Note: Descriptions are shown in the official language in which they were submitted.
COATING SYSTEM AND METHOD
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation-in-part of pending U.S.
Patent Application
Serial No. 16/379,164, filed on April 9, 2019, entitled "COATING SYSTEM AND
METHOD," which claims the benefit of priority to U.S. Provisional Patent
Application
Serial No. 62/654,830, filed on April 9, 2018, entitled "COATING SYSTEM AND
METHOD," the disclosures of which are incorporated by reference herein in
their entireties.
BACKGROUND
[0002] Pultrusion is a continuous process for manufacturing a composite
material that
entails simultaneously pulling a reinforcement material through a resin
impregnating
processing equipment and peripheral manufacturing equipment and cross-head
extruding the
composite material onto a component. Pultrusion systems used in industry can
include a
resin mixer and a resin impregnator for impregnating or injecting the resin
into the
reinforcement material, such as one or more reinforcement fibers. The resin
impregnated
reinforcement material can be pulled through a heated die (e.g., a pultrusion
die) to form a
substrate. The resulting substrate formed by the pultrusion process can
include a three-
dimensional shape formed through one or more pultrusion dies.
[0003] In various examples, a pultrusion process can include coating
the substrate,
for example with a coating that can improve weatherability, durability, and
aesthetics of the
finished article.
SUMMARY OF THE DISCLOSURE
[0004] The present disclosure describes systems and methods for
producing one or
more pultrusion articles having a coating. The present disclosure also
describes coated
pultrusion articles, e.g., made from one or more of the systems or methods
described herein.
In some examples, the systems and methods described herein provide for coating
a substrate,
such as a pultrusion substrate, having a coating that is particularly
resistant to weathering
under typical weather conditions that the coated pultrusion article can be
exposed to when
placed in an external environment.
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Date Recue/Date Received 2022-05-11
[0005] In an example, the present disclosure describes a coated article
comprising a
composite substrate formed from a reinforcing feedstock at least partially
embedded in a
matrix polymer, the composite substrate comprising an outer surface and a
coating
comprising a protective bilayer. The protective bilayer includes a first
thermoplastic
protective layer comprising an inner face coupled to the outer surface of the
composite
substrate, wherein the first protective layer is formed from a first acrylic
or acrylic-based
polymer, and a second thermoplastic protective layer coupled to the first
thermoplastic
protective layer at an interface, wherein the interface opposes the inner face
of the first
protective layer, the second protective layer comprising an outer face that
opposes the
interface. The second thermoplastic protective layer is formed from a polymer
blend of a
first thermoplastic polymer and a second thermoplastic polymer, wherein the
first
thermoplastic polymer comprises a first fluoropolymer comprising polymerized
first
monomer units derived from a hydrofluoro-olefin, or a second fluoropolymer
comprising
polymerized second monomer units derived from a perfluorinated alkene, or a
combination
thereof, wherein the second thermoplastic polymer comprises a second acrylic
or acrylic-
based polymer, and wherein the first thermoplastic polymer is at least about
75 wt.% of the
polymer blend.
[0006] In another example, the present disclosure describes a method of
manufacturing a coated article, the method comprising forming a composite
substrate
comprising a reinforcing feedstock at least partially embedded in a matrix
polymer, the
composite substrate comprising an outer surface, applying a first
thermoplastic material
comprising a first acrylic or acrylic-based polymer onto at least a portion of
the outer surface
of the composite substrate to form a first protective layer comprising an
inner face coupled to
the outer surface of the composite substrate and an outer interface, and
applying a second
thermoplastic material onto at least a portion of the outer interface of the
first protective layer
to form a second protective layer coupled to the first protective layer at the
outer interface
such that the second protective layer has an outer face that opposes the outer
interface. The
second thermoplastic material comprises a polymer blend of a first
thermoplastic polymer
and a second thermoplastic polymer, wherein the first thermoplastic polymer
comprises a
first fluoropolymer comprising polymerized first monomer units derived from a
hydrofluoro-
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Date Recue/Date Received 2022-05-11
olefin or a second fluoropolymer comprising polymerized second monomer units
derived
from a perfluorinated alkene, or a combination thereof, wherein the second
thermoplastic
polymer comprises a second acrylic or acrylic-based polymer, and wherein the
first
thermoplastic polymer is at least about 85 wt.% of the second thermoplastic
material.
[0007] This summary is intended to provide an overview of subject
matter of the
present disclosure. It is not intended to provide an exclusive or exhaustive
explanation of the
invention. The detailed description is included to provide further information
about the
present disclosure.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] In the drawings, which are not necessarily drawn to scale, like
numerals may
describe similar components in different views. Like numerals having different
letter
suffixes may represent different instances of similar components. The drawings
illustrate
generally, by way of example, but not by way of limitation, various
embodiments discussed
in the present document.
[0009] FIG. 1 is a schematic diagram of an example system for
manufacturing an
example elongate pultrusion article with a coating.
[0010] FIG. 2 is a schematic diagram of another example system for
manufacturing
an example elongate pultrusion article with a coating.
[0011] FIGS. 3A and 3B are cross-sectional views of example pultrusion
articles, for
example that can be manufactured by the examples systems of FIGS. 1 or 2.
[0012] FIGS. 4 and 5 are cross-sectional views of example pultrusion
articles taken
along line A¨A in FIG. 3A.
[0013] FIG. 6 is a flow diagram of an example method of manufacturing
an example
elongate pultrusion article.
[0014] FIG. 7 is a bar graph of surface free energy measurements for
the coated
articles of EXAMPLE 1 and EXAMPLE 2.
[0015] FIG. 8 is a photograph of an apparatus used for a scrape
adhesion test.
[0016] FIGS. 9A-9D are photographs of samples of coated articles of
EXAMPLE 1
and EXAMPLE 2 after scrape adhesion testing.
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Date Recue/Date Received 2022-05-11
[0017] FIG. 10 is a bar graph of a five finger scratch resistance test
of coated articles
of EXAMPLE 1, EXAMPLE 2, and EXAMPLE 3.
[0018] FIGS. 11 and 12 are graphs of capillary rheometry data for the
coating
materials of EXAMPLE 1, COMPARATIVE EXAMPLE 4, COMPARATIVE EXAMPLE
5, and COMPARATIVE EXAMPLE 6.
DETAILED DESCRIPTION
[0019] The following detailed description includes references to the
accompanying
drawings, which form a part of the detailed description. The drawings show, by
way of
illustration, specific embodiments in which the invention may be practiced.
These
embodiments, which are also referred to herein as "examples," are described in
enough detail
to enable those skilled in the art to practice the invention. The example
embodiments may be
combined, other embodiments may be utilized, or structural, and logical
changes may be
made without departing from the scope of the present invention. While the
disclosed subject
matter will be described in conjunction with the enumerated claims, it will be
understood that
the exemplified subject matter is not intended to limit the claims to the
disclosed subject
matter. The following detailed description is, therefore, not to be taken in a
limiting sense,
and the scope of the present invention is defined by the appended claims and
their
equivalents.
[0020] References in the specification to "one embodiment", "an
embodiment," "an
example embodiment," etc., indicate that the embodiment described can include
a particular
feature, structure, or characteristic, but every embodiment may not
necessarily include the
particular feature, structure, or characteristic. Moreover, such phrases are
not necessarily
referring to the same embodiment. Further, when a particular feature,
structure, or
characteristic is described in connection with an embodiment, it is submitted
that it is within
the knowledge of one skilled in the art to affect such feature, structure, or
characteristic in
connection with other embodiments whether or not explicitly described.
[0021] Values expressed in a range format should be interpreted in a
flexible manner
to include not only the numerical values explicitly recited as the limits of
the range, but also
to include all the individual numerical values or sub-ranges encompassed
within that range as
if each numerical value and sub-range is explicitly recited. For example, a
range of "about
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Date Recue/Date Received 2022-05-11
0.1% to about 5%" or "about 0.1% to 5%" should be interpreted to include not
just about
0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%)
and the sub-
ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated
range. The
statement "about X to Y" has the same meaning as "about X to about Y,'" unless
indicated
otherwise. Likewise, the statement "about X, Y, or about Z" has the same
meaning as "about
X, about Y, or about Z," unless indicated otherwise.
[0022] The terms "a," "an," or "the" are used to include one or more
than one unless
the context clearly dictates otherwise. The term "or" is used to refer to a
nonexclusive "or"
unless otherwise indicated. Unless indicated otherwise, the statement "at
least one of" when
referring to a listed group is used to mean one or any combination of two or
more of the
members of the group. For example, the statement "at least one of A, B, and C"
can have the
same meaning as "A; B; C; A and B; A and C; B and C; or A, B, and C," or the
statement "at
least one of D, E, F, and G" can have the same meaning as "D; E; F; G; D and
E; D and F; D
and G; E and F; E and G: F and G; D, E, and F; D, E, and G; D, F, and G; E, F,
and G; or D,
E, F, and G." A comma can be used as a delimiter or digit group separator to
the left or right
of a decimal mark; for example, "0.000,1' is equivalent to "0.0001."
[0023] The term "about" as used herein can allow for a degree of
variability in a
value or range, for example, within 10%, within 5%, within 1%, within 0.5%,
within 0.1%,
within 0.05%, within 0.01%, within 0.005%, or within 0.001% of a stated value
or of a stated
limit of a range and includes the exact stated value or range.
[0024] The term "substantially" as used herein refers to a majority of,
or mostly, such
as at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%,
99.9%,
99.99%, or at least about 99.999% or more, or 100%.
[0025] The term "layer," as used in describing a layer of the substrate
coatings,
although used in the singular, can refer to a single layer of the particular
material being
described or can refer to a plurality of layers of the same material or
substantially the same
material. In this way, when the term "layer" is used, it will be understood to
mean "one or
more layers" unless the description expressly states that a specific structure
comprises a
"single layer" of the material.
Date Recue/Date Received 2022-05-11
[0026] In methods described herein, the steps can be carried out in any
order without
departing from the principles of the invention, except when a temporal or
operational
sequence is explicitly recited. Furthermore, specified acts can be carried out
concurrently
unless explicit language recites that they be carried out separately. For
example, a recited act
of doing X and a recited act of doing Y can be conducted simultaneously within
a single
operation, and the resulting process will fall within the literal scope of the
process. Recitation
in a claim to the effect that first a step is performed, then several other
steps are subsequently
performed, shall be taken to mean that the first step is commenced before any
of the other
steps, but the other steps can be performed in any suitable sequence, unless a
sequence is
further recited within the other steps. For example, claim elements that
recite "Step A, Step
B, Step C, Step D, and Step E" shall be construed to mean step A is carried
out first, step E is
carried out last, and steps B, C, and D can be carried out in any sequence
between steps A
and E, including concurrently with one on both of steps A and E, and that such
a sequence
still falls within the literal scope of the claimed process. A given step or
sub-set of steps can
also be repeated.
[0027] Furthermore, specified steps can be carried out concurrently
unless explicit
claim language recites that they be carried out separately. For example, a
claimed step of
doing X and a claimed step of doing Y can be conducted simultaneously within a
single
operation, and the resulting process will fall within the literal scope of the
claimed process.
[0028] All publications, patents, and patent documents referred to in
this document
are incorporated by reference herein in their entirety, as though individually
incorporated by
reference. In the event of inconsistent usages between this document and those
documents so
incorporated by reference, the usage in the incorporated reference should be
considered
supplementary to that of this document; for irreconcilable inconsistencies,
the usage in this
document controls.
Pultrusion Forming And Coating System
[0029] FIG. 1 shows a schematic diagram of an example system 100 for
manufacturing a coated pultrusion article 102. In an example, the system 100
manufactures a
pultruded substrate 104 and applies a coating 106 to the substrate 104 to
provide the coated
pultrusion article 102, e.g., wherein the coating 106 can be selected to
provide one or more
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Date Recue/Date Received 2022-05-11
improved properties, such as at least one of improved aesthetics, improved
color, or
improved weatherability compared to the uncoated substrate 104. Therefore, for
the sake of
clarity and brevity, the system 100 may be referred to herein as a pultrusion
and coating
system 100, and the substrate 104 may be referred to herein as a pultrusion
substrate 104.
[0030] In an example, the pultrusion and coating system 100 comprises a
feed system
108, a resin-injection assembly 110, a pultrusion die 112, a coating system
114, and a
finishing system 116. The feed system 108 provides a feedstock 118 to the
pultrusion and
coating system 100, and in particular, to the resin-injection assembly 110.
The feedstock 118
can comprise one or more reinforcement structures to which a resin can be
applied in order to
provide a composite material in the form of the pultrusion substrate 104. In
an example, the
one or more reinforcement structures of the feedstock 118 can comprise one or
more
continuous fibers, such as one or more reinforcing fibers. Examples of the one
or more
reinforcing fibers that can be used as the reinforcement feedstock 118 in the
pultrusion and
coating system 100 include, but are not limited to, glass fibers, basalt
fibers, carbon aramid
fibers, Kevlar fibers, natural fibers, such as flax or hemp, among others.
[0031] The feed system 108 can include one or more systems to store and
feed the
feedstock 118 in such a manner that the feedstock 118 is continuously fed to
the rest of the
pultrusion and coating system 100. In an example, the feed system 108 includes
a carting
system and an aligning system that delivers or provides the feedstock 118 to
another portion
of the pultrusion and coating system 100. In an example, the feedstock 118
comprises one or
more continuous reinforcing fibers and each of the one or more fibers are
stored as a roving
that is continuously fed to the other portion of the pultrusion and coating
system 100.
[0032] In an example, the feed system 108 can deliver or provide the
feedstock 118
to the resin-injection assembly 110. The resin-injection assembly 110 can
include a resin
feed device or devices to feed a polymer resin 120 to the feedstock 118. In an
example, the
resin-injection assembly 110 can inject the polymer resin 120 into contact
with the feedstock
118. The resin-injection assembly 110 can sufficiently inject the polymer
resin 120 so that
the feedstock 118 is at least partially impregnated with and at least
partially surrounded by
the polymer resin 120.
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Date Recue/Date Received 2022-05-11
[0033] In an example, the polymer resin 120 comprises a thermoset
resin, such as a
polyester resin or a polyester-based resin, a polyurethane resin or a
polyurethane-based resin,
or a vinyl ester or vinyl ester-based resin. In other examples, the polymer
resin 120
comprises a low-viscosity thermoplastic resin, such as an acrylic-based
thermoplastic such as
a methyl methacrylate (MMA) based or methyl acrylate-based thermoplastic. In
some
examples, the polymer resin 120 can be formed by mixing one or more precursor
compounds
that, when combined, can form the desired final composition of the polymer
resin 120. The
polymer resin 120 can be pre-mixed or the resin-injection assembly 110 can
include a resin-
mixing system 122 that mixes one or more resin constituents to form a resin
mixture having a
specified composition. The resin-mixing system 122 can include a plurality of
storage
vessels each supplying a resin constituent. In an example, the resin-mixing
system 122
includes a first resin storage vessel 124 for a first resin constituent and a
second resin storage
vessel 126 for a second resin constituent. The resin-mixing system 122 can
optionally
further include one or more additional storage vessels for one or more
additional resin
constituents, such as a third storage vessel for a third resin constituent, a
fourth storage vessel
for a fourth resin constituent, and so on. The plurality of storage vessels
can be
communicatively coupled to a mixing apparatus 128, such as a mixing vessel or
a mixing
device, wherein each corresponding resin constituent from the plurality of
storage vessels
124, 126 can be mixed to provide the polymer resin 120 having the specified
composition.
