated paper product 100/100'/100". First, insulating additives 12
have been added to the
furnish of the fluted medium board 23 in such a way that the insulating
materials 12 are distributed
evenly throughout the thickness of the one or more paper layers 10/100'.
Second, the flutes of the
fluted medium board 23 have been further isolated from heat transfer via
conduction by incorporating
insulating additives 12 into the starch adhesive 40 that bonds each flute of
the fluted medium board
23 to the liner boards 21/22. Third, another coating 30 containing insulating
additives 12 has been
coated onto one of the liner board 21. Fourth, the second liner board 22
contains insulating additives
12 distributed in a non-uniform manner. Fifth, to slow radiative heat
transfer, a low emissivity
coating 30 is overeoated on the outside faces of one of the liner boards 21.
Such a coating 30 will
reflect vs. absorb radiative heat and infra-red radiation. It will also show
reduced heat loss through
radiative cooling because emissivity relates to both a surfaces ability to
absorb and radiate heat.
In addition, any of the insulated paper products of the present invention
described herein may
be configured into a variety of shapes. For example, in some embodiments, the
insulated paper
product is in the form of an insulated cup or mug that may be used to house a
hot beverage such as
coffee. Such insulated paper products may be used instead of STYROFOAM cups,
eliminating the
disposal and environmental problems associated with STYROFOAM cups. In other
embodiments,
the insulated paper product is in the form of insulated packaging for
temporary storage and transport
of items such as food, medicines, etc. Such insulated paper products may be in
the form of an
insulated box, corrugated or not corrugated, as well as many other packaging
items discussed herein.
See, for example, exemplary insulated paper products 100/100'/100" in FIGS. 9A-
13B.
8
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
Regardless of configuration and/or shape, the insulated paper products
100/100'400" of the
present invention provide a degree of insulation due to coating compositions
that reduce heat transfer.
The present invention is further directed to methods of making and using the
herein disclosed
and described coated insulated paper products. The insulated paper products
may be made using
papermalcing equipment and techniques so as to produce one or more paper
layers. As discussed
herein, the methods of making the insulated paper products of the present
invention involve the
strategic placement of one or more insulating materials within a given
insulated paper product and/or
the strategic placement of one or more optional coatings on the insulated
paper product so as to
provide superior insulating properties, as well as other properties to the
insulated paper product.
Exemplary method steps and procedures for forming insulated paper products of
the present
invention are shown/described in FIGS. 7A-7C and FIG. 8.
FIGS. 7A-7C depict an exemplary process of forming paper sheets 10. As shown
in FIG. 7A,
pulp (furnish) is pumped into a header box 204. The fiber content of the
furnish is approximately 1-
2 wt% at this stage. A gate 205 allows furnish to flow out onto the moving
forming wire (a fine mesh
conveyor.) 206. The forming wire 206 may be 75-100 feet long. Initially, water
drains via gravity,
however, further down, vacuum boxes 207 beneath the wire 206 assist water
removal, increasing the
fiber content to around 20-30 wt%.
As shown in FIG. 7B, the material (-2040 wt% fiber) is then fed through one or
more felt
presses 208, which "blot" the precursor paper (i.e., precursor to paper layer
10), removing more
water, and increasing the fiber content to around 45-50 wt%. If starch or
another additive or coating
is to be applied, then that may be done at the size press 209 prior to drying.
Many different materials
may be added at the size press 209 prior to the dryers, including starch,
sizes, waxes, coatings to
impart wet strength, materials to impart water resistance, and materials that
impart grease proofing.
As shown in FIG. 7C, drying may be affected in a number of ways, including
running over
steam cans 210, or entering a long hot air-drying tunnel (not shown). After
passing through calendar
rolls 211 and prior to winding, the paper 10 may be between 6 to 10% moisture
content.
FIG. 8 depicts details of an exemplary linerboard 100 suitable for use in
forming an insulated
paper product 100/100'/100" of the present invention or a component (e.g., a
layer or outer
linerboard) of an insulated paper product 100/100'/100" of the present
invention. As shown in FIG.
8, exemplary linerboard 100 comprises two sheets of paper 10 laminated to one
another. Exemplary
linerboard 100 further comprises a first clay coating 30 directly on an outer
surface 13 of one of the
paper layers 10, and an outermost second white clay coating 30 so as to
provide a printable
surface/layer 38 for exemplary linerboard 100. First clay coating 30 evens out
the valleys and troughs
of the rough paper 10, leaving a smooth surface for additional coatings and
for high-quality printing.
9
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
The methods of using the insulated paper products 10/100/100'/100" of the
present invention
may comprise insulating food, medicines, etc. from hot or cold environments.
In some embodiments,
the method may simply comprise placing an item (e.g., food, medicines, etc.)
within an insulated
paper product 10/100/100'/100" of the present invention (e.g., putting hot
coffee in a cup of the
present invention). In other embodiments, the method may comprise placing an
item (e.g., food,
medicines, etc.) within an insulated paper product 10/100/100'/100" of the
present invention (e.g., a
bag or a box), and sealing the insulated paper product 10/100/100'/100" for
transport.
As discussed herein, methods of using the insulated paper products
10/100/1007100" of the
present invention may involve insulating an item (e.g., food, medicines, etc.)
from hot or cold
environments, wherein the item (e.g., food, medicines, etc.) is placed or
packaged within an insulated
paper product 10/100/1009/100" that has a conventional shape, such as a cup or
box. In other words,
the insulated paper products 10/100/100'/100" of the present invention take
the place or conventional
items such as cups and boxes so as to provide one or more advantages as
discussed above. As
discussed herein, the insulated paper products 10/100/1003/100" of the present
invention may have
a variety of shapes and configurations similar to many conventional items such
as cups and boxes.
During use, the insulated paper products 10/100/1007100"/60 of the present
invention
desirably provide/have one or more of the following features/properties in
addition to providing
insulating properties:
(1) Moisture and Grease Resistance: Desirably, the
insulated paper products
10/100/1007100"/60 of the present invention (e.g., a box 61) can be placed
into a freezer and then
taken out and stacked at room temperature. Such a process usually leads to the
insulated paper
product 10/100/1007100"/60 (e.g., a box 61) "sweating" through condensation in
the warm air
condensing on the surface of the insulated paper product 10/100/1007100"/60
(e.g., a box 61). In
this regard, it is advantageous for the insulated paper product
10/100/1007100"/60 (e.g., a box 61)
to be resistant to moisture ingress. Multiple different additives can be used
to reduce the propensity
of the insulated paper product 10/100/1007100"/60 (e.g., a box 61) to absorb
moisture and weaken
when moist. For example, perlite 12 is more hydrophobic than paper fibers 11,
so the incorporation
of perlite 12 into and/or onto a paper layer 10 renders the paper layer 10
less absorbent. Further, the
adhesive 40 that bonds flutes to liner board (see, FIGS. 6A-6D) can be made
moisture resistant by
adding a moisture resistant adhesive resin, such as Coragum SR available from
Ingredion,
Westchester IL. In addition, a hydrophobic treatment can be applied to the
exterior of the insulated
paper product 10/100/1007100"/60 (e.g., a box 61). Moreover, a chemical cross-
linking agent or
reactive resin (e.g. a methylol melamine) may be applied to the insulated
paper product
10/100/1007100"/60 (e.g., a box 61), so that it is less sensitive to moisture.
Lastly, paper fiber 11
may be treated with rosin, and then aluminum sulfate can be added to the
furnish to impart
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
hydrophobicity to the paper layer 10_ Alternatively, a wax may be added to
paper layer 10 to impart
hydrophobicity. Commercial examples of water-resistant coatings that may be
applied onto paper
layer 10 include, Epotal S440 (BASF) (i.e., a styrene acrylic based copolymer
emulsion), Rhoplex
P-376 (Dow) (i.e., a styrene acrylic copolymer emulsion binder), Diofan B204
(Solvay) (i.e., a
poly(vinylidene chloride) (PVDC) latex), Barrier-Grip 9471A (IGI) (i.e., a
blend including a styrene
acrylic copolymer emulsion, a poly(ethylene) wax and clay), Daran SL143
(Owensboro) (i.e., a
poly(vinylidene chloride) (PVDC) latex). Of particular interest are moisture
barriers that are
repulpable, including Barrier-Grip 9471A, Aquaban, EC404 (a repulpable
moisture bather) from
International Group Inc., (Toronto Canada.) or EcoShield Barrier Coating from
Cortec Packaging.
These proprietary commercial materials may include moisture and gas barrier
additives and
treatments such as low-molecular weight resins, waxes including paraffin wax
and natural waxes
such as beeswax, linear fatty acid esters of fatty alcohols, branched esters
for example esters of 15-
hydroxypalmitic acid, fatty alcohol ethers, hydrocarbons in the range of about
C15 to C50,
hydrocarbon resins, particularly petroleum resins, styrene resins,
cyclopentadiene resins, and terpene
resins. Such additives can be used in effective amounts, which vary depending
upon the properties
required.
While undesirable from an environmental and recycling perspective, a thin
layer of low
density polyethylene (PE) may also be coated onto paper layer 10, fiberboard
21/22/23, and card
stock to impart oil and water resistance, as is common practice in the fast
food and hot & cold
beverage retail industry. Alternatively, the surface of the paper may be cross
linked by applying
reactive groups that react with hydroxyl groups present in cellulose. For
examples, melamine
formaldehyde resins, urea formaldehyde resins, methylol melamine,
epichlorohydrin,
trichlorotriazine, dichlorotriazine, chlorotriazine coupled with diazabicylco-
[2,2,2]-octane which
acts as a catalyst, compounds that can undergo Michael 1,4 addition in the
presence of base, and a
wide range of other bifunctional reactive compounds. In recent years, the
paper industry has
experienced increased pressure to seek alternatives to PE liners and linings
for packaging, leading
the chemical industry to innovate new coatings that impart grease and water
resistance while being
repulpable. US 2019/0077537 to Georgia Pacific Bleached Board LLC teaches the
use of several
different coatings to impart resistance to water and lipid fluids to paper
without the use of PE film,
including Epotal S440 (BASF), Rhoplex P-376 (Dow), Diofan B204 (Solvay),
Barrier-Grip 9471A
(IGI), and Daran SL143 (Owensboro). These coatings were combined to impart
heat seal-ability as
well as water proofing to paper beverage cups.
(2)
Transient Aluminized Layer
for Low Emissivity: Addition of a thin aluminized
coating 30 onto the paper (e.g., paper layer 10 and/or insulated paper product
100/100' and/or
corrugated paper product 100" and/or storage container 60) and/or onto the
penile 12 to lower
11
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
emissivity. Aluminum has a very low emissivity and may be applied to various
materials through a
process called sputtering, or by vapor deposition. In this process, aluminum
atoms traverse a vacuum
and condense onto the surface of another material (e.g., paper layer 10). Many
thermal blankets are
made via a process like this. Perlite particles 12, as well as other types of
particles, may be coated
partially or totally in aluminum via these types of process. Paper or paper
fibers 11 may also be
metallized by an aluminum coating by similar processes. Aluminum foil and
metalized plastic films
do not re-pulp and have to be removed from the OCC and later waste streams, so
these materials are
not preferred in some embodiments of the present invention.
However, it is possible to incorporate a chelating agent in another layer of
the packaging (e.g.,
box 61), or for instance in the adhesive, or in one of the coatings. Such a
chelating agent would
function to remove the aluminum during a pulping process. Chelating agents may
include oxalic
acid and oxalate salts, EDTA (ethylene diamine tetraacetic acid) and its
various salts, salicylate,
sodium hexametaphosphate and other materials. In this way, the aluminum could
be removed.
Soluble aluminum salts are already used in papermaking for instance as a
flocculant for fines, as well
as in combination with rosin soap to impart water resistance.
(3) Repulpable/Recyclable/Biodestructable: A
repulpable/recyclable/biodestructable
thermally insulating coating, comprising one or more inorganic pigments, which
have been found to
reduce the transfer of radiant heat energy when coated onto paper. The
inventors found that a coating
that included certain pigments such as mica, bismuth oxychloride, bismuth
oxychloride coated mica,
sericite, zinc oxide, zinc sulfide, cadmium sulfide will reduce the rate of
radiative heat transfer
through the coated paper.
(4) Odor Control and Taint of Foodstuffs: A concern with packaging and
shipping of
foodstuffs is taint and odor. This may arise from the inherent smell of virgin
or recycled card, or it
could arise when one package containing a strongly odorous material is placed
in contact or adjacent
to a package containing a food, beverage, drug, or tobacco product. There may
be several ways to
mitigate odor and taint of foodstuffs by incorporating materials into the
paper structure. For instance,
transition metal ion modified silica nanoparticles such as those described in
U.S. Patent No.
7,976,855 are able to efficiently capture malodorous chemicals such as
mercaptans, carboxylic acids,
amine and other odors. U.S. Patent No. 8,168,563 teaches that silica
nanoparticles may be modified
by reaction with terminal aminoalkylthrimethoxysilanes and then with copper II
ions to further
enhance the odor capturing capabilities. Molecular sieves may also be included
to sequester low
molecular weight odor forming molecules such as hydrogen sulfide and zeolites
to sequester
ammonia and amine odors. Activated carbon was also found to impart thermal
insulation, and would
also be anticipated to absorb multiple odors. Activated carbon tends to be
acidic in nature, and so
may be especially good at taking up basic and weakly basic odors such as
ammonia and amine odors.
12
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
More complex odors also have an affinity for activated carbon, including
mercaptan, thiol, and
aromatic odors. Cyclodextrins, such as (3-cyclodextrin or y-cyclodextrin and
their derivatives may
also be incorporated for their odor absorbing properties. One or more of these
materials/features
could be incorporated into any of the here-in described paper layer 10 and/or
insulated paper product
100/100' and/or corrugated paper product 100" and/or storage container 60 to
modify and/or
minimize any odors present.
Odor transmission from one package to another, or from one good to another may
also be
mitigated through the use of barrier materials. As one object of the present
invention is repulpability
of packaging, aluminum foil, PE or PET film, and other synthetic materials
would not be consistent
with some embodiments of the present invention. However, some materials that
provide thermal
insulation have a microscopic flake morphology, such as mica and coated mica,
and these materials
may be useful for effectively blocking the transport of low and high MW
malodor causing materials
from ingress into packages (e.g., comprising or formed from insulated paper
product
10/100/100'/100") of the present invention,
(5) Fiber Blend. Recycling. and Strength: Short length fibers tend to come
from refined
hardwood, while longer fibers come from softwood. A good ratio of 75% softwood
25% hardwood
balances the properties of the two types of fiber, optimizing tensile
strength. Recently, hemp fibers
have come under increasing attention as a paper additive. Hemp fibers are far
longer than other pulp
fibers, help increase strength due to increasing contact points and bonding,
and so may be subjected
to multiple recycling steps ¨ far more than regular wood fibers. Hemp fibers,
being much longer
than softwood may be recycled around 40 times vs. 6 for other types of fiber.
