Note: Descriptions are shown in the official language in which they were submitted.
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ENHANCED CELLULOSE NANOFIBRILS (CNF)
FIELD OF THE DISCLOSURE
[0001] The present disclosure relates to an enhanced
cellulose nanofibrils (CNF) (or
enhanced CNF binder), methods of making the enhanced CNF binder, methods of
making
wet-laid, thy-laid, or molded articles with the enhanced CNF binder by
incorporating the
enhanced CNF with the furnish in the wet-end of a paper-making process,
methods of coating
cellulose-based materials, intermediate formed fiber articles, and/or molded
articles with the
enhanced CNF binder, and cellulose-based articles obtained by all of these
methods, wherein
the enhanced CNF includes a saccharide fatty acid ester-, glyceride-, fatty
acid salt-, natural
wax- and/or cellulose crosslinker- (SGF) blend bound to the CNF.
BACKGROUND OF THE DISCLOSURE
[0002] Cellulosic materials have a wide range of applications
in industry as bulking
agents, absorbents, and printing components. Their employment is preferred to
that of other
sources of material for their high thermal stability, good oxygen barrier
function, and
chemical/mechanical resilience (see, e.g., Aulin et al., Cellulose (2010)
17:559-574;
incorporated herein by reference in its entirety). Of great relevance is also
the fact that these
materials are fully biodegradable once dispersed in the environment, and that
they are totally
nontoxic. Cellulose and derivatives thereof are the material of choice for
environmentally
friendly solutions in applications such as packaging for foodstuff and
disposable goods.
[0003] The many advantages of cellulose are nonetheless
countered by the
hydrophilicity/lipophilicity of the cellulose material, which shows a high
affinity for
water/fats and are easily hydrated (see, e.g., Aulin et al., Langmuir (2009)
25(13):7675-7685;
incorporated herein by reference in its entirety). While this is a benefit for
applications such
as absorbents and tissues, it becomes an issue when the safe packaging of
watery/lipid
containing materials (e.g., foodstuffs) is required. Long term storage of
food, especially
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ready-made meals which contain a significant amount of water and/or fat, is
made
problematic in cellulose trays, for example, as they would first become soggy
and then
ultimately fail. Further, multiple coatings may be required to offset low
efficiency of
maintaining sufficient coating on the cellulosic surface due to the high
relative porosity of the
material, resulting in increased costs.
[0004] This problem is usually addressed in the industry by
coating the cellulose fiber
with some kind of hydrophobic organic material/fluorocarbons (e.g., per- and
polyfluoroalkyl
substances (PFAS)), wax, synthetic polymers (e.g., polyethylene), silicones,
which would
physically shield the underlying hydrophilic cellulose from the water/lipids
in the contents,
including the prevention of wicking in the fiber interstices, grease flowing
into creases, or
allowing the release of attached materials. For example, materials such as
PVC/PEI/PE are
routinely used for this purpose and are physically attached (i.e., spray
coated or extruded) on
the surfaces to be treated.
[0005] Industry has utilized compounds based on fluorocarbon
chemistry for many
years to produce articles having improved resistance to penetration by oil and
grease, due to
the ability of fluorocarbons to lower the surface energy of the articles. One
emerging issue
with the use of perfluorinated hydrocarbons is that they are remarkably
persistent in the
environment. The EPA and FDA have recently begun a review of the source,
environmental
fate, and toxicity of these compounds. A recent study reported a very high
(>90%) rate of
occurrence of perfluorooctane sulfonate in blood samples taken from school
children. The
expense and potential environmental liability of these compounds has driven
manufacturers
to seek alternative means of producing articles having resistance to
penetration by oil and
grease.
[0006] While lowering the surface energy improves the
penetration resistance of the
articles, lowering the surface energy also has some disadvantages. For
example, a textile
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fabric treated with a fluorocarbon will exhibit good stain resistance;
however, once soiled, the
ability of cleaning compositions to penetrate and hence release the soil from
the fabric may
be affected, which can result in permanently soiled fabrics of reduced useful
life. Another
example is a greaseproof paper which is to be subsequently printed and/or
coated with an
adhesive. In this case the requisite grease resistance is attained by
treatment with the
fluorocarbon, but the low surface energy of the paper may cause problems
related to printing
ink or adhesive receptivity, including scuffing, back trap mottle, poor
adhesion, and register.
If a greaseproof paper is to be used as a pressure sensitive label having an
adhesive applied
on one side, the low surface energy may reduce the strength of the adhesion.
To improve
their printability, coat-ability or adhesion, the low surface energy articles
can be treated by
post forming processes such as corona discharge, chemical treatment, flame
treatment, or the
like. However, these processes increase the cost of producing the articles and
may have other
disadvantages.
[0007] It would be desirable to design a "green," bio-based
coating which is
hydrophobic, lipophobic and compostable, including a base paper/film that
would allow for
keeping coatings on the surface of said paper and preventing wicking into the
fiber
interstices, or reducing sticking of materials to the cellulosic surface, at
reduced costs,
without sacrificing biodegradability and/or recyclability.
[0008] Another problem is that conventional coatings for
imparting hydrophobic
and/or lipophobic barrier properties, including the fluorocarbon and
petrochemical coatings
noted herein, is that they tend to perform poorly at the folds, creases, and
the like of the
article coated with the material. Specifically, the article typically has
inferior water
resistance and/or grease resistance at these locations. Such a "grease
creasing effect" may be
defined as the sorption of grease in a paper structure that is created by
folding, pressing or
crushing said paper structure. A conventional solution to the grease creasing
effect is to add
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a latex, a polyvinyl alcohol, or similar resin to the coating to achieve
improved coating
coverage at these locations. However, with this conventional solution, the
water resistance
and/or oil and grease resistance of these locations may still be inferior to
the flat portions of
the article; this conventional solution increases cost by the addition of the
resin component;
and this conventional solution is not entirely bio-based, since the latex and
polyvinyl alcohol
may either be synthetic and/or not easily recyclable.
[0009] U.S. Patent Application Publication No. 2018/0066073
(hereinafter -the '073
publication"), which is incorporated herein by reference in its entirety,
discloses tunable
methods of treating cellulosic materials with a composition that provides
increased barrier
properties, such as water resistance and/or oil and grease resistance (OGR),
without
sacrificing the biodegradability thereof. In particular, the '073 application
discloses methods
of binding of saccharide fatty acid esters ("SFAE") on cellulosic materials to
provide treated
materials that display higher water resistance, lipid resistance, barrier
function, and other
mechanical properties.
[0010] U.S. Provisional Patent Application Publication No.
63/022,097, filed May 8,
2020, (hereinafter the '097 application"), which is incorporated herein by
reference in its
entirety, discloses tunable methods of treating cellulosic materials with a
composition that
provides increased barrier properties, such as water resistance and/or OGR
resistance,
without sacrificing the biodegradability thereof. In particular, the '097
application discloses
methods of binding blends of glycerides and/or fatty acid salts. The '097
application
discloses that the barrier formulation including the blends of glycerides
and/or fatty acid salts
can additionally include SFAE for imparting the water and/or OGR resistance
and/or for
providing the function of an emulsifier.
[0011] PCT/US2020/014923 (hereinafter "the '923
application"), which is
incorporated herein by reference in its entirety, discloses methods of
treating fibrous
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cellulosic materials with sucrose fatty acid ester containing particles
(carrier systems) that
allow for modifications of surfaces, including making such surfaces water
resistance and/or
oil/grease resistance. The methods as disclosed provide combining at least one
SFAE with a
polymer (e.g., latexes) to form micellular particles and applying such
particles to substrates
including fibrous cellulose-based materials (e.g., pulp) to form, inter alia,
molded products.
Compositions comprising combinations of SFAE, a latex and optionally a mineral
or other
additives are also disclosed.
[0012] US 16/568,953 (hereinafter "the '953 application"),
which is incorporated
herein by reference in its entirety, discloses tunable methods of treating
cellulosic materials
with a barrier coating comprising a prolamin and at least one polyol fatty
acid ester that
provides increased oil and/or grease resistance to such materials without
sacrificing the
biodegradability thereof The methods as disclosed provide for adhering of the
barrier
coating on articles including articles comprising cellulosic materials and
articles made by
such methods. The materials thus treated display higher lipophobicity and may
be used in
any application where such features are desired.
[0013] US 16/456,499 (hereinafter -the '499 application"),
which is incorporated
herein by reference in its entirety, discloses tunable methods of treating
cellulosic materials
with a barrier coating comprising at least two polyol and/or saccharide fatty
acid ester that
provides increased water, oil and grease resistance to such materials without
sacrificing the
biodegradability thereof. The methods as disclosed provide for adhering of the
barrier
coating on articles including articles comprising cellulosic materials and
articles made by
such methods. The materials thus treated display higher hydrophobicity and
lipophobicity
and may be used in any application where such features are desired.
[0014] US 16/456,433 (hereinafter "the '433 application"),
which is incorporated
herein by reference in its entirety, discloses methods of treating cellulosic
materials with
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compositions that allow greater retention of inorganic particles on cellulosic
substrates. The
methods as disclosed provide combining SFAE with such inorganic particles and
applying
such combinations on cellulosic materials to eliminate or reduce the use of
retention aids or
binders for filler in the paper making process. Compositions comprising such
combinations
of SFAE and inorganic particles are also disclosed.
[0015] The use of a binder obtained from a natural source has
also become of
increasing importance for providing a -green," biobased product.
[0016] Nanocellulose is a term referring to nano-structured
cellulose, which may be
cellulose nanocrystals (CNC or NCC), cellulose nanofibrils (CNF) (which are
also referred to
in the art as cellulose nanofibers and nanofibrilated cellulose), or bacterial
nanocellulose.
[0017] CNF is a material composed of nanosized cellulose
fibrils typically having a
high aspect ratio (length to width ratio). CNF is typically obtained from
woodpulp or another
natural source of cellulose fibers, typically by a process that includes
subjecting the
pulp/fibers to mechanical shear forces.
[0018] CNF has been used as a binder in the papermaking
process. In this regard, the
inventors determined that the use of CNF as an additive on the wet-end and in
coating
applications can provide improved OGR. However, the use of CNF presents
certain
problems. One problem is that, when the CNF is used as a wet-end addition to
the
papermaking furnish, the CNF tends to slow the drainage rate (or dewatering)
of the fiber mat
from the slurry. This is detrimental, for example, because the water removal
rate dictates the
production speed of the cellulose-based product. Another problem is that the
CNF tends to
agglomerate when used as an additive as a slurry or spray, which can
negatively affect its
efficiency and/or its functional properties.
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[00191 Based on the summary above, there is still a need for "green,"
bio-based
coatings for cellulose-based materials that provide improved water and/or OGR
resistance,
and "green" cellulose-based molded articles having improved water and/or OGR
resistance.
SUMMARY OF THE DISCLOSURE
[0020] The present disclosure provides methods that address
one or more of the
limitations and/or concerns in the conventional art discussed above and/or
provide one or
more improvements thereon. However, the present disclosure is not required to
address any
of the limitations and/or concerns.
[0021] In one embodiment, the disclosure is directed to an
enhanced cellulose
nanofibril binder, which includes: cellulose nanofibrils (CNF), and an SGF
blend bound to
the CNF, wherein the SCif blend comprises one or more selected from the group
consisting
saccharide fatty acid esters (SFAE), glycerides, fatty acid salts ("FAS"),
natural waxes, and
cellulose crosslinkers.