[0034] For example, in the case of a polyurethane or polyurethane-based
resin, a first
polyurethane constituent can comprise one or more polyols such that the first
resin storage
vessel 124 can be one or more polyol storage vessels. A second polyurethane
constituent can
comprise one or more isocyanates such that the second resin storage vessel 126
can be one or
more isocyanate storage vessels. The one or more polyol storage vessels 122
and the one or
more isocyanate storage vessels 124 can be communicatively coupled to the
mixing
apparatus 128 where the one or more polyols from the one or more polyol
storage vessels
122 and the one or more isocyanates from the one or more isocyanate storage
vessels 124 can
be mixed to form a polyurethane-based polymer resin 120. Similar combinations
of storage
vessels 122, 124 and the mixing apparatus 128 can be set up for the formation
of a polyester
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Date Recue/Date Received 2022-05-11
or polyester-based resin 120 or for the formation of other compositions of
polymer resin 120,
such as low-viscosity thermoplastic resin systems.
[0035] In an example, the polymer resin 120 that is applied to the
feedstock 118 can
include one or more fillers to modify physical properties of the polymer
formed from the
resin and of the pultrusion substrate 104. Examples of fillers that can be
used in the polymer
resin 120 include, but are not limited to, particles of calcium carbonate
(CaCO3), alumina
trihydrate (A1203 = 3 H20), talc (e.g., a mineral form of hydrated magnesium
silicate,
H2Mg3(SiO3)4), clay, or one or more types of glass filler particles (such as
glass spheres). In
an example, the resin-injection assembly 110 includes a feedstock alignment
system to align
the feedstock 118 in a desired configuration for resin impregnation.
[0036] The resin-mixing system 122 can include a pumping system that is
communicatively coupled to the mixing apparatus 128. The pumping system can
withdraw
the polymer resin 120 from the mixing apparatus 128 and feed the resin mixture
to one or
more resin nozzles 130. Each of the one or more resin nozzles 130 can inject
or otherwise
apply the polymer resin 120 to the feedstock 118.
[0037] In an example, the feed system 108 can include one or more
heating devices
to heat at least one of: (a) one or more of the resin constituents, e.g.,
before mixing the one or
more resin constituents; (b) the resin mixture within the mixing apparatus,
e.g., after mixing
of the one or more resin constituents; or (c) the resin mixture in a feed line
between the
mixing apparatus and the one or more resin nozzles, e.g., after withdrawing
the resin mixture
with the pumping system. Each of the one or more heating devices can heat the
component
being heated (e.g., one or more of the resin constituents or the resin
mixture) to a specified
temperature, e.g., to be more conducive to polymerization and formation of the
polymer of
the pultrusion substrate 104.
[0038] The feedstock 118 can be pulled or otherwise forced through the
pultrusion
die 112 to shape the feedstock 118 into a desired shape in the form of the
pultrusion substrate
104. The pultrusion die 112 can produce a cross-sectional profile of the resin-
injected
feedstock 118. Examples of profiles that can be formed by the resin-injection
assembly 110
and the pultrusion die 112 include, but are not limited to, pultrusion
articles in the form of an
architectural fenestration component, a building component, a solar component,
a furniture
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Date Recue/Date Received 2022-05-11
component, a refrigeration component, or a component of a piece of
agricultural equipment.
Pultrusion of the resin-injected feedstock 118 through the pultrusion die 112
results in a
pultrusion substrate 104 having one or more profile surfaces in a specified
configuration to
form the specified cross-sectional profile.
[0039] FIGS. 3A and 3B show two examples of coated articles 102A and
102B
formed by coating pultrusion substrates 104A and 104B, wherein the pultrusion
substrates
104A, 104B provide two examples of cross-sectional profiles 132A, 132B,
respectively, that
can be formed, for example using the pultrusion die 112. FIG. 3A shows a
profile view of an
example profile 132A for a modular patio door sill, while FIG. 3B shows a
profile view of an
example profile 132B for a window frame cladding. The specific profiles 132A,
132B of the
pultrusion substrates 104A and 104B shown in FIGS. 3A and 3B are included as
examples
for illustration purposes only. As will be understood by a person of ordinary
skill in the art,
the systems, methods, and resulting articles described herein are not limited
to the specific
pultrusion profiles 132A and 132B or forms shown in FIGS. 3A and 3B. The
profile 132
formed by pultruding the feedstock 118 through the pultrusion die 112 can
include one or
more profile surfaces 134A, 134B, e.g., outer surfaces of the pultrusion
substrates 104A,
104B (best seen in FIGS. 3A and 3B).
[0040] Returning to FIG. 1, the pultrusion and coating system 100 can
include one or
more heating devices associated with the pultrusion die 112, such as one or
more heaters, for
example one or more integral die heaters or one or more heaters external to
the pultrusion die
112, or both. The one or more heaters associated with the pultrusion die 112
can provide for
thickening or gelling, or both, of the polymer resin 120, for example by
initiating or
continuing polymerization of the one or more resin constituents in the polymer
resin. The
one or more heating devices can also provide for full or partial curing of the
polymer resin
within or substantially immediately downstream of the pultrusion die 112.
[0041] In an example, the pultrusion and coating system 100 includes
one or more
pre-treatment operations to treat the pultrusion substrate 104 after it exits
the pultrusion die
112 but before the pultrusion substrate 104 is fed into the coating system
114. Pretreatment
can prepare the pultrusion substrate 104 for coating by the coating system
114. In an
example, the pretreatment can prepare the surfaces onto which the coating 106
will be
Date Recue/Date Received 2022-05-11
applied (for example the profile surfaces 134A, 134B on the pultrusion
substrates 104A and
104B in FIGS. 3A and 3B) for bonding with the material of the coating 106.
Examples of
pretreatment operations include, but are not limited to, one or any
combination of: heating
the pultrusion substrate 104, such as by heating at least the surfaces to be
coated (e.g.,
surfaces 134A and 134B in FIGS. 3A and 3B); cleaning one or more of the
surfaces to be
coated, such as with one or more solvents; abrasion treatment of one or more
of the surfaces
to be coated; or applying one or more chemical treatments, such as a plasma.
[0042] In the example shown in FIG. 1, the pretreatment of the
pultrusion substrate
104 comprises heating the pultrusion substrate 104 with one or more in-line
heaters 136
downstream of the pultrusion die 112. The one or more heaters 136 can be
configured, or
can be part of a temperature control system, to control or maintain a
temperature of the
pultrusion substrate 104 downstream of the pultrusion die 112 and before the
pultrusion
substrate 104 enters the coating system 114. In an example, the one or more
heaters 136 can
be configured to control or maintain a temperature of the pultrusion substrate
104 so that the
portions of the one or more surfaces onto which the one or more layer of
coating material is
to be applied (such as the profile surfaces 134A and 134B in FIGS. 3A and 3B)
to form the
coating 106, will be at a specified temperature. The specified temperature can
be a
temperature that will perform one or more of the following: improved or
optimized
polymerization of the one or more constituents of the polymer resin 120 to
form the final
matrix polymer of the pultrusion substrate 104; improved adhesion of the
coating 106 to the
one or more surfaces being coated; or improved formation of the one or more
coating
material layers, e.g., via setting, gelling, or other polymerization of the
one or more coating
materials after application to the pultrusion substrate 104. In an example,
the one or more
heaters 136 include one or more infrared heaters that emit infrared radiation
onto the
pultrusion substrate 104. The pultrusion and coating system 100 can also
include
temperature sensors to measure a temperature of the pultrusion substrate 104
and to control
an output of the one or more heaters 136 based on a measured temperature of
the pultrusion
substrate 104, e.g., in the manner of a feedback control loop.
[0043] In an alternative example, the pultrusion and coating system
can omit in-line
heaters (such as the one or more heaters 136 in FIG. 1A) are omitted, and the
coating system
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Date Recue/Date Received 2022-05-11
can be located in close physical proximity to the exit of the pultrusion die.
In an example,
the exit of the pultrusion die can be in close physical proximity to the
entrance to the first
material extruder that is to coat a material onto the pultrusion substrate
104, i.e., the first
coating material extruder 142. In such a system, the temperature of the
pultrusion substrate
exiting the pultrusion die can be controlled at the pultrusion die, e.g., with
a heater within or
immediately upstream of the pultrusion die that is controlled to not only
provide a
temperature that is conducive to setting or gelling of the matrix polymer, but
also to provide
a temperature of the pultrusion substrate exiting the pultrusion die that is
conducive for
coating with one or more coating materials.
[0044] Returning to FIG. 1, as noted above, the pultrusion and coating
system 100
includes a coating system 114 to apply a coating 106 onto the pultrusion
substrate 104, e.g.,
onto at least a portion of one or more surfaces of the pultrusion substrate
104 (such as the
profile surfaces 134A, 134B in FIGS. 3A and 3B), to provide the coated
pultrusion article
102. As described in more detail below, the coating 106 can include one or
more coating
layers that are coated onto the pultrusion substrate 104. The coating system
114 includes a
coating-material application assembly 140 to apply one or more coating
materials onto the
pultrusion substrate 104 to form the one or more layers of the coating 106.
[0045] The coating-material application assembly 140 can include a
coating material
extruder 142 comprising a coating material storage vessel 144 and a coating
material die 146.
In an example, the coating-material application assembly 140 applies a single
coating layer
onto the pultrusion substrate 104. In such an example, the coating-material
application
assembly 140 may comprise only a single coating material extruder 142 of a
single coating
material storage vessel 144 feeding a single coating material die 146.
[0046] In another example, the coating-material application assembly
140 applies a
plurality of coating layers onto the one or more tie layers to form the coated
pultrusion article
102. Each layer of the plurality of coating layers can be formed from a
different coating
material composition, or each layer can comprise the same coating composition.
In the
example shown in FIG. 1, the pultrusion and coating system 100 is configured
to form a
coating 106 comprising two coating layers. In such an example, the coating-
material
application assembly 140 can include a first coating material extruder 142
configured to form
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Date Recue/Date Received 2022-05-11
a first coating layer on the pultrusion substrate 104 and a second coating
material extruder
148 configured to form a second coating layer on the first coating layer. The
first coating
material extruder 142 can include a first coating material storage vessel 144
and a first
coating die 146 configured to form a first coating layer, e.g., on top of one
or more surfaces
of the pultrusion substrate 104. The second coating material extruder 148
comprises a
second coating material storage vessel 150 and a second coating die 152 to
form a second
coating layer, e.g., on top of the first coating layer. Different example
configurations of one
coating layer or two coating layers are described below. In various examples,
the coating-
material application assembly 140 includes a coating die 146, 152 for each
coating layer or
includes a coextrusion die to apply two or more coating layers at
substantially the same time
to the pultrusion substrate 104.
[0047] Examples of materials that can form each of the one or more
coating layers
include, but are not limited to, at least one of: one or more acrylics, one or
more bioplastics,
polyvinylchloride, poly(vinylidene difluoride), poly(tetrafluoroethylene),
acrylonitrile-
styrene-acrylate, acrylonitrile-butadiene-styrene (ABS) or other styrenic
polymers, weather
stock (e.g., weather capping or a weather resistant coating), aesthetic
coatings, texturization
coatings, one or more clear-coat materials, one or more primer compositions,
or blends
thereof. As described in more detail below, in an example, the coating 106
includes at least
two layers that form a protective bi-layer to provide one or more of
mechanical protection
(e.g., scratch resistance); weatherability; or chemical resistance. In some
examples, the
protective bi-layer includes a first protective layer that is closest to the
pultrusion substrate,
such that the first layer is also referred to as the inner protective layer,
and a second layer that
is applied to an outer surface or interface of the first or inner protective
layer, such that the
second layer is also referred to as an outer protective layer.
[0048] In an example, the inner protective layer is applied directly to
one or more of
the outer surfaces of the pultrusion substrate 104 (such as the profile
surfaces 134A, 134B in
FIGS. 3A and 3B), or the inner protective layer is applied directly to one or
more
intermediate layers, such as one or more adhesive tie layers, that are
disposed between the
coated surface of the pultrusion substrate 104 and the protective bi-layer. In
an example, the
inner protective layer comprises an acrylic-based thermoplastic polymer, such
as a
13
Date Recue/Date Received 2022-05-11
polyacrylate (e.g., poly(methyl methacrylate)), and the outer protective layer
comprises a
polymer blend of an acrylic or acrylic-based thermoplastic polymer (which can
be the same
as or different from the polymer that forms the inner protective layer) and a
fluoropolymer,
such as a poly(vinylidene difluoride) ("PVDF") based polymer or a
poly(tetrafluoroethylene)
("PTFE") based polymer, or combinations thereof.
[0049] Once the coating system 114 applies the coating 106, it
provides the coated
pultrusion article 102, which is further processed by the finishing system
116. In an
example, the finishing system 116 includes one or more of a cooling assembly
164 or a
pulling mechanism 166. The cooling assembly 164 cools the coated pultrusion
article 102,
for example by exposing the coated pultrusion article 102 to a cooling medium,
such as
forced air (e.g., a fan or nozzle providing air at a temperature less than the
coated profile),
ambient air (e.g., non-forced air), or a cooling liquid, such as in an
immersion bath or a
cooling liquid sprayed onto the coated profile.
[0050] The pulling mechanism 166 pulls the coated pultrusion article
102 from the
pultrusion and coating system 100, which in turn will pull the pultrusion
substrate 104 from
the pultrusion die 112 through the coating system 114, which in turn will pull
the feedstock
118 from the feed system 108 through the resin-injection assembly 110 and into
the
pultrusion die 112. The rate that the pulling mechanism 166 can move the
coated pultrusion
article 102, pultrusion substrate 104, and feedstock 118 through the
pultrusion and coating
system 100 can be variable according to a specified production rate, a
specific three-
dimensional profile 132 of the coated pultrusion article 102 being produced,
the materials
being used for the pultrusion substrate 104 (e.g., the feedstock 118 and the
polymer resin
120), the one or more coating layers, factory conditions, or the like. In
various examples, the
finishing system 116 can include additional processing apparatuses, such as,
but not limited
to a cutting mechanism 168 to section the coated pultrusion article 102 to a
specified size
(e.g. to a predetermined length), a stacking assembly (not shown) to package
the cut coated
pultrusion articles 102 for shipment, and the like.