One or more of these
materials/features could be incorporated into any of the here-in described
insulated paper layer 10
and/or insulated paper product 100/100' and/or corrugated paper product 100"
and/or storage
container 60.
In order to increase the ability of wood fibers to bond more through surface
interactions,
additional processes may be used to further fibrillate the fibers. For
instance, the fibers may be
subjected to an extreme high-shear environment, such as a colloid mill. The
high sheer environment
of two plate spinning in contact fibrillates cellulose fiber aggregates,
increasing bonding, as well as
the propensity to retain filler solids. Other ways to fibrillate the fiber can
include prolonged beating
in a mechanical Hollander pulp beater such as disclosed in the US. Patent No.
1,883,051 or by high-
sheer mixing, high-speed mixing, or media milling. Fibrillated cellulose may
increase porosity of
the paper and paper strength due to enhanced bonding area between fibers.
Other ways to increase
strength is by including nanocellulose into the paper formulation. One or more
of these
materials/features could be incorporated into any of the here-in described
paper layer 10 and/or
insulated paper product 100/100' and/or corrugated paper product 100" and/or
storage container 60.
13
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
(6) Water Resistance Repulpability: Rosin is often used as part of a two-
part system to
impart moisture resistance in paper (e.g., paper layer 10 and/or insulated
paper product 100/100'
and/or corrugated paper product 100" and/or storage container 60). The second
part is post addition
of aluminum salt solutions ¨ e.g. aluminum chloride or aluminum sulfate. The
aluminum reacts with
the rosin soap to make a hydrophobic coating, which may impact repulpability
yield. However,
including a chelating agent somewhere in another component of the paper
product may remove the
aluminum from the rosin, thereby increasing the repulpability yield. Other
areas of the paper that
could carry the chelating agent may include the starch adhesive, and internal
layer¨ for instance, the
fluted medium, or an inner layer of the composite. Vapor-Guard R5341B or
Barrier Grip 9471A
(The International Group Inc., Titusville PA) are also useful as barrier
coatings that provide the paper
with a degree of grease and water resistance, and are described along with
other suitable materials in
Georgia Pacific Patent Application Publication No. US2019/0077537.
(7) Binders: Binders are used in coatings to reduce pigment rub-off, ensure
adhesion of
the coating, and generally seal the coating or ink. Binders for water-based
coatings may be solutions
such as poly(vinyl alcohol) or ammonia neutralized poly(acrylic acid). Binders
that are latex based
are more common, as they have a lower viscosity and are easier to formulate
with and handle. Latex
binders in general are a stable emulsion or dispersion of polymer particles or
droplets in water. For
instance, natural rubber latex sourced from trees comprises non-crosslinked
cis-poly(isoprene) in
microscopic droplets dispersed in water, with protein acting as a surfactant
to stabilize the latex
emulsion. Man-made latex binders include polymers synthesized using emulsion
polymerization
such as poly(vinyl acetate), poly(acrylonitrile), poly(acrylates),
poly(methacrylates),
poly(butadiene), poly(styrene), poly(acrylic acid), and various copolymers of
these and other
polymers. As the water evaporates, the dispersed polymer particles come closer
together, until the
spherical droplets begin to touch. At first ,the spheres become distorted in
shape as the get closer. If
the glass transition temperature ("Tg") of the polymer is low enough, chain
intermingling between
the touching droplets will begin to join the droplets together, forming a
continuous film.
Rovene VSR-50 is an acrylic latex binder with pH in the range of 8-9, and
around 45% solids
content. The polymer contained in Rovene VSR-50 has a Tg of around 12 C, and
so a heat treatment
is needed to coalesce the dried polymer particles to form a film.
Rovene 4100 (Mallard Creek Polymers, NC) is a carboxylated styrene-butadiene
copolymer
emulsion with a polymer Tg around -5 C, so no post-dry heating is required to
form a film. The
product contains around 50% solids, and the emulsion has a pH of around 6.
Rovene 6106 is a
styrene-acrylic copolymer emulsion with a high Tg (>100 C), and so a post-heat
treatment is
required. Rovene 6090 is modified vinyl acetate copolymer emulsion with a
polymer Tg of 39 C.
This binder has release properties, allowing adhesive materials to be peeled
from the coating surface.
14
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
Tykote 6160 (Mallard Creek Polymers) is an approximately 50% solids pH 8.0-9.0
acrylic
polymer emulsion, with a polymer Tg of 7 C. This binder is claimed to have
flexibility combined
with moisture vapor barrier properties.
The present invention is further described by the following additional
embodiments,
examples, and claims. It should be understood that any feature and/or
component described herein
may be present alone or in combination with any other feature and/or component
or combination of
features and/or components described herein to form the here-in described
paper layer 10 and/or
insulated paper product 100/100' and/or corrugated paper product 100" and/or
storage container 60
of the present invention. It should be further understood that the numbered
embodiments provided
below describe many embodiments of the present invention, some claimed and
some unclaimed.
Even though some of the features in the numbered embodiments provided below
may not be claimed,
the unclaimed feature(s) in the numbered embodiments provided below do form
part of the present
invention, and may optionally be incorporated into any claimed product.
Additional Embodiments.
Insulated Paper Products
1. An insulated paper product 100 comprising: one or more paper layers 10,
and an insulating
coating 30 on at least one outer surface 13/15 of said one or more paper
layers 10, said insulating
coating 30 comprising (i) one or more insulating materials 12 comprising
bismuth oxychloride, mica,
bismuth oxychloride-coated mica, zinc oxide, aluminum-doped zinc oxide, zinc
sulfide, cadmium
sulfide, bismuth vanadate, gypsum, sericite, powdered silicon, silver-coated
glass bubbles, aluminum
oxide, hollow polymeric microsphere pigments, or any mixture or combination
thereof, and (ii) a
binder. As discussed herein, each paper layer 10 may further comprise one or
more additives, the
one or more additives including, but are not limited to, flocculants and
retention aids such as high
molecular weight poly(acrylamide), poly(ethylene imine), cationic guar gum,
and other cationic
polymers; additives to provide water resistance (e.g., wax, synthetic latexes
and resins); or any
combination thereof In some embodiments, the insulating coating 30 comprises
one or more
insulating materials 12 comprising bismuth oxychloride, mica, zinc oxide, zinc
sulfide, cadmium
sulfide, bismuth vanadate, sericite, or any mixture or combination thereof In
some embodiments,
the insulating coating 30 comprises one or more insulating materials 12
comprising bismuth
oxychloride, mica, zinc oxide, or any mixture or combination thereof.
2. The insulated paper product 100 of embodiment 1, wherein the one or more
paper layers 10
comprises a single paper layer 10,
3. The insulated paper product 100 of embodiment 1, wherein the one or more
paper layers 10
comprises two or more paper layers 10.
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
4. The insulated paper product 100 of any one of embodiments
1 to 3, wherein the insulating
coating 30 comprises one or more insulating materials 12 comprising bismuth
oxychloride, mica,
zinc oxide, aluminum-doped zinc oxide, zinc sulfide, cadmium sulfide, bismuth
vanadate, sericite,
or any mixture or combination thereof.
5. The insulated paper product 100 of any one of embodiments 1 to 4,
wherein the insulating
coating 30 comprises one or more insulating materials 12 comprising bismuth
oxychloride, mica,
zinc oxide, aluminum-doped zinc oxide, or any mixture or combination thereof
6. The insulated paper product 100 of any one of embodiments 1 to 5,
wherein the insulating
coating 30 comprises from about 50.0 weight percent (wt%) to about 99.9 wt% of
the one or more
insulating materials 12 and from about 50.0 wt% to about 0.1 wt% of the
binder. It should be
understood that the insulating coating 30 may comprise (i) any value between
about 50.0 wt% and
99.9 wt%, in increments of 0.1 wt%, e.g., 95.7 wt%, or any range of values
between about 50.0 wt%
and 99.9 wt%, in increments of 0.1 wt%, e.g., from about 90.2 wt% to 98.1 wt%,
of the one or more
insulating materials 12, and (ii) any value between about 50.0 wt% and 0.1
wt%, in increments of
0.1 wt%, e.g., 2.4 wt%, or any range of values between about 50.0 wt% and 0.1
wt%, in increments
of 0.1 wt%, e.g., from about 18.3 wt% to 0.2 wt%, of the binder. Suitable
binders include, but are
not limited to, one or more of the binders discussed on pages 14-15 above.
7. The insulated paper product 100 of any one of embodiments 1 to 6,
wherein the insulating
coating 30 comprises from about 90.0 wt% to about 99.9 wt% of the one or more
insulating materials
12 and from about 10.0 wt% to about 0.1 wt% of the binder.
8. The insulated paper product 100 of any one of embodiments 1 to 7,
wherein the insulating
coating 30 comprises from about 93.0 wt% to about 98.0 wt% of the one or more
insulating materials
12 and from about 7.0 wt% to about 2.0 wt% of the binder.
9. The insulated paper product 100 of any one of embodiments 1 to 8,
wherein the binder
comprises a latex binder. Suitable latex binders include, but are not limited
to, latex binders
comprising a polymer or co-polymer of one or more monomers selected from
styrene, butadiene,
acrylic acid, acrylate, methacrylate, and vinyl acetate.
10. The insulated paper product 100 of any one of embodiments 1 to 9,
wherein each insulating
coating 30 independently comprises one or more coating layers 30 with each
coating layer 30
comprising said insulating material 12 and said binder.
11. The insulated paper product 100 of any one of embodiments 1 to 10,
wherein at least one
insulating coating 30 comprises two or more coating layers 30 with each
coating layer 30 comprising
said insulating material 12 and said binder.
12. The insulated paper product 100 of embodiment 11, wherein said two or
more coating layers
30 comprise (i) a first coating applied onto the one or more paper layers 10
and comprising zinc
16
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
oxide, aluminum-doped zinc oxide, or any mixture or combination thereof, and
(ii) a second coating
applied onto the first coating and comprising bismuth oxychloride, bismuth
oxychloride-coated mica,
or any mixture or combination thereof.
13. The insulated paper product 100 of any one of embodiments 1 to 12,
further comprising a
treatment to impart water or grease resistance to the insulated paper product
100.
14. The insulated paper product 100 of embodiment 13, wherein the treatment
comprises adding
one or more treatment additives to one or more of the one or more paper layers
10.
15. The insulated paper product 100 of embodiment 13 or 14, wherein the
treatment comprises
adding one or more treatment additives to the insulating coating 30.
16. The insulated paper product 100 of any one of embodiments 13 to 15,
wherein the treatment
comprises adding a water or grease resistance layer comprising one or more
treatment additives onto
the insulated paper product 100.
17. The insulated paper product 100 of embodiment 16, wherein
the insulating coating 30 is
applied over the water or grease resistance layer.
18. The insulated paper product 100 of embodiment 16 or 17, wherein the
water or grease
resistance layer is applied onto an outer surface of the insulated paper
product 100 opposite the
insulating coating 30.
19. The insulated paper product 100 of any one of embodiments
14 to 18, wherein the one or
more treatment additives comprise a wax emulsion, a latex binder, Epotal S440
(BASF) (i.e., a
styrene acrylic based copolymer emulsion), Rhoplex P-376 (Dow) (i.e., a
styrene acrylic copolymer
emulsion binder), Diofan B204 (Solvay) (i.e., a poly(vinylidene chloride)
(PVDC) latex), Barrier-
Grip 9471A (IGI) (i.e., a blend including a styrene acrylic copolymer
emulsion, a poly(ethylene) wax
and clay), Daran SL143 (Owensboro) (i.e., a poly(vinylidene chloride) (PVDC)
latex), or any
combination thereof.
20. The insulated paper product 100 of any one of embodiments 14 to 19,
wherein the one or
more treatment additives comprise a wax emulsion, a latex binder, Epotal S440
(BASF) (i.e., a
styrene acrylic based copolymer emulsion), Rhoplex P-376 (Dow) (i.e., a
styrene acrylic copolymer
emulsion binder), Diofan B204 (Solvay) (i.e., a poly(vinylidene chloride)
(PVDC) latex), Barrier-
Grip 9471A (IGI) (i.e., a blend including a styrene acrylic copolymer
emulsion, a poly(ethylene) wax
and clay), Daran SL143 (Owensboro) (i.e., a poly(vinylidene chloride) (PVDC)
latex), or any
combination thereof.
21. The insulated paper product 100 of any one of embodiments
1 to 20, wherein the insulated
paper product 100 has an overall basis weight of less than about 200 grams per
square meter (gsm).
It should be understood that the insulated paper product 100 may have any
overall basis weight
between about 40.0 gsm and 200.0 gsm, in increments of 0.1 gsm, e.g., 97.6
gsm, or any range of
17
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
values between about 40.0 gsm and 200.0 gsm, in increments of 0.1 gsm, e.g.,
from 40.1 gsm to 160.0
gsm.
22. The insulated paper product 100 of any one of embodiments
Ito 21, wherein the insulated
paper product 100 has an overall basis weight ranging from about 50.0 gsm to
about 100 gsm.
23. The insulated paper product 100 of any one of embodiments 1 to 22,
wherein the insulated
paper product 100 comprises a void-containing insulated paper product 100".
24. The insulated paper product 100 of embodiment 23, wherein the void-
containing insulated
paper product 100" comprises voids 19 within at least one paper layer 10, the
voids 19 being
encapsulated by a material other than paper (e.g., a paper layer 10 containing
hollow beads/particles
(not shown)).
25. The insulated paper product 100 of embodiment 23 or 24, wherein the
void-containing
insulated paper product 100" comprises voids 19 within at least one paper
layer 10, the voids 19
being encapsulated by paper (e.g., a paper layer 10 containing air pockets 19
therein, possibly formed
via a molding process or a process in which a void-forming material is removed
from the paper layer
10). See, FIGS. 5-6D.
26. The insulated paper product 100 of any one of embodiments 23 to 25,
wherein the void-
containing insulated paper product 100" comprises a corrugated paper product
100".
27. The insulated paper product 100 of any one of embodiments 1 to 26,
wherein the integral
paper product 100' comprises (i) a first linerboard layer 21 comprising one or
more first paper layers
10/100/1001, (ii) a second linerboard layer 22 comprising one or more second
paper layers
10/100/100', and (iii) (a) a fluted paper layer 23 comprising one or more
fluted paper layers
10/100/100' or (b) a honeycomb layer (not shown) positioned between the first
linerboard layer 21
and the second linerboard layer 22, and (I) each of (i) said first linerboard
layer 21, (ii) said second
linerboard layer 22, and (iii) (a) said fluted paper layer 23 or (b) said
honeycomb layer (not shown)
may independently comprise insulating material 12 therein or thereon, and (II)
said insulating coating
is present on (i) an outer surface of said first linerboard layer 21, (ii) an
outer surface of said
second linerboard layer 22, or (iii) both (i) and (ii).