[0022] As used herein, the term "SGF blend" means one or more
saccharide fatty acid
esters (SF.AE), and/or one or more glycerides), and/or one or more fatty acid
salts (F)..S),
and/or one or more natural waxes, and/or one or more cellulose crosslinkers.
In some
embodiments, the SGF blend used in the present disclosure does not include a
SFAE; in some
embodiments the SGF blend does not include a glyceride; in some embodiments
the SGF
blend does not include a FAS; in some embodiments the SGF blend does not
include the
natural waxes; and in some embodiments the SGF blend does not include the
cellulose
erosslinkers. In some embodiments, the SGF blend consists essentially of the
SFAE,
glycerides, and/or FAS. In some embodiments, the SGF blend consists of the
SFAE,
glycerides, and/or FAS.
[0023] The enhanced cellulose nanofibril binder (or enhanced
CNF) according to the
present disclosure can provide certain benefits. For example, when used in the
furnish on the
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wet-end of the papermaking process, the enhanced CNF maintains or increases
the drainage
rate of the fiber mat from the slurry. Also, the enhanced CNF does not suffer
the same
problem of agglomeration as conventional CNF.
[0024] In one aspect of the present disclosure, the enhanced
cellulose nanofibril
binder consists essentially of the CNF and the SG], blend.
[0025] in another aspect of the enhanced cellulose nanofibril
binder, a weight ratio of
the CNF to the SGF blend is about 1:99 to about 99:1, or about 5:95 to about
95:5, or about
1.0:90 to about 90:10, or about 15:85 to about 85:15, or about 20:80 to about
80:20, or about
25:75 to about 75:25, or about 30:70 to about 70:30, or about 35:65 to about
65:35, or about
40:60 to about 60:40, or about 45:55 to about 55:45, or about 50:50.
[0026] In one embodiment, the enhanced. cellulose nanofibril
binder is obtained by a
method that includes: obtaining an aqueous mixture of cellulose nanofibtils
(CNF); obtaining
an aqueous SGF blend; and mixing the aqueous mixture of CNF with the aqueous
SGF -bkaid
to obtain a CNF/SGF mixture. The mixing of the CNF with the SGF blend (and
thereby
contacting the CM? with the SGF blend) can be sufficient to bind the SGF blend
to the CNF.
Alternatively, the SGF blend can be bound to the CNF by exposing the CNF/SGF
mixture to
heat, radiation, a catalyst, or a combination thereof for a sufficient time.
The method may
further include a step of reducing the water content of the CNF/SGF mixture,
such as by
draining the water.
[0027] In one embodiment, the enhanced cellulose nanofibril
binder according to the
present disclosure is obtained by a method that includes: obtaining an aqueous
M ixtu re of
cellulose pulp (e.g., woodpuip); obtaining an aqueous SGF blend; mixing the
aqueous
mixture of cellulose pulp with the aqueous SGF blend to obtain a cellulose/SGF
mixture; and
subjecting the cellulose/SGF mixture to mechanical shear forces to obtain the
enhanced
cellulose nanofibril binder.
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[0028] In one aspect, the method of obtaining the enhanced
CNF may further include
a step of reducing the water content of cellulose/SGF mixture, such as by
draining the water.
[0029] in one aspect, the method of obtaining the enhanced
CNF may further include
subjecting the cellulose pulp to a pre-treatment prior to obtaining the
cellidose/SGF mixture
and/or prior to subjecting the cellulose/SGF mixture to the mechanical shear
force.
[0030] In one aspect, the pre-treatment may include lower the
pH of the aqueous
mixture of cellulose pulp by adding an acid.
[0031] In one embodiment, the present disclosure provides a
barrier formulation that
includes the enhanced CNF according to the present disclosure. The composition
of the
barrier formulation can be chosen to tuneably derivative a cellulose-based
material by a
method known in the art, such as in the '073 publication or '097 application.
[0032] In one embodiment, the present disclosure provides a
method of making a
cellulose-based article, the method including: adding the enhanced cellulose
nanofibril binder
according to the present disclosure to an aqueous papermaking furnish; and
draining the
water from the furnish to obtain a fibrous web.
[0033] In one aspect, the method further includes molding the
fibrous web into a
molded article having a three-dimensional shape.
[0034] in one embodiment, a method for imparting a barrier
property to a cellulose-
based material is provided, the method including contacting the cellulose-
based material with
an aqueous barrier formulation for imparting the barrier property, the barrier
formulation
including the enhanced cellulose nanofibril binder according to the present
disclosure; and
binding the barrier formulation to a surface of the cellulose-based material
to obtain a bound
cellulose-based material having the barrier property, wherein the barrier
property is one or
more selected from the group consisting of water resistance, lipid resistance,
and gas
resistance,
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[0035] In one embodiment, a bather formulation is provided,
the barrier formulation
including the enhanced cellulose nanofibril binder according to the present
disclosure; a
second SGF blend, the second SGF blend including one or more saccharide fatty
acid esters
(SFAE), one or more glycerides, and/or one or more fatty acid salts; and
water_
[0036] In one aspect, the second SGF blend of the barrier
formulation can be chosen
to tuneably derivative a cellulose-based material by a method known in the
art, such as in the
073 publication or '097 application.
[0037] In one aspect, the barrier formulation of the present
disclosure can include a
pigment conventionally used in the papermaking industry.
[0038] In one embodiment, a method for imparting a barrier
property to a cellulose-
based material, the method including: contacting the cellulose-based material
with a barrier
formulation for imparting the barrier property, the barrier formulation
including (a) cellulose
nanofibrils (CNF), and (b) the SGF blend.; and binding the barrier formidation
to a surface of
the cellulose-based material to obtain a bound cellulose-based material having
the barrier
properly, wherein the barrier property is one or more selected from the group
consisting of
water resistance, lipid resistance, and gas resistance.
[0039] The method for imparting a barrier property according
to the present
disclosure can provide the same benefits noted above, which includes
maintaining or
increasing the drainage rate when the method is applied to a wet-end process,
and preventing
agglomeration of the CNF.
[0040] In one aspect, when a total weight of the barrier
formulation used in the
method for imparting a barrier property according to the present disclosure is
considered to
be 100% by weight, the barrier formulation includes about 4% by weight to
about 96% by
weight of the CNF, and about 4% by weight to about 96% by weight of the SGF
blend.
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100411 In one aspect, the cellulose-based material used in
the method for imparting a
barrier property according to the present disclosure includes cellulose fiber,
and the step of
contacting includes forming an aqueous mixture of the barrier formulation and
cellulose
fiber.
[0042] In one aspect, the SGF blend can. be present in the
aqueous mixture or
dispersion at a total concentration of at least 0.025% (wt/wt) of the total
cellulose fiber
present in the aqueous mixture.
[0043] In one aspect, the aqueous mixture includes one or
more pigments
conventionally used in the papermaking industry.
[0044] In one aspect, the aqueous mixture is in the form of a
slurry having a solid
content of about 0.1 to 10.0 wt.%, 0.1 to 6.0 wt.%, or about 0.1 to 2.0 wt.%,
or about 0.2 to
1.5 wt.%.
[0045] In one aspect, the method further includes reducing
the water content of the
aqueous mixture, such as by draining the water.
[0046] In another aspect, the step of contacting in the
method for imparting a barrier
property according to the present disclosure includes coating the surface of a
cellulose-based
substrate with the formulation by a process of immersion, spraying, painting,
printing, or any
combination of any of these processes.
[0047] In one aspect, the SGF blend is present at a weight of
at least about 0.05 g/m2
on the surface of the substrate.
[0048] The cellulose-based substrate is not particularly
limited. In one aspect,
examples of the cellulose-based substrate include a surface of an article
selected from paper,
paperboard, bacon board, insulating material, paper pulp, a carton fur food
storage, a compost
bag, a bag for food storage, release paper, a shipping bag, weed-block/barrier
fabric or film,
mulching film, plant pots, packing beads, bubble wrap, oil absorbent material,
laminates,
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envelops, gift cards, credit cards, gloves, raincoats. OGR paper, a shopping
bag, diapers,
membranes, eating utensil, a tea bag, a container for coffee or tea, a
container for holding hot
or cold beverages, a cup, a plate, a bottle for carbonated liquid storage, a
bottle for non-
carbonated liquid storage, a lid, film for wrapping food, a garbage disposal
container, a food
handling implement, a fabric fibre, a water storage and conveying implement, a
storage and
conveying implement for alcoholic or non-alcoholic beverages, an. outer casing
or screen for
electronic goods, an internal or external piece of furniture, a curtain,
upholstery, fabric, film,
a box, a sheet, a tray, a pipe, a water conduit, clothing, a medical device,
pharmaceutical.
packaging, a contraceptive, camping equipment, cellulosic material that is
molded, and
combinations thereof.
[0049] In one aspect, the method for imparting a barrier
property according to the
present disclosure provides a bound cellulose-based material that exhibits a
water contact
angle of equal to or greater than 90 .
[0050] In one aspect, the method for imparting a barrier
property according to the
present disclosure provides a bound cellulose-based material that exhibits a
TAPPI T 559
KIT test value of from 3 to 12.
[0051] In one aspect, the method for imparting a barrier
property according to the
present disclosure provides a bound cellulose-based material that exhibits a
water contact
angle of equal to or greater than 90 and/or a TAPPI T 559 KIT test value of
from 3 to 12 in
the absence of any secondary hydrophobes.
[0052] In one embodiment, a method of making an enhanced
cellulose nanofibril
binder is provided, the method including: obtaining an aqueous mixture of
cellulose
nanofibiils (CNF); obtaining an aqueous SGF blend; and mixing the aqueous
mixture of (21\1F
with the aqueous SGF blend to obtain a CNF/SGF mixture and allowing the SEW
blend bind
to the C1N-F.
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[0053] In one aspect, the method of making the enhanced CNF
further includes
reducing the water content of the CNF/SGF mixture.
[0054] in one embodiment, a method of making an. enhanced
cellulose nanofibril
binder is provided, the method including: obtaining an aqueous mixture of
cellulose pulp;
obtaining an aqueous SGF blend; mixing th.e aqueous mixture of cellulose pulp
with th.e
aqueous SGF blend to obtain a cellulose/SUP mixture; and subjecting the
cellulose/SW'
mixture to mechanical shear forces to obtain the enhanced cellulose nanofibril
binder.
[0055] In one aspect, the method includes subjecting the
cellulose pulp to a pre-
treatment prior to obtaining the cellulose/SW,' mixture and/or prior to
subjecting the
cellulose/SW' mixture to the mechanical shear force.
[0056] In one embodiment, a method of making a molded article
is disclosed, the
method including: providing a fomfing tool having a three-dimensional shape
having a
forming portion, bringing said -16rining portion into contact with a cellulose
composition so
that said forming portion is covered with a wet layer of pulp, and dewatering
the layer of pulp
on the forming tool to achieve the molded article, wherein the cellulose
composition includes
cellulose pulp and an enhanced cellulose nanofibril binder according to the
present
disclosure.
[0057] In one embodiment, another method of making a molded
article is disclosed,
the method including: providing a forming tool having a three-dimensional
shape having a
forming portion, bringing the forming portion into contact with a cellulose
composition so
that said forming portion is covered with a wet layer of pulp; and dewatering
the layer of pulp
on the forming tool to achieve the molded article, wherein the cellulose
composition includes
cellulose pulp and a barrier formulation according to the present disclosure.
