Note: Descriptions are shown in the official language in which they were submitted.
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WET FORMED MAT HAVING IMPROVED
HOT WET TENSILE STRENGTHS
TECHNICAL FIELD AND INDUSTRIAL
APPLICABILITY OF THE INVENTION
The present invention relates generally to chopped strand mats utilized in
roofing
applications, and more particularly, to chopped strand glass mats that have
improved hot
wet tensile strengths.
BACKGROUND OF THE INVENTION
Glass fibers are conunonly used as reinforcements in the building composite
industiy because they do not shrink or stretch in response to changing
atmospheric
conditions. Roofing materials such as roofing shingles, roll roofing, and
commercial
roofing, are typically constructed of a glass fiber mat, an asphalt coating on
the fibrous
mat, and a surface layer of granules embedded in the asphalt coating.
To foim a chopped strand mat suitable for use in a roofing material, glass
fibers are
first foinied by attenuating streams of a molten glass material from a bushing
or orifice.
The molten glass may be attenuated by a winder which collects gathered
filaments into a
package or by rollers which pull the fibers before they are collected and
chopped. An
aqueous sizing composition is typically applied to the fibers after they are
drawn from the
bushing to protect the fibers from breakage during subsequent processing, to
retard
interfilament abrasion, and to improve the compatibility of the fibers with
the matrix resins
that are to be reinforced. After the fibers are treated witli the sizing
composition, they may
be packaged in their wet condition as wet use chopped strand glass (1A7UCS).
The wet, chopped fibers are then dispersed in a water sluny which contains
surfactants, viscosity modifiers, dispersants, and/or other chemical agents
and agitated to
disperse the fibers. The sluriy containing the dispersed fibers is then
deposited onto a
moving screen where a substantial portion of the water is removed. A polymeric
binder is
then applied, and the resulting mat is heated to remove the remaining water
and cure the
binder. A urea-formaldehyde binder is typically utilized due to its low cost.
Next, asphalt
is applied to the mat, such as by spraying the asphalt onto one or both sides
of the mat or
by passing the mat tlirough a bath of molten asphalt to place a layer of
asphalt on both
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sides of the mat. A protective coating of granules may be applied to the
asphalt-coated
mat. The asphalt-granule coated mat may be used to foi7n a variety of rooflng
materials,
such as a roofing sliingle.
Properties such as tear strength, diy tensile strength, and wet tensile
strength are
measured to deteiniine the usefulness of the chopped strand glass mat in
roofing
applications. One especially important property for a roofing mat is the
retention of hot
wet tensile strength. The hot wet strength provides an estimation of the
durability of the
roofing mat. However, some of the conventional binders utilized to foi7n the
roofing mats,
such as urea-foz7naldehyde resins, tend to deteriorate under wet conditions
such as would
be found in an external environment in which the roofing mat would be used.
Modifying
the urea-formaldehyde binder, such as with a latex modifier, has been found to
increase the
tear strength as well as the hot tensile strength over umnodified urea-
formaldehyde resins.
Other examples of modifying the binder to improve mat properties such as
tensile
properties and tear strength are set forth below.
U.S. Patent No. 6,642,299 to Wertz et al. discloses an aqueous fiber mat
adhesive
binder composition that includes a theiynosetting urea-formaldehyde resin and
an additive
that is either (1) a styrene aciylic acid or styrene aciylate, (2) an adduct
of styrene, maleic
anhydride, and an acrylic acid or aciylate, or (3) a physical mixture of a
styrene aciylic
acid or styrene-aciylate copolymer and a styrene-maleic anhydride copolymer.
The binder
may be used in the foiniation of glass fiber mats that demonstrate hot tensile
strength
tensile retention.
U.S. Patent No. 6,566,459 to Dopico et al. discloses a melamine-urea-
foimaldehyde resin modified with a cyclic urea prepolymer and sodium
metabisulfite. It is
asserted that glass mats foi7ned with the modified melaniine-urea-
foi7naldehyde resins
have improved hot wet tensile strength retention and superior moisture
resistance
compared to urea-fonnaldehyde resins.
U.S. Patent No. 6,384,116 to Chan et al. describes a binder composition that
is
foi-med of a urea-formaldehyde resin modified with a water soluble non-ionic
amine oxide.
Optionally, the urea-formaldehyde resin may be fiu-ther modified with an
anionic acrylic
latex and/or a water soluble polymer having a weight average molecular weight
froni
100,000 - 2,000,000. It is asserted that the tensile strengths of glass mats
foimed with the
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modified urea-formaldehyde resin possess superior tear strength and improved
tensile
strengths.
U.S. Patent Nos. 5,914,365 and 6,084,021 to Chang et al. describe an aqueous
binder composition that contains a urea-formaldehyde resin modified with a
water-soluble
styrene-maleic anhydride copolymer (SMA). The binder composition is used in
the
preparation of fiber mats which may be used as substrates in the manufacture
of roofing
shingles atid composite flooring. It is asserted that glass fiber mats made
using the binder
coinpositions exhibit eiihanced wet tensile strength, wet mat strength, diy
tensile strength,
and tear strength.