28. An insulated paper product 100 comprising a corrugated integral paper
product 100", said
corrugated integral paper product 100" comprising: a first linerboard layer 21
comprising one or
30 more first paper layers 10/100/100', a second linerboard layer 22
comprising one or more second
paper layers 10/100/100', and (a) a fluted paper layer 23 comprising one or
more fluted paper layers
10/100/100' or (b) a honeycomb layer (not shown) positioned between the first
linerboard layer 21
and the second linerboard layer 22, wherein one or more of (i) said first
linerboard layer 21, (ii) said
second linerboard layer 22, and (iii) (a) said fluted paper layer 23 or (b)
said honeycomb layer (not
shown) each independently comprise optional insulating material 12 therein or
thereon; and an
18
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
insulating coating 30 on (i) an outer surface of said first linerboard layer
21, (ii) an outer surface of
said second linerboard layer 22, or (iii) both (i) and (ii).
29. The insulated paper product 100 of embodiment 27 or 28, wherein (a)
said fluted paper layer
23 or (b) said honeycomb layer (not shown) provides pockets of air 19 between
said first linerboard
layer 21 and said second linerboard layer 22.
30. The insulated paper product 100 of embodiment 29, wherein said pockets
of air 19 represent
from about 20 to 80 volume percent of a total volume occupied by (a) said
fluted paper layer 23 or
(b) said honeycomb layer (not shown)(i.e., a total volume between innermost
opposing surfaces 25/27
of said first linerboard layer 21 and said second linerboard layer 22). See,
for example, FIG. 6A.
31. The insulated paper product 100 of any one of embodiments 27 to 30,
further comprising an
adhesive 40 that bonds portions of (a) said fluted paper layer 23 or (b) said
honeycomb layer (not
shown) to portions of said first linerboard layer 21 and said second
linerboard layer 22. Suitable
materials for adhesive 40 include, but are not limited to, starch adhesives,
synthetic latex adhesives
such as poly(vinyl acetate), natural rubber latex, modified starches,
hydrocolloids such as
hydroxypropylcellulose, carboxymethylcellulose, and other water-soluble
polymers such as
poly(vinyl alcohol). A cross-linking agent may also be added to the adhesive
to avoid potential
swelling of the adhesive and weakening of the bonds when wet. Flocculants and
retention aids may
also be included such as high molecular weight poly(aarylamide), poly(ethylene
imine), cationic quar
gum, and other cationic polymers. As discussed herein, in some embodiments,
adhesive 40 is at least
partially filled with one or more of the herein disclosed insulating materials
12.
32. The insulated paper product 100 of embodiment 31, wherein said adhesive
40 has insulating
material 12 dispersed therein.
33. The insulated paper product 100 of any one of embodiments 27 to 32,
wherein each of (i) said
first linerboard layer 21, (ii) said second linerboard layer 22, and (iii) (a)
said fluted paper layer 23
or (b) said honeycomb layer (not shown) independently comprises the insulated
paper product 100
of any one of embodiments Ito 25.
34. The insulated paper product 100 of any one of embodiments 27 to 32,
wherein each of (i) said
first linerboard layer 21, (ii) said second linerboard layer 22, and (iii) (a)
said fluted paper layer 23
or (b) said honeycomb layer (not shown) is substantially free of insulating
material 12.
35. The insulated paper product 100 of any one of embodiments 27 to 34,
wherein the integral
paper product 100' comprises said fluted paper layer 23.
36. The insulated paper product 100 of any one of embodiments 27 to 34,
wherein the integral
paper product 100' comprises said honeycomb layer (not shown).
37. The insulated paper product 100 of any one of embodiments 1 to 36,
wherein the insulated
paper product 100' further comprises one or more additional non-paper layers
20/30. As used herein,
19
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
the term "non-paper layer" is used to describe a layer that contains less than
5.0 wt% paper pulp or
cellulosic fiber, and typically contains 0 wt% to less than 4.0 wt% paper pulp
or cellulosic fiber.
Conversely, as used herein, the term "paper layer" (such as each paper layer
10) is used to describe
a layer that contains 5.0 wt% or more paper pulp or cellulosic fiber, and
typically contains greater
than 6.0 wt% up to 100 wt% paper pulp or cellulosic fiber (or any value
between 6.0 wt% and 100
wt%, in increments of 0.1 wt%, e.g., 50.0 wt%, or any range of values between
6.0 wt% and 100
wt%, in increments of 0.1 wt%, e.g., from 40.1 wt% to 70.2 wt%).
38. The insulated paper product 100 of embodiment 37, wherein the one or
more additional non-
paper layers 20/30 comprise a gypsum layer, a clay-containing layer, a polymer
coating, a pigment-
containing layer, a fabric layer (e.g., a nonwoven, woven or knit fabric
layer), a fiber-reinforcement
layer (e.g., a layer of unidirectional fibers), a second layer of insulating
material 12, a metal film
layer, a foam layer, or any combination thereof. One or more of the additional
non-paper layers
20/30 may be added to the insulated paper product 100 in order to provide a
desire property such as
lower (or higher) emissivity, lower (or higher) thermal conductivity, enhanced
water-repellency, an
aesthetically pleasing color and/or texture, or any combination thereof.
39. The insulated paper product 100 of embodiment 37 or 38, wherein the one
or more additional
non-paper layers 20/30 comprise a gypsum layer (not shown).
40. The insulated paper product 100 of any one of embodiments 37 to 39,
wherein the one or
more additional non-paper layers 20/30 comprise a clay-containing layer 30, a
coating 30 that
provides a lower or higher emissivity of the insulated paper product 100, a
pigment-containing layer
30, or any combination thereof. See, FIG. 6A.
41. The insulated paper product 100 of any one of embodiments 37 to 40,
wherein the one or
more non-paper layers 20/30 comprise at least two non-paper layers 20/30.
42. The insulated paper product 100 of any one of embodiments Ito 41,
wherein at least one
paper layer 10 of the one or more non-paper layers 10 comprise a paper
insulating material 12.
43. The insulated paper product 100 of embodiment 42, wherein the paper
insulating material 12
comprises perlite, perlite coated with copper ions, expanded perlite, perlite
hollow microspheres
(such as available from Richard Baker Harrison Ltd., UK, or CenoStar
Corporation (US), or Sit-Cele
microcellular aluminum silicate filler particles made by creating a structure
of multicellular spherical
bubbles comprising perlite, available from Silbrico (US), Sil-Cel
microspheres are available in a
range of particle sizes, and may be coated or uncoated, or Dicaperl HP-2000
perlite microspheres, as
sold by Dicalite (US), or flaked or milled perlite (such as Dicaperl LD1006,
cryogenic grades of
perlite, Dicaperl HP-100, HP-200, and HP100-40 grades, also sold by Dicalite),
porous volcanic
materials (such as pumice), vermiculite (including MicroLitee vermiculite
dispersions, available
from Dicalite), hollow expanded vermiculite, glass foams (such as Owens
Corning), recycled glass
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
foams (such as manufactured by GrowStone Inc.), cellular glass insulation
materials, cenospheres
(such as available from CenoStar Corp.), glass bubbles (such as available from
3M under the trade
designations iM30K, iM16k, and K20, as well as Q-Cel glass), ceramic
microspheres, plastic
microspheres, and synthetic hollow microspheres (such as available from Kish
Company Inc.), silica
aerogels (such as those available from Aspen Aerogels, and those that may be
incorporated into paints
and coatings under the Enova and Lumira brand from Cabot), microporous
polyolefin-based
aerogels (such as disclosed in US Patent Application Publication No.
2016/0272777 to Aspen
Aerogels Inc.), organic aerogels such as those disclosed in PCT WO 2019121242
to Henkel AG &
Co. KGAA which comprise thiol-epoxy based aerogels, xerogels (i.e., collapsed
aerogels), seagels
(i.e., microfoams made from agar and alginates), foamed starch, foamed paper
pulp, agar, foamed
agar, alginates, foamed alginates, bismuth oxychloride, metalized ceramics,
metalized fibers,
cadmium yellow pigment (cadmium disulfide), or any combination thereof.
Examples of
commercially available insulating materials 12 include, but are not limited
to, FOAMGLAS
products commercially available from Owens Corning (Pittsburg PA); and
Growstone products
commercially available from Growstone, LLC, a subsidiary of Earthstone
International Inc. (Santa
Fe, NM). Recycled glass suitable for use as insulating materials 12 is
typically crushed to a finely
divided powder and mixed with a blowing agent, e.g., carbon or limestone. It
is then passed into a
furnace hot enough to begin to melt the glass. As the glass powder particles
begin to fuse, the blowing
agent gives off a gas or vapor, forming bubbles inside the glass. This
generates a porous, mostly
closed cell glass foam, with high thermal and sound insulation properties.
Vermiculite may also be
used as a suitable insulating material 12. Vermiculite is a hydrous
phyllosilicate mineral that
undergoes significant expansion when heated. Exfoliation occurs when the
mineral is heated
sufficiently, and the effect is routinely produced in commercial furnaces.
Vermiculite is formed by
weathering or hydrothermal alteration of biotite or phlogopite.
44. The insulated paper product 100 of embodiment 42 or 43, wherein the
paper insulating
material 12 comprises perlite (e.g., in the paper 10, the adhesive 40, the
coating 30, and/or the
emissivity coating 30), aerogel (e.g., in the paper 10 and/or the adhesive
40), glass bubbles (e.g., in
the adhesive 40 and/or the coating 30), activated carbon (e.g., in the paper
10, the adhesive 40, the
coating 30, and/or the emissivity coating 30), or any combination thereof
45. The insulated paper product 100 of any one of embodiments 1 to 44,
wherein the insulating
material 12 comprises particles having an average particle size of less than
about 1000 microns (pm)
(or any average particle size greater than about 1.0 gm to less than about
1000 pm, in increments of
1.0 pm, e.g., 25 pm, or any range of average particle size less than about
1000 Lim, in increments of
1.0 pm, e.g., from about 50 Lim to about 500 pm). For example, perlite
particles typically have an
average particle size ranging from about 5.0 to about 150 pm, aerogel
particles typically have an
21
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
average particle size ranging from about 10 to about 800 gm, and glass bubble
particles typically
have an average particle size ranging from about 10.0 to about 50 pm.
46. The insulated paper product 100 of any one of embodiments
1 to 45, wherein the insulating
material 12 comprises particles having a multi-modal particle size
distribution.
47. The insulated paper product 100 of any one of embodiments 1 to 46,
wherein any paper layer
that contains insulating material 12 comprises from 4.0 weight percent (wt%)
to 99.0 wt% fibers
11, and from about 96.0 wt% to about 1.0 wt% insulating material 12, based on
a total weight of the
paper layer 10. It should be understood that a given paper layer 10 that
contains insulating material
12 can have (a) any weight percent of fibers 11 between 4.0 wt% and 99.0 wt%
(i.e., in increments
10 of 0.1 wt%, e.g., 55.5 wt%, or any range of values between 4.0 wt% and
99.0 wt%, in increments of
0.1 wt%, e.g., from 35.6 wr/0 to 74.1 wt%).
48. The insulated paper product 100 of any one of embodiments 1 to 47,
wherein any paper layer
10 that contains insulating material 12 comprises from 5.0 wt% to 75.0 wt%
fibers 11, and from
about 95.0 wt% to about 25.0 wt% insulating material 12, based on a total
weight of the paper layer
10.
49. The insulated paper product 100 of any one of embodiments 1 to 48,
wherein the insulating
material 12 has a material density of less than 1.0 gram per cubic centimeter
(g/cm3), more typically,
less than 0.6 g/cm3. It should be understood that the insulating material 12
can have any material
density less than 11.0 g/cm3 such as from greater than 0.01 g/cm3 to about
0.99 g/cm3 (or any value
between 0.01 and 0.99, in increments of 0.01 g/cm3, e.g., 0.48 g/cm3, or any
range of values between
0.01 and 0.99, in increments of 0.01 g/cm3, e.g., from 0.10 g/cm3 to 0.50
g/cm3).
50. The insulated paper product 100 of any one of embodiments 1 to 49,
wherein at least one
layer 10 of said one or more paper layers 10 has a layer density of less than
1.0 g/cm3. It should be
understood that the at least one layer 10 can have any layer density less than
1.0 Wcm3 such as from
greater than 0.01 g/cm3 to about 0.99 g/cm3 (or any value between 0.01 and
0.99, in increments of
0.01 g/cm3, e.g., 0.78 g/cm3, or any range of values between 0.01 and 0.99, in
increments of 0.01
g/cm3, e.g., from 0.20 g/cm3 to 0.60 g/cm3). It should be further understood
that any number of layers
10 of said one or more paper layers 10 may have an independent layer density,
each of which is less
than 1.0 g/cm3 (or any value between 0.01 and 0.99, in increments of 0.01
g/cm3, e.g., 0.88 g/cm3, or
any range of values between 0.01 and 0.99, in increments of 0.01 g/cm3, e.g.,
from 0.15 g/cm3 to 0.55
g/cm3).
51. The insulated paper product 100 of any one of embodiments 1 to 50,
wherein the insulated
paper product 100 is molded to form a three-dimensional object (e.g., a cup 62
or container 60).
52. A storage container 60 comprising the insulated paper product 100 of
any one of embodiments
1 to 51. See, FIGS. 9A-9C.
22
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
53. The storage container 60 of embodiment 52, wherein the storage
container 60 comprises a
storage volume 66 at least partially surrounded by one or more container walls
68.
54. The storage container 60 of embodiment 52 or 53, wherein the storage
volume 66 is
completely surrounded by or surroundable (i.e., the storage container 60 can
be configured to
surround the storage volume 66) by one or more container walls 68.
55. The storage container 60 of embodiment 53 or 54, wherein the one or
more container walls
68 comprise the insulated paper product 100 of any one of embodiments 1 to 49.
56. The storage container 60 of any one of embodiments 53 to 55, wherein
the one or more
container walls 68 comprise a gypsum layer, a clay-containing layer, a polymer
coating, a pigment-
containing layer, a bismuth oxychloride-containing layer, a mica containing
layer, an aerogel
containing layer, a fabric layer (e.g., a nonwoven, woven or knit fabric
layer), a fiber-reinforcement
layer (e.g., a layer of unidirectional fibers), a layer of insulating material
12, a metal film layer, a
foam layer, a layer of air, a coating that lowers an emissivity of the one or
more container walls (e.g.,
such as mica, bismuth oxychloride, zinc oxide, zinc sulfide, kaolin clay, or
cadmium sulfide), a
coating that lowers a thermal conductivity of the one or more container walls,
a coating that enhances
a water-repellency of the one or more container walls such as a wax, or a
fluorocarbon, or a reactive
cross-linking agent such as an epoxy or a urethane, or a silicone-based
coating, or one or more
coatings mentioned in U.S. Patent Application Publication No. 2019/077537, or
any combination
thereof
57. The storage container 60 of any one of embodiments 52 to 56, wherein
the storage container
60 comprises an insulating wrapper for a food item.