[0058] In one embodiment, another method of making a molded
article is disclosed,
the method including: providing a forming tool having a three-dimensional
shape having a
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forming portion, bringing the forming portion into contact with a cellulose
composition so
that said forming portion is covered with a wet layer of pulp; dewateting the
layer of pulp on
the forming tool to obtain an intermediate molded article; and coating a
surface of the
intermediate molded article with a barrier formulation according to the
present disclosure by
a process of immersion, spraying, painting, printing, or any combination of
any of these
processes to achieve the molded article,
[0059] In one aspect, the method of making the molded article
includes conducting
the dewatering at temperatures >100 C to achieve a thy content of at least
about 70 wt.%,
preferably at least about 80 wt.%.
[0060] In one aspect, the layer of pulp present on the
forming tool is dewatered by
means of press-drying performed at temperatures >100 C, preferably at
temperatures
between about 120 to 250 C or more preferably between about 150 to 220 C.
[0061] In one aspect, the cellulose composition for the
method of making the molded
articles comprises a fiber mixture consisting essentially of
chemithermomechanical pulp
(CTMP), thermomechanical pulp (TMP), chemical pulp or semichemical pulp, or a
combination thereof. The pulps can be either bleached or unbleached.
[0062] In one aspect, the forming tool is porous or
perforated so that water can be
removed during forming during a dewatering/drying step.
[0063] In one aspect, the method of making the molded article
further includes
coating a surface of the molded article with a barrier formulation comprising
the SGF blend
by a process of immersion, spraying, painting, printing, or any combination of
any of these
processes.
[0064] In one aspect, the coating of the surface of the
molded article with the barrier
formulation takes place while the molded article is an intermediate molded
article having a
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relatively high aqueous content and a fiber content of about 20 to 50 wt.%,
preferably about
30 to 40 wt.%.
[0065] In one embodiment, the disclosure provides a cellulose-
based product obtained
according to any of the methods disclosed herein, which is a three dimensional
molded
product, such as a molded food packaging product, made from cellulose fibers.
[0066] in one aspect, the three dimensional shape obtained by
the methods of making
the molded article is not particularly limited.
[0067] In one aspect, examples of the three dimensional shape
are a bowl, a cup, a
plate, a fork, a spoon, or a knife.
[0068] In some embodiments, the barrier formulation consists
essentially of CNF and
the SGF blend.
[0069] In some embodiments, a weight ratio in the barrier
formulation of CNF to SGF
blend is from about 20:1 to about 1:5. In some embodiments, the weight ratio
may be about
5:1 to about 1:5.
[0070] in some embodiments, when a total weight of the
barrier formulation is
considered to be 100% by weightõ the barrier formulation includes about 4% by
weight to
about 96% by weight of CM?, and about 4% by weight to about 96% by weight of
the SGF
blend. In some embodiments, the amount of the CNF can be about 10% by weight
to about
70% by weight. In some embodiments, the amount of the SGF blend can be about
30 % by
weight to about 90% by weight.
[0071] In some embodiments, the barrier formulation further
includes one or more
prolamins.
[0072] In some embodiments, the one or more prolamins are
selected from wheat
(gliadin), barley (hordcin), rye (sccalin), corn (zein), sorghum (kafirin),
and/or oats (avenin).
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[0073] In some embodiments, the cellulose-based material
includes cellulose fiber
suitable for making paper, and the aqueous mixture or dispersion is a
papermaking furnish or
stock.
[0074] In some embodiments, the molded article exhibits a
water contact angle of
equal to or greater than 90 , equal to or greater than 100', equal to or
greater than 1100, or
equal to or greater than 1200
.
[0075] In some embodiments, the molded article exhibits TAPPI
T 559 KIT test value
of from 3 to 12.
[0076] In some embodiments, the molded article exhibits
reduced permeability to
gases (referred to as "gas resistance") (e.g., resistance to oxygen, nitrogen,
and carbon
dioxide). In some aspects, the gas resistance is a reduced permeability to
oxygen.
[0077] In some embodiments, the molded article exhibits a
water contact angle of
equal to or greater than 90 and/or a TAPPI T 559 KIT test value of from 3 to
12 in the
absence of any secondary hydrophobes.
[0078] In some embodiments, the barrier formulation is in the
form of an emulsion.
[0079] In some embodiments, the barrier formulation is a
stable aqueous composition.
[0080] In another embodiment, a method of making a cellulose-
ba.sed product having
a barrier property is provided, the method including: obtaining a furnish that
includes an
aqueous mixture of cellulose fiber; adding the SGF blend to the furnish;
adding CNF to the
furnish; and adding a retention aid to the furnish for aiding in the retention
of the SGF blend
on the cellulose fiber.
[0081] In some embodiments, one or more charged polymers can
be added in the wet-
end to aid in the retention of the SFAE on the cellulose-based material. The
one or more
charged polymers may include one or more cationic polymers, anionic polymers,
nonionic
polymers, and/or zwitterionic polymers. In some embodiments, the charged
polymer
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includes a combination of a relatively low molecular weight cationic polymer
and a relative
high molecular weight anionic polymer.
[0082] In some embodiments, the charged polymer consists of
one or more cationic
polymer. The one or more cationic polymer may include a polyacrylamide. The
polyacrylamide may include polyDADMAC (poly diallyldimethylammonium chloride)
or
alum (aluminum sulfate).
[0083] In some embodiments, one or more prolamins can be
added in the wet-end to
aid in the retention of the SGF blend, CNF, and/or enhanced CNF on the
cellulose-based
material.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0084] Before the present compositions, methods, and
methodologies are described in
more detail, it is to be understood that the disclosure is not limited to
particular compositions,
methods, and experimental conditions described, as such compositions, methods,
and
conditions may vary. It is also to be understood that the terminology used
herein is for
purposes of describing particular embodiments only, and is not intended to be
limiting, since
the scope of the present invention will be limited only in the appended
claims.
[0085] As used in this specification and the appended claims,
the singular forms "a,"
"an," and "the" include plural references unless the context clearly dictates
otherwise. Thus,
for example, references to "a saccharide fatty acid ester includes one or more
saccharide
fatty acid esters and/or compositions of the type described herein which will
become apparent
to those persons skilled in the art upon reading this disclosure and so forth.
[0086] Unless defined otherwise, all technical and scientific
terms used herein have
the same meaning as commonly understood by one of ordinary skill in the art to
which this
disclosure belongs. Any methods and materials similar or equivalent to those
described
herein may be used in the practice or testing of the disclosure, as it will be
understood that
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modifications and variations are encompassed within the spirit and scope of
the instant
disclosure.
[0087] The present disclosure provides an enhanced cellulose
nanofibril binder.
[0088] Cellulose nanofibrils (also referred to herein as CNF)
and their method of
production are well known in the art.
[0089] The CNF for use in the embodiments of the present
disclosure is not
particularly limited. The CNF can be commercially obtained, or the CNF can be
made by
known methods, which typically include subjecting a source of cellulose fibers
(e.g.,
woodpulp) to a mechanical shearing force.
[0090] The properties of the CNF are not particularly
limited. The CNF may have
typical fibril widths of about 5 to 20 nanometers, and may have lengths of
several
micrometers.
[0091] In some embodiments, the enhanced CNF can be obtained
by contacting
conventionally made CNF with an SGF blend and allowing the SGF blend to bind
to the
CNF. In other embodiments, the enhanced CNF can be made obtained by subjecting
a source
of cellulose fibers (e.g., woodpulp) to a mechanical shearing stress while the
CNF is in
mixture with an SGF blend.
[0092] As noted above, the enhanced CNF provides benefits
compared to
conventionally used CNF, such as maintaining or increasing the drainage rate
of the fiber mat
from the slurry and reduced agglomeration of the CNF.
[0093] The present disclosure provides methods for imparting
a barrier property to a
cellulose-based material. The methods include contacting the cellulose-based
material with a
barrier formulation for imparting the barrier property, and binding the
barrier formulation to a
surface of the cellulose-based material to obtain a bound cellulose-based
material having thc
barrier property, wherein the barrier property is one or more selected from
the group
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consisting of water resistance, gas resistance, and lipid resistance. The
barrier formulation
may include the enhanced CNF, or the barrier formulation may include the
enhanced CNF
and the SGF blend.
[0094] The methods of the present disclosure can provide a
solvent-free, bio-based,
high temperature-tolerant barrier (or barrier coating) for oil and grease
(OGR), water, and/or
gases (e.g., oxygen, nitrogen, and carbon dioxide) and/or formed fiber (e.g.,
molded) products
having these properties.
[0095] Another aspect of the present disclosure is that the
barrier coatings can be
configured to provide improved water resistance and lipid (oil/grease)
resistance without the
use of PFAS. These barrier properties can be provided by the SGF blend (see,
e.g., the '073
publication, the '953 publication, the '923 application, the '499 application,
the '433
application, and the '097 application, all of which have been incorporated
herein by
reference).
[0096] In some embodiments, the enhanced CNF can be used on
the wet end of the
papermaking process by adding the enhanced CNF directly into the papermaking
furnish.
Alternatively, in other embodiments, a combination of CNF and the SGF blend
can be added
directly into the papermaking furnish to obtain similar benefits.
[0097] One or more charged polymers, such as polyDADMAC or
polyacrylamide,
could also be added to the furnish as a retention aid for promoting the
absorption of the SGF
blend and/or the CNF onto the cellulosic surfaces. In some aspects, the
charged polymer can
be used to control the electrostatic charge of the formulation containing the
SGF blend.
[0098] In other embodiments, prolamins can be used as a
binder. This is explained,
for example, in U.S. provisional application No. 63/044,820 filed June 26,
2020 (hereinafter
"the '820 application), which is incorporated herein by reference in its
entirety.
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[0099] Prolamins may be used as a binder not only for the SGF
blend and/or the CNF,
but also for conventional pigments added to a papermaking furnish. Pigments
are typically
relatively small and charged on their surfaces, including their edges. Thus,
the pigments can
easily be caught up in (and selectively retained by) the prolamin matrix.
[0100] In addition to being added directly into the
papermaking furnish, the barrier
formulations can be coated onto a cellulose-based material or substrate (e.g.,
an already
formed paper product) by immersion, spraying, painting, printing, extrusion
coating,
metering or any combination of any of these processes. The barrier formulation
may contain
the enhanced CNF in a sufficient amount to impart a desired water resistance
and/or OGR to
the cellulose-based material.
[0101] Alternatively, the barrier formulation may contain CNF
and the SGF blend in
suitable amounts to impart a desired water resistance and/or OGR to the
cellulose-based
material.
[0102] Alternatively, the barrier formulation may contain the
enhanced CNF and the
SGF blend in suitable amounts to impart a desired water resistance and/or OGR
to the
cellulose-based material.
[0103] In the present disclosure, the interaction between the
SGF blend and the CNF
may be by ionic, hydrophobic, van der Waals interaction, covalent bonding, or
a combination
thereof. As used herein, "bind", including grammatical variations thereof,
means to cohere or
cause to cohere essentially as a single mass, and may refer to ionic,
hydrophobic, van der
Waals interaction, or covalent bonding, or a combination thereof.
[0104] In the present disclosure, the interaction between the
SGF blend and the
cellulose-based material may be by ionic, hydrophobic, van der Waals
interaction, covalent
bonding, or a combination thereof.