U.S. Patent No. 5,851,933 to Swartz et al. disclose methods for making non-
woven
fibrous mats that produce superior tear strengths in roofing products. The
mats are foi7ned
by a wet-laid process in which the applied binder contains an aqueous urea-
foi7naldehyde
resin and a self-crossliiiking copolymer of a vinyl aciylic or polyvinyl
acetate.
U.S. Patent Nos. 5,445,878, 5,518,586, and 5,656,366 to Mirous describe a urea-
foi7naldehyde resin modified with a water-insoluble anionic phosphate ester.
Glass fiber
mats formed using the modified urea-formaldehyde resin as a binder and a
liydroayetllyl
cellulose-containing wliite water glass slui-iy is asserted to exhibit high
tear strengtlis.
U.S. Patent No. 4,430,158 to Jackey et al. discloses a method of improving the
wet
tensile strength of sized glass fiber mats by applying a binder composition
that contains a
urea-foi7naldehyde resin and 0.01 - 5% by weight of a surfactant that is
highly soluble and
capable of wetting the surfaces of the sized glass fibers. The su.rfactant is
preferably an
ionic surfactant such as a sodium dodecylbenzene sulfonate.
U.S. Patent Publication No. 2005/0070136 to Shoemake et al. describes a
thermosetting urea-forinaldehyde resin modified with a binding-eiihancing
amount of a
protein useful as a binder in the formation of glass fiber mats. Preferably
the protein is a
vegetable protein, and even more preferably, a soy protein. The glass mats are
asserted to
demonstrate wet tensile strengths, tear strengths, and diy tensile strengths
substantially
equivalent to urea-foimaldehyde resin binders modified with synthetic
additives.
Despite these disclosures, there exists a need in the art for new binder
compositions
for fiber mats that provide even f-urther improvements in mat tensile and/or
tear strength
properlies.
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SUMMARY OF THE INVENTION
It is an object of the present invention to provide a two-part binder
composition
formed of a binder pre-mix and at least one coupling agent. The choice of
binder forming
the binder pre-mix is not particularly limited, and may include a modified
urea-
formaldehyde binder, a non-modified urea-formaldehyde binder, foi7naldehyde-
fi=ee
binders, and combinations thereof. In addition, the binders may formed as
a"one-part
package" in which the binder is pre-mixed with a modifying agent and packaged
as a one
component system or a"two-part package" in which the binder and the modifying
agent
are not pre-mixed. In a prefeiTed embodiment, the binder is a standard urea-
formaldehyde
binder modified with a styrene butadiene rubber latex modifier. Suitable
examples of
coupling agents for use in the inventive binder composition include silane
coupling agents
and reactive siloxanes. In prefeiTed embodiments, the coupling agent is an
aminosilane
coupling agent. A weak organic acid may be added to the binder composition to
hydrolyze
the silane coupling agent.
It is also an object of the present invention to provide a chopped strand mat
for use
in roofing applications that has improved hot wet tensile strength. The
chopped strand
may be foixned of a plurality of glass fibers held together in a sheet foi7n
by a two-part
binder composition. The glass fibers used to form the chopped strand glass
mats may be
any type of glass fiber, such as A-type glass fibers, C-type glass fibers, E-
type glass fibers,
S-type glass fibers, E-CR-type glass fibers (for exaMple, Advantex'RD glass
fibers
comniercially available from Owens Corning), wool glass fibers, or
combinations thereof.
Optionally, other reinforcing fibers such as mineral fibers, carbon fibers,
ceramic fibers,
natural fibers, and/or synthetic fibers may present in the chopped strand mat
in addition to
the glass fibers. The binder is preferably the two-part binder composition
described above.
It is a further object of the present invention to provide a method of making
a
chopped strand glass mat that has improved hot wet tensile strengths in which
a coupling
agent is added to the chopped strand mat via the binder in a wet-laid mat
processing line.
Chopped glass fibers are added to white water containing various surfactants,
viscosity
modifiers, defoaniing agents, and/or other chemical agents with agitation to
foim a glass
fiber sluny. The slurry is deposited onto a moving foi7ning wire or foraminous
conveyor
to form a web of intermeshed fibers. Water is removed, such as by a vacuum
system, and
a binder containing at least one coupling agent is applied to the web of
fibers. The binder-
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coated web is passed tllrough a diying oven to remove any of the water
remaining in the
web, cure the binder, and form the chopped strand glass mat. The binder is
preferably the
two-part binder composition described above.
It is yet another object of the present invention to provide a method of
making a
chopped strand glass mat that has improved hot wet tensile strengths in wluch
a coupling
agent (or coupling agents) is separately added to the web of chopped fibers
during the
forniation of the chopped strand mat in a wet-laid mat processing line.
Chopped glass
fibers are added to white water containing various surfactants, viscosity
modifiers,
defoaming agents, and/or other chemical agents with agitation to foiin a glass
fiber slui7y.
The sluriy is deposited onto a moving forming wire or foraminous conveyor to
form a web
of intermeshed fibers. Water is removed from the web by conventional vacuum or
air
suction system. A binder is applied to the web by a binder applicator. The
binder utilized
is not particularly limited, and may include any conventional one- or two-part
binder
compositions known to those of skill the art. A coupling agent is also applied
to the
surface of the web, either before or after the application of the binder. The
coupling agent
may be added to the web at any location prior to the web entering the diying
oven.