58. The storage container 60 of any one of embodiments 52 to 56, wherein
the container 60
comprises a cup 62, a mug, a flask, or a thermos 62. As shown in FIG. 9C, the
storage container 60
may be a hot beverage cup 62, which could replace both STYROFOAM cups, as
well as lined paper
cups along with the insulating paper ring currently provided to prevent
burning fingers of the person
holding the cup.
59. The storage container 60 of any one of embodiments 52 to 56, wherein
the container 60
comprises a clam shell type box packaging 60 for hot food 80. Such a container
may be made via
molding pulp using a vacuum forming machine. See, for example, FIG. 10.
60. The storage container 60 of any one of embodiments 52 to 56, wherein
the container 60
comprises a salad container 60 for chilled food 80. See, for example, FIG. 11.
61. The storage container 60 of any one of embodiments 52 to 56, wherein
the container 60
comprises a padded envelope 60. See, for example, FIG. 12.
62. The storage container 60 of any one of embodiments 52 to 56, wherein
the container 60
comprises a shipping container 60. See, for example, FIG. 13A. As shown in
FIG. 13B, exemplary
23
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
shipping container 60 comprises (i) multiple thinner paper layers 10, each of
which optionally
includes insulating materials 12 incorporated therein, optionally with (ii) a
non-uniform distribution
of material particles 92 (which could be insulating material 12), optionally
(iii) air 90 or an insulative
filler material between the layers 10, and (iv) optionally additional
coating(s) 30 on one or more of
the paper layers 10.
63. The storage container 60 of embodiment 62, wherein the
shipping container 60 comprises
shipping container walls 69 that comprise a closed cell foam 30'. See, for
example, FIG. 14. In
this embodiment, the closed cell foam 30' may be a biodegradable foam 30', for
instance a foamed
starch such as GreenCelle sold by KTM Industries Inc. Holt, MI, or a foamed
alginate, or pectin, or
gelatin, or agar material that has been foamed through one means or another,
and optionally
chemically cross-linked to a certain extent. As shown in FIG. 14, the shipping
container 60 may
include paper layers 10 that may optionally include insulating material 12,
and may also contain a
thermal barrier coating 30. The coating 30 could be designed to reduce
radiative heat transfer, or it
could be designed to reduce conductive heat transfer, or it could be designed
to reduce both.
64. A storage container 60 of any one of embodiments 52 to 63 or the
insulated paper product
100 of any one of embodiments 1 to 51, wherein the insulating coating 30 is
present on (i) an inner
surface 63, 00 an outer surface 13/15, or (iii) both (i) and (ii) of the
storage container 60 or the
insulated paper product 100, the insulating coating 30 having a low thermal
emissivity or thermal
barrier property. As used herein, the phrase "a low thermal emissivity" refers
to a thermal emissivity
of less than 0.90, as measured using Thermal Emissivity Method #3 Recommended
by Flir Systems
Inc. (described in the "Example" section below). Suitable materials for use in
a given "emissivity
coaling" include, but are not limited to, bismuth oxychloride, mica flakes,
perlite, kaolin, and any
combination thereof (e.g., mica flakes partially or completely coated with
bismuth oxychloride).
65. A storage container 60 of embodiment 64 or the insulated
paper product 100 of any one of
embodiments 1 to 51, wherein the treatment comprising a coating 20/30 on (i)
an inner surface 63,
(ii) an outer surface 13/15, or (iii) both (i) and (ii) of the storage
container 60 or the insulated paper
product 100, the coating 30 comprising one or more materials that increase the
water resistance of (i)
the inner surface 63, (ii) the outer surface 13/15, or (iii) both (i) and (ii)
of the storage container 60
or the insulated paper product 100.
66. A storage container 60 of any one of embodiments 52 to 65 or the
insulated paper product
100 of any one of embodiments 1 to 51, further comprising a coating 20/30 on
(i) an inner surface
63, (ii) an outer surface 13/15, or (iii) both (i) and (ii) of the storage
container 60 or the insulated
paper product 100, the coating 20/30 water-proofing the inner surface 63, (ii)
the outer surface
13/15, or (iii) both (i) and (ii) of the storage container 60 or the insulated
paper product 100. By
"waterproofing," it is meant that the outer surface 13/15 of the storage
container 60 or the insulated
24
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
paper product 100 can be in contact with water for 24 hours and maintain its
structural integrity.
Methods of Making Insulated Paper Products
67. A method of making the insulated paper product 100 of any one of
embodiments 1 to 51, said
method comprising coating the one or more paper layers on at least one side
with the insulating
coating 30.
68. The method of embodiment 67, said method further comprising at least
one papermaking step
to form the one or more paper layers.
69. The method of embodiment 67 or 68, said method further comprising a
treatment step to
impart water or grease resistance to the insulated paper product 100.
70. The method of embodiment 69, wherein the treatment comprises adding one
or more
treatment additives to one or more of the one or more paper layers 10.
71 The method of embodiment 69 or 70, wherein the treatment
comprises adding one or more
treatment additives to the insulating coating 30.
72. The method of any one of embodiments 69 to 71, wherein the treatment
comprises adding a
water or grease resistance layer comprising one or more treatment additives
onto the insulated paper
product 100.
73. The method of any one of embodiments 69 to 72, wherein the
insulating coating 30 is applied
over the water or grease resistance layer 30.
74. The method of any one of embodiments 69 to 73, wherein the water or
grease resistance layer
is applied onto an outer surface of the insulated paper product 100 opposite
the insulating coating 30.
75. The method of any one of embodiments 70 to 74, wherein the one or more
treatment additives
comprise a wax emulsion, a latex binder, Epotal S440 (BASF) (i.e., a styrene
acrylic based
dispersion), Rhoplex P-376 (Dow) (i.e., a styrene acrylic binder), Diofan B204
(Solvay) (i.e., a
polyvinylidene chloride (PVDC) latex), Barrier-Grip 9471A (IGI) (i.e., a
styrene acrylic/PE wax/clay
blend), Daran SL143 (Owensboro) (i.e., a polyvinylidene chloride (PVDC)
latex), or any
combination thereof
76. The method of any one of embodiments 70 to 75, wherein the one or more
treatment additives
comprise a wax emulsion, a latex binder, Epotal S440 (BASF) (i.e., a styrene
acrylic based copolymer
emulsion), Rhoplex P-376 (Dow) (i.e., a styrene acrylic copolymer emulsion
binder), Diofan B204
(Solvay) (i.e., a poly(vinylidene chloride) (PVDC) latex), Barrier-Grip 9471A
(IGI) (i.e., a blend
including a styrene acrylic copolymer emulsion. a poly(ethylene) wax and
clay), Daran 5L143
(Owensboro) (i.e., a poly(vinylidene chloride) (PVDC) latex), or any
combination thereof.
77. The method of any one of embodiments 67 to 76, said method further
comprising
incorporating one or more additives into at least one paper layer 10 within
the one or more paper
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
layers 10. Suitable additives include, but are not limited to, one or more
insulating materials 12,
copper ions, waxes, synthetic (e.g., polymeric or glass) fibers, silica,
surface modified silica,
transition metal surface modified silica, cyclodextrin, sodium bicarbonate,
silicones to impart grease
and water resistance, metalized ceramic particles, metalized fibers, cationic
starches, cationic
polymers, such as cationic guar gum, poly(ethylene imine) (e.g., poly(ethylene
imine marketed as
Polymin P and available from Aldrich Chemical), fillers, sizes, binders, clays
including bentonite
clay, kaolin clay, and other minerals, calcium carbonate, calcium sulfate, and
other materials that
may be added to paper products for different reasons, and any combinations
thereof The filler may
make the paper more receptive to printing, for instance, or make the paper
glossy. Many fillers have
a density greater than 1.0 g/cm3. Flocculants and retention aids, may also be
included such as high
molecular weight poly(acrylamide), poly(ethylene imine), cationic guar gum,
and other cationic
polymers. Sizes and binders may also be added to help provide strength to
papers, and can include
starches, hydrocolloids, artificial and natural polymer latexes, such as
RHOPLEX acrylic resins
from Dow Chemical and ROVENE binders from Mallard Creek Polymers (Charlotte
NC). Water
soluble polymers, such as poly(vinyl alcohol), and poly(acrylic acid) may also
be added to the paper.
Sometimes, water resistance on the final box is required. Vapor-Guard R5341B
or Barrier Grip
9471A (The International Group Inc., Titusville PA) are useful as bather
coatings that provide a
given paper layer 10 with a degree of grease and/or water resistance.
78. The method of any one of embodiments 67 to 77, said method further
comprising forming at
least one fluted paper layer 10 within the one or more paper layers 10. See,
for example, FIGS. 6A-
6D.
79. The method of any one of embodiments 67 to 78, further comprising:
applying at least one
additional layer onto the insulated paper product 100. The additional layer
could be another layer 20
of insulating material 12, a coating 20/30 (e.g., a coating 30 that increases
or decreases an emissivity
of a paper layer 10/100" or an integrated product 100"), a non-paper layer 30,
a layer of air 90, or
any combination thereof See, for example, FIGS. 6A-6D and 14.
80. The method of any one of embodiments 67 to 79, said method further
comprising forming a
storage container 60.
81. The method of embodiment 80, wherein the storage container 60 comprises
the storage
container 60 of any one of embodiments 52 to 66.
82. The method of any one of embodiments 67 to 81, said method further
comprising forming at
least one paper layer 10 within the one or more paper layers 10 using recycled
insulated paper product
100 of any one of embodiments 1 to 51 For example, one method of making at
least one paper layer
10 and a container 60 formed therefrom comprises forming a corrugated
structure 100" with at least
one outer ply/liner 21/22 that contains fiber 11 and insulating material 12,
and a fluted median
26
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
ply/liner 23 without insulating material 12, comprising: suspending cellulose
fibers 11 in water to
make paper pulp 11; forming a fibrous first layer 10 from the pulp 11;
suspending cellulose fibers 11
in water, adding voided materials (e.g., hollow insulating material 12),
optionally adding surface
active agents, optionally adding a flocculent; forming this layer 10 on top of
the first layer of pulp
10; suspending cellulose fibers 11 in water to make paper pulp 11; forming a
fibrous top layer 10 on
top of the second layer 10; pressing and drying the resultant three-ply
insulated paper sheet 100';
optionally coating at least one of the surfaces of the three-ply insulated
paper sheet 100' with a
coating 30 selected from comprising aluminum, silver, mica, sericite, zinc
oxide, zinc sulfide,
cadmium sulfide, bismuth oxychloride, bismuth oxychloride coated mica, bismuth
vanadate,
gypsum, or combinations thereof; passing a paper sheet 10 through a corrugator
to make a fluted
layer 23 while adhering two insulated paper sheets 100' as liner boards 21/22
to the fluted layer 23
to form corrugated board 100"; optionally adding an additional fluted layer 23
and another liner
board 21or 22 to make a double walled corrugated structure 100", containing
three insulated liner
boards 21/22 and two fluted layers 23; cutting the double walled corrugated
structure 100" into the
form/shape of a box 60; and allowing the off-cuts (e.g., scraps from the
cutting step) to be sent back
to the repulping mill mixed with off-cuts from non-insulating board. Another
method of making at
least one paper layer 10 and a container 60 formed therefrom comprises forming
a corrugated
structure 100" with at least one outer ply/liner 21/22 that contains a paper
layer 10 and an insulating
material layer 20, and a fluted median ply/liner 23 without insulating
material 12, comprising:
suspending cellulose fibers 11 in water to make paper pulp 11, and optionally
adding a flocculant;
forming a fibrous first layer 10 from pulp 11; suspending voided materials
(e.g., hollow insulating
material 12) in water, optionally adding surface active agents, and optionally
adding a flocculent
and/or a binder; forming this layer 20 on top of the first layer 10 of pulp
11, through curtain coating,
slot-die coating, rod coating, spray application, etc.; suspending cellulose
fibers 11 in water to make
paper pulp 11 optionally adding a flocculant; forming a fibrous top layer 10
on top of the second
layer 20; pressing and drying the resultant insulated paper sheet 100';
optionally coating at least one
of the surfaces of the resultant insulated paper sheet 100' with a coating 30
comprising aluminum,
silver, mica, sericite, zinc oxide, zinc sulfide, cadmium sulfide, bismuth
oxychloride, bismuth
oxychloride coated mica, bismuth vanadate, gypsum, or combinations thereof;
passing a paper sheet
10 through a corrugator to make a fluted layer 23 while adhering two insulated
paper sheets 100' as
liner boards 21/22 to the fluted layer 23 to form corrugated board 100";
optionally adding an
additional fluted layer 23 and another liner board 21or 22 to make a double
walled corrugated
structure 100", containing three insulated liner boards 21/22 and two fluted
layers 23; cutting the
double walled corrugated structure 100" into the form/shape of a box 60; and
allowing the off-cuts
(e.g., scraps from the cutting step) to be sent back to the repulping mill
mixed with off-cuts from non-
27
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
insulating board. Yet another method of making at least one paper layer 10 and
a container 60 formed
therefrom comprises forming a corrugated structure 100" with at least one
outer ply/liner 21/22 that
contains fiber 11 and insulating material 12, and a fluted median ply/liner 23
that comprises insulating
material 12, comprising: suspending cellulose fibers 11 in water to make paper
pulp 11; forming a
fibrous first layer 10 from the pulp 11; suspending cellulose fibers 11 in
water, adding voided
materials (e.g., hollow insulating material 12), optionally adding surface
active agents, optionally
adding a flocculent; forming this layer 10 on top of the first layer of pulp
10; suspending cellulose
fibers 11 in water to make paper pulp 11; forming a fibrous top layer 10 on
top of the second layer
10; pressing and drying the resultant three-ply insulated paper sheet 100';
optionally coating at least
one of the surfaces of the three-ply insulated paper sheet 100' with a coating
30 selected from
comprising aluminum, silver, mica, sericite, zinc oxide, zinc sulfide, cadmium
sulfide, bismuth
oxychloride, bismuth oxychloride coated mica, bismuth vanadate, gypsum, or
combinations thereof;
passing the resultant three-ply insulated paper sheet 100' through a
corrugator to make a fluted layer
23 while adhering two insulated paper sheets 100' as liner boards 21/22 to the
fluted layer 23 to form
corrugated board 100"; optionally adding an additional fluted layer 23 and
another liner board 21or
22 to make a double walled corrugated structure 100", containing three
insulated liner boards 21/22
and two fluted layers 23; cutting the double walled corrugated structure 100"
into the form/shape of
a box 60; and allowing the off-cuts (e.g., scraps from the cutting step) to be
sent back to the repulping
mill mixed with off-cuts from non-insulating board. Yet another method of
making at least one paper
layer 10 and a container 60 formed therefrom comprises forming a corrugated
structure 100" with at
least one outer ply/liner 21/22 that contains a paper layer 10 and an
insulating material layer 20, and
a fluted median ply/liner 23 with an insulating layer 20, comprising:
suspending cellulose fibers 11
in water to make paper pulp 11, and optionally adding a flocculant; forming a
fibrous first layer 10
from pulp 11; suspending voided materials (e.g., hollow insulating material
12) in water, optionally
adding surface active agents, and optionally adding a flocculent and/or a
binder; forming this layer
20 on top of the first layer 10 of pulp 11, through curtain coating, slot-die
coating, rod coating, spray
application, etc.; suspending cellulose fibers 11 in water to make paper pulp
11 optionally adding a
flocculant, forming a fibrous top layer 10 on top of the second layer 20;
pressing and drying the
resultant insulated paper sheet 100'; optionally coating at least one of the
surfaces of the resultant
insulated paper sheet 100' with a coating 30 comprising aluminum, silver,
mica, sericite, zinc oxide,
zinc sulfide, cadmium sulfide, bismuth oxychloride, bismuth oxychloride coated
mica, bismuth
vanadate, gypsum, or combinations thereof; passing the insulated paper sheet
100' through a
corrugator to make a fluted layer 23 while adhering two insulated paper sheets
100' as liner boards
21/22 to the fluted layer 23 to form corrugated board 100"; optionally adding
an additional fluted
layer 23 and another liner board 21 or 22 to make a double walled corrugated
structure 100",
28
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
containing three insulated liner boards 21/22 and two fluted layers 23;
cutting the double walled
corrugated structure 100" into the form/shape of a box 60; and allowing the
off-cuts (e.g., scraps
from the cutting step) to be sent back to the repulping mill mixed with off-
cuts from non-insulating
board.