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[0105] In the present disclosure, the interaction between the
enhanced CNF and the
cellulose-based material may be by ionic, hydrophobic, van der Waals
interaction, covalent
bonding, or a combination thereof.
[0106] In some embodiments, the barrier formulation may also
contain one or more
conventional binders used in papermaking, such as latex, Pv0H, and starch.
[0107] As used herein, "cellulosic" means natural, synthetic,
or semisynthetic
materials that can be molded or extruded into objects (e.g., bags, sheets) or
films or filaments,
which may be used for making such objects or films or filaments, that is
structurally and
functionally similar to cellulose, e.g., coatings and adhesives (e.g.,
carboxymethylcellulose).
In another example, cellulose, a complex carbohydrate (C6Hio05)11 that is
composed of
glucose units, which forms the main constituent of the cell wall in most
plants, is cellulosic.
[0108] Examples of the cellulosic material (or cellulose-
based material) for use herein
can be cellulose fibers conventionally used in the paper industry,
microfibrillated cellulose
(MFC), nanofibrilated cellulose (or CNF), or cellulose nanocrystals.
[0109] As used herein, "coating weight" is the weight of a
material (wet or dry)
applied to a substrate. It is expressed in pounds per specified ream or grams
per square meter
[0110] As used herein, "effect", including grammatical
variations thereof, means to
impart a particular property to a specific material.
[0111] As used herein, "hydrophobe" means a substance that
does not attract water.
For example, waxes, rosins, resins, saccharide fatty acid esters, fatty acid
salts, glycerides
having long fatty acid chains; di- and triglycerides, diketenes, shellacs,
vinyl acetates, PLA,
PEI, oils, fats, lipids, other water repellant chemicals or combinations
thereof are
hydrophobes.
[0112] As used herein, "hydrophobicity" means the property of
being water-repellent,
tending to repel and not absorb water.
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[0113] As used herein, "lipid resistance" or "lipophobicity"
means the property of
being lipid-repellent, tending to repel and not absorb lipids, grease, fats
and the like. In a
related aspect, the grease resistance may be measured by a "3M KIT" test, a
TAPPI T559 Kit
test, or a Cobb oil test.
[0114] As used herein, "cellulose-containing material" or
"cellulose-based material"
means a composition which consists essentially of cellulose. For example, such
material may
include, but is not limited to, paper, paper sheets, paperboard, paper pulp, a
carton for food
storage, parchment paper, cake board, butcher paper, release paper/liner for a
pressure
sensitive adhesive, a bag for food storage, a shopping bag, a shipping bag,
bacon board,
insulating material, tea bags, containers for coffee or tea, a compost bag,
eating utensil,
container for holding hot or cold beverages, cup, a lid, plate, a bottle for
carbonated liquid
storage, gift cards, a bottle for non-carbonated liquid storage, film for
wrapping food, a
garbage disposal container, a food handling implement, a fabric fibre (e.g.,
cotton or cotton
blends), a water storage and conveying implement, alcoholic or non-alcoholic
drinks, an
outer casing or screen for electronic goods, an internal or external piece of
furniture, a curtain
and upholstery.
[0115] As used herein, "fibers in solution" or "pulp" means a
lignocellulosic fibrous
material prepared by chemically or mechanically separating cellulose fibers
from wood, fiber
crops or waste paper. In a related aspect, where cellulose fibers are treated
by the methods as
disclosed herein, the cellulose fibers themselves contain bound SFAE,
glyceride, and/or FAS
as isolated entities, and where the bound cellulose fibers have separate and
distinct properties
from free fibers (e.g., pulp- or cellulose fiber- or nanocellulose or
microfibrillated cellulose-
SFAE blend bound material would not form hydrogen bonds between fibers as
readily as
unbound fibers).
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[0116] As used herein, "repulpable" means to make a paper or
paperboard product
suitable for crushing into a soft, shapeless mass for reuse in the production
of paper or
paperboard.
[0117] As used herein, "tunable", including grammatical
variations thereof, means to
adjust or adapt a process to achieve a particular result.
[0118] As used herein, "water contact angle" means the angle
measured through a
liquid, where a liquid/vapor interface meets a solid surface. It quantifies
the wettability of the
solid surface by the liquid. The contact angle is a reflection of how strongly
the liquid and
solid molecules interact with each other, relative to how strongly each
interacts with its own
kind. On many highly hydrophilic surfaces, water droplets will exhibit contact
angles of 0
to 300. Generally, if the water contact angle is larger than 900, the solid
surface is considered
hydrophobic. Water contact angle may be readily obtained using an Optical
Tensiometer
(see, e.g., Dyne Testing, Staffordshire, United Kingdom).
[0119] As used herein, "water vapour permeability" means
breathability or a textile's
ability to transfer moisture. There are at least two different measurement
methods. One, the
MVTR Test (Moisture Vapour Transmission Rate) in accordance with ISO 15496,
describes
the water vapor permeability (WVP) of a fabric and therefore the degree of
perspiration
transport to the outside air. The measurements determine how many grams of
moisture
(water vapor) pass through a square meter of fabric in 24 hours (the higher
the level, the
higher the breathability).
[0120] In one aspect, TAPPI T 530 Hercules size test (i.e.,
size test for paper by ink
resistance) may be used to determine water resistance. Ink resistance by the
Hercules method
is best classified as a direct measurement test for the degree of penetration.
Others classify it
as a rate of penetration test. There is no one best test for "measuring
sizing." Test selection
depends on end use and mill control needs. This method is especially suitable
for use as a
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mill control sizing test to accurately detect changes in sizing level. It
offers the sensitivity of
the ink float test while providing reproducible results, shorter test times,
and automatic end
point determination.
[0121] Sizing, as measured by resistance to permeation
through or absorption into
paper of aqueous liquids, is an important characteristic of many papers.
Typical of these are
bag, containerboard, butcher's wrap, writing, and some printing grades.
[0122] This method may be used to monitor paper or board
production for specific
end uses provided acceptable correlation has been established between test
values and the
paper's end use performance. Due to the nature of the test and the penetrant,
it will not
necessarily correlate sufficiently to be applicable to all end use
requirements. This method
measures sizing by rate of penetration. Other methods measure sizing by
surface contact,
surface penetration, or absorption. Size tests are selected based on the
ability to simulate the
means of water contact or absorption in end use. This method can also be used
to optimize
size chemical usage costs.
[0123] As used herein, "oxygen permeability" means the degree
to which a polymer
allows the passage of a gas or fluid. Oxygen permeability (Dk) of a material
is a function of
the diffusivity (D) (i.e., the speed at which oxygen molecules traverse the
material) and the
solubility (k) (or the amount of oxygen molecules absorbed, per volume, in the
material).
Values of oxygen permeability (Dk) typically fall within the range 10-150 x 10-
11 (cm2 ml
02)/(s ml mmHg). A semi-logarithmic relationship has been demonstrated between
hydrogel
water content and oxygen permeability (Unit: Barrer unit). The International
Organization
for Standardization (ISO) has specified permeability using the SI unit
hectopascal (hPa) for
pressure. Hence Dk = 10-11 (cm2 ml 02) /(s ml hPa). The Barrer unit can be
converted to hPa
unit by multiplying it by the constant 0.75.
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[0124] As used herein "biodegradable", including grammatical
variations thereof,
means capable of being broken down especially into innocuous products by the
action of
living things (e.g., by microorganisms).
[0125] As used herein, "recyclable", including grammatical
variations thereof, means
a material that is treatable or that can be processed (with used and/or waste
items) so as to
make said material suitable for reuse.
[0126] As used herein, "Gurley second" or "Gurley number" is
a unit describing the
number of seconds required for 100 cubic centimeters (deciliter) of air to
pass through 1.0
square inch of a given material at a pressure differential of 4.88 inches of
water (0.176 psi)
(ISO 5636-5:2003)(Porosity). In addition, for stiffness, "Gurley number" is a
unit for a piece
of vertically held material measuring the force required to deflect said
material a given
amount (1 milligram of force). Such values may be measured on a Gurley
Precision
Instruments device (Troy, New York).
[0127] HLB¨The hydrophilic-lipophilic balance of a surfactant
is a measure of the
degree to which it is hydrophilic or lipophilic, determined by calculating
values for the
different regions of the molecule.
[0128] Griffin's method for non-ionic surfactants as
described in 1954 works as
follows:
JILLI 20 A< MAIM
[0129] where Mh is the molecular mass of the hydrophilic
portion of the molecule,
and M is the molecular mass of the whole molecule, giving a result on a scale
of 0 to 20. An
HLB value of 0 corresponds to a completely lipophilic/hydrophobic molecule,
and a value of
20 corresponds to a completely hydrophilic/lipophobic molecule.
[0130] The HLB value can be used to predict the surfactant
properties of a molecule:
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< 10 : Lipid-soluble (water-insoluble)
> 10 : Water-soluble (lipid-insoluble)
1.5 to 3 : anti-foaming agent
3 to 6 : W/O (water in oil) emulsifier
7 to 9 : wetting and spreading agent
13 to 15 : detergent
12 to 16 : 0/W (oil in water) emulsifier
15 to 18 : solubiliser or hydrotrope.
[0131] In some embodiments, the HLB values for the
SFAE/glyceride/FAS blend (or
the entire formulation comprising said blend) as disclosed herein may be in
the lower range.
In some embodiments. the HLB values for the SFAE/glyceride/FAS blend (or the
entire
formulation comprising said blend) as disclosed herein may be in the middle to
higher ranges.
[0132] As used herein, SEFOSE ! denotes a sucrose fatty acid
ester made from
soybean oil (soyate) which is commercially available from Procter & Gamble
Chemicals
(Cincinnati, OH) under the trade name SEFOSE 1618U (see sucrose polysoyatc
below),
which contains one or more fatty acids that are unsaturated. SEFOSE is an
exemplary
SFAE for use in the methods and barrier formulations of the present disclose.
[0133] As used herein, "soyate" means a mixture of salts of
fatty acids from soybean
oil. The SFAE for use in the methods and barriers formulas of the present
disclosure may
include or be derived from "soyate."
[0134] As used herein, "oilseed fatty acids" means fatty
acids from plants, including
but not limited to soybeans, peanuts, rapeseeds, barley, canola, sesame seeds,
cottonseeds,
palm kernels, grape seeds, olives, safflowers, sunflowers, copra, corn,
coconuts, linseed,
hazelnuts, wheat, rice, potatoes, cassavas, legumes, camelina seeds, mustard
seeds, and
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combinations thereof. The fatty acid chains of the SFAE/glyceride/FAS blend
can be oilseed
fatty acids.
[0135] As used herein "wet strength" means the measure of how
well a web of fibers
holding paper together (or other three-dimensional, solid, cellulose-based
product) can resist
a force of rupture when the paper is wet. The wet strength may be measured
using a Finch
Wet Strength Device from Thwing-Albert Instrument Company (West Berlin, NJ).
Where
the wet strength is typically effected by wet strength additives such as
kymene, cationic
glyoxylated resins, polyamidoamine-epichlorohydrin resins, polyamine-
epichlorohydrin
resins, including epoxide resins. In embodiments, the barrier formulation
coated cellulose-
based material as disclosed herein effects such wet strength in the absence of
such additives.
[0136] As used herein "wet" means covered or saturated with
water or another liquid.