Suitable coupling agents include silane coupling agents and reactive
siloxanes. Preferably,
the coupling agent is one or more aminosilanes. Once the binder and coupling
agent have
been applied to the web, the web is passed tluough a diying oven to remove any
remaining
water and cure the binder composition.
It is another object of the present invention to provide a method of forming a
chopped strand mat that has improved hot wet tensile strengths in which a
coupling agent
is added to the white water in a wet-laid, chopped strand mat processing line.
Suitable
coupling agents include silane coupling agents and reactive siloxanes.
Preferably, the
coupling agent is one or more aminosilanes. Glass fibers are deposited into
the white
water containing the coupling agent(s) and any conventionally used
surfactants, viscosity
modifiers, defoaming agents and/or other suitable chemical agents to form a
glass slui7y.
The slurry is deposited onto a foraminous conveyor or wire mesh and a
substantial portion
of the water is removed, such as by a vacuum system. A binder is applied to
the web of
fibers, the web is conveyed to a diying oven where the remaining water is
removed, and
the binder is cured. The binder may be any conventional binder k.nown to those
of skill in
the art.
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It is an advantage of the present invention that chopped strand mats formed
according to any embodiment of the present invention as disclosed herein may
be formed
with fibers treated with a size composition that does or does not include a
coupling agent.
As a result, virtually any glass fiber may be utilized in forming the chopped
strand glass
mats of the present invention.
It is another advantage of the present invention that the two-part binder
composition of the present invention may utilized in a chopped strand mat
forming process
without having to change process parameters or modi~7 the equipment on
existing wet-laid
mat processing lines.
It is yet another advantage of the present invention that the application or
inclusion
of at least one coupling agent to the chopped strand mat during a wet-laid mat
forming
process improves the hot wet tensile strengths of the chopped strand mats.
It is a fi,trther advantage of the present that the inclusion of a coupling
agent or
agents to the chopped strand mat during the wet-laid process results in an
improvement in
the dty tensile strength of the formed shingles. As a result, perrnit
manufacturers can run
their shingle production lines at a faster rate with less tearing or "break
up" of the shingles
and increase productivity may be achieved by.
The foregoing and other objects, features, and advantages of the invention
will
appear more fully hereinafter from a consideration of the detailed description
that follows.
It is to be expressly understood, however, that the drawings are for
illustrative purposes
and are not to be constiued as defining the limits of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The advantages of this invention will be apparent upon consideration of the
?5 following detailed disclosure of the invention, especially when taken in
conjtuiction with
the accompairying drawings wherein:
FIG. I is a schematic illustration of a wet-laid processing line for fonning a
chopped strand mat utilizing a two-part binder composition according to at
least one
exemplary embodiment of the present invention; and
FIG. 2 is a schematic illustration of a wet-laid processing line for fomiing a
chopped strand mat depicting the application of a coupling agent to a web
according to at
least one exemplary embodiment of the present invention.
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DETAILED DESCRIPTION AND
PREFERRED EMBODIMENTS OF THE INVENTION
Unless defined otherwise, all technical and scientific terms used herein have
the
sanie meaning as conunonly understood by one of ordinaiy skill in the art to
which the
invention belongs. Although any methods and materials similar or equivalent to
those
described herein can be used in the practice or testing of the present
invention, the
preferred methods and materials are described herein. All references cited
herein,
including published or coiTesponding U.S. or foreign patent applications,
issued U.S. or
foreign patents, or any other references, are each incorporated by reference
in their
entireties, including all data, tables, figures, and text presented in the
cited references.
In the drawings, the thiclcness of the lines, layers, and regions may be
exaggerated
for clarity. It is to be noted that like numbers found throughout the figures
denote like
elements. It will be understood that when an element is refeiTed to as being
"on," another
element, it can be directly on or against the other element or intervening
elements may be
present. It is also to be understood that the term "web" and "mat" may be used
interchangeably herein.
The present invention relates to non-woven, wet-laid chopped strand glass mats
for
use in roofing applications that have improved hot wet tensile strengths. The
present
invention is predicated, at least in part, on the discoveiy that improved hot
wet tensile
strengths in chopped strand mats may be obtained by the application or
inclusion of at least
one coupling agent to the chopped strand mat during a wet-laid mat foiming
process.
Conventionally, a coupling agent has been added to the size forinulation
applied to the
glass fibers during the forination of the glass fiber.
The glass fibers used to form the chopped strand glass mats may be any type of
glass fiber, such as A-type glass fibers, C-type glass fibers, E-type glass
fibers, S-type
glass fibers, E-CR-type glass fibers (fof- exairaple, Advantex glass fibers
conunercially
available from Owens Corning), wool glass fibers, or combinations thereof. In
at least one
preferred embodiment, the glass fibers are wet use chopped strand glass fibers
(WUCS).
Wet use chopped strand glass fibers may be fonned by conventional processes
known in
the ai-t. It is desirable that the wet use chopped strand glass fibers have a
moisture content
of from 5 - 300/'o, and even more desirably a moisture content of fi=om 5 -
15%.