[0051] In some examples, the pultrusion substrate has one or more
surfaces that are
relatively smooth or that have a relatively low surface energy, such as a
pultruded
polyurethane or polyurethane-based substrate. In some examples, a pultrusion
and coating
14
Date Recue/Date Received 2022-05-11
system can provide for adequate bonding of a coating material to surfaces that
are relatively
smooth or have a relatively low-surface energy, or both. In examples, the
terms "highly
smooth," "relatively smooth," and/or "low surface energy" or "relatively low
surface
energy," as used herein, can refer to a surface having a water contact angle
of less than 65 ,
such as less than about 600, for example less than 55 . For example, a
particular
polyurethane-based pultrusion substrate composition has a water contact angle
in the range of
about 45 to about 55 , when measured by the contact angle measurement
instrument having
the model number FTA125, sold by First Ten Angstroms, Inc., Portsmouth, VA,
USA. It
was found to be difficult to bond coating materials directly to this
particular polyurethane-
based substrate with the water contact angle of about 45 to about 55 .
[0052] FIG. 2 shows an example of a pultrusion and coating system 200
that is
substantially similar to the pultrusion and coating system 100 of FIG. 1 in
that the system
200 of FIG. 2 is configured to manufactures a pultruded substrate 204 and
applies a coating
206 to the substrate 204 to provide the coated pultrusion article 202, e.g.,
wherein the coating
206 can be selected to provide one or more improved properties, such as at
least one of
improved aesthetics, improved color, or improved weatherability compared to
the uncoated
substrate 204. For example, like the system 100, the pultrusion and coating
system 200 of
FIG. 2 includes a feed system 208 that provides a feedstock 218 to the system
200, a resin-
injection assembly 210, a pultrusion die 212, a coating system 214, and a
finishing system
216.
[0053] Each of the systems or assemblies 208, 210, 212, and 216 can be
substantially
similar or identical to that which is described above with respect to the
system 100 of FIG. 1.
For example, the feed system 208 can deliver a feedstock 218 that is
substantially similar or
even identical to the feedstock 118 in the system 100, such as by comprising
one or more
reinforcement structures, such as reinforcing fibers, to which a resin can be
applied in order
to provide a composite material in the form of the pultrusion substrate 204.
The feed system
208 can also deliver a polymer resin 220 to the resin-injection assembly 210,
where the
polymer resin 220 is contacted with and impregnated into the feedstock 218.
For example,
the resin-injection assembly 210 can include a resin-mixing system 222
comprising one or
more resin storage vessels 224, 226 to store one or more resin constituents. A
mixing
Date Recue/Date Received 2022-05-11
apparatus 228 can mix resin constituents to form the final desired polymer
resin 220, which
is then fed to one or more resin nozzles 230, which inject or otherwise apply
the polymer
resin 220 to the feedstock 218. The resin-injected feedstock 218 is then
pulled or otherwise
forced through the pultrusion die 212 to shape the resin-injected feedstock
218 into the form
of the pultrusion substrate 204. One or more heaters 236 to maintain a
temperature of the
pultrusion substrate 204, e.g., to improve adhesion of an adhesive material to
the pultrusion
substrate 204 (as described in more detail below). In alternative embodiments,
the system
can omit in-line heaters and control the temperature of the pultrusion
substrate 204 at the
pultrusion die 212 itself, as described above.
[0054] The coating 206 is applied onto the pultrusion substrate 204
with the coating
system 214. Like the coating system 114 shown in FIG. 1, the coating system
214 in the
pultrusion and coating system 100 of FIG. 2 includes a coating-material
application assembly
240. The coating-material application assembly 240 includes one or more
coating material
extruders 242, 248 that each apply a coating material to form one or more
corresponding
coating material layers. For example, a first coating material extruder 242,
comprising a first
coating material storage vessel 244, forms a first coating layer, and a second
coating material
extruder 248, comprising a second coating material storage vessel 250, forms a
second
coating layer, e.g., on top of the first coating layer. The coating material
extruders 242, 248
can each include separate extrusion dies, similar to the first and second
coating material dies
146 and 152 shown in FIG. 1, or, as shown in the example of FIG. 2, the first
and second
coating layers can be coextruded through a coextrusion die 260 (discussed in
more detail
below).
[0055] The primary difference between the system 200 of FIG. 2 and the
system 100
of FIG. 1 is that the coating system 214 further includes an adhesive-
application assembly
254 so that the coating 206 includes one or more adhesive tie layers disposed
between the
pultrusion substrate 204 and the other coating-material layers. As used
herein, the term
"adhesive tie layer" or "tie layer," can refer to one or more layers of an
adhesive material
between the pultrusion substrate 204 and the one or more layers of the coating
material. The
one or more adhesive tie layers provide for coating the one or more layers of
the coating
material onto a pultrusion substrate 204 that is not generally conducive to
being directly
16
Date Recue/Date Received 2022-05-11
coated with the coating material, such as a substrate with relatively smooth
surfaces or that
has a relatively small surface energy such as polyurethane or polyurethane-
based pultrusion
substrates. In an example, the one or more adhesive tie layers provide an
adhesive strength
between the one or more coating layers and the pultrusion substrate 204 that
is higher than
could be possible if the coating material was applied directly to the
pultrusion substrate 204.
[0056] The adhesive-application assembly 254 applies one or more
adhesive
materials onto at least a portion of the profile surfaces on the pultrusion
substrate 204 in
order to form the one or more adhesive tie layers. In examples where the
coating system 214
includes the adhesive-application assembly 254, the coating-material
application assembly
240 applies one or more coating materials onto the one or more adhesive tie
layers in order to
form the one or more layers of the coating 206. In an example, the adhesive-
application
assembly 254 includes an adhesive material extruder 256 comprising at least
one adhesive
material storage vessel 258. The at least one adhesive material storage vessel
258 stores the
one or more adhesive materials for delivery to an adhesive material die, which
can include
one or more material dies if needed (e.g., if two or more adhesive tie layers
are being
applied). The adhesive material die can comprise a separate die for the
adhesive material,
similar to the separate dies 146, 152 for the separate coating materials from
the coating
material extruders 142, 148 in FIG. 1, or the adhesive material die can be
part of a
coextrusion die 260 that is combined with one or both of the dies used for the
coating
material extruders 242, 248. As shown in the example of FIG. 2, the system 200
includes a
single coextrusion die 260 that coextrudes the adhesive material from the
adhesive material
extruder 256 and the coating materials from the first and second coating
material extruders
242, 248 in a single die.
[0057] In an example, the adhesive-application assembly 254 includes an
adhesive
heater (such as a stand-alone heater, a heater as part of the adhesive
material die, or a heater
in the adhesive material extruder 256. The adhesive heater can heat the one or
more adhesive
materials to the adhesive-application temperature, described above. In an
example, the
adhesive-application temperature is at least about the temperature of the
pultrusion substrate
204.
17
Date Recue/Date Received 2022-05-11
[0058] In an example, the adhesive-application assembly 254 applies one
or more
extrudable adhesive materials onto the pultrusion substrate 204 so that the
one or more
extrudable adhesive materials form one or more adhesive tie layers on the
pultrusion
substrate 204. In an example, the one or more extrudable adhesive materials
include an
extrudable thermoplastic adhesive. In some examples, the extrudable
thermoplastic adhesive
includes, but is not limited to, one or more of: a polyamide; a copolyamide; a
block
copolymer of a polyamide and a polyester; a thermoplastic polyurethane; an
acrylic; a
styrenic or butadiene-based block copolymer; a functionalized olefin; a
functionalized
acrylic; polylactic acid (PLA); or acrylonitrile-butadiene-styrene (ABS). In
an example with
a polyurethane-based pultrusion substrate 204 and at least one acrylic-based
coating layer,
copolyamide-based adhesive materials were found to be particularly useful,
such as a
copolyamide blend, for example a copolyamide blend of two or more different
and varying
polyamide repeat units. An example of such a copolyamide-based adhesive
material is the
extrudable polyamide adhesive blend sold under the trade name PLATAMID by
Arkema
Inc., Colombes, France.
[0059] In some cases, an adhesive material comprising a thermoplastic
polyurethane
was found to be particularly effective for coated articles that are to be used
in exterior
applications, such as with exterior facing surfaces of window frames or door
frames. The
thermoplastic polyurethane material used to form the one or more adhesive tie
layers can be
an aliphatic thermoplastic polyurethane or an aromatic thermoplastic
polyurethane.
Examples of thermoplastic polyurethanes that can be used for such applications
include, but
are not limited to, the polyether-based thermoplastic polyurethanes sold under
the following
trade names: TEXIN by Covestro AG (formerly Bayer MaterialScience),
Leverkusen,
Germany; KRYSTALGRAM by Huntsman International LLC, The Woodlands, TX, USA;
and PEARLBOND by Lubrizol Advanced Materials, Inc., Brecksville, OH, USA.
[0060] The finishing system 216 of the pultrusion and coating system
200 can be
substantially identical to the finishing system 116 of system 100. For
example, the finishing
system 116 can include a cooling assembly 264, pulling mechanism 266, and a
cutting
mechanism 268, which can each be similar or identical to the cooling assembly
164, pulling
mechanism 166, and cutting mechanism 168 described above with respect to FIG.
1.
18
Date Recue/Date Received 2022-05-11
Coated Pultrusion Articles
[0061] FIGS. 4 and 5 show cross-sectional views of examples of coated
pultrusion
articles 300, 400 formed by coating a pultrusion substrate 302, 402 with a
respective coating
304, 404. The cross-sections of FIGS. 4 and 5 are enlarged to show the
structures that make
up the example coated pultrusion articles 300 and 400 and are not necessarily
drawn to scale.
[0062] The coated pultrusion article 300 shown in FIG. 4 is an example
of a coated
article that is produced by the pultrusion and coating system 100 described
above with
respect to FIG. 1. The pultrusion substrate 302 in the example coated
pultrusion article 300
can comprise a resin injected feedstock that has been shaped, e.g., by
pultrusion through a
pultrusion die, into a three-dimensional profile having one or more profile
surfaces,
including, but not limited to coated forms of the example pultrusion
substrates 104A and
104B shown in FIGS. 3A and 3B. For purposes of illustration, the coated
pultrusion article
300 in FIG. 4 is shown as a cross section of a coated modular patio door sill
102A taken
along line /I /I in FIG. 3A, although this particular section line is shown
merely to provide
context. Those of skill in the art will appreciate that the example layers of
the coated
pultrusion article 300 can be from any profile shape, not necessarily the
profile 132A shown
in FIG. 3A.
[0063] In the example coated pultrusion article 300 shown in FIG. 4,
the material of
the example pultrusion substrate 302 is one onto which the coating materials
described below
can be directly coated, e.g., the pultrusion substrate 302 has a roughness or
high enough
surface energy such that the coating material will sufficiently adhere and/or
bond directly to
an outer surface 312 of the pultrusion substrate 302, such as when the
pultrusion substrate
302 is formed using a polyester or polyester-based resin. The example coating
304
comprises a pair of coating layers 306, 308. In an example, the coating layers
306, 308
comprise a protective bi-layer with a first protective layer 306 (also
referred to as the inner
protective layer 306) having an inner face 310 that is in direct contact with
an outer surface
312 of the pultrusion substrate 302. A second protective layer 308 (also
referred to as the
outer protective layer 308) forms an interface 314 with the inner protective
layer 306.
[0064] The term "interface," e.g., in reference to the interface 314
between the inner
and outer protective layers 306, 308, can refer to a physical boundary, e.g.,
between
19
Date Recue/Date Received 2022-05-11
physically distinct layers, or to an amorphous transition zone between
different materials
(e.g., when two thermopolymer materials are thermally coextruded to form a
substantially
continuous multi-layer structure). As shown in FIG. 4, the interface 314
opposes the inner
face 310 of the inner protective layer 306 and opposes an outer face 316 of
the outer
protective layer 308, e.g., such that the inner face 310 and the interface 314
are on opposite
sides of the inner protective layer 306 and such that the outer face 316 and
the interface 314
are on opposite sides of the outer protective layer 308.
[0065] In an example, the inner protective layer 306 has a thickness of
from about 3
mils (wherein the measurement term "mil," as used herein, refers to one one-
thousandth of an
inch, or 0.001 inches) to about 5 mils and the outer protective layer 408 has
a thickness of
from about 1 mils to about 5 mils. The example coated pultrusion article 300
shown in FIG.
4 can be made using the pultrusion and coating system 100 shown in FIG. 1,
e.g., the system
100 with a coating system 114 that includes only a coating-material
application assembly 140
without an adhesive material application assembly.
[0066] Turning to the example coated pultrusion article 400 shown in
FIG. 5, like the
coating 304 in FIG. 4, the example coating 404 also comprises a pair of
coating layers 406,
408, such as a protective bi-layer with a first protective layer 406 (also
referred to as the
inner protective layer 406) having an inner face 410 and a second protective
layer 408 (also
referred to as the outer protective layer 408) that forms an interface 414
with the inner
protective layer 406 and that has an outer face 416. Like the interface 314
between the
protective layers 306 and 308 in FIG. 4, the interface 414 between the inner
and outer
protective layers 406, 408, can be a physical boundary, e.g., between
physically distinct
layers, or to an amorphous transition zone between different materials.
[0067] Unlike the material of the pultrusion substrate 302 in FIG. 4,
the material of
the example pultrusion substrate 402 in FIG. 5 is one onto which the coating
materials
described below will not reliably bond, e.g., an outer surface 412 of the
pultrusion substrate
402 is relatively smooth or has a relatively small surface such that the
coating materials do
not readily bond to the outer surface 412, such as when the pultrusion
substrate 402 is formed
using a polyurethane or polyurethane-based resin. Therefore, the coated
pultrusion article
400 includes an adhesive tie layer 418 disposed between the pultrusion
substrate 402 and the
Date Recue/Date Received 2022-05-11
coating layers 406, 408. For example, the adhesive tie layer 418 is deposited
directly onto
the substrate outer surface 412 while the inner protective layer 406 is
deposited onto the
adhesive tie layer 418, e.g., such that the inner face 410 of the inner
protective layer 406 is in
contact with an outer surface 420 of the adhesive tie layer 418. The example
coated
pultrusion article 400 shown in FIG. 5 can be made using the pultrusion and
coating system
200 shown in FIG. 2, e.g., the system 200 with a coating system 214 that
includes a coating-
material application assembly 240 and an adhesive material application
assembly 254. In an
example, the adhesive tie layer 418 has a thickness from about 1.5 mils to
about 5 mils. In an
example, the inner protective layer 406 has a thickness from about 3 mils to
about 5 mils and
the outer protective layer 408 has a thickness of about 1 mils to about 5
mils.
[0068] In
an example, the adhesive tie layer 418 comprises an adhesive material that
adheres to both the outer surface 412 of the pultrusion substrate 402 and to
the material of the
inner protective layer 406. In some examples, the adhesive tie layer 418 is
formed from an
extrudable adhesive material, such as an extrudable thermoplastic adhesive. In
some
examples, the extrudable thermoplastic adhesive includes, but is not limited
to, one or more
of: a polyamide; a copolyamide; a block copolymer of a polyamide and a
polyester; a
thermoplastic polyurethane; an acrylic; a styrenic or butadiene-based block
copolymer; a
functionalized olefin; a functionalized acrylic; polylactic acid (PLA); or
acrylonitrile-
butadiene-styrene (ABS). In an example wherein the pultrusion substrate 402
was formed
from a polyurethane or polyurethane-based resin and the inner protective layer
406 comprises
an acrylic-based coating layer, copolyamide-based adhesive materials were
found to be
particularly useful, such as a copolyamide blend, for example a copolyamide
blend of two or
more different and varying polyamide repeat units. An example of such a
copolyamide-
based adhesive material is the extrudable polyamide adhesive blend sold under
the trade
name PLATAMID by Arkema Inc., Colombes, France. In another example, the
adhesive tie
layer 418 comprises a thermoplastic polyurethane adhesive material to bond the
protective
layer 406 to the pultrusion substrate 402, for example an aliphatic
thermoplastic polyurethane
or an aromatic thermoplastic polyurethane.