[0137] The methods disclosed herein may include an additional
step of exposing the
contacted cellulose-based material to heat, radiation, a catalyst or a
combination thereof for a
sufficient time to bind the SGF blend, CNF, and/or enhanced CNF to the
cellulose-based
material. In a related aspect, such radiation may include, but is not limited
to UV, IR, visible
light, or a combination thereof. In another related aspect, the reaction may
be carried out at
room temperature (i.e., 25 C) to about 150 C, about 50 C to about 100 C, or
about 60 C to
about 80 C.
[0138] As used herein, the term "natural waxes- refers to
relatively high molecular
weight / high melting point materials. Specific examples of "natural waxes"
include, for
example, biowaxes obtained from renewable resources, such as vegetable oils,
fatty acids,
and fatty esters, etc., (see, e.g.,
hap s ://www .re searchgate .net/publication/318385619J-ligh_Q uality_B iowaxe
s_from_Fatty_
Acids_and_Fatty_Esters_Catalyst_and_Rcaction_Mcchanism_for_Accompanying_Rcactio
ns
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; and https://www.researchgate.net/figure/a-Preparation-of-canola-PFFA-18-
biowax-b-
Preparation-of-nanocellulose-from-canola_fig1_306527797).
[0139] As used herein, the term "cellulose crosslinkers"
means known cellulose
crosslinkers such as glyoxal, and small reactive dialdehydes or anhydrides.
[0140] The term -glycerides- as used herein has its common
meaning and refers to
acylglycerols, which are esters formed from glycerol and fatty acids. Glycerol
has three
hydroxyl functional groups, which can be esterified with one, two, or three
fatty acids to form
mono-, di-, and triglycerides. These structures can vary in their aliphatic
chain as they can
contain different carbon numbers, different degrees of unsaturation, and
different
configurations and positions of olefins.
[0141] The glycerides may be obtained by esterification with
substantially pure fatty
acids by known processes of esterification. The glycerides can also be
extracted from plant
oils and animal fats by known methods of extraction.
[0142] The term "fatty acid" as used herein has its common
meaning and refers to a
carboxylic acid with an aliphatic chain, which may be saturated or
unsaturated. The term
fatty acid as used herein may refer to the fatty acid group bound to the
glycerol residue of the
glyceride.
[0143] The fatty acid groups of the glycerides can be any
known fatty acid. In
preferred embodiments, the fatty acid is known to be present in food, is
edible, and/or is
approved by the FDA. In some embodiments, the fatty acids are obtained from
oilseeds. In
other embodiments, the fatty acids are obtained from other sources of
naturally edible fats
and oil.
[0144] The fatty acids of the glycerides can be independently
selected from one or
more saturated fatty acids, one or more monounsaturated fatty acids, and/or
one or more
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polyunsaturated fatty acids. By independently, this means, for example, that a
triglyceride
may comprise three different fatty acid groups attached to the glycerol
residue.
[0145] Exemplary saturated fatty acids for use in the
formulations/compositions of
the disclosure can be selected from butyric acid (butanoic acid), caproic acid
(hexanoic acid),
caprylic acid (octanoic acid), capric acid (decanoic acid), lauric acid,
(dodecanoic acid),
myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic
acid
(octadecanoic acid), arachidic acid (icosanoic acid), behenic acid (docosanoic
acid), or
lignoceric acid (tetracosanoic acid).
[0146] Exemplary monounsaturated fatty acids for use in the
formulations/compositions of the disclosure can be selected from caproleic
acid, (dec-9-enoic
acid), lauroleic acid ((Z)-dodec-9-enoic acid), myristoleic acid ((Z)-tetradec-
9-enoic acid),
palmitoleic acid ((Z)-hexadec-9-enoic acid), oleic acid ((Z)-octadec-9-enoic
acid), elaidic
acid ((E)-octadec-9-enoic acid), vaccenic acid ((E)-oc-tadec-11-enoic acid),
gadoleic acid
((Z)-icos-9-enoic acid), erucic acid ((Z)-docos-13-enoic acid), brassidic acid
((E)-docos-13-
enoic acid), or nervonic acid ((Z)-tetracos-15-enoic acid).
[0147] Exemplary polyunsaturated fatty acids for use in the
formulations/compositions of the disclosure can be selected from linoleic acid
(LA)
((9Z,12Z)-octadeca-9,12-dienoic acid), alpha-Linolenic acid (ALA)
((9Z,12Z,15Z)-octadeca-
9,12,15-trienoic acid), gamma-Linolenic acid (GLA) ((6Z,9Z,12Z)-octadeca-
6,9,12-trienoic
acid), columbinic acid ((5E,9E,12E)-octadeca-5,9,12-trienoic acid),
stearidonic acid
((6Z,9Z,12Z,15Z)-octadeca-6,9,12,15-tetraenoic acid), mead acid ((5Z,8Z,11Z)-
icosa-5,8,11-
trienoic acid), dihomo-y-linolenic acid (DGLA) ((8Z,11Z,14Z)-icosa-8,11,14-
trienoic acid),
arachidonic acid ((5Z,8Z,11Z,14Z)-icosa-5,8,11,14-tetraenoic acid),
eicosapentaenoic acid
(EPA) ((5Z,8Z,11Z,14Z,17Z)-icosa-5,8,11,14,17-pentacnoic acid),
docosapentacnoic acid
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(DPA) ((7Z,10Z,13Z,16Z,19Z)-docosa-7,10,13,16,19-pentaenoic acid),
docosahexaenoic acid
(DHA) ((4Z,7Z,10Z,13Z,16Z,19Z)-docosa-4,7,10,13,16,19-hexaenoic acid).
[0148] In some embodiments, the one or more glycerides may
include a blend of one
or more monoglycerides, one or more diglycerides, and/or one or more
triglycerides. In this
regard, the mono-, di-, and triglycerides can be blended in any weight ratio.
That is, any one
of the mono-, di-, or triglycerides could be the major glyceride component of
the formulation
by weight (that is, greater than 50% by weight when a total weight of
glycerides is considered
to be 100% by weight). In other embodiments, the formulation does not include
a
monoglyceride; does not include a diglyceride; or does not include a
triglyceride.
[0149] The one or more glycerides may vary in their fatty
acid alkyl groups. For
example, the one or more glycerides may contain fatty acid groups having
different carbon
numbers, different degrees of unsaturation, and/or different configurations
and positions of
olefins. The plurality of glycerides may include tripalmitin and/or
tristearin.
[0150] In some embodiments, the glycerides may include a
combination of one or
more water insoluble glycerides (e.g., as noted above, triglycerides are
typically strongly
nonpolar and hydrophobic) and one or more water soluble glycerides (in any
weight ratio
from 0.1:99.9 to 99.9:0.1); or only insoluble glycerides; or only insoluble
glycerides. The
solubility of the glyceride can be determined, for example, by its HLB value.
[0151] A person of ordinary skill in the art will appreciate
that the HLB value of the
one or more glycerides can be selected by varying one or more of the
parameters of the
glycerides noted above. In this regard, when a plurality of glycerides are
used, each glyceride
may have be chosen to have similar or different HLB values (e.g., lower range
used in
combination with higher range).
[0152] The term "fatty acid salt" (or "FAS") as used herein
has its common meaning
and refers to a salt of any one or more of the fatty acids disclosed herein
above. Exemplary
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cations for the fatty acid salts include but are not limited to calcium,
potassium, and sodium
salts. The fatty acid salts can be synthesized by known methods or extracted
from plant oils
or animal fats by known methods. One exemplary process comprises adding sodium
hydroxide to fatty acids found in animal fats or plant oils (such as from
oilseeds). For
example, sodium palmitate can be obtained from palm oil.
[0153] The one or more fatty acid salts may include one or
more calcium, potassium
or sodium salts. The calcium, potassium or sodium salts of fatty acids can be
obtained from a
naturally occurring source, such as oil seeds. The one or more fatty acid
salts can include one
or more selected from sodium oleate, sodium stearate, sodium palmitate,
calcium oleate,
calcium stearate, or calcium palmitate.
[0154] In some embodiments, the SGF blend may contain only
one or more
glycerides, may contain only one or more fatty acid salts, or may contain both
one or more
glycerides and one or more fatty acid salts. When the SGF blend contains both
one or more
glycerides and one or more fatty acid salts, the weight ratio of glycerides to
fatty acid salts
can be from about 0.1:99.9 to about 99:0.1, from about 10:90 to about 90:10,
from about
20:80 to about 80:20, from about 35:65 to about 65:35, from about 40:60 to
about 60:40,
from about 45:55 to about 55:45, or about 50:50.
[0155] The weight ratio of the SFAE in the SGF blend may be
0:100 to 100:0 or any
weight ratio therebetween (e.g., 1:99; 5:95; 10:90;20:80; 30:70;40:60; 50:50;
60:50; 70:30;
80:20; 90:10; 95:5; 99:1).
[0156] The weight ratio of the glycerides in the SGF blend
may be 0:100 to 100:0 or
any weight ratio therebetween (e.g., 1:99; 5:95; 10:90; 20:80; 30:70;40:60;
50:50; 60:50;
70:30; 80:20; 90:10; 95:5; 99:1).
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[0157] The weight ratio of the fatty acid salts in the SGF
blend may be 0:100 to 100:0
or any weight ratio therebetween (e.g., 1:99; 5:95; 10:90; 20:80: 30:70;
40:60; 50:50; 60:50;
70:30; 80:20; 90:10; 95:5; 99:1).
[0158] The weight ratio of the natural waxes in the SGF blend
may be 0:100 to 100:0
or any weight ratio therebetween (e.g., 1:99; 5:95; 10:90; 20:80; 30:70;
40:60; 50:50; 60:50;
70:30; 80:20; 90:10; 95:5; 99:1).
[0159] The weight ratio of the cellulose crosslinkers in the
SGF blend may be 0:100
to 100:0 or any weight ratio therebetween (e.g., 1:99; 5:95; 10:90; 20:80;
30:70; 40:60;
50:50; 60:50; 70:30; 80:20; 90:10; 95:5; 99:1).
[0160] At a sufficient concentration, and based on the
selection of the blend, the
binding of the SGF blend alone is enough to make the contacted substrate
hydrophobic: i.e.,
hydrophobicity is achieved in the absence of the addition of waxes, rosins,
resins, diketenes,
shellacs, vinyl acetates, PLA, PEI, oils, other water repellant chemicals or
combinations
thereof (i.e., secondary hydrophobes), including that other properties such
as, inter al/a,
strengthening, stiffing, and bulking of the cellulose-based material is
achieved by
glyceride/fatty acid salt binding alone.
[0161] The use of CNF alone as a binder has also been shown
to increase the
hydrophobicity of the contacted substrate.
[0162] Saturated SFAE, glycerides, and fatty acid salts are
typically solids at nominal
processing temperatures, whereas unsaturated SFAE, glycerides, and fatty acid
salts are
typically liquids. This permits the formation of uniform, stable dispersions
of saturated
glycerides and fatty acid salts in aqueous coatings without significant
interactions or
incompatibilities with other coating components, which are typically
hydrophilic. In
addition, this dispersion allows for high concentrations of saturated
glycerides and fatty acid
salts to be prepared without adversely affecting coating rheology, uniform
coating
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application, or coating performance characteristics. The coating surface will
become
hydrophobic when the particles of saturated glycerides and fatty acid salts
melt and spread
upon heating, drying and consolidation of the coating layer. The natural waxes
of the present
disclosures are also solids at nominal processing temperatures.