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The use of other reinforcing fibers such as mineral fibers, carbon fibers,
ceramic
fibers, natural fibers, and/or synthetic fibers such as polyester,
polyethylene, polyethylene
terephthalate, polyolefin, and/or polypropylene fibers in the chopped strand
glass mat is
considered to be within the purview of the invention. As used herein, the
tei7n "natural
fiber" is meant to indicate plant fibers extracted from any part of a plant,
including, but not
limited to, the stem, seeds, leaves, roots, or bast. The term "synthetic
fibers" as used
herein is meant to indicate any man-made fiber having suitable reinforcing
characteristics.
However, it is prefeiTed that all of the fibers in the chopped strand mat are
glass fibers.
The glass fibers may be foi-ined by conventional methods l:nown to those of
skill in
the art. For example, the glass fibers may be fonned by attenuating streams of
a molten
glass material from a bushing or orifice. The attenuated glass fibers may have
diaineters of
about 5 - 30 microns, preferably fi-om 10 - 20 microns. After the glass fibers
are drawn
from the bushing, an aqueous sizing composition is applied to the fibers. The
sizing may
be applied by conventional methods such as by an application roller or by
spraying the size
directly onto the fibers. The size protects the glass fibers from breakage
during subsequent
processing, helps to retard interfilament abrasion, and ensures the integrity
of the strands
of glass fibers, for example, the intercoiuiection of the glass filaments that
foi7n the strand.
The size composition applied to the glass fibers typically includes one or
more film
forming agents (such as a polyvinyl alcohol film foi-rner, cellulose film
foimer,
polytu=ethane film fonner, a polyester film former, and/or an epoxy resin film
former), at
least one lubricant, and at least one silane coupling agent (such as an
aminosilane or
methacryloxy silane coupling agent). The coupling agent chemically interacts
with the
glass fibers to couple the glass fibers with a binder or polymer matrix. When
needed, a
weak acid such as acetic acid, boric acid, metaboric acid, succinic acid,
citric acid, fonnic
acid, and/or polyaciylic acids may be added to the size composition to assist
in the
hydrolysis of the silane coupling agent. The size composition may be applied
to the glass
fibers with a Loss on Ignition (LOI) of approximately 0.05 - 2.0% on the dried
fiber. LOI
may be defined as the percentage of orgaiiic solid matter that remains on the
glass fiber
surfaces after heating them to a temperature sufficient to burn or pyrolyze
the organic size
from the fibers.
The inclusion of a coupling agent in the size composition requires that the
sized
fiber be aged a predetermined period of time to permit the coupling agent to
react with the
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fiber so that the cotipling agent is not washed away froni the fiber in the
white water slut7y
of a wet-laid mat fonning process such as is described in detail below. It is
hypothesized
that by removing the coupling agent fi-om the sizing composition applied to
the glass fibers
during fiber formation and applying or incozporating a coupling agent or
agents to the
chopped strand mat in the mat foi7ning line, the need to age the glass fibers
prior to
formation into a chopped strand mat may be reduced or eliminated. It is
believed that the
elimination of the coupling agent the size composition will result in fibers
having
improved stability and a longer shelf life. In addition, it is believed that
fibers sized with a
size that does not include a coupling agent would have the ability to be
iirunediately
utilized in a wet-laid process (for exanzple, directly from a glass forming
line), which
would decrease the total manufacturing time for the production of chopped
strand mats
and roofing shingles.
It is further hypothesized that by removing the coupling agent from the sizing
coniposition, the negative impact caused by chemical interactions between the
coupling
agent and the other chemicals in the size composition (for exafnple,
lubricants and
dispersants) will be eliminated and the efficiency of the remaining chemicals
in the size
will be increased. In particular, because there is little to no reaction with
the lubricants in
the size composition, it is believed that product dispersion performance will
be improved.
In conventional size compositions, the coupling agents react with the glass
fibers.
Occasionally, the coupling agent is highly reactive (such as aminosilane A-
1100 from GE
Silicones) and reacts with more than one glass fiber simultaneously. This
inter-reaction
between the glass fibers may cause a "clumping" or interconnection of the
glass fibers. By
removing the coupling agent froin the size composition, there is no active
agent remaining
within the size composition to react with the glass fibers and cause such
undesirable
"clumping". Therefore, a problem that was caused by the coupling agent in the
size (that
is, the intercomiection of the glass fibers by the coupling agent) is
eliminated by the
present invention.
After the fibers are treated with the sizing composition, they may be chopped
and
packaged in their wet condition as wet use chopped strand glass (WUCS) and
processed
into a wet-laid chopped strand mat as described below. It is to be appreciated
that the
chopped strand mats fotmed according to any embodiment of the present
invention as
disclosed herein may be forined with fibers treated with a size composition
that does or
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does not include a coupling agent. This is an advantageous feature in that
unlike
conventional wet-laid processes, virtually any glass fiber may be utilized in
forming the
chopped strand glass mats of the present invention. The cliopped glass fibers
may have a
length of 0.5 - 2.0 inches. Preferably, the chopped glass fibers have a length
of 1-1.5
inches.
In one embodiment of the invention, the coupling agent (or agents) is added to
the
chopped strand mat as part of a two-part binder composition. In particular,
the chopped
strand mat is fornied of a plurality of glass fibers held together in a sheet
form by a two-
part binder composition that includes a binder pre-mix and a coupling agent or
a coupling
agent package that contains two or more coupling agents.