83. The method of any one of embodiments 67 to 82, said method further
comprising a molding
step so as to form a three-dimensional object from the insulated paper product
100.
84. The method of embodiment 83, wherein the molding step comprises a
pressure molding step,
a thermoforming step, a vacuum forming step, or any combination thereof
85. The method of any one of embodiments 67 to 84, wherein each paper layer
10 that contains
insulating material 12 comprises from 15.0 wt% to 99.0 wt% fibers 11, and from
about 85.0 wt% to
about 1.0 wt% insulating material 12, based on a total weight of the paper
layer 10.
86. The method of any one of embodiments 67 to 85, wherein each paper layer
10 that contains
insulating material 12 comprises from 15.0 wt% to 80.0 wt% fibers 11, and from
about 85.0 wt% to
about 20.0 wt% insulating material 12, based on a total weight of the paper
layer 10.
87. The method of any one of embodiments 67 to 86, wherein the insulating
material 12 has a
material density of less than 1.0 g/cm3 (or any value between 0.01 g/cm3 and
0.99 g/cm3, in
increments of 0.01 g1cm3, e.g., 0.48 g/cm3, or any range of values between
0.01 g/cm3 and 0.99 g/cm3,
in increments of 0.01 g/cm3, e.g., from 0.10 g/cm3 to 0.50 g/cm3).
88. The method of any one of embodiments 67 to 87, wherein at least one
layer 10 of the one or
more paper layers 10 has a layer density of less than 1.0 g/cm3 (or any value
between 0.01 g/cm3 and
0.99 g/cm3, in increments of 0.01 g/cm3, e.g., 0.78 g/cm3, or any range of
values between 0.01 g/cm3
and 0.99 g/cm3, in increments of 0.01 g/cm3, e.g., from 0.20 g/cm3 to 0.75
g/cm3). It should be further
understood that any number of layers 10 of the one or more paper layers 10 may
have an independent
layer density, each of which is less than 1.0 g/cm3 (or any value between 0.01
g/cm3 and 0.99 g/cm3,
in increments of 0.01 g/cm3, e.g., 0.44 g/cm3, or any range of values between
0.01 g/cm3 and 0.99
g/cm3, in increments of 0.01 g/cm3, e.g., from 0.18 g/cm3 to 0.85 g/cm3).
89. The method of any one of embodiments 67 to 88, wherein the integral
paper product 100 has
an integral paper product density of less than 1.0 g/cm3 (or any value between
0.01 g/cm3 and 0.99,
g/cm3 in increments of 0.01 g/cm3, e.g., 0.77 g/cm3, or any range of values
between 0.01 g/cm3 and
0.99 g/cm3, in increments of 0.01 g/cm3, e.g., from 0.18 g/cm3 to 0.53 g/cm3).
Methods of Using Insulated Paper Products
90. A method of using the insulated paper product 100 of any one of
embodiments 1 to 51 or the
storage container 60 of any one of embodiments 452 to 66, said method
comprising: insulating an
object via the insulated paper product 100 or the storage container 60.
29
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
91. The method of embodiment 90, wherein the object is a surface_
92. The method of embodiment 90, wherein the object is a food item, a
medicine, or any other
item that is desirably kept at a cool temperature (e.g., a temperature below
room temperature or a
refrigerating temperature) or at an elevated temperature (e.g., a temperature
above room temperature
or a hot-out-of-the-oven temperature).
93. The method of embodiment 90 or 92, wherein the object is a food item.
94. The method of any one of embodiments 90 to 93, wherein the method uses
the storage
container 60 of any one of embodiments 52 to 66.
95. The method of any one of embodiments 90 to 94, wherein the insulated
paper product 100
comprises an insulating wrapper for a food item.
96. The method of any one of embodiments 90 to 94, wherein the method uses
the storage
container 60 and the storage container 60 comprises a box 61, a container 62
for temporarily housing
a liquid (not shown), a cup, a mug, a flask, or a thermos 62, a clam shell 60
for hot food 80 (See, for
example, FIG. 10.), a salad container 60 for chilled food 80 (See, for
example, FIG. 11.), a padded
envelope 60 (See, for example, FIG. 12.), a shipping container 60 (See, for
example, FIG. 13A), a
shipping container 60 comprising shipping container walls 69 that comprise a
closed cell foam 30'
(See, for example, FIG. 14), or any combination thereof. For example, in one
method of use, the
method comprises a method of maintaining an object at a controlled temperature
comprising: heating
or chilling an object (e.g., food, medicine, meat, fish, salad, vegetables,
flowers, pharmaceuticals,
biological specimens) to a pre-determined temperature T; packaging the object
inside any herein-
described storage container 60.
97. The method of any one of embodiments 90 to 94 and 96, wherein the
storage container 60 of
dimensions 12" x 10" x 7" is capable of keeping a combination of 900 g cooked
pork (or simulant)
and 1800 g of frozen water gel packs (conditioned to -20 C prior to placing
into the container) below
0 C after 10 hours in an external temperature of 23 C.
98. The method of any one of embodiments 90 and 92, further comprising
transporting the object
within the insulated paper product 100 or the storage container 60.
99. The method of any one of embodiments 90 and 92 to 98, further
comprising shipping the
object within the insulated paper product 100 or the storage container 60. For
example, in one method
of use, the method comprises a method of shipping an object at a controlled
temperature comprising:
chilling an object (e.g., food, medicine, meat, fish, salad, vegetables,
flowers, pharmaceuticals,
biological specimens) to below a spoiling temperature of the object; packaging
the chilled object
inside any herein-described storage container 60, along with frozen water gel
packs, dry ice, etc.;
closing the container; placing the storage container 60 into a vehicle (e.g.,
car, train, bus, airplane,
etc.); transporting the package to a pre-determined destination, removing the
storage container 60
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
from the vehicle; and delivering the storage container 60 to either the front
door of a residence, or to
the loading dock of a distribution center, or the entrance of a restaurant, or
the receiving department
of a business, wherein the temperature inside the unopened storage container
60 remains below the
food spoiling temperature for at least 24 hours.
100. The method of any one of embodiments 90 to 99, further comprising
repulping the insulated
paper product 100 and/or the storage container 60 after said insulating step,
wherein at least 80% of
the insulating filler is removed from the pulp during the repulping operation.
101. The method of any one of embodiments 90 to 100, further comprising
incorporating any fibers
11 and/or insulating particles 12 from a repulped insulated paper product 100
and/or a repulped
storage container 60 into a newly formed insulated paper product 100 and/or a
newly formed storage
container 60.
In addition, it should be understood that although the above-described
insulated paper
products and methods are described as "comprising" one or more components or
steps, the above-
described insulated paper products and methods may "comprise," "consists of,"
or "consist
essentially of' the above-described components or steps of the insulated paper
products and methods.
Consequently, where the present invention, or a portion thereof, has been
described with an open-
ended term such as "comprising," it should be readily understood that (unless
otherwise stated) the
description of the present invention, or the portion thereof, should also be
interpreted to describe the
present invention, or a portion thereof, using the terms "consisting
essentially of" or "consisting of'
or variations thereof as discussed below.
As used herein, the terms "comprises," "comprising," "includes," "including,"
"has,"
"having," "contains", "containing," "characterized by" or any other variation
thereof, are intended to
encompass a non-exclusive inclusion, subject to any limitation explicitly
indicated otherwise, of the
recited components. For example, an insulated paper product and/or method that
"comprises" a list
of elements (e.g., components, layers or steps) is not necessarily limited to
only those elements (or
components or steps), but may include other elements (or components or steps)
not expressly listed
or inherent to the insulated paper product and/or method.
As used herein, the transitional phrases "consists of' and "consisting of'
exclude any element,
step, or component not specified For example, "consists of' or "consisting of"
used in a claim would
limit the claim to the components, materials or steps specifically recited in
the claim except for
impurities ordinarily associated therewith (i.e., impurities within a given
component). When the
phrase "consists of' or "consisting of' appears in a clause of the body of a
claim, rather than
immediately following the preamble, the phrase "consists of' or "consisting
of' limits only the
elements (or components or steps) set forth in that clause; other elements (or
components) are not
31
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
excluded from the claim as a whole.
As used herein, the transitional phrases "consists essentially of' and
"consisting essentially
of' are used to define an insulated paper product and and/or a method that
includes materials, steps,
features, components, or elements, in addition to those literally disclosed,
provided that these
additional materials, steps, features, components, or elements do not
materially affect the basic and
novel characteristic(s) of the claimed invention. The term "consisting
essentially of' occupies a
middle ground between "comprising" and "consisting of'.
Further, it should be understood that the herein-described insulated paper
products and/or
methods may comprise, consist essentially of, or consist of any of the herein-
described components,
layers and features, as shown in the figures with or without any feature(s)
not shown in the figures.
In other words, in some embodiments, the insulated paper products of the
present invention do not
have any additional features other than those shown in the figures, and such
additional features, not
shown in the figures, are specifically excluded from the insulated paper
products. In other
embodiments, the insulated paper products of the present invention do have one
or more additional
features that are not shown in the figures.
The present invention is described above and further illustrated below by way
of examples,
which are not to be construed in any way as imposing limitations upon the
scope of the invention.
On the contrary, it is to be clearly understood that resort may be had to
various other embodiments,
modifications, and equivalents thereof which, after reading the description
herein, may suggest
themselves to those skilled in the art without departing from the spirit of
the present invention and/or
the scope of the appended claims.
EXAMPLES
Insulated paper products similar to exemplary insulated paper products
100/100'/100"M
shown and described in FIGS. 1-21 were prepared.
Example 1. Preparation of Insulated Paper Products:
Test Methods:
% solids analysis:
A polystyrene disposable weigh boat was accurately weighed to 4 decimal places
(tare mass).
Approximately 1-2 gram of liquid was placed in the weigh boat, and promptly
weighed to four
decimal places (gross-wet mass.) Subtracting the tare from the gross-wet mass
gives the net-wet
mass. The weigh boat was carefully tilted and rocked from side to side,
allowing the liquid to coat
the bottom of the weigh boat evenly, then it was placed in a cupboard for 24-
48 hours to evaporate
at room temperature. The dry weigh boat was re-weighed to four decimal places
(gross-dry mass).
Subtracting the tare from the gross-dry mass gives the net-dry mass.
32
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
% solids = 100 * net-dry / net-wet
pL-1:
All pH measurements were made using universal indicator paper, as supplied by
Micro
Essential Laboratories Inc. The color of the paper and the chart were compared
under indoor
fluorescent strip lighting.
Thermal Emissivity Comparison Method #1 (via conduction):
A modified version of Leslie's cube was used to screen multiple materials
rapidly. The
equipment is depicted in FIG. 15. FIG. 16 shows the view from directly above
the hotplate 70,
viewing the sample 10 in visible light. FIG. 17 shows the thermal view using
the Flir E40 thermal
camera 74.
One complication with this test is that it highly thermally insulating
materials will skew the
results, as the method relies upon conduction of heat from the back to reach
the same temperature.
So, if the flux of heat traveling through is reduced significantly, then the
black painted area will be
cooling faster (through radiation) than sample area, leading to a slightly
misleading result. For this
reason, we developed several other tests to screen materials for emissivity.
Materials:
= Paperboard sample(s) 10
= Rectangular corrugated strips, 1.5" x 3"
= Calipers
= Digital hot plate 70 that heats to at least 37 C (98.6 F) and with a
heating surface 71 at least
113 mm in diameter
= IR Camera 74 & Image Analysis Software
= Timer
= Polished aluminum strip 76, 0.75mm thick, 2" x 3"
= Mane black spray paint (Rust-oleum High Performance Wheel, matte black)
= 3M Spray Adhesive
Assumptions:
This test method assumes constant heat flow, and no edge losses or other
effects from
convection or radiation-based heat transfer (all the heat flows through the
sample).
Method:
1. Set the IR camera 74 to have an emissivity value of 0.95, or similar.
2. Turn on the hot plate 70 and set the temperature to 37 C. Once the hot
plate 70 has reached
33
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
37 C, sample testing can begin. The temperature can be checked by using the IR
camera 74.
3. Cut 1.5" x 3" cardboard strips. Spray them evenly with 3M aerosol adhesive.
4. Generously sprinkle the material 12 to be testing over the cardboard, then
tap to remove
the excess.
5. Mask one half of the cardboard with aluminum foil, then spray paint the
unmasked half of
the sample with the matte black paint. Allow to dry (-45 minutes).
6. Turn on the hot plate 70 and set the temperature to 37'C. Once the hot
plate 70 has reached
37 C, sample testing can begin. The temperature can be checked by using the IR
camera 74.
7. When ready to test:
- Place the corrugated sample on top of the hot plate, painted side up
- Place the polished aluminum also on the hotplate as a control.
- Start a timer for 2 minutes
8. At the end of two minutes, take an IR image of the top surface 75 of the
sample. Remove
the cover plate and paper sample.
9. Repeat steps 6 & 7 until all samples have been tested.
Analysis:
Use the thermal images to compare whether the sample is more or less emissive
than the shiny
or black painted portions.
The portion of the sample painted black has a high emissivity (approx. 0.90),
and thus shows
up red and displays the correct temperature. The polished aluminum material
has a low emissivity
(approx. 0.03), and thus shows up blue and displays a lower temperature than
the object actually is.
So, for this test, one should be able to say whether the emissivity of the
test sample is higher,
lower, or roughly equal to the emissivity of the black or silver samples.