[0163] Saccharide fatty acid esters of all saccharides,
including mono-, di-saccharides
and tri-saccharides, are adaptable for use in connection with aspects of the
present disclosure.
The saccharide fatty acid ester may be a mono-, di-, tri-, tetra-, penta-,
hexa-, hepta-, or
octaester, and combinations thereof, including that the fatty acid moieties
may be saturated,
unsaturated or a combination thereof
[0164] The SFAE may comprise or consist essentially of
sucrose esters of fatty acids.
[0165] Many methods are known and available for making or
otherwise providing the
SFAE of the present disclosure, and all such methods are believed to be
available for use
within the broad scope of the present disclosure. For example, in certain
embodiments it may
be preferred that the fatty acid esters are synthesized by esterifying a
saccharide with one or
more fatty acid moieties obtained from oil seeds including but not limited to,
soybean oil,
sunflower oil, olive oil, canola oil, peanut oil, and mixtures thereof
[0166] The SFAE may comprise a saccharide moiety, including
but not limited to a
sucrose moiety, which has been substituted by an ester moiety at one or more
of its hydroxyl
hydrogens. In a related aspect, disaccharide esters for use in this disclosure
can have the
structure of Formula I of the '073 publication, which is incorporated herein
by reference.
[0167] Suitable disaccharides for the SFAE may also include
xylose, glucose,
raffinose, maltodextrose, galactose, combinations of glucose, combinations of
fructose,
maltose, lactose, combinations of mannose, combinations of erythrose,
isomaltose,
isomaltulosc, trchalosc, trchalulosc, ccllobiosc, laminaribiosc, chitobiosc
and combinations
thereof.
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[0168] In other embodiments, a starch fatty acid ester can be
used, where the starch
may be derived from any suitable source such as dent corn starch, waxy corn
starch, potato
starch, wheat starch, rice starch, sago starch, tapioca starch, sorghum
starch, sweet potato
starch, and mixtures thereof.
[0169] For use in the compositions of the present disclosure,
the SFAE compounds
may have a high degree of substitution. In some embodiments, the saccharide
fatty acid ester
is a sucrose polysoyatc.
N.zirr?
LI.N.
p ..= 0
., . = 0
0
. .
1
,
A Sucrose Polysoyate (SEFOSE 1618U)
[0170] The SFAE can be produced in the manner disclosed in
the '073 application.
For example, saccharide fatty acid esters may be made by esterification with
substantially
pure fatty acids by known processes of esterification. They can be prepared
also by trans-
esterification using saccharide and fatty acid esters in the form of fatty
acid glycerides
derived, for example, from natural sources, for example, those found in oil
extracted from oil
seeds, for example soybean oil. Trans-esterification reactions providing
sucrose fatty acid
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esters using fatty acid glycerides are described, for example, in U.S. Patent
Nos. 3,963,699;
4,517,360; 4,518,772; 4,611,055; 5,767,257; 6,504,003; 6.121,440; and
6,995,232, and
International Publication W01992004361, herein incorporated by reference in
their
entireties.
[0171] The cellulose-based products generated by the methods
disclosed herein can
be configured to exhibit greater hydrophobicity (or water resistance) relative
to the same
cellulose-containing material without the treatment. In a related aspect, the
treated cellulose-
containing material exhibits greater lipophobicity (or OGR) relative to the
same cellulose-
containing material without the treatment. In a further related aspect, the
treated cellulose-
containing material may be biodegradable, compostable, and/or recyclable. In
one aspect, the
treated cellulose-containing material is both hydrophobic (water resistant)
and lipophobic
(lipid resistant) (OGR).
[0172] The cellulose-based products of the present disclosure
may have improved
mechanical properties compared to that same material untreated. For example,
paper bags
treated by the process as disclosed herein show increased burst strength,
Gurley Number,
Tensile Strength and/or Energy of Maximum Load. In one aspect, the burst
strength is
increased by a factor of between about 0.5 to 1.0 fold, between about 1.0 and
1.1 fold,
between about 1.1 and 1.3 fold, between about 1.3 to 1.5 fold. In another
aspect, the Gurley
Number increased by a factor of between about 3 to 4 fold, between about 4 to
5 fold,
between about 5 to 6 fold and about 6 to 7 fold. In still another aspect, the
Tensile Strain
increased by a factor of between about 0.5 to 1.0 fold, between about 1.0 to
1.1 fold, between
about 1.1 to 1.2 fold and between about 1.2 to 1.3 fold. And in another
aspect, the Energy of
Max Load increased by a factor of between about 1.0 to 1.1 fold, between about
1.1 to 1.2
fold, between about 1.2 to 1.3 fold, and between about 1.3 to 1.4 fold
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[0173] The cellulose-containing material can be a base paper
comprising
microfibrillated cellulose (MFC) or cellulose nanofiber (CNF) as described for
example in
U.S. Pub. No. 2015/0167243 (incorporated herein by reference in its entirety),
where the
MFC or CNF is added during the forming process and paper making process and/or
added as
a coating or a secondary layer to a prior forming layer to decrease the
porosity of said base
paper. In embodiments, the resulting contacted base paper is tuneably water
and lipid
resistant. In a related aspect, the resulting base paper may exhibit a Gurley
value of at least
about 10-15 (i.e., Gurley Air Resistance (sec/100 cc, 20 oz. cyl.)), or at
least about 100, at
least about 200 to about 350. In one aspect, the barrier coating disclosed
herein may be a
laminate for one or more layers or may provide one or more layers as a
laminate or may
reduce the amount of coating of one or more layers to achieve the same
performance effect
(e.g., water resistance, grease resistance, and the like). In a related
aspect, the laminate may
comprise a biodegradable and/or composable heat seal or adhesive.
[0174] In embodiments, the SGF blend may be combined with one
or more coating
components for internal and surface sizing (alone or in combination),
including but not
limited to, pigments (e.g., clay, calcium carbonate, titanium dioxide, plastic
pigment), binders
(e.g., starch, soy protein, polymer emulsions, Py0H, casein), and additives
(e.g., glyoxal,
glyoxalated resins, zirconium salts, polyethylene emulsion, carboxymethyl
cellulose, acrylic
polymers, alginates, polyacrylate gums, polyacrylates, microbiocides, oil
based defoamers,
silicone based defoamers, stilbenes, direct dyes and acid dyes). In a related
aspect, such
components may provide one or more properties, including but not limited to,
building a fine
porous structure, providing light scattering surface, improving ink
receptivity, improving
gloss, binding pigment particles, binding coatings to paper, base sheet
reinforcement, filling
pores in pigment structure, reducing water sensitivity, resisting wet pick in
offset printing,
preventing blade scratching, improving gloss in supercalendering, reducing
dusting, adjusting
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coating viscosity, providing water holding, dispersing pigments, maintaining
coating
dispersion, preventing spoilage of coating/coating color, controlling foaming,
reducing
entrained air and coating craters, increasing whiteness and brightness, and
controlling color
and shade. It will be apparent to one of skill in the art that combinations
may be varied
depending on the property(ies) desired for the final product
[0175] In a wet end application, the SGF blend may be present
in the aqueous mixture
or dispersion at a concentration of at least 0.025% (wt/wt) of the total
cellulose fiber present
in the dispersion. In related aspects, the SGF blend may be present at about
0.05% (wt/wt) to
about 0.1% (wt/wt), about 0.1% (wt/wt) to about 0.5% (wt/wt), about 0.5%
(wt/wt) to about
1.0% (wt/wt), about 1.0% (wt/wt) to about 2.0% (wt/wt), about 2.0% (wt/wt) to
about 3.0%
(wt/wt), about 3.0% (wt/wt) to about 4.0% (wt/wt), about 4.0% (wt/wt) to about
5.0%
(wt/wt), about 5.0%(wt/wt) to about 10% (wt/wt), or about 10% (wt/wt) to about
50% (wt/wt)
of the total fiber present.
[0176] In a wet end application, CNF may be present in the
aqueous mixture or
dispersion at a concentration of at least 0.025% (wt/wt) of the total
cellulose fiber present in
the dispersion. In related aspects, the CNF may be present at about 0.05%
(wt/wt) to about
0.1% (wt/wt), about 0.1% (wt/wt) to about 0.5% (wt/wt), about 0.5% (wt/wt) to
about 1.0%
(wt/wt), about 1.0% (wt/wt) to about 2.0% (wt/wt), about 2.0% (wt/wt) to about
3.0%
(wt/wt), about 3.0% (wt/wt) to about 4.0% (wt/wt), about 4.0% (wt/wt) to about
5.0%
(wt/wt), about 5.0%(wt/wt) to about 10% (wt/wt), about 10% (wt/wt) to about
20% (wt/wt),
about 20% (wt/wt) to about 30% (wt/wt), about 30% (wt/wt) to about 40%
(wt/wt), about
40% (wt/wt) to about 50% (wt/wt), about 60% (wt/wt) to about 70% (wt/wt),
about 70%
(wt/wt) to about 80% (wt/wt), or about 80% (wt/wt) to about 90% (wt/wt) of the
total fiber
present.
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[0177] In a wet end application, the enhanced CNF may be
present in the aqueous
mixture or dispersion at a concentration of at least 0.025% (wt/wt) of the
total cellulose fiber
present in the dispersion. In related aspects, the enhanced CNF may be present
at about
0.05% (wt/wt) to about 0.1% (wt/wt), about 0.1% (wt/wt) to about 0.5% (wt/wt),
about 0.5%
(wt/wt) to about 1.0% (wt/wt), about 1.0% (wt/wt) to about 2.0% (wt/wt), about
2.0% (wt/wt)
to about 3.0% (wt/wt), about 3.0% (wt/wt) to about 4.0% (wt/wt), about 4.0%
(wt/wt) to
about 5.0% (wt/wt), about 5.0%(wt/w-t) to about 10% (wt/wt), about 10% (wt/wt)
to about
20% (wt/wt), about 20% (wt/wt) to about 30% (wt/wt), about 30% (wt/wt) to
about 40%
(wt/wt), about 40% (wt/wt) to about 50% (wt/wt), about 60% (wt/wt) to about
70% (wt/wt),
about 70% (wt/wt) to about 80% (wt/wt), or about 80% (wt/wt) to about 90%
(wt/wt) of the
total fiber present.
[0178] As used herein, "coating weight" is the weight of a
material (wet or dry)
applied to a substrate. It is expressed in pounds per specified ream or grams
per square meter
[0179] In a coating application, the enhanced CNF may be
present at a coating weight
of at least about 0.05 g/m2 on the surface of the substrate. In related
aspects, the SGF blend
may be present at a coating weight of about 0.05 g/m2 to about 1.0g/m2, about
1.0g/m2 to
about 2.0g/m2, about 2g/m2 to about 3g/m23g/m2 to about 4g/m2, about 4g/m2 to
about 5g/m2,
about 5g/m2 to about 10g/m2, or about 10g/m2 to about 20g/m2 on a surface of
the cellulose-
based material.
[0180] In a coating application, the SGF blend may be present
at a coating weight of
at least about 0.05 g/m2 on the surface of the substrate. In related aspects,
the SGF blend
may be present at a coating weight of about 0.05 g/m2 to about 1.0g/m2, about
1.0g/m2 to
about 2.0g/m2, about 2g/m2 to about 3g/m23g/m2 to about 4g/m2, about 4g/m2 to
about 5g/m2,
about 5g/m2 to about 10g/m2, or about 10g/m2 to about 20g/m2 on a surfacc of
the cellulose-
based material.