An exemplaiy process of forming the chopped strand mat utilizing the inventive
two-part binder composition is illustrated in FIG. 1. Chopped glass fibers 10
may be
provided to a conveying apparatus such as a conveyor 12 by a storage container
14 for
conveyance to a mixing tanlc 16 that contains various surfactants, viscosity
modifiers,
defoaming agents, and/or other chemical agents with agitation to disperse the
fibers and
fonn a chopped glass fiber slurry (not shown). The glass fiber sluny may be
transfei7=ed to
a head box 18 where the slui7y is deposited onto a conveying apparatus such as
a moving
screen or foraminous conveyor 20 and a substantial portion of the water from
the sluny is
removed to form a fibrous web (mat) of intermeshed fibers 22. The water may be
removed
from the web (mat) 22 by a conventional vacuum or air suction system (not
shown). A
two-part binder composition 24 according to the present invention is then
applied to the
web by a binder applicator 26. The binder-coated web 28 is then passed through
a diying
oven 30 to remove any remaining water and cure the binder composition 24. The
cured
binder 24 provides integrity to the glass mat 32. The foimed non-woven chopped
strand
mat 32 that emerges from the oven 30 is formed of randomly dispersed glass
fiber
filaments. The non-woven chopped strand mat 32 may be rolled onto a take-up
roll 34 for
storage for later use as illustrated.
The two-part binder composition of the present invention may utilized in a
chopped strand mat forining process without having to change process
parameters such as
oven drying time, conveyor speed, etc. In addition, the inventive binder
composition may
be applied to the chopped strand mat in conventional wet-laid mat
manufacturing lines
without a modification of the existing equipment.
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The two-part binder composition is fornzed of a binder pre-mix and a coupling
agent or a coupling agent package containing two or more coupling agents. The
binder
pre-mix may include a modified or non-modified formaldehyde binder (for
exararple a
phenol-formaldeliyde binder), a modified urea-formaldehyde binder (for
exaiyrple,
modified with latex, styrene butadiene latex, a styrene/maleic anhydride
copolymer,
polyvinyl acetate, a vinyl aciylic copolymer, melainine, or melamine
derivatives), a non-
modified urea-foi7naldehyde binder, formaldehyde-free binders such as an
aciylic binder, a
styrene aciylonitrile binder, a styrene butadiene ilibber binder, polyvinyl
acetate binders,
vinyl aciylic binders, polyurethane binders, and combinations thereof. In
addition, the
binders may formed as a"one-part package" in which the binder is pre-mixed
with a
modi~7ing agent and packaged as a one component system or a"tNvo-part package"
in
which the binder and the modifying agent are not pre-mixed. In a prefeiTed
embodiment,
the binder is a standard urea-formaldehyde binder modified with a styrene
butadiene
rubber latex modifier such as DL 490NA (available con~unercially from Dow
Reichhold).
Examples of suitable binders for use in the binder pre-mix of the present
invention
include Bordon FG 472 (a urea-foitinaldehyde resin binder coinmercially
available from
Bordon Chemical Co.), GP ' -2984 (a modified urea-formaldehyde resin binder
available
from Georgia-Pacific), GP O-2948 (a modified urea-foi7naldehyde resin binder
available
from Georgia-Pacifc), and GP -2928 (a modified tuea-foi-rnaldehyde resin
binder
available from Georgia-Pacific). The binder pre-mix may be present in the
binder
composition in an amount of 40 - 80% by weight based on the active solids in
the binder
composition, and preferably from 55 - 70% by weight based on the active solids
in the
binder composition.
The inventive binder composition also includes at least one coupling agent. It
is to
be appreciated that the coupling agents described below may be utilized in any
of the
embodiments described herein. Aiiy suitable coupling agent identified by one
of skill in
the art may be utilized in the instant invention. The coupling agent or
coupling agent
package may be present in the binder composition in an ainount of 0.02 - 5.0%
by weight
based on the active solids in the binder composition, preferably in an amount
of 0.1 - 1.0
% by weiglit of the active solids in the binder composition, even more
preferably 0.1 -
0.5% by weight of the active solids in the binder composition, and most
preferably 0.2 -
0.5% by weight of the active solids in the binder composition.
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Preferably, at least one of the coupling agents is a silane coupling agent.
Examples
of silane coupling agents which may be used in the present size coniposition
may be
characterized by the fiinctional groups amino, epoxy, vinyl, methaciyloxy,
azido, ureido,
and isocyanato. Suitable silane coupling agents include, but are not limited
to,
aminosilanes, silane esters, vinyl silanes, methaciyloxy silanes, epoxy
silanes, sulfiir
silanes, ureido silanes, and isocyanato silanes. Specific non-lirniting
examples of silane
coupling agents for use in the instant invention include y-
aminopropyltriethoxysilane (A-
1100), n-phenyl-y-aminopropyltrim.ethoxysilane (Y-9669), n-trimethoxy-silyl-
propyl-
ethylene-diamine (A- 1120), methyl-trichlorosilane (A- 154), Y-chloropropyl-
trimethoxy-
silane (A-143), vinyl-triacetoxy silane (A-188), methyltrimethoxysilane (A-
1630). Other
examples of suitable silane coupling agents for are set forth in Table 1. All
of the silane
coupling agents identified above and in Table 1 are available conunercially
from GE
Silicones.