Thermal Emissivity Method # 2 (By Illumination with an Incandescent Light
Bulb):
FIG. 18 shows the test apparatus used to quickly visually compare the thermal
emissivity of
materials directly from the way that they absorb and then re-emit heat
radiated from a hot-filament
light bulb 83. Samples were mounted onto a shiny metal plate 82. Half of the
sample was sprayed
with mat black paint, and half was left exposed. All paint and adhesives used
were allowed to dry at
room temperature for at least 40 minutes. The camera 74 was switched on, and
the spotlight was
shone onto the samples from a low angle, so that stray heat radiation
reflected away from the thermal
camera 74. Immediately, black and high emissivity materials lit up in the
thermal camera screen, as
the absorbed heat and then re-emitted it back out in all directions ¨
including towards the thermal
camera 74.
34
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
Materials with low emissivity were generally much darker in color, after
illumination for a
few seconds.
Thermal Emissivity Method #3 Recommended by Fur Systems Inc.:
The following procedure was found it the Flir E40 manual, to give an actual
emissivity
number. Method #3 is as follows:
Step 1: Determine the reflected apparent temperature. This is needed to
compensate for reflected
ambient radiation sources, reflecting from your sample. Here are the steps:
i) Scrunch up a sheet of aluminum foil into a ball,
and then uncrumple it.
ii) Attach this to a sheet of card of the same size.
iii) Put the cardboard in front of the object to me measured, with the foil
pointing towards
the camera 74.
iv) Set the internal camera emissivity setting to 1Ø
v) Record the apparent temperature of the aluminum foil
Step 2: Measuring the thermal emissivity:
vi) Adhere a strip of black electrical tape to the sample.
vii) Warm the sample up to at least 20 C warmer than the ambient temperature.
viii) With the camera 74 pointing to the tape, change the emissivity setting
to 0.97 and use
one of the on-screen temperature measurement selection tools to measure the
temperature of the tape.
ix) Move the temperature measurement tool to the sample surface without
the tape. Now,
change the internal emissivity setting until the measured temperature matches
that of the insulating
tape.
x) Record the emissivity of the sample.
Thermal Emissivity Test Method #4:
Thermal emissivity of certain samples was also tested by Thermophysical
Properties
Research Laboratory, Inc. of West Fayetteville IN using the following test
methodology.
The Table Top Emissimetry apparatus measures total normal emissivity over a
broad
wavelength band. Thin, square samples, 0.5" on a side are mounted facing
downward on an
isothermal copper block heated by a resistance heater and surrounded by
ceramic insulation. Five
type-K thermocouples are mounted on the bottom face of the isothermal plate.
Sample temperatures
during emissivity measurements are inferred from the closest thermocouple. The
samples are exposed
to ambient air with convection losses minimized by the face-down orientation
of the samples and the
small gap to the detector head.
The IR detector is a broadband thermopile with a 1 mm diameter sensitive area
and flat
spectral response from 1 ¨ 40 micrometers wavelength. The detector and
radiation shield are water
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
cooled and view the sample through a 3.56 mm aperture 5 mm from the sample
surface. The detector
is sensitive to radiation from an approximately 4.57 mm diameter spot on the
sample. Stray radiation
on the detector is minimized by a flat optical black coating on the inner
surface of the shield and both
faces of the aperture plate and by cooling the shield and aperture plates. The
shield temperature is
monitored by two type-K thermocouples embedded in the shield walls.
Thermocouple and detector
voltages are fed to an analog to digital module and attached to a personal
computer. The emissivity
E is calculated by the equation:
= Eshutter (Tstutter Tstield) SE bikbody (T:Ikbody 7w:hied)
e
(1 + S)(Tel
zample Tgensor)
where:
S = (VSensor Vshutter)
(Vbikbody Vsensor)
and V is the detector voltage, T is the temperature measured in Kelvin. The
subscripts are as follows:
Tsbuttcr is the temperature of the shutter.
Tshiekt is the temperature of the infrared detector when the shutter is in
place.
Tsensor is the temperature of the infrared detector during measurements.
Tblackbody is the temperature of the standard blackbody used to calculate the
unknown values.
Tsampie is the temperature of the sample using the thermocouple nearest the
sample.
Vshutler is the voltage from the infrared detector when the shutter is in
place.
Vblackbody is the voltage from the two black body readings taken.
Vsensor is the voltage of the infrared detector from each sample.
eshutter is the emissivity of the shutter at the temperature when read (e =
0.09)
Ebtkbody is the emissivity of the blackbody standard (e = 0.95)
e is the emissivity of sample.
In operation, power to the heater is adjusted by a computer controlled
Eurotherm temperature
controller to achieve a desired plate temperature and the system is allowed to
stabilize. The detector
is aligned with the sample to be viewed and its output voltage recorded. All
samples on the isothermal
plate are maintained in a constant radiation and convective heat transfer
environment as the X-Y
table is moved by the extended insulation block surrounding the detector head.
Measurement of an
oxidized copper reference standard with E = 0.96 0.01 and a closed aperture
measurement are made
before and after each sample suite at each temperature. Total hemispherical
emissivity is estimated
from total normal/total hemispherical relationships developed for metals and
insulators. The current
temperature range covered is from room temperature to around 150 C.
36
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
Expanded Polystyrene Cooler Window Test Method #5
This test was devised to measure the amount of heat flowing through a given
sample, as if it
were placed in direct sunlight on a hot day. While a steady-state test would
be ideal, the inventors
sought methods to make rapid assessments of thermal properties for further
research. While not
wishing to be limited by theory, this test combines both emissivity
(absorption of radiative heat) and
conduction to give a measure of the amount of heat passing through a given
sample.
Approximately 5 US gallons of Atlanta city water was placed into a 6-gallon
bucket and
sealed with a lid to equilibrate to room temperature for at least 24 hours.
Expanded polystyrene
coolers were purchased from Uline (Pleasant Prairie WI) (part number S21529)
Inside dimensions:
8" x 6" x7", wall thickness 1.5", and outside dimensions 11" x 9" x 10". A
100mm diameter acrylic
circular template was used to draw a circle on one of the 11" x 9" faces of
the cooler. The circle was
positioned 60mm from the top of the cooler, and 88mm from either side, as
shown in FIG. 43A-43B.
The circle was carefully cut out using an electrically heated hot knife (e.g.
RoMech Pro Hot Knife
Kit 200W Styrofoam cutter, made in China).
Two-part liquid silicone compound was mixed and used to seal the inside of the
insulated
cooler by painting the inner surfaces. The silicone resin (for example,
Diamond Driven Liquid
Silicone Compound, available from Amazon.com, or Oomoo 30 Silicone Mold Making
Rubber
available from Amazon.com, or Smooth-On Ecoflex 00-35 fast platinum cure
silicone rubber
compound kit, available from Smooth-On through Amazon.com, or RTV Silicone
Rubber for Mold
Making available from Specialty Resin & Chemical LLC, Dowagiac MI, or similar)
was allowed to
cure overnight. The following day, excess silicone resin was cut from the
exterior of the cooler in
the vicinity of the cut circular hole, to ensure bondability between the
expanded polystyrene and the
sample. Although silicone resins were used, it was also found that epoxy
resins could alternately be
used to waterproof seal coolers without destroying the expanded polystyrene
structure.
Sample preparation: Coatings were made onto 35 lb per 1000 sq ft (35 MSQ or
170 gsm)
kraft board using meyer rods and dried. Example board is available from Juvo
Plus Inc. (Irwindale
CA) in the form of "200 pack kraft laser and ink jet printer post cards 2 up
per page" SKU LJ-
WACHG-031218-11-1. This paper was selected as it proved to be a more
consistent source of !craft
fiberboard than obtaining samples of 35 lb MSQ liner board from various
corrugated board
manufacturers. In some tests, the kraft fiberboard was substituted with a
sheet of paper containing
fillers, or thermal insulation elements or other materials that the inventors
wished to assess, such as
metallized bubble wrap.
Aluminum foil (e.g. Glad Heavy Duty Aluminum Foil, distributed by Phoenix
Industries
Inc Denver CO, and available in grocery stores) was cut into sheets which were
sprayed black on the
dull side, using matt black spray paint (e.g. Rust-Oleum Painter's Touch 2X
Ultracover Paint +
37
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
Primer, Rust-Oleum Corporation, Vernon Hills IL) and allowed to dry. The
acrylic 100mm diameter
template was then used to mark and cut circular samples of coated haft board.
The back (kraft paper)
sides of these were then sprayed with an adhesive such as 3M Super 77 TM
Multipurpose Adhesive,
made by 3M Company (Minneapolis MN) and sold in many craft, office, and
hardware stores. The
discs were carefully bonded to the shiny side of the painted foil, and placed
between paper sheets
under several books (about 1 kg pressure) until dry, to maintain flatness of
the sample. The foil
sheet was trimmed so that approximately 0.5" to 1" of shiny foil remained
surrounded each sample.
3M Marine Adhesive Sealant Fast Cure 4000 UV (part # 05280) was then used to
carefully
adhere the black surface of the foil-sample composite to the outside of the
cooler, so that the sample
was in line with the opening into the cooler. Other sealants could be used
provided that they bond to
both painted foil and expanded polystyrene, do not destroy expanded
polystyrene by partially
dissolving it, and that they form a waterproof seal. This was then allowed to
cure overnight.
The cooler with the sample window was placed on the test rig built and
illustrated in FIGS.
19A-19B. The test rig allows the repeatable location of the test window in
front of the 110V 250W
tungsten filament heat lamp such as those used in restaurants to keep prepared
food hot prior to
serving (e.g. Intertek 5000707, white incandescent tungsten heat lamp). The
test rig shown in FIGS.
19A-19B includes adjustment of angle of incidence and distance from the
surface of the lamp to the
center of the test material. 4,500 g of water that had been allowed to
equilibrate to room temperature
was weighed to the nearest gram (using a Philips Essence kitchen electronic
top pan scale lg
increments to 5 kg capacity) and poured into the cooler. The stirrer blade was
inserted through the
lid, and a digital thermometer probe was also inserted through the lid. A
strobe light was used to
time the rotation of the stir blade to 600 rpm.
The water was stirred for several minutes until the temperature stabilized, at
which time it
was recorded. A timer was set for 15 minutes. The heat lamp was switched on,
and the timer started
simultaneously. The temperature of the water in the cooler was recorded every
15 minutes for one
hour.
All tests were conducted in an air-conditioned temperature-controlled
environment with an
air temperature between 68 F and 71 F. Positive control sample was a haft disk
that also had a layer
of aluminum foil laminated to it before adhering it to the shiny side of black
painted foil, and a
negative control consisted of an uncoated haft disk mounted onto a similar
foil sheet.
The temperature rise (DT) over one hour was used to determine the amount of
energy (Joules)
flowing through the coated haft board per unit time (Watts) using the
equation:
E (Joules) = 4.2 * DT * 4500
where 4.2 is the specific heat capacity of water in J.K-1.g-1; and 4500 is the
mass of the water
present in the container.
38
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
Rate of energy transfer into the water Watts (ER) through the window is
calculated by
dividing by the number of seconds in one hour, viz.:
ER=E/3600 Watts
As the surface area of the disc is known, then the energy flux Watts per
square meter can also be
calculated (W.m-2)
In some experiments, an infrared thermometer (Etekcity Lasergrip 1025D) was
also used to
measure the outside temperature of the disk, to give an approximation of the
temperature difference
over the thickness of the sample.
% Ash Content:
These tests were carried out by SGS Integrated Paper Services Inc., Appleton
WI according
to TAPPI T 211 om-16 Ash in wood, pulp, paper and paperboard: combustion at
525 C.
Approximately 10.0 g of paper was accurately weighed, and then ashed in a
muffle furnace at 525 C.
The remaining ash was then re-weighed to determine ash content.
% Moisture:
These tests were carried out by SGS Integrated Paper Services Inc., Appleton
WI according
to TAPPI T 550 om-13 Determination of equilibrium moisture in pulp, paper and
paperboard.
Repulpability:
Repulpability was tested by SGS Integrated Paper Services Inc., Appleton WI
according to
the "Voluntary Standard for Repulping and Recycling Corrugated Fiberboard
treated to Improve its
Performance in the Presence of Water and Water Vapor Protocol of 2013",
generated by the Fiber
Box Association, headquartered in Elk Grove Village, IL, 60007. Repulpable
means the test material
that can undergo the operation of re-wetting and fiberizing for subsequent
sheet formation, using the
process defined in this standard. In the repulpability test, materials are
weighed, pulped in a specific
manner using laboratory equipment, run through a laboratory disintegrator, and
then run through a
screen. The amount of rejected material is compared to the material that could
be reused as pulp to
make board as a % by mass. Two figures are derived: The first is the
acceptable recovery of the
fiber based upon the mass of material first entered into the test, and the
second is the percentage of
the recovered fiber that is accepted, not rejected. These figures constitute
the "% re-pulpability", and
the fiber box association has determined that a pass for both measures of
repulpability is >85%. Other
parameters recorded are: a) material fouling the equipment during pulping or
forming b) material
that does not disintegrate and has to be removed (becomes part of the rejects)
39
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
Coating Method:
A clip attached to a 3/4" thick glass plate is used to hold a stack of
photocopy paper and the
sheet of paper to be coated. A strip of masking tape was placed along the top
of the sheet to be
coated, and a paper towel was left hanging off the end. A transfer pipette was
used to make a line of
coating on the masking tape. This prevented the coating from prematurely
soaking into the paper
board to be coated. Meyer rods (available from RD Specialties Inc.) were used
to draw the coating
down over the sheet. The coating was then dried under ambient conditions.
Wetting Out and Stabilization:
Before materials can be included in a coating or into the fibrous matrix of
paper, materials
first have to be wetted out and dispersed. Some materials such as glass have
high enough surface
free energy that the wet out spontaneously ¨ whereas materials such as perlite
and aerogel require
surfactants to lower the surface free energy of the water enough to wet out
the material.
Surfactants may be non-ionic, cationic, or anionic. They may be high molecular
weight
polymers or copolymers, or they may be low molecular weight, and able to reach
newly created
interfaces rapidly. Surfactants for aqueous systems may be characterized by
their HIS value, HLB
stands for Hydrophilic-Lipophilic Balance, and is a measure of the capability
of the particular
surfactant to wet out various surfaces of differing surface free energy. Very
hydrophobic materials
have a low surface free energy, so a matching surfactant should also have a
low HLB value. More
hydrophilic surfaces ¨ those with multiple polar groups perhaps, require
surfactants with higher 1-1LB
values.
Microspersion EZ manufactured by Micropowders Inc. of Tarrytown NJ is a non-
ionic low
molecular weight surfactant with a low HLB. Dawn liquid dish soap,
manufactured by the Procter
& Gamble Co (Cincinnati OH) is an example of a low molecular weight anionic
surfactant. E-Sperse
100 (from Ethos, Greenville SC), Triton BG-10 (Dow) Glucopon 425 N (BASF) and
Glucopon 215
UP (BASF) are additional materials that can wet out certain hydrophobic
materials. The Suit/nal
range available from Evonik are ethoxylated acetylenic dials of fairly low
molecular weight. They
are non-ionic, and low foaming due to the molecular interactions of the
acetylenic moiety with the
water surface. Surfynol 104, 440,420 are representative examples.