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[0181] In a coating application, the CNF may be present at a
coating weight of at least
about 0.05 g/m2 (gsm) on the surface of the cellulose-based material (or
substrate). In
related aspects, the CNF can be present at a coating weight of about 0.05 g/m2
to about
1.0g/m2, about 1.0g/m2 to about 2.0g/m2, about 2g/m2 to about 3g/m2, 3g/m2 to
about 4g/m2,
about 4g/m2 to about 5g/m2, about 5g/m2 to about 10g/m2, about 10g/m2 to about
20g/m2, or
about 20g/m2 to about 30g/m2 on a surface of the cellulose-based material.
[0182] The hydrophobic barrier property might be imparted to
the substrate by the
SGF blend and/or the enhanced CNF in the absence of any secondary hydrophobes.
[0183] The barrier formulation may include one or more
emulsifiers or emulsifying
agents in a concentration sufficient to form an emulsion of the SGF blend and
water and/or to
form an emulsion of the enhanced CNF and water. Suitable emulsifiers or
emulsifying
agents include buffers, polyvinyl alcohol (Pv0H), carboxymethyl cellulose
(CMC), milk
proteins, gelatins, starches, acetyl ated polysaccharides, alginates, can-
ageenans, chitosans,
inulins, long chain fatty acids, waxes, agar, alginates, glycerol, gums,
lecithins, poloxamers,
mono-, di-glycerols, monosodium phosphates, monostearate, propylene glycols,
detergents,
cetyl alcohol, glycerol esters, (saturated) (polyunsaturated) fatty acid
methyl esters, and
combinations thereof.
[0184] The methods disclosed herein may include a step of
predetermining a content
of the SGF blend and/or the components of the SGF blend to be included in the
enhanced
CNF. In some aspects, this step of predetermining can be performed prior to
the preparing
the enhanced CNF. The step of predetermining can be performed to achieve the
desired
effects. The step of predetermining can be performed to achieve a desired
level of water
resistance and/or a desired level of oil and grease resistance when the
enhanced CNF is used
in a barrier formulation and/or added to the papennaking furnish on the wet
end. In some
aspects, the step of predetermining can be performed to increase dewatering
rate of the
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furnish or fiber slurry. Increasing the dewatering rate improves the rate, for
example, of
producing a cellulose-based article. As noted above, dewatering a slurry
containing CNF is
one of the biggest problems directed to use of CNF. The increased dewatering
rate applies,
for example, to both the making of the enhanced CNF binder and the use of the
enhanced
CNF binder in a barrier formulation. Dewatering is well known in the
papermaking industry,
and is also explained in Smook, which is incorporated herein by reference in
its entirety
elsewhere in this disclosure.
[0185] The methods disclosed herein may include a step of
predetermining a content
of the SGF blend and/or predetermining the components of the SGF blend to be
included in
the barrier formulations. In some aspects, this step of predetermining can be
performed prior
to the preparing the barrier formulation, or can be performed prior to the
contacting the
cellulose-based material with the formulation. The step of predetermining can
be performed
to achieve the desired effects. The step of predetennining can be performed to
achieve a
desired level of water resistance and/or a desired level of oil and grease
resistance.
[0186] As noted above, the barrier formulations may include
one or more pigments
commonly used in the paper industry. The one or more pigments can be present
in the
formulation in a concentration of about 0.1% to about 90% by weight based on a
total weight
of the formulation. In other aspects, the concentration of the pigment can be
from about 1%
to 10% by weight, from about 11% to 20% by weight, from about 21% to 30% by
weight,
from about 31% to 40% by weight, from about 41% to 50% by weight, 51% to 60%
by
weight, 61% to 70% by weight, 71 to 80% by weight, 81% to 90% by weight, or
any other
range between 0.1% to 90% by weight. The use of pigments is well known in the
paper
industry, and the pigment concentration can be chosen to vary the properties
of the final
product. Example pigments include clay, calcium carbonate, titanium dioxide,
kaolin, talc,
plastic pigment, silica, silicates, metal oxides, alumina, aluminates, and
diatomaceous earth.
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[0187] As noted above, the barrier formulation may include
one or more charged
polymers to aid in the retention of the enhanced CNF and/or the SGF blend on
the cellulose-
based substrate. The one or more charged polymers may include one or more
cationic
polymers, anionic polymers, nonionic polymers, and/or zwitterionic polymers.
The charged
polymer may include a combination of a relatively low molecular weight
cationic polymer
and a relative high molecular weight anionic polymer.
[0188] The charged polymer may consist of one or more
cationic polymer. The one
or more cationic polymer may include a polyacrylamide. The polyacrylamide may
include
polyDADMAC (poly diallyldimethylammonium chloride).
[0189] The cationic polymer may have a weight average
molecular weight of 500,000
to 10,000,000. In some aspects, the weight average MW is 500,000 to 1,000,000,
1,000,001
to 2,000,000, 2,000,001 to 3,000,000, 3,000,001 to 4,000,000, 4,000,001 to
5,000,000,
5,000,001 to 6,000,000, 6,000,001 to 7,000,000, 7,000,001 to 8,000,000,
8,000,001 to
9,000,000, or 9,000,001 to 10,0000. In some aspects, a blend of charged
polymers are used
to achieve a "bimodal"-type weight average MW using a combination of charged
polymers
having any MW in the ranges above (e.g., a first charged polymer having a
weight average
MW of less than 1,000,000 used in combination with a second charged polymer
having a
weight average MW greater than 2,000,000; wherein the weight ratio of the
first charged
polymer to the second charged polymer is 10:90 to 90:10). In some embodiments,
a
concentration of the cationic polymer in the formulation is from about 0.01%
to about 5% by
weight, from about 0.01% to about 3% by weight, 0.05% to about 0.1% by weight,
or from
about 0.1% to about 1% by weight, or from about 1% to about 3% by weight when
a total
weight of the formulation is considered 100%. In some aspects, a weight ratio
in the
formulation of the cationic polymer to the enhanced CNF is from about 0.1:99.9
to about
20:80, from 0.5:99.5 to about 15:85, from about 1:99 to about 10:90, or from
about 2.5:97.5
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to about 7.5:92.5. In some aspects, a weight ratio in the formulation of the
cationic polymer
to the SGF blend is from about 0.1:99.9 to about 20:80, from 0.5:99.5 to about
15:85, from
about 1:99 to about 10:90, or from about 2.5:97.5 to about 7.5:92.5.
[0190] In some aspects, as noted above, prolamins can be used
as the retention aid of
a barrier formulation including the enhanced CNF and/or the SGF blend instead
of a charged
polymer.
[0191] The barrier formulation may also include one or more
conventional
papennaking binders. Example binders include CNF, the enhanced CNF of the
present
disclosure, starch, polymers, polymer emulsions, Pv0H, prolamins, or
combinations thereof.
In some aspects, the formulation may not contain any binder other than the
enhanced CNF.
[0192] The barrier formulation can be provided in the fonn of
an emulsion. The
emulsion can be used as the barrier formulation of the methods of the present
disclosure. In
some aspects, the emulsion may not contain any emulsifier other than an SGF
blend.
Alternatively, the emulsion can include about 0.01% to about 80% by weight of
one or more
emulsifiers. The emulsion may also include material for stabilizing the
emulsion over a
period of time (e.g., weeks, months, etc.). such as a nano or microfibrilized
cellulose, a gum,
or a thickening agent. A list of exemplary emulsifiers is described above.
[0193] The cellulose-based material or substrate, which may
be dried prior to
application (e.g., at about 80-150 C), may be treated with the modifying
formulations by
dipping, for example, and allowing the surface to be exposed to the
composition for less than
1 second. The substrate may be heated to dry the surface, after which the
modified material
is ready for use. In one aspect, according to the method as disclosed herein,
the substrate
may be treated by any suitable coating/sizing process typically carried out in
a paper mill
(see, e.g., Smook, G., Surface Treatments in Handbook for Pulp & Paper
Technologists,
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(2016), 4th Ed., Cpt. 18, pp. 293-309, TAPPI Press, Peachtree Corners, GA USA,
herein
incorporated by reference in its entirety).
[0194] No special preparation of the cellulose-based material
is necessary in
practicing this disclosure, although for some applications, the material may
be dried before
treatment. In embodiments, the methods as disclosed may be used on any
cellulose-based
surface, including but not limited to, a film, a rigid container, fibers,
pulp, a fabric or the like.
In one aspect, the barrier formulations may be applied by conventional size
press (vertical,
inclined, horizontal), gate roll size press, metering size press, calender
size application, tube
sizing, on-machine, off-machine, single-sided coater, double-sided coater,
short dwell,
simultaneous two-side coater, blade or rod coater, gravure coater, gravure
printing,
flexographic printing, ink-jet printing, laser printing, water box on a
calender, and
combinations thereof.
[0195] Depending on the source, the cellulose treated in the
methods herein may be
paper, paperboard, pulp, softwood fiber, hardwood fiber, or combinations
thereof,
nanocellulose, cellulose nanofibres, whiskers or microfibril,
microfibrillated, cotton or cotton
blends, cellulose nanocrystals, or nanofibrilated cellulose.
[0196] In addition, fibers and cellulose-based material
modified as disclosed herein,
may be repulped. Further, for example, water cannot be easily "pushed h past
the low surface
energy barrier into the sheet.
[0197] In embodiments, the amount of the barrier formulation
applied is sufficient to
completely cover at least one surface of a substrate, such as at least one
surface of a cellulose-
containing material. For example, in embodiments, the barrier formulation may
be applied to
the complete outer surface of a container, the complete inner surface of a
container, or a
combination thereof, or one or both sides of a base paper. In other
embodiments, the
complete upper surface of a film may be covered by the barrier formulation, or
the complete
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under surface of a film may be covered by the barrier formulation, or a
combination thereof.
In some embodiments, the lumen of a device/instrument may be covered by the
barrier
formulation or the outer surface of the device/instrument may be covered by
the barrier
formulation or a combination thereof
[0198] In embodiments, the amount of barrier formulation
applied is sufficient to
partially cover at least one surface of a cellulose-based material. For
example, only those
surfaces exposed to the ambient atmosphere are covered by the barrier
formulation, or only
those surfaces that are not exposed to the ambient atmosphere are covered by
the barrier
formulation (e.g., masking). As will be apparent to one of skill in the art,
the amount of
barrier formulation applied may be dependent on the use of the material to be
covered. In
one aspect, one surface may be coated with a barrier formulation and the
opposing surface
may be coated with an agent including, but not limited to, proteins, wheat
glutens, gelatins,
prolamins, soy protein isolates, starches, modified starches, acetylated
polysaccharides,
alginates, carrageenans, chitosans, inulins, long chain fatty acids, waxes,
and combinations
thereof. In a related aspect, the barrier formulation can be added to a
furnish, and the
resulting material on the web may be provided with an additional coating of
the barrier
formulation (having the same or different composition as the formulation added
on the wet
end).
[0199] Any suitable coating process may be used to deliver
any of the various barrier
formulations in the course of practicing the methods. In embodiments, the
coating processes
include immersion, spraying, painting, printing, and any combination of any of
these
processes, alone or with other coating processes adapted for practicing the
methods as
disclosed.