21
Date Recue/Date Received 2022-05-11
Protective Bilayer
[0069] In an example, each coated pultrusion article 300, 400 includes
a protective
bilayer with an inner protective coating layer 306, 406 (also referred to as
the "inner coating
layer 306, 406" or simply the "inner layer 306, 406" for brevity) comprising a
first protective
material and an outer protective coating layer 308, 408 (also referred to as
the "outer coating
layer 308, 408" or simply the "outer layer 308, 408" for brevity) comprising a
second
protective coating material. In an example, one or both of the inner layer
306, 406 and the
outer layer 308, 408 comprises at least one of: a weather resistant layer, or
the like.
Additional layers (not shown) beyond the inner layer 306, 406 and the outer
layer 308, 408
can be include on each of the coated pultrusion articles 300, 400. For
example, the coated
pultrusion article 300, 400 can also include one or more of a clear-coat
layer, a capping layer,
a gloss layer, a texturized outer layer, or a sealant layer.
[0070] In an example, the first protective coating material that forms
the inner layer
306, 406 is different from the second protective coating material that forms
the outer layer
308, 408. For example, the first protective coating material of the inner
layer 306, 406 can
comprise a composition configured to provide for a first type of protection
and the second
protective coating material of the outer layer 308, 408 can comprise a
composition
configured to provide for a second type of protection. Each type of protection
(e.g., the first
type for the inner layer 306, 406 and the second type for the outer layer 308,
408) can
include, but is not limited to, at least one of: UV protection, precipitation
protection,
temperature protection, chemical resistance, scratch resistance protection, or
color fading
protection.
[0071] In an example that has been found to be particularly conducive
for providing
weathering and chemical resistance with improved gloss retention and color
retention, the
inner layer 306, 406 comprises a first thermoplastic material that is an
acrylic or acrylic-
based polymer, while the outer layer 308, 408 comprises a second thermoplastic
material that
is a polymer blend of a first thermoplastic polymer and a second thermoplastic
polymer,
wherein the first thermoplastic polymer comprises a fluoropolymer (e.g., that
consists of or
substantially principally comprises a fluoropolymer) and wherein the second
thermoplastic
polymer comprises an acrylic or acrylic-based polymer (e.g., that consists of
or substantially
22
Date Recue/Date Received 2022-05-11
entirely comprises an acrylic or acrylic-based polymer). One or both of the
inner layer 306,
406 and the outer layer 308, 408 may optionally include one or more additives
such as
colorant or dye and one or more stabilizer compounds such as an antioxidant or
a UV-
resistant compound.
[0072] As used herein, the term "acrylic or acrylic-based polymer"
refers to a
polymer formed from polymerized monomer units that are derived from acrylic
acid
including, but not limited to: an ester derived from acrylic acid (often
referred to as an
acrylate) (e.g., poly(methyl methacrylate) or "PMMA" or poly(methyl acrylate)
or "PMA"),
or an acyl compound derived from acrylic acid, such as poly(acryloy1), or a
polyacetyl. As
used herein, the term "fluoropolymer" refers to an organic polymer wherein at
least one of
the monomer units that are polymerized to form the fluoropolymer include at
least one
fluorine atom. In some examples, the fluorocarbon can include, but is not
limited to,
fluorovinyl-based monomer units, hydrofluorocarbon-based monomer units,
chlorofluorocarbon-based monomer units, perfluorinated alkene-based monomer
units,
perfluoroether-based monomer units, and perfluorocycloalkene-based monomer
units.
Examples of polymerized monomer units that can form at least a portion of the
fluoropolymer include, but are not limited to monomer units derived from a
hydrofluoro-
olefin and monomer units derived from a perfluorinated alkene.
[0073] As used herein, the term "hydrofluoro-olefin" refers to an
unsaturated organic
compound that includes carbon, hydrogen, and fluorine that comprises at least
one carbon-
carbon double bond, as well as substituted forms of such compounds. A non-
limiting
example of polymerized monomer units derived from a hydrofluoro-olefin are
monomer
units derived from vinylidene difluoride (also referred to herein as "VDF") or
commonly
substituted versions of VDF. A non-limiting example of a polymer formed from
polymerized monomer units derived from a hydrofluoro-olefin is the polymer
having the
IUPAC name poly(1,1-difluoroethylene) (also referred to by the trade name
"KYNAR" as
sold by Arkema S.A., Colombes, France, and which will also be referred to
herein as
"poly(vinylidene difluoride)" or "PVDF").
[0074] As used herein, the term "perfluorinated alkene" refers to an
unsaturated
organic compound that includes only carbon and fluorine atoms with only C-C
bonds and C-
23
Date Recue/Date Received 2022-05-11
F bonds and at least one carbon-carbon double bone, as well as substituted
forms of such
compounds. A non-limiting example of polymerized monomer units derived from a
perfluorinated alkene are monomer units derived from tetrafluoroethylene (also
referred to
herein as "TFE") or commonly substituted versions of TFE. A non-limiting
example of a
polymer formed from polymerized units derived from a perfluorinated alkene is
the polymer
having the IUPAC name poly(1,1,2,2-tetrafluoroethylene) (also referred to by
the trade name
"TEFLON" as sold by The Chermours Co., Wilmington, DE, USA, and which will
also be
referred to herein as "poly(tetrafluoroethylene)" or "PTFE"), or combinations
thereof.
Another perfluorinated alkene that is often used in fluoropolymers is
hexafluoropropylene
(C3F6, also referred to herein as "HFP"), although HFP is most commonly used
as a
comonomer in combination with another copolymerized monomer unit (such as with
VDF
monomer units to form a PVDF-based copolymer, or with TFE monomer units to
form a
PTFE-based copolymer) rather than as the monomer in a homopolymer.
[0075] As used herein, the term "substituted" can refer to any organic
compound
wherein one or more hydrogen atoms or one or more moieties can be replaced
with a
different elemental atom or moiety, including those substituted with one or
more or any
combination of: hydrogen, chlorine or another halide, an alkyl group
(including a cycloalkyl
group), aryl group, alkoxy group, aryloxy group, aralkyloxy group,
oxo(carbonyl) group,
carboxyl group including a carboxylic acid, carboxylate, and a carboxylate
ester; a sulfur-
containing group such as an alkyl and aryl sulfide; and other heteroatom-
containing groups.
Non-limiting examples of further organic substitution groups include OR, 00R,
OC(0)N(R)2, CN, CF3, OCF3, R, C(0), methylenedioxy, ethylenedioxy, N(R)2, SR,
SOR,
502R, 502N(R)2, 503R, C(0)R, C(0)C(0)R, C(0)CH2C(0)R, C(S)R, C(0)0R, OC(0)R,
C(0)N(R)2, OC(0)N(R)2, C(S)N(R)2, (CH2)0_2N(R)C(0)R, (CH2)0_2N(R)N(R)2,
N(R)N(R)C(0)R, N(R)N(R)C(0)0R, N(R)N(R)CON(R)2, N(R)502R, N(R)502N(R)2,
N(R)C(0)0R, N(R)C(0)R, N(R)C(S)R, N(R)C(0)N(R)2, N(R)C(S)N(R)2, N(COR)COR,
N(OR)R, C(=NH)N(R)2, C(0)N(OR)R, or C(=NOR)R, wherein R can be hydrogen (in
examples that include other carbon atoms) or a carbon-based moiety, wherein
the carbon-
based moiety can itself be further substituted.
24
Date Recue/Date Received 2022-05-11
[0076] The inventors have found that including a specified amount of
the
fluoropolymer, such as a PVDF based polymer or a PTFE based polymer or a
combination of
the two, in a blend with an acrylic or acrylic-based polymer to form the outer
layer 308, 408
provides for particularly good results in terms of weatherability and chemical
resistance for
the overall coated pultrusion article 300, 400 that were beyond that which was
expected. In
prior examples where an acrylic-acrylic/fluoride bilayer was used, the
inventors hypothesized
that an outer layer 308, 408 comprising from about 25 wt.% to about 50 wt.% of
the
fluoropolymer, with the balance of the outer layer 308, 408 (e.g., from about
50 wt.% to
about 75 wt.%) comprising the acrylic or acrylic-based polymer was believed to
be an
optimal amount of the fluoropolymer. See, e.g., U.S. Patent Application No.
16/379,164,
which was published on October 10, 2019 as U.S. Patent Application Publication
No.
2019/0308396 Al, whose inventors are the same as the present application.
[0077] The present inventors have now found that, contrary to their
earlier patent
application (U.S. Pub. No. 2019/0308396A1), the outer layer 308, 408 can have
a
substantially higher percentage of the fluoropolymer than was previously
thought to be
effective, e.g., wherein a polymer blend that is used to form the outer layer
308, 408
comprises at last 60 wt.% of the fluoropolymer, such as at least about 75 wt.%
of the
fluoropolymer, and in a preferred example, wherein the outer layer 308, 408
comprises at
least about 90 wt.% of the fluoropolymer. The inventors have found that when
the bilayer is
formed with this particular combination of the inner layer 306, 406 formed
from an acrylic or
acrylic-based polymer inner and the outer layer 308, 408 formed from a polymer
blend of a
fluoropolymer and an acrylic or acrylic-based polymer wherein the outer layer
308, 408 has
such a high amount of the fluoropolymer, then the protective bilayer
comprising the inner
layer 306, 406 and the outer layer 308, 408 can provide for better
weatherability and
chemical resistance as compared to a comparable coating wherein the outer
layer 308, 408
has a lower relative amount of the fluoropolymer while still having adequate
adhesion to
underlying inner layer 306, 406 (as discussed below in the EXAMPLES section).
[0078] For example, in the inventors previous patent application (U.S.
Pub. No.
2019/0308396A1), the inventors had believed that if the polymer blend of the
outer layer had
a very high percentage of PVDF, that it would not adequately adhere to an
acrylic-based
Date Recue/Date Received 2022-05-11
inner protective layer such that it was believed that a relatively high-
percentage PVDF outer
layer would tend to delaminate and fail. It was also believed that when the
polymer blend of
the outer layer had too high of a percentage of the fluoropolymer that the
outer layer would
be crystalline or semi-crystalline when in the solid state, wherein
crystalline or semi-
crystalline outer protective layers had been found to result in less robust
chemical or
weathering protection (e.g., an overall protective coating that would be less
able to withstand
long-term weather or chemical exposure than an outer layer formed from an
acrylic/fluoride
blend that results in an amorphous solid). The inventors also believed that an
outer layer
formed from an acrylic/fluoride-polymer blend with a relative amount of the
fluoropolymer
at or below about 50 wt.% so that the outer layer is formed from an amorphous
solid would
be more resistant to mechanical damage (e.g., from scratching), more resistant
to weathering
(e.g., is better able to withstand longer periods of exposure and to more
extreme weather
conditions with less change in appearance, such as less color fading and less
loss in
glossiness), and more resistant to chemical exposure (e.g., is better able to
withstand
exposure to certain chemicals) than when the outer layer comprises a relative
amount of the
fluoropolymer that is higher than 50 wt.%.
[0079]
In some examples, the protective bi-layer described above, e.g., with the
inner
layer 306, 406 comprising an acrylic or acrylic-based polymer and the outer
layer 308, 408
comprising a specified blend of a fluoropolymer and an acrylic or acrylic-
based polymer that
is able to pass the highest weathering performance standards. In some
examples, the
protective bilayer described herein is able to pass the American Architectural
Manufacturers
Association ("AAMA") 625 Voluntary Specification, including, but not limited
to, achieving
color retention with a delta E of 5 or less and a gloss retention of at least
50% gloss retention
after 10 years of weathering. The higher percentage of the fluoropolymer in
the outer layer
308, 408 was able to withstand weathering for a longer period of time and/or
with more color
retention and/or more gloss retention. The addition of the relatively high
amount of the
fluoropolymer to the polymer blend with the acrylic or acrylic-based polymer
for use in the
outer layer 308, 408 of the bilayer was also able to better withstand exposure
to typical
cleaning chemicals compared to a bilayer wherein the outer layer has a lower
relative amount
of the fluoropolymer. Cleaning chemicals are known to cause stress cracking,
delamination,
26
Date Recue/Date Received 2022-05-11
or both, in coated pultrusion articles. The higher relative amount of the
fluoropolymer in the
outer layer 308, 408 of the bilayer coating 304, 404 of the coated articles
300, 400 is
particularly helpful in providing for longer-term resistance to cleaning
chemicals without
substantial cracking or delamination.
[0080] In an example, the fluoropolymer forms from about 50 wt.% to
about 98 wt.%
of the polymer blend that is extruded to form the outer layer 308, 408, with
the remaining
balance of the outer layer 308, 408 (e.g., from about 2 wt.% to about 50 wt.%)
comprising an
acrylic or acrylic-based polymer. In another example, the fluoropolymer makes
up from
about 60 wt.% to about 95 wt.% of the polymer blend that forms the outer layer
308, 408,
such as from about 70 wt.% to about 92.5 wt.%, for example from about 80 wt.%
to about 90
wt.% of the polymer blend that forms the outer layer 308, 408. In an example,
the outer layer
308, 408 can comprise an effective amount of no more than about 5 wt.% to 8
wt.%, of
additives such as antioxidants, ultraviolet-resistant additives, colorants or
dyes, or other
additives that are typical for protective coatings on pultrusion articles. In
an example, the
remaining balance of the polymer blend that forms the outer layer 308, 408
(e.g., from about
2 wt.% to about 50 wt.%) comprises an acrylic or acrylic-based polymer, which
can be the
same acrylic or acrylic-based polymer as that which makes up the inner layer
306, 406 or can
be a different acrylic or acrylic-based polymer. In an example, the acrylic or
acrylic-based
polymer makes up from about 5 wt.% to about 40 wt.% of the polymer blend, such
as from
about 7.5 wt.% to about 30 wt.%, for example from about 10 wt.% to about 20
wt.% of the
polymer blend that forms the outer layer 308, 408.