Higher molecular weight materials are useful for stabilizing dispersions of
various materials
in water. Polymers may be anionic, cationic, or non-ionic ¨ or have a mixture
of characteristics.
Polymeric dispersants, also known as "grid aids" are often co-polymeric in
nature, for instance some
of the Joncryl resins from BASF are believed to be methacrylic acid ¨ styrene
¨ butylmethacrylate
copolymers, containing anionic ionizable groups. Zetasperse 3100, Zetasperse
3800, TegoDispers
752W, and TegoDispers 755W are also higher molecular weight dispersing agents
with a net negative
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
formal charge when ionized available from Evonik. Disperbyk 190, as well as
other Disperbyk
products available from BYK Chemie (Wallingford CT) are also polymeric /
copolymeric materials
that help stabilize dispersions through a) increasing particle surface
negative charge (electrokinetic
stabilization), and b) by allowing steric stabilization by dint of segments of
polymer dissolving into
the continuous medium.
Low Emissivity Insulative Clay Coatings:
Many corrugated cardboard boxes and fiberboard packages are coated with a clay
coating.
This coating provides a smooth flat ink-receptive surface that allows high
quality printing, it covers
the brown color of unbleached pulp with white, and gives the packaging a
higher quality feel. Often
the coating is applied in two layers. The first layer is kaolin clay based,
whitened by calcium
carbonate. This layer helps smooth the surface by filling in low spots. The
second layer also contains
titanium dioxide and calcium carbonate. The formulations of clay coatings
vary. Usually, they
contain kaolin clay, along with a film forming binder, such as an acrylic
latex, or sometimes a
cornstarch. A polymeric dispersant is usually included to stabilize the clay
coating, and a viscosity
control agent is usually also included, such as carboxymethyl cellulose, or an
hydrophobically
associated alkali swellable polymer (HASE polymer.) Calcium carbonate is also
usually included,
along with titanium dioxide pigment for whitening. The clay coating offers
another opportunity to
incorporate insulative elements that reduce conduction and radiative heat
transfer.
Emissivity Screening Results of Materials ¨ Conductivity Method #1:
Powdered materials were sampled and tested to observe emissivity differences
through a
thermal camera. The emissivity of the powder surface and the powder surface
sprayed with black
paint were compared. NVD = no visible difference.
Material
Comment after 2 minutes of heating
Aerogel IC 3120 powder
Possible lower emissivity
Perlite P-32 75 micron (cenosphere)
NVD
Thermacel powder
Possible lower emissivity
Hi Refractive Index glass beads 60g
Possible lower emissivity
Hi Refr. Index glass beads
NVD
35 p-45g
Hi Refr. Index glass beads
NVD
180 g-600g
Titanium dioxide powder
Lower
Zinc oxide powder
NVD
Yellow oxide pigment (iron oxide)
NVD
Bismuth oxychloride powder
Lower
Party pink mica powder
NVD
Super pearly white mica powder
NVD
Snowflake sparkle mica powder
Lower
Queens purple mica powder
NVD
41
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
Diatomaceous Earth powder NVD
Mica Sheet
Lower
Kaolin Clay powder NVD
Silicon powder
Lower
Kaolin Coating ¨ 42-02
Lower (slight)
Diatomaceous earth coating 43-01
Lower (slight)
These powder sample data gave us several ideas for follow up tests. Curiously,
some of the
materials gave different results if they are first formulated into a coating
(e.g. kaolin and
diatomaceous earth). In other cases, low thermal conductivity may have skewed
some readings.
Emissivity Screening Results of Materials ¨ Illumination Method #2:
Both powdered materials, as well as materials incorporated into coatings
coated onto
fiberboard were sampled and tested to observe emissivity differences through a
thermal camera. The
emissivity of the powder surface/coating surface and regular Cardboard were
compared when
illuminated by an incandescent tungsten spot light. NVD = no visible
difference in emissivity vs.
cardboard. Coating formulas follow below. NT = not tested
Material
Comment 4 seconds of illumination
Aerogel IC 3120 powder NVD
Silicon powder
NVD
Snowflake Sparlde Mica Lower
Pewter Silver mica
NVD
Hi RI glass beads 601.t Al coated
NVD
Hi Refr. Index glass beads 35 -45
Slightly lower
Thermacels
NVD
Titanium dioxide
Lower
Zinc oxide
Lower
Mica Sheet
Much Lower
Bismuth oxychloride powder
Much Lower
Perlite P-32 (75 1.0
NVD
30-03, Meyer #130 (25% glass bubbles)
Slightly lower
22-02, Meyer#130, (24% Aerogel in starch)
Lower
19-01, Meyer#130, (37% Perlite in starch)
Much Lower
19-01, Meyer #40, (37% Perlite in starch)
Lower
Kaolin Powder
Slightly Lower
Kaolin Coating ¨ 42-02 Meyer #40
Much Lower
Diatomaceous Earth powder
Lower
Diatomaceous earth coating 43-01
NVD
Aerogel Coating 38-02 (-50% aerogel)
Much Lower
Bismuth Vanadate
Much Lower
BiLite 20
Much Lower
Gypsum
Lower
Sericite Pigment Lower
Aluminum Oxide Powder Lower
42
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
These data gave us additional ideas to pursue insulating against thermal
radiative emission
and absorption, in addition to insulating against thermal conduction.
Additional Material Sources:
Glass beads, including high refractive index glass, and retroreflective hemi-
spherically
mirrored glass beads ¨ Cole Safety Products,
Glass microbubbles ¨ 3M specialty materials, iM30K
Bismuth oxychloride ¨ Making Cosmetics Inc (Redmond WA). This is a pearlescent
pigment, commonly used in cosmetics and packaging to impart a pearl effect.
Other sources include
BASF, as Biju Ultra UFC and Pearl Glo.
BiLite 20 powder ¨ Bi0C1 coated onto mica flakes (BASF)
Bismuth Vanadate ¨ Dominion Colour, Ontario
Titanium Dioxide ¨ Brambleberry (Bellingham, WA)
Zinc Oxide ¨ Brambleberry (Bellingham, WA), and Sky Organics
Snowflake Sparkle Mica ¨ Brambleberry (Bellingham, WA)
Super Pearly White Mica ¨ Brambleberry (Bellingham, WA)
Pewter Mica ¨ Brambleberry (Bellingham, WA)
Party Pink Mica ¨ Brambleberry (Bellingham, WA)
Queens Purple Mica ¨ Brambleberry (Bellingham, WA)
Yellow iron oxide powder ¨ Brambleberry (Bellingham, WA)
Thertnacels ¨ HyTech Thermal Solutions, Melbourne FL This material is an
additive that is
advertised to be mixed into paint in order to increase the paint's insulating
properties.
Rhoplex VSR-50 is an acrylic low VOC film forming binder emulsion in water.
Commonly
used in architectural coatings. Originally sold by Rohm & Haas, now available
from Dow Chemical.
Sericite comprised sericite mica surface treated with magnesium myristate or
Sericite White
sparkle luxury mica colorant pigment powder by H&B Oils Center Co.
Supertherm paint, from Eagle Specialty Coatings, British Columbia, Canada
Coatings to test for Emissivity on Fiberboard or Card
Formulation ID Materials
Quantity / g
IL 48-01
CaCO3
50.00
Water
50.00
10% Rhoplex VSR-50 in water
20.00
IL 48-02
Kaolin Clay
50.00
Water
70,00
43
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
10% Rhoplex VSR-50
20.00
ft 48-03
Bismuth Oxychloride
20.13
water
33.55
10% Rhoplex VSR-50 in water
8.05
HT 50-01
Eagle Specialized Coating
Low Emissivity Coatings on Fiberboard - Cooler Window Tests
Based upon the rapid testing using Emissivity tests 1 & 2, several materials
were selected for
further investigation. In preparation for printing, fiberboard is often coated
with a clay coating, which
smooths the surface and gives it a white color. A simple clay coat formulation
was generated:
Kaolin Clay Coating 127-01:
Material Quantity (g)
Water 130
Tego Dispers 755W 4.86
Evonik
Rovene 6400 52.89
Mallard Creek Polymers
Hydrite SB60 157.8
Imerys
Low Emissivity Coating Formulations by % composition
TS110 137- TS111 TS112 TS113 137- 127- 137- 137- 136-
02
06 02 04 05 01
Water 62,5 68.15 64.28 65.51 65.51 65.51 65,51
17.5 30.48 65.55
T-755W 8.18 2.5 5.01 5.10 5.10
5.1 5.1 5.1
R-6090 2.75
R-4100 2.85 2.71 2.85 2.85 2.85 2.85
2.85 2.85 2.85
HPMC 1.96
BiOC1 26.56
BiLite 26.5
ZnO 26.04
ZnS 26.54
MgO
26.54
TiO2
26.5
Al-ZnO
26.54
TH1000
80
TH500EF
66.67
Ag-Glass bubbles
26.5
ZnO - Sky Organics
T-755W - a slightly anionic, polymeric high performance wetting and dispersing
additive
commercially available under tradename 1E600 Dispers 755 W (Evonik (Allemon,
Pennsylvania))
R-6090 - all acrylic. emulsion commercially available under traderiame Reverie
6090 (Mallard
Creek Polymers (Charlotte, NC))
44
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
R-4100 denotes Rovene 4100 (Mallard Creek Polymers, NC) is a carboxylated
styrene-butadiene
copolymer emulsion with a polymer Tg around -5 C, so no post-dry heating is
required to form a
film. The product contains around 50% solids, and the emulsion has a pH of
around 6.
R-6090 denotes Rovene 6090 (Mallard Creek Polymers, NC) is a modified
vinylacetate copolymer
emulsion with a polymer Tg of 39 C. This binder has release properties,
allowing adhesive materials
to be peeled from the coating surface.
HPMC ¨3% aq solution of hydroxypropyl methyl cellulose.
Bi0C1¨ Bismuth oxychloride, sold as Pearl Glo (BASF)
Al-ZnO ¨ Aluminum-doped zinc oxide particles, AZO 100, 20-40 nm particle size,
available from
Oocap Inc. Las Crusas NM.
TH500 EF is RopaqueTM TH500EF from Dow Chemical hollow polymeric microsphere
pigment of
approximate size 0.4 micron diameter, and 30% solids.
TH1000 is RopaqueTm TH1000 from Dow Chemical hollow polymeric microsphere
pigment of
approximate size 1 micron diameter, and 26.5% solids
Silver (Ag) -coated glass bubbles, available from CoSpheric LLC.
Conductive silver metal coated hollow glass microspheres 5-30 microns, density
0.75g/cm3, product
ID: M-18-Ag-0.75
Kaolin clay coating 127-01 was coated onto 170 gsm (35 lbs/1000 sq 11) kraft
laser & ink jet
printer post cards, available from Juvo Plus Inc Irwinsdale CA, using a # 5
Meyer rod and dried in a
hot air oven at 250 F for 5 mins. Various coatings were selected and coated
onto the board, drying
the coatings between each application. A representative area was selected, and
tested on the test rig
illustrated in FIG. 19A-19B. The distance to the lamp was set to 4.5", 4500
grams of water were
weighed into the cooler, and the stirrer rotation was set to 600 rpm. The
water temperature rise over
1 hour of lamp exposure was recorded.
Exp: Al foil none
1 clay 2 clay 3 clay BiOC1 BiLite MgO
Base: Kraft Kraft Kraft Kraft Kraft Kraft Kraft Kraft
Coat! Al foil
127-01 127-01 127-01 127-01 127-01
127-01
Coat 2
127-01 127-01 TS110 137-02 TS113
Coat 3
127-01
Temp 1.3 4.1 3.7 3.5
3.5 3.4 3.1 3.5
Rise/ C
wn-2 87 274 247 234
234 227 207 234
Al foil: Aluminum foil (Reynolds heavy duty kitchen foil) was mounted dull
face down to Juvo kraft
paper using 3M spray adhesive.
Exp: ZnO ZnS
TiO2 Al.ZnO AgGls* TH1000 TH500
TiO2
EF on Foil
Base: Kraft Kraft Kraft Kraft Kraft Kraft Kraft Kraft
Coat! 127-01 127-01 127-01 127-01 127-01 127-01 127-01 Foil
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
Coat 2 TS111 TS112 137-06 127-02 136-01 137-05 137-04 137-06
Coat 3
Temp 3.2
3.3 3.5 5.1 3.1 3.7 33 2.9
Rise/ C
W.m-2 214 221 234 341
207 247 221 194
* Ag-coated glass bubbles, available from CoSpheric LLC. Conductive silver
metal coated hollow
glass microspheres 5-30 microns, density 0.75g/cm3, product ID: M-18-Ag-0.75
Exp: BiLite ZnO
Bi0C1 ZnO / BiLite /
BiLite ZnO
Base: Kraft Kraft Kraft
Kraft Kraft
Coat 1 127-01 127-01 127-
01 127-02 127-02
Coat 2 127-01 127-01 127-
01 TS111 137-02
Coat 3 137-02 TS111
TS110 137-02 TS111
Temp Rise/ C 3.2 3.1
3.3 3 3.1
vv,m-2 214 207
221 201 207
These data suggest that we can reduce the amount of energy absorbed by a box,
or emitted
from the inside surfaces of a box using coatings, by around 30%. While
aluminum foil, as well as
aluminized bubble wrap are very effective, they can cause problems if
introduced into the repulping
stream, and in any case are challenging to recycle. Not only could many of
these coatings be applied
to the interior and or exterior of the box, but could also be used as separate
sheets of packaging, as
illustrated as the loose sheets in FIG. 13A-13B.
Results of Emissivity Testing by Test Method #4:
Exp:
Contrl 1 clay 2 clay 3 clay TiO2 ZnS AgGls* ZnO
Base: Kraft Kraft Kraft Kraft Kraft Kraft Kraft Kraft
Coat 1 - 127-01 127-01 127-01 127-01
127-01 127-01 127-01
Coat 2 - - 127-01 127-01 137-
06 TS112 136-01 TS111
Coat 3 - - -
127-01 - - - -
E 0 23QC 0.900 0.859 0.883
0.885 0.869 0.519 0.888
c @ 30QC 0.909 0.866 0.894
0.895 0.873 0.530 0.918
E 0 40QC 0.915 0.866 0.894
0.904 0.874 0.536 0.933
* Ag-coated glass bubbles, available from CoSpheric LLC. Conductive silver
metal coated hollow
glass microspheres 5-30 microns, density 0.75g/cm3, product ID: M-18-Ag-0.75
Exp: BiLite BiLite ZnO
BiOC1 ZnO / BiLite BiLite / ZnO
Base: Kraft Kraft Kraft
Kraft Kraft Kraft
Coat 1 127-01 127-01 127-01
127-01 127-02 127-02
Coat 2 137-02 127-01 127-01
127-01 TS111 137-02
Coat 3 - 137-02 TS111
TS110 137-02 TS111
46
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
e@ 23 C 0.856 0,873 0.885
0.861 0.848 0.868
E@ 309C 0.873 0.875 0.897
0.876 0.860 0.877
e @ 40 C 0.882 0.871 0.902
0.881 0.856 0.881
Discussion of Emissivity vs. Heat Transfer Results
The inventors were surprised by the results of their own emissivity tests
methods 1 and 2, as
well as the emissivity results provided by the outside laboratory (Thermal
Emissivity Test Method
#4). Several coatings have been discovered by the inventors that apparently
reduce the transfer of
radiant heat energy from an incandescent light bulb (as a proxy to the full-
sun illumination of a
delivered package) through sheets of paper. The inventors were surprised to
find that the emissivity
results from the third-party laboratory did not correlate with the heat
transfer through the materials
measured by the cooler window tests. Clearly, the inventors may have
discovered several coatings
with non-obvious and unexpected thermal properties.