TABLE 1
Silanes Label Formula
Silane Esters
octyltriethoxysilane A-137 CH3(CH2)7(Si(OCH-2CH3)3
methyltriethoxysilane A-162 CH3Si(OCHzCH3)3
methyltrunethoxvsilane A-163 CH3Si(OCH3)3
proprietary A-1230 roprietaiy
tris-[3-(trimethoYysilyl) Y-
propyl] isocyanurate 11597
Vinyl Silanes
proprietai-y RC-1 proprietai-y
vinyltriethoxysilane A-151 CH2=CHSi(OCH2CH3)3
vinylh=imethoxysilane A-171 CH2=CHSi(OCH3)3
vinyl-tris-(2-methoxyethoxy)
silane A-172 CHz=CHSi(OCH,)CHZOCH3)3
Methaci lox Silanes
y-inethaciyloxypropyl- A-174 CH,=C(CH3)CO2CH2CH2CH~Si(OCH3)3
trimethoxysilane
Epoxy Silanes
/3-(3,4-epoxycyclohexyl)- Q
ethyltrimethoxysilane A-186 ~_CH2CH2Si(OCH3)3
y-glycidoxypropyltrunethoxy A /O\
silane -187 CH2CHCH2 OCH2CH2CH2Si(OCH3) j
Sulfur Silanes
y-mercaptopropyltrunethoxy A-189 HSCH,CH-,CHZSi(OCH3)3
silane
propi-ietary polysulfidesilane RC-2 proprietary
Aniino Silanes
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y-aminopropyltriethoxysilane A-1101 H2NCH2CH2CH2Si(OCH?CH3)3
A-1102
aminoalkvl silicone A-1106 (H2NC.H2CH2CH2SiO1.5)õ
modified aminoor anosilane A-1103 ---
A-1110 H,,NCHZCH~CH~Si(OCH3)3
amino ro yltrimethoxysilane
N /3-(aminoethyl)-y-
amino ro yltrimetliowsilane A-1120 H2NCH2CH2NHCH CH,CH,Si(OCH3)3
modified aminoorganosilane A-1126 ---
modified aniinosilaue A-112S ---
triamiiiofunctional silane A-1130 H2NCH2CH,NHCH,CH,NHCH2CH2CH2Si OCH3)3
bis-(y- A-1 170 HN -CH2CH2CH2 Si(OCH3)3
trimethoxysilylpropyl)amine '-CH2CH2 CH2 Si(OCH 3)3
oganomodified y- CH3SiO[CH3)2SiO],,[CH3SiO],,l[CH3SiO]zSiCH3)3
plydiniethylsiloxane 11343 1 1
NR2 NHIIt'Si(OR')3
plyazamide silatie A-1387 ---
Ureido Silanes
O
y-ureidopropyltrialkoxysilane A-1160 11
H2XCNHCH2CH~,CH2Si(OCH3 )x(OCH3CH2)3-,
~'- Y- ~
ureidopropyltrimethoxysilane 11542 H2nCHHC3 H6Si(OCHS)3
Isocyanato Silanes
y-isocyanatopropyltriethoxy A-1310 O=C=NCH2CH2CH2CH2Si(OCHJ,CH3)3
silane
The silane coupling agents used in the present invention may be replaced by
alternative coupling agents or mixtures. For exaniple, A-1387 may be replaced
by a
version in which the methanol solvent is replaced by ethanol. A- 1126, an
aminosilane
coupling agent including a mixture of approximately 24% by weight
diaminosilane
modified by a surfactant in a methanol solution (GE Silicones), may be
replaced with
trimethoxy-silyl-propyl-ethylene-diamine (Z-6020 from Dow Corning). A-1120 or
Z-6020
may be substituted by a pre-hydrolyzed version. Z-6020 may be replaced by Z-
6137, a
pre-hydrolyzed version lacking the alcohol solvent and including 33%
diaminosilane in
water at a concentration of 24% solids (commercially available from Dow
Corning). I
addition, A-1100 may be replaced by its hydrolyzed form Y-9244, which will
reduce or
eliminate the ethanol emission.
Vinyl aminosilanes, such as Z-6032 and Z-6224, both conunercially available
from
Dow Coi7iing, are also useful as coupling agents in the present invention. Z-
6032 is a 40%
silane solution in methanol. a specific gravity of 0.9% at 25 C, a refractive
index of 1.395
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WO 2007/024683 PCT/US2006/032320
at 25 C, and a viscosity of 2.2 at 25 C. The chemical formula is (CH5O)3-
SiCH2CH2CHzNHCH2CH2NHCHZ-O-CH=CH2-HCl and is designated N-2-(vinyl
benzylamino)-ethyl-3-anlino propyltrimethoxy silane-monohydrogen chloride. Z-
6224 has
a specific gravity of 0.88 at 25 C, a refractive index of 1.388 at 25 C and
is the
neutralized (chloride-free) version of Z-6032.
In addition, the coupling agent may include a functionalized organic substrate
(that
is, at least one organic functional group bonded to an organic substrate).