[0081] In an example, the fluoropolymer of the polymer blend makes up
at least
about 50 wt.% of the outer protective layer, for example at least about 55
wt.%, at least about
60 wt.%, at least about 61 wt.%, at least about 62 wt.%, at least about 63
wt.%, at least about
64 wt.%, at least about 65 wt.%, at least about 66 wt.%, at least about 67
wt.%, at least about
68 wt.%, at least about 69 wt.%, at least about 70 wt.%, at least about 71
wt.%, at least about
72 wt.%, at least about 73 wt.%, at least about 74 wt.%, at least about 75
wt.%, at least about
76 wt.%, at least about 77 wt.%, at least about 78 wt.%, at least about 79
wt.%, at least about
80 wt.%, at least about 81 wt.%, at least about 82 wt.%, at least about 83
wt.%, at least about
84 wt.%, at least about 85 wt.%, at least about 86 wt.%, at least about 87
wt.%, at least about
27
Date Recue/Date Received 2022-05-11
88 wt.%, at least about 89 wt.%, at least about 90 wt.%, at least about 91
wt.%, at least about
92 wt.%, at least about 92.5 wt.%, at least about 93 wt.%, at least about 94
wt.%, at least
about 95 wt.%, at least about 96 wt.%, at least about 97 wt.%, at least about
97.5 wt.%, at
least about 98 wt.%, at least about 99 wt.%, at least about 99.5 wt.%, and at
least about 99.9
wt.% of the outer protective layer is formed from the fluoropolymer, with the
acrylic or
acrylic-based polymer being the primary component taking up the majority of
the balance for
each weight percentage of the fluoropolymer, if not all or substantially all
of the balance for
each percentage of the fluoropolymer.
[0082] In particular, when the primary fluorocompound that is used to
form a
majority of the fluoride-containing portion of the polymer blend is PVDF or
another
fluoropolymer formed from polymerized monomer units derived from VDF or a
substituted
vinylidene fluoride monomer, then the resulting outer layer 308, 408 at the
bilayer coating
304, 404 comprising it tend to be particularly able to exhibit weathering and
chemical
resistance. Therefore, in an example, a polymer formed from polymerized
monomer units
derived from a hydrofluoro-olefin, and in particular monomer units derived
from VDF or a
substituted vinylidene fluoride, makes up at least about 50 wt.% of the total
fluoropolymer of
the polymer blend (e.g., the first thermoplastic polymer that is mixed with
the second
thermoplastic polymer which comprises the acrylic or acrylic-based polymer to
form the
polymer blend that is extruded to form the outer layer 308, 408), such as at
least about 55
wt.%, for example at least about 60 wt.%, at least about 61 wt.%, at least
about 62 wt.%, at
least about 63 wt.%, at least about 64 wt.%, at least about 65 wt.%, at least
about 66 wt.%, at
least about 67 wt.%, at least about 68 wt.%, at least about 69 wt.%, at least
about 70 wt.%, at
least about 71 wt.%, at least about 72 wt.%, at least about 73 wt.%, at least
about 74 wt.%, at
least about 75 wt.%, at least about 76 wt.%, at least about 77 wt.%, at least
about 78 wt.%, at
least about 79 wt.%, at least about 80 wt.%, at least about 81 wt.%, at least
about 82 wt.%, at
least about 83 wt.%, at least about 84 wt.%, at least about 85 wt.%, at least
about 86 wt.%, at
least about 87 wt.%, at least about 88 wt.%, at least about 89 wt.%, at least
about 90 wt.%, at
least about 91 wt.%, at least about 92 wt.%, at least about 93 wt.%, at least
about 94 wt.%, at
least about 95 wt.%, at least about 96 wt.%, at least about 97 wt.%, at least
about 97.5 wt.%,
at least about 98 wt.%, at least about 98.5 wt.%, at least about 99 wt.%, at
least about 99.5
28
Date Recue/Date Received 2022-05-11
wt.%, at least about 99.75 wt.%, at least about 99.9 wt.%, at least about
99.95 wt.%, at least
about 99.99 wt.%, at least about 99.999 wt.%, at least about 99.9999 wt.%, or
in some
examples all 100 wt.% of the fluoropolymer portion of the polymer blend for
the outer layer
308, 408. If another fluoropolymer is used in addition to the PVDF or the
polymer formed
from polymerized monomer units comprising a hydrofluoro-olefin other than VDF,
the most
commonly used other fluoropolymer would be a polymer formed from polymerized
monomer units comprising a perfluorinated alkene, and in particular those
derived from TFE
or a substituted TFE, e.g., PTFE. In an example, the fluoropolymer can include
about 0.0001
wt.% PTFE or a different polymer formed from polymerized monomer units
comprising a
different perfluorinated alkene, such as about 0.001 wt.%, about 0.01 wt.%,
about 0.1 wt.%,
about 0.5 wt.%, about 0.75 wt.%, about 0.9 wt.%, about 1 wt.%, about 1.1 wt.%,
about 1.2
wt.%, about 1.3 wt.%, about 1.4 wt.%, about 1.5 wt.%, about 1.6 wt.%, about
1.7 wt.%,
about 1.8 wt.%, about 1.9 wt.%, about 2 wt.%, about 2.1 wt.%, about 2.2 wt.%,
about 2.3
wt.%, about 2.4 wt.%, about 2.5 wt.%, about 2.6 wt.%, about 2.7 wt.%, about
2.8 wt.%,
about 2.9 wt.%, about 3 wt.%, about 3.1 wt.%, about 3.2 wt.%, about 3.3 wt.%,
about 3.4
wt.%, about 3.5 wt.%, about 3.6 wt.%, about 3.7 wt.%, about 3.8 wt.%, about
3.9 wt.%,
about 4 wt.%, about 4.1 wt.%, about 4.2 wt.%, about 4.3 wt.%, about 4.4 wt.%,
about 4.5
wt.%, about 4.6 wt.%, about 4.7 wt.%, about 4.8 wt.%, about 4.9 wt.%, about 5
wt.%, about
5.1 wt.%, about 5.2 wt.%, about 5.3 wt.%, about 5.4 wt.%, about 5.5 wt.%,
about 5.6 wt.%,
about 5.7 wt.%, about 5.8 wt.%, about 5.9 wt.%, about 6 wt.%, about 6.1 wt.%,
about 6.2
wt.%, about 6.3 wt.%, about 6.4 wt.%, about 6.5 wt.%, about 6.6 wt.%, about
6.7 wt.%,
about 6.8 wt.%, about 6.9 wt.%, about 7 wt.%, about 7.1 wt.%, about 7.2 wt.%,
about 7.3
wt.%, about 7.4 wt.%, about 7.5 wt.%, about 7.6 wt.%, about 7.7 wt.%, about
7.8 wt.%,
about 7.9 wt.%, about 8 wt.%, about 8.1 wt.%, about 8.2 wt.%, about 8.3 wt.%,
about 8.4
wt.%, about 8.5 wt.%, about 8.6 wt.%, about 8.7 wt.%, about 8.8 wt.%, about
8.9 wt.%,
about 9 wt.%, about 9.1 wt.%, about 9.2 wt.%, about 9.3 wt.%, about 9.4 wt.%,
about 9.5
wt.%, about 9.6 wt.%, about 9.7 wt.%, about 9.8 wt.%, about 9.9 wt.%, about 10
wt.%, about
10.1 wt.%, about 10.2 wt.%, about 10.3 wt.%, about 10.4 wt.%, about 10.5 wt.%,
about 10.6
wt.%, about 10.7 wt.%, about 10.8 wt.%, about 10.9 wt.%, about 11 wt.%, about
11.1 wt.%,
about 11.2 wt.%, about 11.3 wt.%, about 11.4 wt.%, about 11.5 wt.%, about 11.6
wt.%, about
29
Date Recue/Date Received 2022-05-11
11.7 wt.%, about 11.8 wt.%, about 11.9 wt.%, about 12 wt.%, about 12.1 wt.%,
about 12.2
wt.%, about 12.3 wt.%, about 12.4 wt.%, about 12.5 wt.%, about 12.6 wt.%,
about 12.7
wt.%, about 12.8 wt.%, about 12.9 wt.%, about 13 wt.%, about 13.1 wt.%, about
13.2 wt.%,
about 13.3 wt.%, about 13.4 wt.%, about 13.5 wt.%, about 13.6 wt.%, about 13.7
wt.%, about
13.8 wt.%, about 13.9 wt.%, about 14 wt.%, about 14.1 wt.%, about 14.2 wt.%,
about 14.3
wt.%, about 14.4 wt.%, about 14.5 wt.%, about 14.6 wt.%, about 14.7 wt.%,
about 14.8
wt.%, about 14.9 wt.%, about 15 wt.%, about 15.1 wt.%, about 15.2 wt.%, about
15.3 wt.%,
about 15.4 wt.%, about 15.5 wt.%, about 15.6 wt.%, about 15.7 wt.%, about 15.8
wt.%, about
15.9 wt.%, about 16 wt.%, about 16.1 wt.%, about 16.2 wt.%, about 16.3 wt.%,
about 16.4
wt.%, about 16.5 wt.%, about 16.6 wt.%, about 16.7 wt.%, about 16.8 wt.%,
about 16.9
wt.%, about 17 wt.%, about 17.1 wt.%, about 17.2 wt.%, about 17.3 wt.%, about
17.4 wt.%,
about 17.5 wt.%, about 17.6 wt.%, about 17.7 wt.%, about 17.8 wt.%, about 17.9
wt.%, about
18 wt.%, about 18.1 wt.%, about 18.2 wt.%, about 18.3 wt.%, about 18.4 wt.%,
about 18.5
wt.%, about 18.6 wt.%, about 18.7 wt.%, about 18.8 wt.%, about 18.9 wt.%,
about 19 wt.%,
about 19.1 wt.%, about 19.2 wt.%, about 19.3 wt.%, about 19.4 wt.%, about 19.5
wt.%, about
19.6 wt.%, about 19.7 wt.%, about 19.8 wt.%, about 19.9 wt.%, and about 20
wt.%, or any
range of values using any two of these values as endpoints of the range.
[0083]
The remainder of the polymer blend that forms the outer layer 308, 408 (e.g.,
the second thermoplastic polymer that is mixed with the one or more
fluoropolymers of the
first thermoplastic polymer to form the polymer blend) comprises an acrylic or
acrylic-based
polymer, which can be the same acrylic or acrylic-based polymer that is used
to form the
inner layer 306, 406 or it can be a different acrylic or acrylic-based
polymer. In an example,
the outer layer 308, 408 comprises about 0.01 wt.% of the outer protective
layer, for example
about 0.05 wt.%, about 1 wt.%, about 2 wt.%, about 2.5 wt.%, about 3 wt.%,
about 4 wt.%,
about 5 wt.%, about 6 wt.%, about 7 wt.%, about 7.5 wt.%, about 8 wt.%, about
9 wt.%,
about 10 wt.%, about 11 wt.%, about 12 wt.%, about 13 wt.%, about 14 wt.%,
about 15
wt.%, about 16 wt.%, about 17 wt.%, about 18 wt.%, about 19 wt.%, about 20
wt.%, about
21 wt.%, about 22 wt.%, about 23 wt.%, about 24 wt.%, about 25 wt.%, about 26
wt.%,
about 27 wt.%, about 28 wt.%, about 29 wt.%, about 30 wt.%, about 31 wt.%,
about 32
wt.%, about 33 wt.%, about 34 wt.%, about 35 wt.%, about 36 wt.%, about 37
wt.%, about
Date Recue/Date Received 2022-05-11
38 wt.%, about 39 wt.%, or about 40 wt.% of the outer protective layer, or any
range of
values using any two of these values as endpoints of the range.
Functionalized Copolymerization
[0084] In an example, one or more of the polymers that form the
fluoropolymer
portion of the polymer blend that forms the outer layer 308, 408 can be a
copolymer
comprising one or more additional polymerized monomer units (which will also
be referred
to herein as the "polymerized comonomer units") in addition to the primary
monomer units
described above (e.g., vinylidene difluoride ("VDF") or another hydrofluoro-
olefin for a
PVDF based polymer or tetrafluoroethylene ("TFE") or another perfluorinated
alkene for a
PTFE based polymer). In some examples, the polymerized comonomer units may be
referred to as "polymerized second monomer units" or "polymerized second
comonomer
units" in order to clarify the difference between the comonomer units and the
primary
polymerized monomer units, which may be referred to as the "polymerized first
monomer
units" or the "polymerized primary monomer units."
[0085] Each of the one or more polymerized comonomer units can be
selected to
impart one or more physical or chemical properties to the fluoropolymer that
results from
copolymerization of the polymerized primary polymer units and the secondary
polymerized
copolymer units. For example, as mentioned above, the weatherability and/or
the chemical
resistance of the coating 304, 404 can depend on the relative crystallinity of
the solid outer
layer 308, 408, i.e., on the degree to which the outer layer 308, 408 is an
amorphous polymer
or a crystalline polymer. As is also mentioned above, a polymer that is pure
polyvinylidene
fluoride or that has a high mole % of the VDF monomer units tends to have a
high
crystallinity. PVDF-based polymers with high crystallinity tend to have less
weatherability
and chemical resistance. Therefore, in an example, the one or more polymerized
comonomer
units for inclusion in the fluoropolymer of the polymer blend can include a
comonomer
compound that will tend to reduce the crystallinity of the resulting
fluoropolymer resin. In an
example, after the inclusion of the one or more comonomer units into the
fluoropolymer
backbone, the resulting fluoropolymer can have a lower crystallinity than the
fluoropolymer
without the one or more comonomer units.
31
Date Recue/Date Received 2022-05-11
[0086] Pure poly(vinylidene difluoride) resins or those with high VDF
mole
percentages tend to be somewhat hard and not very pliable, making them
difficult to extrude
as a thin film layer. Therefore, in an example, the one or more polymerized
comonomer
units that can be included in the fluoropolymer of the polymer blend can
include a
comonomer compound that can make the resulting polymer resin softer and/or
more pliable
so that the polymer resin is easier to extrude into a thin film for use as the
outer layer 308,
408. In some examples, the reduction in crystallinity for the resulting
fluoropolymer resin
can also tend to provide for the softening and increased pliability.
[0087] In an example, comonomer units that provide for both the reduced
crystallinity and the increased softness and/or pliability when copolymerized
with VDF
monomer units are polymerized comonomer units derived from hexafluoropropylene
(C3F6,
also referred to herein as "HFP"). The resulting fluoropolymer can have the
general
chemical formula [A]:
F F F CF3
- x - -y [A]
wherein "x" is the relative molar amount of the VDF monomer units within the
fluoropolymer chain of formula [A] and "y" is the relative molar amount of the
HFP
comonomer units within the polymer chain of formula [A]. Other comonomer units
that can
copolymerized with the VDF monomer units include, but are not limited to,
chlorotrifluoroethylene (C2C1F3, also referred to herein as "CTFE") or
tetrafluoroethylene
(C2F4, or "TFE").
[0088] In an example, the relative amount of the polymerized comonomer
units
derived from HFP in the fluoropolymer (e.g., y in chemical formula [A]) is
from about 0.5
mol.% to about 15 mol.%, such as from about 1 mol.% to about 10 mol.%, for
example from
about 2.5 mol.% to about 7 mol.%, such as from about 4 mol.% to about 6 mol.%,
for
example from about 4.5 mol.% to about 5 mol.% HFP, e.g., from about 4.4 mol.%
HFP to
about 4.6 mol.% HFP, such as from about 4.5 mol.% HFP to about 4.55 mol.% HFP,
such as
about 4.52 mol.% HFP.