[0200] The permeability of a surface to various gases such as
water vapour and gases
(e.g., oxygen, nitrogen, and carbon dioxide) may also be altered by the
barrier formulations
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as the barrier function of the material is enhanced. The standard unit
measuring permeability
is the Barrer and protocols to measure these parameters are also available in
the public
domain (ASTM std F2476-05 for water vapour and ASTM std F2622-8 for oxygen,
for gas
testing in general - https://www.ametekmocon.com/products/searchbybrand/mocon.
MOCON Permeation Testing Analyzers are recognized as the industry-leading
solution for
over 50 years and are the basis for many global permeability testing standards
such as ASTM
D3985 and ASTM F1249. The extensive line of MOCON analyzers represent decades
of
technical leadership and continuous innovation in partnership with our
customers, distributors
and institutions. Our MOCON Permeation Analyzers offer a wide range of testing
capabilities across the most diverse range of products and materials"..). In
some aspects,
permeability to vapours and gases can be further reduced by adding one or more
prolamins to
the barrier formulation.
[0201] In embodiments, materials treated according to the
disclosed methods display
a complete biodegradability as measured by the degradation in the environment
under
microorganismal attack.
[0202] Various methods are available to define and test
biodegradability including the
shake-flask method (ASTM E1279 ¨ 89(2008)) and the Zahn-Wellens test (OECD TG
302
B).
[0203] Various methods are available to define and test
compostability including, but
not limited to, ASTM D6400.
[0204] The barrier coated product of the present disclosure
may have a TAPPI T 559
KIT test value of from about 3 to about 12, greater than 4, greater than 5,
greater than 6,
greater than 7, greater than 8, greater than 9, greater than 10, greater than
11, etc.
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[0205] The barrier coated product of the present disclosure
may have an HST value of
at least about 65 seconds, at least about 120 seconds, at least about 240
seconds, at least about
480 seconds, etc.
[0206] A surface of the barrier coated product of the present
disclosure may exhibit a
water contact angle between about 60 to 120 degrees, of at least about 90
degrees, at least
about 100 degrees, at least about 110 degrees, at least about 120 degrees,
etc.
[0207] In some embodiments, the barrier formulation of the
present disclosure forms
a stable aqueous composition, the term "stable aqueous composition" is defined
as an
aqueous composition which is substantially resistant to viscosity change,
coagulation, and
sedimentation over at least an 8-hour period when contained in a closed vessel
and stored at a
temperature in a range of from about 0 degrees C to about 60 degrees C. Some
embodiments
of the barrier formulation are stable over at least a 24-hour period, and
often over at least a 6-
month period.
[0208] In some embodiments, the barrier coated product
obtained by the methods of
the present disclosure does not include a PFAS. In some embodiments, the
barrier coated
product of the present disclosure does not include a PFAS in the barrier
coating.
[0209] In some embodiments, the barrier coated product
obtained by the methods of
the present disclosure is folded into a three-dimensional shape and is
contained within a
sealed package. In these embodiments, the barrier layer may be an exposed
layer (or outer
layer) within the inside of the package. The material of the package can be
any conventional
material for storing, shipping, selling, etc. a food or beverage product. In
these embodiments,
the sealed package may also contain therein a food or beverage product. In
these
embodiments, the food or beverage product may contact the barrier paper layer.
The seal of
the sealed package may be a hermetic seal.
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[0210] In some embodiments, the barrier coated product
obtained by the methods of
the present disclosure is compatible with traditional paper recycling
programs: i.e., poses no
adverse impact on recycling operations, like polyethylene, polylactic acid, or
wax coated
papers do.
[0211] In some embodiments, the barrier coated product
obtained by the methods of
the present disclosure is bio-based. As used herein, "bio-based" (or
"biobased") means a
material intentionally made from substances derived from living (or once-
living) organisms.
In a related aspect, material containing at least about 50% of such substances
is considered
bio-based. In some aspects, the barrier coated product obtained by the methods
of the present
disclosure may be entirely bio-based. In some aspects, the barrier
formulations of the present
disclosure may be entirely bio-based.
[0212] In some embodiments, the barrier coated product
obtained by the methods of
the present disclosure is recyclable. As used herein, "recyclable", including
grammatical
variations thereof, means a material that is treatable or that can be
processed (with used
and/or waste items) so as to make said material suitable for reuse.
[0213] In some embodiments, the barrier coated product of the
present disclosure is
biodegradable. As used herein "biodegradable", including grammatical
variations thereof,
means capable of being broken down especially into innocuous products by the
action of
living things (e.g., by microorganisms).
EXAMPLES
[0214] In the following, although embodiments of the present
disclosure are
described in further detail by means of Examples, the present disclosure is
not limited thereto.
[0215] Example 1
[0216] Example 1 is a lab study regarding the use of CNF in
molded pulp products
with barrier properties.
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[0217] The equipment used in Example 1 are as follows:
= Buchner funnel - large (which is believed to be about 8" diameter)
= Vacuum flask
= Lab vacuum pump
= Spray bottle
= Stop watch
[0218] The materials that may be used in Example 1 are as
follows:
= Bleached kraft pulp (50% SWK, 50% HWK) slurried at 1% solids
= CNF slurry - 0.5% solids
= CNF slurry with 10% SE-15* added, 0.5% solids
= SE-9**/SE 30*** emulsion, 1% solids
= C-PAM (Cationic polyacrylamide), 0.1% solids
= Cationic Coagulant, 0.1% solids
= Pigment, 1% solids Capim DG Clay slurry from IMERYS.
[0219] * SE-15 was obtained from HANGZHOU UNION BIOTECHNOLOGY
CO.,
LTD. SE-15 is marketed as a sucrose fatty acid ester. SE-15 was analyzed and
was found to
contain about 15 to 30% by weight saccharide fatty acid ester, about 40 to 60%
by weight
glycerides, and a balance fatty acid salts plus trace components.
[0220] ** SE-9 was obtained from ZHEJIANG SYNOSE TECH. SE-9
is marketed
as a sucrose fatty acid ester. SE-9 was analyzed and was found to be similar
in composition
to SE-15, except for having a higher glycerides content and about 10 to 20%
less sucrose
ester.
[0221] *** SE-30 was obtained from EAST CHEMSOURCES LIMITED.
SE-30 is
marketed as a sucrose fatty acid ester. SE-30 was analyzed and was found to
contain greater
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than 80% sucrose esters with a variety of substitutions. The remainder of the
product was
glycerides with relatively low (less than 5% by weight) salt.
[0222] The test procedure for Example 1 was as follows:
[0223] Blank or Control
[0224] (1) Add a sufficient quantity of bleached kraft slurry
to the Buchner funnel to
produce a fiber pad with a grammage of 150 gsm. Note the volume of furnish
used for future
runs.
[0225] (2) Start vacuum pump once slurry has been added to
Buchner funnel.
[0226] (3) Note the time to drain furnish to the "wet line,"
which is the point during
the drainage process where the surface of the fiber slurry goes from shiny or
"wet" look to a
dull, textured surface.
[0227] (4) Continue to apply vacuum to the wet sample for 10
seconds.
[0228] (5) Remove the wet mat from the Buchner funnel, and
place the wet mat
between two blotters. Roll standard hand sheet roller across blotters twice to
press test
sample.
[0229] (6) Removed pressed sample and place in a 100 C oven
until dry.
[0230] Internally treated (wet end application)
[0231] (1) Add one or more additives to an aliquot of furnish
(volume determined
during the production of the control sample) slurry and mix. See Table 1
below.
[0232] (2) Add a sufficient quantity of blended slurry to the
Buchner funnel to
produce a fiber pad with a grammage of 150 gsm.
[0233] (3) Start vacuum pump once slurry has been added to
Buchner funnel.
[0234] (4) Note time to drain furnish to the "wet line."
[0235] (5) Continue to apply vacuum to the wet sample for 10
seconds.
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[0236] (6) Remove the wet mat from the Buchner funnel, and
place the wet mat
between two blotters. Roll standard hand sheet roller across blotters twice to
press test
sample.
[0237] (7) Remove pressed sample and place in a 100 C oven
until dry.
[0238] Spray Treated (coating formed article)
[0239] (1) Add a sufficient quantity of bleached kraft slurry
to the Buchner funnel to
produce a fiber pad with a grammage of 150 gsm.
[0240] (2) Start vacuum pump once slurry has been added to
Buchner funnel.
[0241] (3) Note time to drain furnish to the "wet line."
[0242] (4) Spray a known amount of a dilute suspension of the
additive onto the
surface of the wet mat. See Table 2 below.
[0243] (5) Continue to apply vacuum to the wet sample for 10
seconds.
[0244] (6) Remove the wet mat from the Buchner funnel, and
place the wet mat
between two blotters. Roll standard hand sheet roller across blotters twice to
press test
sample.
[0245] (7) Remove pressed sample and place in a 100 C oven
until dry.
[0246] Table 1¨Internal Treatment
Run TD CNF SE-9/SE-30 C-PAM Cat. Coag
Blend
1 Control 0 0 0.025 0.5
2 1NT-1 1 0 0.025 0.5
3 1NT-2 0 4 0.025 0.5
4 INT-3 1 4 0.025 0.5
[0247] In Table 1, the additives are listed by their weight %
on a dry basis.
[0248] Table 2¨Spray Treatment
Run ID CNF SE-9/SE-30 C-PAM Cat. Coag
Blend
Control 0 0 0 0
6 SPR-1 2 0 0 0
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7 SPR-2 0 4 0 0
8 SPR-3 2 4 0 0
[0249] In Table 2, the additives are listed by their weight % on a dry
basis.
[0250] Based on experimental testing of the example embodiments, the data
in
Table 3 shows the improvement obtained in water resistance and/or oil and
grease resistance.
Water resistance has been tested using a water Cobb test adapted from Tappi
Standard Test
Method T 441 om-20 "Water Absomtiveness of Paper.- Oil and grease resistance
has been
tested using a 3M KIT Test (Tappi Standard Test Method T 559 "Grease
resistance") and an
oil Cobb test using vegetable oil adapted from Tappi Standard Test Method T
441 om-20.
[0251] Table 3
Run # ID Oil Cobb Water Cobb 3M Kitt Oil Cobb test
(2 min) (2 min) Test (85
C)
(Room Temp) (Room Temp)
g/cm2
g/cm2
Internal Treatment
I Control 1280 790 0
2 1NT-1 1185 850 0
3 INT-2 728 27 3
4 1NT-3 95 20 4
Spray Treatment
5 Control 868 1730 0 1244
6 SPR-1 22 1505 6 16
7 SPR-2 588 165 3 764
8 SPR-3 15 81 6 17
[0252] While there have been shown and described fundamental novel features
of the
disclosure as applied to the preferred and exemplary embodiments thereof, it
will be
understood that omissions and substitutions and changes in the form and
details of the
disclosure may be made by those skilled in the art without departing from the
spirit of the
disclosure. Moreover, as is readily apparent, numerous modifications and
changes may
readily occur to those skilled in the art. For example, any feature(s) in one
or more
embodiments may be applicable and combined with one or more other embodiments.
Hence,
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it is not desired to limit the present disclosure to the exact construction
and operation shown
and described and, accordingly, all suitable modification equivalents may be
resorted to
falling within the scope of the present disclosure as claimed. In other words,
although the
embodiments of the disclosure have been described with reference to the above
examples, it
will be understood that modifications and variations are encompassed within
the spirit and
scope of the disclosure. Accordingly, the invention is limited only by the
following claims.
[0253] All references disclosed herein are hereby
incorporated by reference in their
entireties.
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