Sample Emissivity at 23 C Thermal Conduction / W.m-2
Clay+ZnO+BiLite 0.848
201
Ag-coated glass 0.519
207
Clay+BiLite+ZnO 0.868
207
Clay+Clay+ZnO 0.885
207
Clay+BiLite NT
207
Clay+Clay+BiLite 0.861
214
Clay+ZnO 0.888
214
Clay+ZnS 0.869
221
Clay+Clay+BiOCI 0.861
221
Clay+TiO2 0.885
234
Clay+Clay 0.883
234
Clay 0.859
237
Kraft 0.900
274
Example 3. Sheets Containing Insulating Elements:
Approximately 5.35g portions of 35 lb liner board (International Paper) was
shredded and re-
pulped. Additional materials were added, along with surfactants if necessary
for wetting. While not
yet optimum formulations, we had found that we could make paper sheets
containing insulating
elements by adding surfactant, along with a cationic polysaccharide, such as
cationic Guar Gum,
available from Making Cosmetics Inc., or a cationic starch sizing, or a
synthetic retention aid, such
as Polymin P (BASF), also known as poly(ethylene imine), or a high molecular
weight
poly(acrylamide) available from various sources. Hydrophobically associating
polymers may also
be incorporated, such as N-alkyl poly(acrylamides.) We wished to understand
the amount of retained
insulation in the paper following drying.
47
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
The following formulations were made up and cast as paper, dried at room
temperature and
then sent for ash content and moisture content analysis:
Formulation
% % Ash
1D Materials Mass/g
Target % Moisture
By mass
paper Paper
J1_, 24-02
Control Water 800.00
Pulp 535
0% 8+4% 0.84%
.11, 23-01 Water 800.00
Pulp 5.35
Microspersion EZ
(neat) 2.00
Perlite P-50 (20
15.9 %
micron) 1.78
25% 6.2%
Cationic Guar
Gum 0.80
.11, 23-02 Water 800.00
Pulp 5.35
Microspersion EZ
(neat) 2.00
Perlite P-50 (20
28.5 %
micron) 5.35
50% 7.2%
Cationic Guar
Gum 0.80
M 24-01 Water 800.00
Pulp 5.35
Microspersion EZ
(neat) 2.00
Perlite P-50 (20
22.9 %
micron) 5.35
50% 6.7%
Cationic Guar
Gum 2.00
J1_, 25-02 800.00
Pulp 535
Microspersion EZ
(neat) 2.50
Perlite P-50 (20
8.8 %
micron) 1.78
25% 8.0 %
pH = 8-9 Polymin P 0.80
.I1_, 26-01 Water 800.00
Pulp 5.35
Microspersion 17
(neat) 2.00
Perlite P-50 (20
16.8 %
pH = 6.0 micron) 5.35
50% 7.3%
JIL 32-01 Water 800.00
Pulp 5.35
3M Glass Bubbles 1.78
25% 7.5 % 14.7%
0.5% a.q. Cationic 10.00
48
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
Guar Gum
JL 32-02 Water 800.00
Pulp 5.35
3M Glass Bubbles
28.5 %
iM30K 5.35
50% 6.8%
0.5% a.q. Cationic
Guar Gum 10.00
A mass balance was performed to confirm that a portion of the perlite and a
portion of the
finer was lost during the drawing and pressing process.
Repulpability Tests: Insulated Paper vs. Uline Insulated Cardboard Box
90 lb fiberboard was fed through a paper shredder. 5.35g was weighed and
pulped in hot
water as usual. The pulp was more dense and more difficult to disperse than
the pulp from the 35 lb
paper. Paper sheets were made using the following formulations:
JL 41-01
water
800.00
Pulp - 90# shredded paper
12.50
iM30K glass bubbles .. 12.50
0.5% cationic guar gum
solution
25.00
IL 41-02
water
800.00
Pulp - 90# shredded paper
1230
Microspersion EZ (neat)
1.60
Perlite P-50
12.50
0.5% cationic guar gum
solution
25.00
As a control (i1. 44-01), the existing method of shipping cold objects was
also tested for
repulpability. Corrugated cardboard from a BS121007 single walled 12" x 10" x
17' box sections
were laminated to an insulated box liner, made from 3/16" cool-shield bubble &
metallized film,
available from Uline as model number S-15223. The materials were laminated
using 3M aerosol
spray adhesive.
Designation Summary Yield based
upon Yield based upon Operational
total fiber
original charge to the impact
collected. (%
pulper (% accepts) (Pass/Fail)
accepts) Av. of 2
Av. of 2
44-01 Control 64.7 % 56.4 %
Fail
41-01 50% iM3OK 98 % 70 %
Pass
41-02 50% perlite P-50 93 % 66.9 %
Pass
49
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
These data illustrate the validity that the approach of incorporating
insulating elements into
the paper structure has the potential to produce a repulpable thermally
insulating material for
packaging.
Example 4. Additional Sheets Made for Moisture, Ash Content, and
Repulpability:
35 lbs per 1000 sq. ft. single-ply sheets containing additives were made for
additional
repulpability tests, consistent with the Fiberboard Association voluntary
standard for repulpability.
Sheets FA, FD, FE, FF, FG were made using Grade 100 bleached pulp secondary
fiber (supplied by
Donco Recycling Solutions with offices in Chicago IL.) The target basis weight
for each sheet was
35 lbs per 1000 square feet (MSQ). Taking sample FD as an example, to make 35
MSQ board with
50% additive, 17.5 lbs of dry pulp is mixed with 17.5 lbs of additive for
every 1,000 square feet of
paper. Once ash content and moisture were measured, the sheets were then run
through the repulping
test in duplicate:
Sample Details, Moisture, and Ash Content:
Sample Details
Test Results
Measured
Based upon Dried Material
ID Additive %
% Moisture % Fiber % Ash % additive
Additive Content
retention
FA (control) 0 8.4
98.7 1.4 N/A
FD 20R spherical perlite 50 5.4
56.9 43.1 86.1
FE iM30k glass bubbles 50 5.1
54.5 45.5 90.9
FF Dicalite LD 1006 50 5.0
52.6 47.4 94.7
FG Mit spherical perlite 50 6.2
62.1 37.9 75.7
Repulpability test data:
ID Initial Repulped Total Repulped Total
Repulped Total
Charge / g Mass / g mass
accepted / g mass Rejected / g Fines/ g
FA 25.20 21.06 21.06
0.000 4.14
FA 21.60 17,62 17,62
0.000 3.98
FD 25.20 14.21 13.87
0.251 11.08
FD 25.10 14.81 14.80
0.008 10.29
FE 25.70 12.09 12.09
0.000 13.61
FE 25.40 12.74 12.74
0.000 12.66
FF 25.10 14.64 14,64
0.004 10.46
FF 25.60 15.98 15.24
0.036 10.32
Repulpability Test Results Analysis - Taking Ash Content Into Account:
ID % Accepts based % Accepts % accepts based on
the Deposition
upon total fiber based upon
amount of fiber present in
on equipment
collected initial charge the initial
charge (additive noted:
ash excluded)
FA 100.0 83.6
84.0 No
FA 100.0 81.6
82.1 No
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
FD 982 55.0
85.8 No
FD 99.9 59.0
89.6 No
FE 100.0 47.0
75.2 No
FE 100.0 50.2
80.0 No
FF 100.0 58.3
84.3 No
FF 99.8 59.5
91.9 No
Example 6. Corrugated Samples of 3-ply Paper Sheets
An antique desk-top hand cranked corrugator was purchased. The corrugator
indicated U.S.
Reexam Patent No. RE009,127 "Fluting-Machine", re-issued March 23s, 1880 toll.
Albrecht.
A sheet of TL1 was hung from inside an inverted 5-gallon pail and held over a
boiling tea
kettle to steam the sheet. The cast iron hand-cranked corrugator was warmed
with a hair dryer, and
the warm steamed sheet was promptly rippled. This was promptly bonded between
two non-
corrugated sheets of TL1 to make a rudimentary corrugated structure.
Single ply filled sheets were hand pressed in the lab and dried:
Sheet Composition ID
EJ EK
Water / g
800 800
Pulp / g
4.5 4.5
Flaked Perlite LD1006 / g
9.0
iM3OK glass bubbles / g
9.0
Household ammonia / g
2 ¨ 4
A sheet of EJ was hung from inside an inverted 5-gallon pail and held over a
boiling tea kettle
to steam the sheet. The cast iron hand-cranked corrugator was warmed with a
hair dryer, and the
warm steamed sheet was promptly fluted. This was promptly bonded between two
non-corrugated
sheets of EJ to make a rudimentary corrugated structure. This procedure was
repeated using EK
sheets for all three layers.
A sheet of TL1, EJ, and EK were each coated with Kaolin clay formulation 127-
01, then
dried, and then coated with 137-02 (BiLite (BASF) ¨ bismuth oxychloride coated
mica flakes) and
dried. More uncoated sheets were steamed and fluted, and similar corrugated
structures were
produced incorporating one of the coated sheets with the coating side facing
out as depicted in FIG.
20.
10 cm diameter disks were cut of each sample, and mounted into a cooler window
for thermal
testing. Prior to sealing with marine adhesive, the samples were gently pushed
into the front of the
cooler window so that the face of the composite was flush with the front of
the cooler. 10cm discs
of the following were also cut as controls: Aluminized bubble wrap, corrugated
C-flute (351bs.MSQ
lcraft liners with 231b medium, Corrugated Supplies Inc.), corrugated B-flute
(351bs.MSQ kraft liners
51
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
with 231b medium, Corrugated Supplies Inc.), triple wall corrugated B-C flute
(351bs.MSQ haft
liners with 231b medium, Corrugated Supplies Inc.)
Because these samples had significant thickness, temperature rise was
monitored over an
initial period of time until three consecutive 15-minute temperature readings
showed an increase in
temperature within +/- 0.1 C of each other. Upon attaining consistent
temperature increase readings
over 15 minutes, this was designated as pseudo-steady state. The temperature
of the outside lamp-
facing surface was also measured using a hand-held pyrometric infra-red
thermometer, taking care
to try not to allow reflections of the hot lamp from interfering. Usually, a
pseudo-steady state
situation of incremental temperature increases was established within 15
minutes of run time.
Results of Controls
Paper corrugate corrugate Corrugate
Bubblewrap
C-Flute B-Flute
BC Flute Aluminized
Ave. Thickness/mm 4 3.175
6.35 3.175
Coating 1
Coating 2 (lamp facing) -
lhr Water T Rise / 3.04 3.2
2.8 1.4
Ave temp difference 96.4 91.1
133.8 Very noisy data.
outer face of window vs.
74+!- 25 C
water / C
Wm-2 203 214
187 94
Paper corrugate corrugate corrugate corrugate
corrugate corrugate
Control Flake Pen. GIs Bubls
Coated Elk Pert. GIs Bubls
TL1 EJ EK
TL1 EJ EK
Av. Thlms / mm 3.87 5.51 5.68
4.11 5.44 6.36
Coating 1
127-01 127-01 127-01
Coat. 2 (lamp) -
137-02 137-02 137-02
1 hr T Rise PC 2.4 2.13 NT*
2 1.73 1.8
Av. Delta Touter 78.5 87.1 NT*
74.2 86.2 77.5
face of window
vs. water / C
Wm-2 154 143
134 116 120
* Structure failed during testing ¨ delaminated.
These data demonstrate the additive combination of addressing both radiative
heat transfer as
well as conductive heat transfer.
Example 7:
JL3-113-02 ¨ Clay:
543g Municipal Water
66.9g Tego Dispers 752W (Evonik)
221.4g Rovene 6400 (Mallard Creek Polymers)
669g Hydrite SB60 kaolin clay (Imerys)
52
CA 03153211 2022-3-30
WO 2021/067367
PCT/US2020/053421
Stir to disperse. Shake vigorously immediately prior to use.
JL3-118-01 ¨ Thermal Top Coat
202g Municipal Water
7.89g Tego Dispers 752W (Evonik)
158 Rovene 4100 (Mallard Creek Polymers)
74g BiLite 20 (Bi0C1 coated mica pigment) (BASF)
Stir to disperse. Shake vigorously immediately prior to use.
Approximately 20 square feet of 40 lbs per 3,000 square feet kraft paper was
hung vertically
and coated with clay formulation JL3-113-02 using a 32 psi compressed air
atomized high-pressure
low volume paint spray gun, from about a 6" distance. The coating was applied
in multiple passes
until a uniform white layer was formed. A similar technique was used to
overcoat a thin layer of
JL3-118-01 coating, containing bismuth oxychloride-coated mica and a binder
system. The paper
was dried using a hair dryer, and allowed to equilibrate overnight. An average
of 17 dried cut samples
of coated and uncoated paper were weighed to determine a total coat weight of
80.8 g / m2.
The paper had improved pigment rub-off compared to earlier formulations using
similar
materials, presumably, although without wishing to be bound by theory, because
the binder
concentration was increased and the surfactant package was changed.
Interestingly, when the paper
was folded or pleated, it made very little noise compared to the uncoated
paper. Furthermore, the
paper was found to be repulpable when tested.
It was noted that coated paper had a much smoother hand-feel than the uncoated
paper. Haptic
experiences can be difficult to describe, however, the paper felt more like
handling a smooth fabric
such as a microfiber polyester knit vs. kraft paper. The paper felt smoother,
almost softer, and it
made less noise when being handled compared to the uncoated paper.
Furthermore, the paper was
able to be folded without the coating flaking off. The paper was pleated to
form pleats at
approximately 1" intervals, with the intention for it to be used as insulating
packaging.
The present invention is described above and further illustrated below by way
of claims,
which are not to be construed in any way as imposing limitations upon the
scope of the invention.
On the contrary, it is to be clearly understood that resort may be had to
various other embodiments,
modifications, and equivalents thereof which, after reading the description
herein, may suggest
themselves to those skilled in the art without departing from the spirit of
the present invention and/or
the scope of the appended claims.
53
CA 03153211 2022-3-30