32
Date Recue/Date Received 2022-05-11
[0089] In
an example, the relative amount of the polymerized comonomer units, e.g.,
those that can provide for reduced crystallinity and/or increased softness or
pliability such as
comonomer units derived from HFP, in the final fluoropolymer is about 20
mol.%, for
example about 19.5 mol.%, about 19 mol.%, about 18.5 mol.%, about 18 mol.%,
about 17.5
mol.%, about 17 mol.%, about 16.5 mol.%, about 16 mol.%, about 15.5 mol.%,
about 15
mol.%, about 14.9 mol.%, about 14.8 mol.%, about 14.7 mol.%, about 14.6 mol.%,
about
14.5 mol.%, about 14.4 mol.%, about 14.3 mol.%, about 14.2 mol.%, about 14.1
mol.%,
about 14 mol.%, about 13.9 mol.%, about 13.8 mol.%, about 13.7 mol.%, about
13.6 mol.%,
about 13.5 mol.%, about 13.4 mol.%, about 13.3 mol.%, about 13.2 mol.%, about
13.1
mol.%, about 13 mol.%, about 12.9 mol.%, about 12.8 mol.%, about 12.7 mol.%,
about 12.6
mol.%, about 12.5 mol.%, about 12.4 mol.%, about 12.3 mol.%, about 12.2 mol.%,
about
12.1 mol.%, about 12 mol.%, about 11.9 mol.%, about 11.8 mol.%, about 11.7
mol.%, about
11.6 mol.%, about 11.5 mol.%, about 11.4 mol.%, about 11.3 mol.%, about 11.2
mol.%,
about 11.1 mol.%, about 11 mol.%, about 10.9 mol.%, about 10.8 mol.%, about
10.7 mol.%,
about 10.6 mol.%, about 10.5 mol.%, about 10.4 mol.%, about 10.3 mol.%, about
10.2
mol.%, about 10.1 mol.%, about 10 mol.%, about 9.95 mol.%, about 9.9 mol.%,
about 9.85
mol.%, about 9.8 mol.%, about 9.75 mol.%, about 9.7 mol.%, about 9.65 mol.%,
about 9.6
mol.%, about 9.55 mol.%, about 9.5 mol.%, about 9.45 mol.%, about 9.4 mol.%,
about 9.35
mol.%, about 9.3 mol.%, about 9.25 mol.%, about 9.2 mol.%, about 9.15 mol.%,
about 9.1
mol.%, about 9.05 mol.%, about 9 mol.%, about 8.95 mol.%, about 8.9 mol.%,
about 8.85
mol.%, about 8.8 mol.%, about 8.75 mol.%, about 8.7 mol.%, about 8.65 mol.%,
about 8.6
mol.%, about 8.55 mol.%, about 8.5 mol.%, about 8.45 mol.%, about 8.4 mol.%,
about 8.35
mol.%, about 8.3 mol.%, about 8.25 mol.%, about 8.2 mol.%, about 8.15 mol.%,
about 8.1
mol.%, about 8.05 mol.%, about 8 mol.%, about 7.95 mol.%, about 7.9 mol.%,
about 7.85
mol.%, about 7.8 mol.%, about 7.75 mol.%, about 7.7 mol.%, about 7.65 mol.%,
about 7.6
mol.%, about 7.55 mol.%, about 7.5 mol.%, about 7.45 mol.%, about 7.4 mol.%,
about 7.35
mol.%, about 7.3 mol.%, about 7.25 mol.%, about 7.2 mol.%, about 7.15 mol.%,
about 7.1
mol.%, about 7.05 mol.%, about 7 mol.%, about 6.95 mol.%, about 6.9 mol.%,
about 6.85
mol.%, about 6.8 mol.%, about 6.75 mol.%, about 6.7 mol.%, about 6.65 about
6.6 mol.%,
about 6.55 about 6.5 mol.%, about 6.45 about 6.4 mol.%, about 6.35 about 6.3
mol.%, about
33
Date Recue/Date Received 2022-05-11
6.25 about 6.2 mol.%, about 6.15 about 6.1 mol.%, about 6.05 about 6 mol.%,
about 5.95
about 5.9 mol.%, about 5.85 about 5.8 mol.%, about 5.75 about 5.7 mol.%, about
5.65 about
5.6 mol.%, about 5.55 mol.%, about 5.5 mol.%, about 5.45 mol.%, about 5.4
mol.%, about
5.35 mol.%, about 5.3 mol.%, about 5.25 mol.%, about 5.2 mol.%, about 5.15
mol.%, about
5.1 mol.%, 5.05 mol.%, about 5 mol.%, about 4.95 mol.%, about 4.9 mol.%, about
4.85
mol.%, about 4.8 mol.%, about 4.75 mol.%, about 4.7 mol.%, about 4.65 mol.%,
about 4.6
mol.%, about 4.59 mol.%, about 4.58 mol.%, about 4.57 mol.%, about 4.56 mol.%,
about
4.55 mol.%, about 4.54 mol.%, about 4.53 mol.%, about 4.52 mol.%, about 4.51
mol.%,
about 4.5 mol.%, about 4.49 mol.%, about 4.48 mol.%, about 4.47 mol.%, about
4.46 mol.%,
about 4.45 mol.%, about 4.44 mol.%, about 4.43 mol.%, about 4.42 mol.%, about
4.41
mol.%, about 4.4 mol.%, about 4.39 mol.%, about 4.38 mol.%, about 4.37 mol.%,
about 4.36
mol.%, about 4.35 mol.%, about 4.34 mol.%, about 4.33 mol.%, about 4.32 mol.%,
about
4.31 mol.%, about 4.3 mol.%, about 4.29 mol.%, about 4.28 mol.%, about 4.27
mol.%, about
4.26 mol.%, about 4.25 mol.%, about 4.2 mol.%, about 4.15 mol.%, about 4.1
mol.%, about
4.05 mol.%, about 4 mol.%, about 3.95 mol.%, about 3.9 mol.%, about 3.85
mol.%, about
3.8 mol.%, about 3.75 mol.%, about 3.7 mol.%, about 3.65 mol.%, about 3.6
mol.%, about
3.55 mol.%, about 3.5 mol.%, about 3.45 mol.%, about 3.4 mol.%, about 3.35
mol.%, about
3.3 mol.%, about 3.25 mol.%, about 3.2 mol.%, about 3.15 mol.%, about 3.1
mol.%, about
3.05 mol.%, about 3 mol.%, about 2.95 mol.%, about 2.9 mol.%, about 2.85
mol.%, about
2.8 mol.%, about 2.75 mol.%, about 2.7 mol.%, about 2.65 mol.%, about 2.6
mol.%, about
2.55 mol.%, about 2.5 mol.%, about 2.45 mol.%, about 2.4 mol.%, about 2.35
mol.%, about
2.3 mol.%, about 2.25 mol.%, about 2.2 mol.%, about 2.15 mol.%, about 2.1
mol.%, about
2.05 mol.%, about 2 mol.%, about 1.9 mol.%, about 1.8 mol.%, about 1.7 mol.%,
about 1.6
mol.%, about 1.5 mol.%, about 1.4 mol.%, about 1.3 mol.%, about 1.2 mol.%,
about 1.1
mol.%, about 1 mol.%, about 0.9 mol.%, about 0.8 mol.%, about 0.7 mol.%, about
0.6
mol.%, about 0.5 mol.%, about 0.4 mol.%, about 0.3 mol.%, about 0.25 mol.%,
about 0.2
mol.%, or about 0.1 mol.% of the final fluoropolymer.
[0090] Other factors that may be important for the final fluoropolymer
and/or the
polymer blend made up of the fluoropolymer blended with the acrylic or acrylic-
based
polymer include, but are not limited to: processability at a specified
extrusion temperature
34
Date Recue/Date Received 2022-05-11
and pressure; coating performance (e.g., wettability of the extruded molten
polymer on the
outer surface of the acrylic or acrylic-based polymer of the inner layer 306,
406); color of the
final set outer layer 308, 408; gloss of the final set outer layer 308, 408;
water contact angle
(e.g., as a measure of the surface free energy of the outer layer 308, 408);
adhesion bonding
of the polymer blend to the acrylic or acrylic-based polymer of the inner
layer 306, 406 (e.g.,
as measured in terms of positester adhesion and scrape adhesion); adhesion
bonding of a
sealant or other capping layer material onto the outer surface of the outer
layer 308, 408;
compatibility of the sealant or other capping layer material with the polymer
blend of the
outer layer 308, 408; resistance to scratching (e.g., as measured by a "five
finger" scratch
test); impact resistance; chemical resistance; and weatherability resistance
(e.g., as measured
by a boil test, a boil anneal test, and a thermal and humidity cycle test).
[0091] FIG. 6 is a diagram of an example method 500 for coating a
substrate, such as
a pultrusion substrate, to form a coated article. The method includes, at step
502, injecting a
feedstock with a polymer resin to provide a resin-injected feedstock. In an
example, resin-
injecting the feedstock 502 can include aligning the feedstock prior to
injecting the polymer
resin, such as by aligning the feedstock from one or more roving.
[0092] In an example, the feedstock can comprise one or more
reinforcing structures,
such as one or more reinforcing fibers. The polymer resin can comprise a
composition of
one or more resin components. The one or more resin components can be mixed,
for
example with a mixing apparatus, to form the polymer resin. In an example, the
polymer
resin comprises a polyester-based resin. In another example, the polymer resin
comprises a
polyurethane-based resin, such as a resin formed from a mixture of one or more
polyols and
one or more isocyanates. Resin-injecting the feedstock 502 can be performed by
one or more
injections nozzles, such as the resin nozzles 130, 230 described above. In an
example.
Resin-injecting the feedstock 502 can be performed, for example, with the
resin-injection
assembly 110, 210 described above with respect to FIGS. 1 and 2.
[0093] The method 500 can include, at step 504, pulling the resin-
injected feedstock
through a pultrusion die. The pultrusion die can shape the resin-injected
feedstock into a
three-dimensional profile shape having one or more profile surfaces. In an
example, the step
of pulling the feedstock 504 can be performed by the pulling mechanism 166,
266 described
Date Recue/Date Received 2022-05-11
above with respect to FIGS. 1 and 2. The pultrusion die used in the step of
pulling the
feedstock 504 can be the pultrusion die 112, 212 described above with respect
to FIGS. 1 and
2.
[0094] Continuing with FIG. 6, the method 500 includes, at 506,
applying a coating
onto the pultrusion substrate. Applying the coating 506 can include: at 508,
optionally
adhering one or more adhesive materials onto at least a portion of the one or
more profile
surfaces of the pultrusion substrate to form one or more adhesive tie layers
on the pultrusion
substrate; and, at 510, applying a protective bilayer comprising an inner
protective layer (e.g.,
the inner layer 306, 406) and an outer protective layer (e.g., the outer layer
308, 408) to the
pultrusion substrate (e.g., either directly to one or more profile surfaces of
the pultrusion
substrate or to the one or more adhesive tie layers formed in step 508) to
provide the coated
pultrusion article. Whether the method 500 includes just applying the
protective bilayer such
that applying the coating 506 only includes step 510 or comprises both forming
the one or
more adhesive tie layers and applying the protective bilayer such that
applying the coating
506 includes both steps 508 and 510, will depend on the material of the
pultrusion substrate,
and in particular the material of the polymer resin. As described above, when
a polyester-
based resin is used, the protective bilayer materials described above are able
to be applied
and bonded directly to the pultrusion substrate, such that step 508 can be
omitted. However,
when a polyurethane-based resin is used, it is often difficult to bond the
protective bilayer
directly to the urethane-based substrate, such that step 508 can be included
to provide an
adhesive bilayer that can adhere the protective bilayer to the pultrusion
substrate.
[0095] In examples that include the step of forming the one or more
adhesive tie
layers 508, the step 508 can include heating the pultrusion substrate to an
adhesive-
application temperature. The adhesive-application temperature can be a
temperature that will
enable one or more of: improved adhesion of the adhesive material to the
pultrusion substrate
or improved formation of the one or more adhesive tie layers. In an example,
the pultrusion
substrate is heated to an adhesive-application temperature is at least about
110 F. In an
example, heating the pultrusion substrate to promote adhesion of the adhesive
tie layers (e.g.,
as part of step 508) can include raising the temperature of the pultrusion
substrate to at least
about 250 F so that the pultrusion substrate can cool slightly before the
adhesive material is
36
Date Recue/Date Received 2022-05-11
applied to the pultrusion substrate, and such that the adhesive material can
still sufficiently
adhere. Forming the one or more adhesive tie layers 508 can further include
extruding the
one or more adhesive materials onto at least the one or more profile surfaces
of the pultrusion
substrate, such as through an adhesive extrusion die, for example a cross-head
extrusion die,
i.e., so that the adhesive layers 508 (if used) are extruded in-line directly
onto the profile
surfaces of the pultrusion substrate. In an example, the adhesive-application
assembly 254
described above with respect to FIG. 2 can be used to apply and adhere the one
or more
adhesive materials, for example with the adhesive material extruder 256.
[0096] Applying the protective bilayer 510 can include extruding a
coating material
of the inner protective layer and the outer protective layer onto the
pultrusion substrate. In
examples where the method 500 includes forming the one or more adhesive tie
layers (step
508), then the step of applying the protective bilayer 510 includes applying
the protective
bilayer onto the one or more adhesive tie layers. In examples where step 508
is omitted, the
step of applying the protective bilayer 510 includes applying the protective
bilayer directly
onto one or more profile surfaces of the pultrusion substrate, e.g., cross-
head extruding the
one or more protective layers 510 directly onto the one or more profile
surfaces of the
pultrusion substrate or onto the one or more adhesive layers already cross-
head extruded onto
the pultrusion substrate. In an example, the step of applying the protective
bilayer 510 can
include extruding each of the coating materials of the inner and outer
protective layers
through an extrusion die, such as a cross-head extrusion die that can cross-
head extrude the
coating material or materials onto the profile surfaces of the pultrusion
substrate or onto the
one or more adhesive tie layers.
[0097] In some examples, the inner protective layer and the outer
protective layer can
each be applied by its own coating extrusion die. For example, in the system
100 shown in
FIG. 1, a first protective coating material (e.g., a thermoplastic material
comprising a first
acrylic or acrylic-based polymer) can be extruded through a first coating
material extruder
142 to form the inner protective layer and a second protective coating
material (e.g., a second
thermoplastic material comprising a polymer blend of a first thermoplastic
polymer and a
second thermoplastic polymer, wherein the first thermoplastic polymer
comprises a
fluoropolymer and the second thermoplastic polymer comprises a second acrylic
or acrylic-
37
Date Recue/Date Received 2022-05-11
based polymer) can be extruded through a second coating material extruder 148
to form the
outer protective layer. In other examples, the inner protective layer (e.g.,
the inner layer 306,
406) and the outer protective layer (e.g., the outer layer 308, 408) can be
formed by
coextrusion. For example, the system 200 shown in FIG. 2 includes a
coextrusion die 260
that coextrudes a first protective coating material to form the inner
protective layer (such as
one comprising the first acrylic or acrylic-based polymer) and a second
coating material to
form the outer protective layer (such as one formed from a polymer blend of a
fluoropolymer
and a second acrylic or acrylic-based polymer). In an example, the protective
coating
materials of the inner and outer protective layers are selected to have as
closely matching
viscosity as possible to optimize adhesion between the coextruded and adjacent
protective
layers that form the protective bilayer.