Exemplary types
of functionalized organic substrates include alcohols, ainines, esters,
ethers, hydrocarbons,
siloxanes, silazanes, silanes, silanols, lactams, lactones, anhydrides,
carbenes, nitrenes,
orthoesters, imides, enamines, imines, amides, imides, and olefins. The
fiuictionalized
organic substrate is capable of interacting and/or reacting with the surface
of the glass
fibers to provide sufficient coupling or bonding between the glass fibers and
the binder
material. In particular, one end of the molecule reacts or interacts with the
glass surface
and the other end of the molecule reacts or interacts with the binder. By
choosing one or
more suitable functionalized organic substrates for the coupling agent system,
desired
mechanical properties between the glass fibers and the binder can be obtained.
Another example of compounds useful as coupling agents in the present
invention
include silicon contaiiiing coupling agents (for exaiizple, silane, silanol,
and/or siloxane)
tailored or functionalized with an organic polymer. For example, silanes
tailored with
polyurethane are capable of perfonning coupling agent fiuictions to bond the
glass fiber
and the binder. Another example includes a silanol tailored or functionalized
with a
polyamide. It is believed that in this example, if the amine is neutralized, a
cationic charge
forms on the amine, permitting an ionic bond to form between the amine and the
glass
fiber. The organic portion of the molecule, that is, the organic polymer, then
covalently
bonds with the binder.
Reactive siloxanes may also be utilized as coupling agents. Examples of
reactive
siloxanes include DC-1171, DC-75SF, aiid DC-2-7887, all conlniercially
available from
Dow Corning. Reactive siloxanes are thought to be linear or branched
stiuctures with the
following monomeric units (I):
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R1 R2 R3
I l I
Si-0-Si-O-Si
R4 R5 R6 J n
(I>
Rl, R2, R3, R4, R5, and R6 may differ from one monomeric unit to another and
may
be an alkyl (preferabl), a methyl group) or a hydride. When branched, Rl, R2,
R3, R4, R5,
and R6 may be formed of one or more monomeric units (I). The reactivity of
reactive
siloxanes and their ability to act as blocking agents increases with increased
number of
hydride groups for Rl, R2, R3, R4, R5, and R6.
The binder composition may also contain a trace amount of a weak organic acid
such as acetic acid, foi7nic acid, succinic acid, and/or citric acid hydrolyze
the silane in the
coupling agent. It is prefei7=ed that the organic acid is acetic acid. The
organic acid may be
present in the binder composition in an amount of from 0.1 - 1.0% by weight of
the binder
composition, preferably 0.3 - 0.6% by weight of the binder composition.
In addition, the binder composition may optionally contain conventional
additives
for the improvement of process and product performance such as fire
retardants, dyes, oils,
fillers, colorants, UV stabilizers, lubricants, wetting agents, surfactants,
and/or antistatic
agents.
In a second embodiment of the present invention, the coupling agent (or
coupling
agents) is separately added to the web of chopped fibers during the formation
of the
chopped strand mat in a wet-laid mat processing line. One eYemplaiy process of
separately adding the coupling agent to the chopped strand mat is depicted in
FIG. 2.
Chopped glass fibers 10 may be provided to a conveying apparatus such as a
conveyor 12
by a storage container 14 for conveyance to a mixing tank 16 that contains
various
surfactants, viscosity modifiers, defoaming agents, and/or other chemical
agents with
agitation to,disperse the fibers and foi7n a chopped glass fiber sluriy (not
shown). The
glass fiber s1u.wTy may be transferred to a head box 18 where the slui7y is
deposited onto a
conveying apparatus such as a moving screen or foraminous conveyor 20 and a
substantial
portion of the water from the slui-ly is removed to form a web (mat) 22. The
water may be
removed fi=om the web 22 by a conventional vacuum or air suction system (not
shown).
A binder 24 is applied to the web 22 by a binder applicator 26. The binder
utilized
is not particularly limited, and may include any conventional one- or two-part
binder
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WO 2007/024683 PCT/US2006/032320
conzpositions laiown to those of skill the art. A coupling agent 36 may then
be applied to
the web (mat) 22 by a suitable applicator 38 such as a spray applicator or a
curtain coater.
The coupling agent 36 may be added to the fibrous web 22 in an amount up to
approximately 1% by weiglit of the mat 22. Ttie coupling agent may be any one
or more
of the coupling agents described in detail herein. The coupling agent(s) 36
may be in the
form of a liquid, a sluny, an emulsion, or a foam. Preferably, the coupling
agent 36 is a
liquid. Although FIG. 2 depicts the coupling agent 36 being added after the
binder 24, the
coupling agent 36 may be added prior to the application of the binder 24
(embodiment not
illustrated in FIG. 2). In fact, the coupling agent 36 may be added to the web
22 at any
location prior to the web 22 entering the oven 30. Once the binder 24 and
coupling agent
36 have been applied to the mat 22, the mat 22 is passed tlu=ough a diying
oven 30 to
remove any remaining water and cure the binder composition 24. The foi7ned non-
woven
chopped strand mat 32 that emerges from the oven 30 may be rolled onto a take-
up roll 34
for storage for later use as illustrated.
In at least one preferred embodiment of the invention, the chopped strand mat
32
depicted in FIGS. 1 and 2 is used to fonn a roofing shingle. To foi7n a
roofing shingle,
asphalt is applied to the chopped strand mat 32, such as by spraying the
asphalt onto one or
both sides of the mat or by passing the mat through a bath of molten asphalt
to place a
layer of asphalt on both sides of the chopped strand mat 32 and fill in the
interstices
between the individual glass filaments. The hot asphalt-coated mat may then be
passed
beneath one or more granule applicators which apply protective surface
granules to
portions of the asphalt-coated mat prior to cutting into the desired shape.