[0098] In some examples where applying the coating 506 includes both
forming the
one or more adhesive tie layers 508 and applying the protective bilayer 510,
the step of
applying the coating 506 can comprise coextruding the one or more adhesive
materials and
the protective coating materials in substantially the same step. For example,
as shown in the
system 200 of FIG. 2, the coextrusion die 260 not only coextrudes the first
and second
protective coating materials, but also coextrudes the adhesive material to
form the one or
more adhesive tie layers. In an example, the one or more adhesive materials
and the
protective coating materials are selected to have as closely matching
viscosity as possible to
optimize adhesion between the coextruded and adjacent adhesive tie layer and
coating layer.
[0099] In an example, two or more of resin-injecting the feedstock 502,
pulling the
feedstock 504, forming the one or more adhesive tie layers 508 (if performed),
and applying
the protective bilayer 510 can be conducted in a common in-line continuous
process. In an
example, all of the steps of resin-injecting the feedstock 502, pulling the
feedstock 504,
forming the one or more adhesive ties layers 508, and applying the protective
bilayer 510 are
conducted in a common in-line continuous process.
[00100] In an example, the method 500 can optionally include, at 512,
cooling the
coated pultrusion article. Cooling the coated pultrusion article 512 can
include one or more
of: passively exposing the coated pultrusion article to cooling air, such as
air at ambient
conditions or further chilled air; applying forced air to the coated
pultrusion article, for
38
Date Recue/Date Received 2022-05-11
example at ambient temperature or a cooled or chilled temperature; applying a
liquid cooling
medium to one or more surfaces of the coated pultrusion article, such as by
immersing the
coated pultrusion article in a cooling immersion bath or by spraying a liquid
cooling medium
onto one or more surfaces of the coated pultrusion article coated profile.
[00101] The method 500 can further include, at 514, cutting the coated
pultrusion
article to a specified size. Cutting the coated pultrusion article 514 can be
performed with
any device capable of accurately cutting the elongate coated pultrusion
article to a specified
size, such as a specified length. Cutting the coated pultrusion article 514
can also include
cutting the coated pultrusion article with a specified cutting shape, e.g., a
straight cut, a
beveled cut, a chamfered cut, a fillet cut, and the like.
EXAMPLES
[00102] Various embodiments of the present invention can be better
understood by
reference to the following Examples which are offered by way of illustration.
The present
invention is not limited to the Examples given herein.
COATED ARTICLES
[00103] Each of the coating materials described in EXAMPLES 1-3 are an
extrudable
polymer blend of a PVDF-based polymer and an acrylic polymer. Each of the
coating
materials described in COMPARATIVE EXAMPLES 4-6 are either another extrudable
polymer blend of a PVDF-based polymer and an acrylic polymer or are a PVDF-
based
polymer that is not blended with an acrylic or acrylic-based polymer, which is
included for
the purposes of comparison with one or more of the coating materials described
in
EXAMPLES 1-3.
[00104] Each extrudable coating material of EXAMPLES 1-3 and COMPARATIVE
EXAMPLES 4-6 can be used to form one or more layers of a protective coating
for use on a
fenestration article. In particular, each extrudable coating material of
EXAMPLES 1-3 and
COMPARATIVE EXAMPLES 4-6 is used to form the outer layer of a bilayer coating
structure, such as the outer layer 408 in the protective bilayer coating 404
described above
with respect to FIG. 5. Therefore, in each EXAMPLE or COMPARATIVE EXAMPLE, the
coating material described is coextruded with a poly(methyl methacrylate)
("PMMA") that is
39
Date Recue/Date Received 2022-05-11
sold by Arkema S.A., Colombes France (also referred to as "Arkema"), through
its Altuglas
International division (hereinafter "Altuglas"), with catalog or item number
A212M (also
referred to hereinafter as "A212 PMMA" or simply as "A212"), to form the inner
layer of the
bilayer coating, e.g., the inner layer 406 of the bilayer coating 404 in FIG.
5. For each
EXAMPLE or COMPARATIVE EXAMPLE, a thermoplastic polyurethane extrudable
adhesive was coextruded along with the specified coating material and the
A212. The
extrudable adhesive material forms an adhesive tie layer between a pultruded
substrate and
the A212 inner layer, e.g., the adhesive tie layer 418 to bond the inner layer
406 to the
pultrusion substrate 402. The resulting coated article, e.g., article 400, for
each EXAMPLE
and COMPARATIVE EXAMPLE are tested as described below.
EXAMPLE 1
[00105] A first coating material was formed by blending the PVDF-based
copolymer
sold under the trade name KYNAR FLEX 2850 by Arkema (referred to hereinafter
as the
"Kynar 2850 fluoropolymer," the "Kynar 2850 copolymer," or simply "Kynar
2850") with
an acrylic polymer. The exact chemical composition of the Kynar 2850
fluoropolymer is
proprietary, however, the present inventors believe that the Kynar 2850
fluoropolymer
comprises primarily polymerized first monomer units derived from vinylidene
difluoride
(also referred to as "VDF monomer units," "VDF units," or simply "VDF")
copolymerized
with second monomer units derived from hexafluoropropylene (also referred to
as "HFP
monomer units," "HFP units," or simply "HFP") with the general chemical
formula [A]
provided above, wherein the molar percentage of the VDF monomer units in the
Kynar 2850
fluoropolymer is believed to be from about 92.5 mol.% to about 97.5 mol.%,
e.g., wherein
the molar percentage of the HFP monomer units are from about 2.5 mol% to about
7.5
mol.%.
[00106] The Kynar 2850 is melted to form a molten resin, which is
blended with clear
beads of PMMA sold by Arkema S.A., Colombes France (also referred to as
"Arkema"),
through its Altuglas International division (hereinafter "Altuglas"), with
catalog or item
number A212M (also referred to hereinafter as "A212 PMMA" or simply as "A212",
also
referred to herein as "A212 beads", which is 10% crosslinked. The A212 beads
are added in
a proportion so that the final blend of the Kynar 2850 and the A212 is 10 wt.%
of the A212
Date Recue/Date Received 2022-05-11
PMMA and 90 wt.% of the Kynar 2850. When extruded, this composition forms the
coating
material of EXAMPLE 1. Two separate samples of the coating material of EXAMPLE
1
were made for testing, identified as EXAMPLE 1¨Sample A (or "Sample 1(A)") and
EXAMPLE 1¨Sample B (or "Sample 1(B)").
EXAMPLE 2
[00107] A second coating material was formed by blending the PVDF-based
homopolymer sold under the trade name KYNAR 705 by Arkema (referred to
hereinafter as
the "Kynar 705 fluoropolymer," "the Kynar 705 polymer" or simply "Kynar 705")
with an
acrylic polymer. The composition of the Kynar 705 resin is proprietary,
however, the present
inventors believe that the primary component (e.g., at least 98%) is a PVDF
homopolymer,
e.g., a polymer where 100% of the monomer units are derived from VDF with no
copolymerized comonomer units, i.e., the fluoropolymer has no HFP comonomer
units, in
contrast to the PVDF-based Kynar 2850 copolymer used to form the first coating
material in
EXAMPLE 1.
[00108] Similar to the polymer blend formed in EXAMPLE 1, the Kynar 705
is melted
to form a molten resin, which is blended with the same A212 beads as in
EXAMPLE 1 such
that the final blend of the Kynar 705 and the A212 is 10 wt.% of the A212 PMMA
and 90
wt.% of the Kynar 705. When extruded, this composition forms the second
coating material
of EXAMPLE 2. Two separate samples of the coating material of EXAMPLE 2 were
made
for testing, identified as EXAMPLE 2¨Sample A (or "Sample 2(A)") and EXAMPLE
2¨
Sample B (or "Sample 2(B)").
EXAMPLE 3
[00109] A third coating material that is similar to the second coating
material of
EXAMPLE 2 was formed by blending the same Kynar 705 PVDF-based homopolymer
with
an acrylic polymer. But, instead of blending the Kynar 705 with the PMMA sold
by item
number A212, in EXAMPLE 3 the Kynar 705 is blended with the PMMA that is sold
by
Altuglas with catalog or item number A210 (also referred to hereinafter as
"A210 PMMA" or
simply as "A210"). Similar to the polymer blends formed in EXAMPLES 1 and 2,
in
EXAMPLE 3 the Kynar 705 is melted to form a molten resin, which is blended
with the
41
Date Recue/Date Received 2022-05-11
A210 such that the final blend of the Kynar 705 and the A210 is 10 wt.% of the
A210
PMMA and 90 wt.% of the Kynar 705. When extruded, this composition forms the
second
coating material of EXAMPLE 3.
COMPARATIVE EXAMPLE 4
[00110] For the purpose of a control comparison, a fourth coating
material was used
that is entirely or substantially entirely formed from the Kynar 705 PVDF
homopolymer
(e.g., that is 100 wt.% of the Kynar 705 or that is approximately 100 wt.%
Kynar 705 with
only small amounts of other additives and with 0 wt.% of an acrylic or acrylic-
based polymer
blended with the Kynar 705). In other words, the fifth coating material of
COMPARATIVE
EXAMPLE 5 consists of the Kynar 705 or consists essentially of the Kynar 705.
COMPARATIVE EXAMPLE 5
[00111] For the purpose of a control comparison, a fifth coating
material was used that
is entirely or substantially entirely formed from the Kynar 2850 PVDF
copolymer (e.g., that
is 100 wt.% of the Kynar 2850 or that is approximately 100 wt.% Kynar 2850
with only
small amounts of other additives and with 0 wt.% of an acrylic or acrylic-
based polymer
blended with the Kynar 2850). In other words, the fourth coating material of
COMPARATIVE EXAMPLE 4 consists of the Kynar 2850 or consists essentially of
the
Kynar 2850.
COMPARATIVE EXAMPLE 6
[00112] For the purpose of comparison, a sixth coating material was used
that is
similar to the polymer blends of Examples 1-3, but that comprises different
relative amounts
of the PVDF-based fluoropolymer and the acrylic or acrylic-based polymer. The
sixth
coating material was formed by blending the Kynar 705 PVDF-based polymer with
the A210
PMMA, but instead of the 10 wt.% PMMA as in the blends of EXAMPLES 1-3, the
blend of
COMPARATIVE EXAMPLE 6 is 40 wt.% of the A210 PMMA and 60 wt.% of the Kynar
705.
42
Date Recue/Date Received 2022-05-11
PERFORMANCE TESTING
SURFACE FREE ENERGY
[00113] Surface free energy (also referred to as "SFE") is one means of
measuring the
wettability of coated articles by liquids. Often, the SFE of a solid surface
is subdivided into a
polar fraction and a non-polar fraction (usually referred to as the "disperse
fraction" when
referring to the SFE). For the coated articles for which SFE was tested, the
polar fraction
SFE was measured by contacting the outer surface with water and measuring the
resulting
surface free energy, while the disperse fraction SFE was measured by
contacting the outer
surface with diiodomethane (CH2I2) and then measuring the resulting surface
free energy.
[00114] A low value for the polar SFE fraction of a solid surface
results in low
wettability of the solid by polar liquids such as water and aqueous solutions,
while a low
value for the disperse SFE fraction will result in low wettability of the
solid by non-polar
liquids such as liquid alkanes.
[00115] A high value for each SFE fraction will also tend to repel a
liquid of the other
type of liquid. For example, a high value for the disperse SFE fraction will
mean that the
solid surface will tend to repel polar liquids such as water, at least if the
surface does not also
have a correspondingly high polar SFE fraction. Similarly, a high polar SFE
fraction will
tend to repel non-polar liquids, at least if the surface does not have a
correspondingly high
disperse SFE fraction.
[00116] In the case of the protective coating materials of the present
disclosure, the
SFE and its separate fraction can give an idea of how susceptible the coating
materials and
the underlying layers that are protected thereby will be to corrosive
materials such as
cleaning chemicals or detergents. The majority of cleaning chemicals that may
be applied to
articles coated with the materials described in the present application are
solutions of
compounds that are soluble or dispersible in water such that most cleaning
compounds are
polar. Therefore, the lower the overall SFE and, more importantly, the polar
SFE fraction
will be instructive for the purpose of evaluating potential corrosion
resistance.
[00117] FIG. 7 is a bar graph of the overall SFE, the disperse
fraction, and the polar
fraction for the outer surface of the coating materials of EXAMPLE 1, Sample
1(A) (data
bars 550), EXAMPLE 1, Sample 1(B) (data bar 552), EXAMPLE 2, Sample 2(A) (data
bars
43
Date Recue/Date Received 2022-05-11
554), and EXAMPLE 2, Sample 2(B) (data bars 556). As can be seen in FIG. 7,
the first
coating material of EXAMPLE 1 has an overall SFE (data bars 550Tot and 552Tot
for Samples
1(A) and 1(B), respectively) that is about 15% to 20% lower than (i.e., from
about 80% to
about 85% of) the overall SFE of the second coating material of Example 2
(data bars 554Tot
and 556Tot for Samples 2(A) and 2(B), respectively). In addition, the first
coating material of
EXAMPLE 1 demonstrated a polar SFE fraction (data bars 550p and 552p for
Samples 1(A)
and 1(B), respectively) that is from about 40% to 60% lower than (i.e., from
about 40% to
about 60% of) the polar SFE fraction of the second coating material of EXAMPLE
2 (data
bars 554p and 556p for Samples 2(A) and 2(B), respectively).
[00118] The SFE data indicates that there is a difference in reaction to
polar
components between the coating materials of EXAMPLES 1 and 2. It is believed
that the
polar fraction of SFE gives an indication of wetting and adherability of polar
compounds to
the outer surface of the coating materials. It is also believed that the polar
fraction SFE
measurements may be indicative of the compatibility of the coating materials
with glazing or
sealing of the coating material with glazing or sealant materials applied over
the top of the
coating material.
ADHESION TESTING
[00119] Multiple test methods were used to test adhesion performance of
several of the
coating materials described in EXAMPLES 1-3 and COMPARATIVE EXAMPLES 4-6
PULL-OFF ADHESION
[00120] Samples were tested for pull-off adhesion by applying a
specified amount of
force on a specified area of the coating material, typically measured in
pounds-force per
square inch or "psi," until the coating portion to which the force is applied
or one or more
underlying substrates or layers to which the coating material is adhered fails
such that the
coating material is "pulled off" of its underlying substrate or layer. The
force applied during
the pull-off adhesion test is applied in a direction that is normal or
substantially normal to the
plane of the outer surface of the coating material. The pull-off adhesion was
tested using a
pull-off adhesion testing device sold by Defelsko Corp. (Ogdensburg, New York,
USA)
under the trade name POSITEST AT, such that the pull-off adhesion test is also
sometimes
44
Date Recue/Date Received 2022-05-11
referred to as a "positester test" and the pull-off adhesion testing device is
sometimes referred
to as a "positester." The pull-off adhesion test was conducted generally
according to one or
more standardized test procedures including, but not limited to, the standards
published by
ASTM International (formerly the American Society for Testing and Materials or
"ASTM")
as ASTM D4541 and ASTM D7522, the standard published by the International
Organization for Standardization ("ISO") as ISO 4624, the standard published
by the
European Standards body ("EN") as EN 1542, and the standard jointly published
by the
Standards Australia body ("AS") and Standards New Zealand boy ("NZS") as
AS/NZS
1580.408.5.
[00121] The coating formed using the first coating material of EXAMPLE 1
had a
pull-off adhesion value of after four different pull-off adhesion tests of
1,204 psi, 1,124 psi,
1,202 psi, and 408 psi. The 408 psi test result was believed to be an anomaly
value and that
the other three values are a better indication of the pull-off adhesion
strength of the first
coating material of EXAMPLE 1. Any value over 1,000 psi is considered
"acceptable" for
the purposes of the scratch-resistant coating such as the coating material of
EXAMPLE 1.
BOIL ADHESION
[00122] Each of the samples of EXAMPLES 1-3 and COMPARATIVE EXAMPLES
4-6 were subjected to the boil adhesion test as defined in the AAMA 625
Voluntary
Specification. All samples were able to satisfactorily pass the AAMA 625
standard boil test.
SCRAPE ADHESION
[00123] Samples 1(A) and 1(B) of EXAMPLE 1 and Samples 2(A) and 2(B) of
EXAMPLE 2 were tested for scrape adhesion strength using a testing device sold
by BYK-
Gardner GmbH (Wesel, Germany, hereinafter "BYK-Gardner") as a "Balanced Beam
Scrape
and Mar Tester." The scrape adhesion test was conducted substantially in
compliance with
standardized test procedures for scrape adhesion tests such as those described
in the
standards published by ASTM as ASTM D2197 and ASTM D5178.
[00124] FIG. 8 shows the scrape arm portion of the scrape adhesion
testing device.
The scrape adhesion testing device also includes a horizontal balance beam
(not shown in
FIG. 8) upon which is placed a specified weight. The balance beam is
configured so that the
Date Recue/Date Received 2022-05-11
weight is positioned directly above the distal end of the scrape arm so that
substantially
constant force is applied by the scrape arm in a direction that is coaxially
aligned with a
central axis of the scrape arm. As can be seen in FIG. 8, the scrape arm
central axis is
oriented at an angle of about 450 relative to the outer surface of the coating
being scraped by
the scrape adhesion testing device.
[00125] For each sample coating material, a set amount of weight was
added to the
scrape adhesion testing device was set, starting with a weight of three (3)
kilograms (kg) and
increasing by increments of one (1) kg until a particular coating sample
failed (e.g., with a
specified amount of the coating being scraped off by the scrape adhesion
testing device).
The resulting samples of the scrape adhesion test are shown in FIGS. 9A-9D.
The coating
material of EXAMPLE 1, Sample 1(A) is shown in FIG. 9A, the coating material
of
EXAMPLE 1, Sample 1(B) is shown in FIG. 9B, the coating material of EXAMPLE 2,
Sample 2(A) is shown in FIG. 9C, and the coating material of EXAMPLE 2, Sample
2(B) is
shown in FIG. 9D. As can be seen in FIGS. 9A and 9B, the coating material of
EXAMPLE 1
(i.e., with the outer coating layer formed from a blend of 90 wt.% Kynar 2850
and 10 wt.%
A212) produced slightly better scrape adhesion performance compared to that of
EXAMPLE
2 (shown in FIGS. 9C and 9D, i.e., with the outer coating layer formed from a
blend of 90
wt.% Kynar 705 and 10 wt.% A212). For example, Sample 1(A) did not fail until
eight (8)
kg was added to the scrape adhesion testing device, while Sample 1(B) did not
fail until nine
(9) kg was added. In contrast, Samples 2(A) and 2(B) failed at six (6) kg and
seven (7) kg,
respectively.
SCRATCH RESISTANCE
[00126] Samples 1(A) from EXAMPLE 1, Samples 2(A) and 2(B) from EXAMPLE
2,
and the coating material of EXAMPLE 3 were tested for scratch resistance using
a scratch
resistance testing device sold by Paul N. Gardner Co. (Pompano Beach, FL, USA,
which is a
division of BYK-Gardner) as the "Multi-Finger Scratch/Mar Tester 710." The
scrape
adhesion test was conducted substantially similarly to scratch and mar
resistance testing that
is typically performed in the automotive industry, such as: test procedures LP-
463DD-18-01
and PF-10938 for Chrysler (division of Stellantis North America, Auburn Hills,
MI, USA);
test procedure BO 162-01 for Ford Motor Co. (Dearborn, MI, USA); test
procedure GMW
46
Date Recue/Date Received 2022-05-11
14698 for General Motors Corp. (Detroit, MI, USA); and test procedure NEW
M0159 for
Nissan Motor Corp. (Yokohama, Japan).
[00127] The scratch resistance testing device included five different
testing arms, also
referred to as "fingers," that were each forced down with a different
specified weight while
passing across the outer surface of the coating. For this reason, the scratch
resistance testing
device will also be referred to herein as "the five-finger scratch tester."
The results of the
five-finger scratch test are shown in FIG. 10. For each finger of the five-
finger scratch tester,
the width (in mils) of any resulting scratch was measured, with a wider
scratch corresponding
to the coating being less resistant to scratching by the finger having that
specified weight
applied.
[00128] For the five-finger scratch tester data of FIG. 10, the
specified weights placed
on the fingers were¨(1) a 2 Newton ("N") weight on a first finger (also
referred to herein as
the "2 N finger," data series 560 in FIG. 10); (2) a 4.5 N weight on a second
finger (the "4.5
N finger," data series 562); (3) a 6 N weight on a third finger (the "6 N
finger," data series
564); (4) a 10 N weight on a fourth finger (the "10 N finger," data series
566); and (5) a 15 N
weight on a fifth finger (the "15 N finger," data series 568). The device is
configured to drag
all of the fingers across the outer surface of the coating being tested so
that the tip of each
finger is scraped across the outer surface in order to test the coating's
scratch resistance to the
force being applied by each specified weight.
[00129] As can be seen, the coating material of EXAMPLE 1 (Sample
1(A))
performed significantly better (e.g., resulted in narrower scratches) than the
coatings of
EXAMPLE 2 and 3 for all of the applied weights except for the 15 N finger. For
the 15 N
finger, the difference between the width for the coating material of EXAMPLE 1
does not
appear to have been significantly different from that of the coating materials
of EXAMPLES
2 and 3.
IMPACT RESISTANCE
[00130] Samples 1(A) from EXAMPLE 1, Samples 2(A) and 2(B) from EXAMPLE
2,
and the coating material of EXAMPLE 3 were tested for impact resistance using
an impact
testing device sold by Intertek Group plc (London, England, UK) as the
"Falling Dart
Impact" tester (also referred to as a "Gardner Impact" tester). The impact
resistance test was
47
Date Recue/Date Received 2022-05-11
conducted according to the ASTM standard published as ASTM D5420. The test
involved
dropping an impactor with a four (4) pound weight from a specified height of
20 inches
(equating to 80 in-lbf). After impact, a tape with a pressure sensitive
adhesive was applied to
the impact site and then removed to see how much any of the coating material
comes off
with the tape.
[00131] All four samples generally had the same generally acceptable
performance,
with Sample 1(A) exhibiting the least amount of damage.
CHEMICAL RESISTANCE
[00132] Samples 1(A) from EXAMPLE 1, Samples 2(A) and 2(B) from EXAMPLE
2,
and the coating material of EXAMPLE 3 were tested for chemical resistance by
exposing
each sample to a 50 vol.% solution of isopropyl alcohol ("IPA") for twenty
four (24) hours
and with each sample being bent with a specified induced strain of about 0.3%
bending.
[00133] After the 24 hours of exposure, the samples were removed from
the 50% IPA
solution and were inspected. All four samples showed excellent chemical
resistance, with no
cracks, discoloration, or visible defects being observed in any of the samples
after exposure
to the relatively highly corrosive IPA at a high concentration.
THERMAL STABILITY
[00134] Samples 1(A) from EXAMPLE 1, Samples 2(A) and 2(B) from EXAMPLE
2,
and the coating material of EXAMPLE 3 were tested for thermal stability by
exposing each
sample to 10 thermal-exposure cycles, with each cycle comprising ramping up
from
approximately room temperature conditions to 85 C (about 185 F) and 85%
relative
humidity and holding at this temperature and humidity for 600 minutes (10
hours), then
cooling down to -40 C (about -40 F) and holding at that temperature for 30
minutes (0.5
hours), before finally ramping up to 23 C (about 73 F) and 50% relative
humidity for the
end of the cycle. The thermal stability test was performed generally
consistently with the
standard published by the International Electrotechnical Commission ("IEC") as
IEC 591/08.
[00135] After the 10 thermal-exposure cycles, the samples were examined
for any
delamination, cracking, or any other visual effects of their corresponding
coating materials.
The adhesion of the coatings were also tested using the positestor pull-off
adhesion test
48
Date Recue/Date Received 2022-05-11
described above. The samples were also tested for chemical resistance to 50%
IPA as
described above. All four samples showed excellent response to the thermal
cycling test,
with no noticeable physical damage to the coating materials and no appreciable
change in the
pull-off adhesion or the chemical resistance of the coating materials.
CAPILLARY RHEOMETRY
[00136] Sample 1(A) from EXAMPLE 1 and the coating materials of
COMPARATIVE EXAMPLES 4-6 were tested for processability (e.g., extrudability)
using
a capillary rheometer sold under the trade name RHEOGRAPH 20 by Gottfert
Werkstoff-
Priifmaschinen GmbH (Buchen, Germany). The capillary rheometry testing was
performed
generally consistently with the ASTM standard published by ASTM D3835. Both
shear
stress (measured in kilopascals (KPa)) and shear viscosity (measured in pascal-
seconds
(Pa=S)) for the materials were measured across a broad range of shear rates
(measured in
inverse seconds, s-1) at an extrusion temperature of 240 C (about 465 F).
The shear stress
data is shown in FIG. 11 and the shear viscosity data is down in FIG. 12.
[00137] As can be seen FIGS. 11 and 12, across the entire range of
shear rates tested,
the coating material of EXAMPLE 1 (Sample 1(A)) (i.e., the blend of 90 wt.%
Kynar 2850
PVDF copolymer and 10 wt.% A212 PMMA) has a significantly higher shear stress
and
shear viscosity than the coating material of COMPARATIVE EXAMPLE 6 (i.e., the
blend of
60 wt.% Kynar 705 PVDF and 40 wt.% A212 PMMA). As can also be seen in FIGS. 11
and
12, the coating material of COMPARATIVE EXAMPLE 6 has a comparable shear
stress and
shear viscosity profile to that of COMPARATIVE EXAMPLE 4 (i.e., 100 wt.% Kynar
2850
PVDF copolymer), which are both significantly higher than the shear stress and
shear
viscosity for the coating material of COMPARATIVE EXAMPLE 5 (i.e., 100 wt.%
Kynar
705 PVDF homopolymer). The higher shear stress and higher shear viscosity
correspond to
the coating material being easier to process, e.g., easier to extrude at
typical processing
conditions for cross-head extrusion onto a pultrusion substrate by providing
for a wider
processability window at a nominal processing temperature and a lower
pressure. The
viscosity of the EXAMPLE 1 coating material is a better match for the
viscosity of the inner
layer material (e.g., the PMMA layer) during coextrusion compared to those of
COMPARATIVE EXAMPLES 4,5, and 6.
49
Date Recue/Date Received 2022-05-11
[00138] The above detailed description includes references to the
accompanying
drawings, which form a part of the detailed description. The drawings show, by
way of
illustration, specific embodiments in which the invention can be practiced.
These
embodiments are also referred to herein as "examples." Such examples can
include elements
in addition to those shown or described. However, the present inventors also
contemplate
examples in which only those elements shown or described are provided.
Moreover, the
present inventors also contemplate examples using any combination or
permutation of those
elements shown or described (or one or more aspects thereof), either with
respect to a
particular example (or one or more aspects thereof), or with respect to other
examples (or one
or more aspects thereof) shown or described herein.
[00139] In the event of inconsistent usages between this document and
any documents
so incorporated by reference, the usage in this document controls.
[00140] In this document, the terms "a" or "an" are used, as is common
in patent
documents, to include one or more than one, independent of any other instances
or usages of
"at least one" or "one or more." In this document, the term "or" is used to
refer to a
nonexclusive or, such that "A or B" includes "A but not B," "B but not A," and
"A and B,"
unless otherwise indicated. In this document, the terms "including" and "in
which" are used
as the plain-English equivalents of the respective terms "comprising" and
"wherein." Also,
in the following claims, the terms "including" and "comprising" are open-
ended, that is, a
system, device, article, composition, formulation, or process that includes
elements in
addition to those listed after such a term in a claim are still deemed to fall
within the scope of
that claim. Moreover, in the following claims, the terms "first," "second,"
and "third," etc.
are used merely as labels, and are not intended to impose numerical
requirements on their
objects.
[00141] Method examples described herein can be machine or computer-
implemented
at least in part. Some examples can include a computer-readable medium or
machine-
readable medium encoded with instructions operable to configure an electronic
device to
perform methods as described in the above examples. An implementation of such
methods
can include code, such as microcode, assembly language code, a higher-level
language code,
or the like. Such code can include computer readable instructions for
performing various
Date Recue/Date Received 2022-05-11
methods. The code may form portions of computer program products. Further, in
an
example, the code can be tangibly stored on one or more volatile, non-
transitory, or non-
volatile tangible computer-readable media, such as during execution or at
other times.
Examples of these tangible computer-readable media can include, but are not
limited to, hard
disks, removable magnetic disks, removable optical disks (e.g., compact disks
and digital
video disks), magnetic cassettes, memory cards or sticks, random access
memories (RAMs),
read only memories (ROMs), and the like.
[00142] The above description is intended to be illustrative, and not
restrictive. For
example, the above-described examples (or one or more aspects thereof) may be
used in
combination with each other. Other embodiments can be used, such as by one of
ordinary
skill in the art upon reviewing the above description. The Abstract is
provided to comply
with 37 C.F.R. 1.72(b), to allow the reader to quickly ascertain the nature
of the technical
disclosure. It is submitted with the understanding that it will not be used to
interpret or limit
the scope or meaning of the claims. Also, in the above Detailed Description,
various features
may be grouped together to streamline the disclosure. This should not be
interpreted as
intending that an unclaimed disclosed feature is essential to any claim.
Rather, inventive
subject matter may lie in less than all features of a particular disclosed
embodiment. Thus,
the following claims are hereby incorporated into the Detailed Description as
examples or
embodiments, with each claim standing on its own as a separate embodiment, and
it is
contemplated that such embodiments can be combined with each other in various
combinations or permutations. The scope of the invention should be determined
with
reference to the appended claims, along with the full scope of equivalents to
which such
claims are entitled.
51
Date Recue/Date Received 2022-05-11