The coated mat
is then cut to an appropriate shape and size to form the shingle. It is to be
appreciated that
the application of asphalt to the glass strand mat 32 may be conducted in-line
with a wet-
laid mat-foi-niing processing line such as is depicted in FIGS. 1 or 2 or in a
separate
processing line.
In a third embodiment of the present invention, the coupling agent is added to
the
white water in a wet-laid, chopped strand mat processing line such as is
illustrated in FIG.
1. Thus, the white water (such as may be contained in the mixing tank 16
depicted in FIG.
1) contains the surfactants, viscosity modifiers, defoaming agents, and/or
other chemical
agents conventionally utilized in the white water as well as one or more of
the coupling
agents described above. The wliite water containing the glass fibers and
coupling agent is
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WO 2007/024683 PCT/US2006/032320
agitated to form a glass fiber sluiTy. The coupling agent is deposited onto
the glass fibers
in the white water and incoiporated into the formed glass mat via the glass
fibers. The
glass fiber sluL-ty is then deposited onto conveying apparatus such as a wire
screen or
foraminous conveyor and a binder is applied. The binder is not particularly
limited and
includes any conventional binder suitable for use in a wet-laid mat forming
process. The
binder is then cured, such as in an oven, to form the chopped strand mat.
Although the inclusion of a coupling agent or agents to the white water
results in
the addition of the coupling agent to the chopped strand mat, adding a
coupling agent to
the white water may be cost-prohibitive due to the large amount of coupling
agent that
would have to be added to the white water for adhesion onto the glass fibers
and the high
cost of the coupling agents.
It is to be appreciated that the coupling agent may be added to the chopped
strand
mat by one or more of the embodiments described above. For example, it may be
desirable in some instances to add a coupling agent to the chopped strand mat
via the two-
part binder composition and to add a coupling agent to the sasne chopped
strand mat
independent of the binder composition by a separate applicator. Alternatively,
it may be
desirable to add a coupling agent to the white water and also add a coupling
agent via the
two-part binder composition. The application or inclusion of a coupling agent
(or agents)
to a chopped strand mat by any combined embodiments described herein are
considered to
be within the purview of the invention.
As discussed above, the application or iiiclusion of at least one coupling
agent to
the chopped strand mat during aNvet-laid mat foi7ning process improves the hot
wet tensile
strengths of the chopped strand mats. The ability of a shingle to resist water
degradation is
a desired property if the shingle is to have long teml perfonnance. An
estimate of the long
ternz perfonnance of shingles is typically detei7nined in the industry by
obtaiiiing the hot
wet tensile strengths of the chopped strand mats forming the shingles. It is
believed that
the hot wet tensile strength performance of the chopped strand mat coiTelates
to the
performance of the shingle. For example, an increase or improvement in the hot
wet
tensile strength results in an increase or improvement in the long tei~rn
perfoimance in the
shingle, whereas a decrease in the hot wet tensile strength results in a
decrease in the
performance of the shingle. Therefore, it is believed that adding a coupling
agent(s) to the
chopped strand mat during the wet-laid process as in the present invention,
which
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WO 2007/024683 PCT/US2006/032320
improves the hot wet tensile strength of the chopped strand mat, would result
in shingles
having inlproved lifetime performance.
Additionally, including at least one coupling agent to the chopped strand mat
during the wet-laid mat forming process increases the dzy tensile strength of
a shingle
formed from that mat. This increase in tensile strength may permit
manufacturers to run
their production lines at a faster rate with less tearing or "break up" of the
chopped strand
mats. As a result, an increase in the productivity may be achieved by the
inclusion of a
coupling agent or agents to the chopped strand mat during the wet-laid
process.
Having generally described this invention, a fiirther understanding can be
obtained
by reference to certain specific examples illustrated below which are provided
for puiposes
of illustration only and are not intended to be all inclusive or limiting
unless otherwise
specified.
Examples
Example 1: Hot Tensile Strength Retention of Chopped Strand Glass Mats
Formed With Two-Part Inventive Binder Compositions
Binder compositions set forth in Tables 2 - 6 were prepared in buckets as
described
generally below. In particular, Control Binder Composition A (Table 2) was
prepared by
mixing the urea-formaldehyde resin (Bordon FG 472 from Bordon Chemical Co.),
the
latex binder (DL 490NA from Dow Reichhold), and water.
Binder pre-mixes for inventive Binder Compositions B - E (Tables 3 - 6) were
prepared by mixing the urea-foi7naldehyde resin (Bordon FG 472), latex binder
(DL
490NA from Dow Reichhold), and water. Acetic acid and water were mixed to
forin an
acidic solution. Aininosilanes A- 1100 and Y-9669 (GE Silicones) were added to
the
acidic solutions as designated in Tables 3 - 6 and moderately agitated to
permit
hydrolyzation. The hydrolyzed aminosilane(s) were then added to the binder pre-
mixes
with agitation to foi7n Binder Compositions B - E. Once formed, Binder
Compositions B
- E were diluted with water to achieve the target mix solids of approximately
50.00%.
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WO 2007/024683 PCT/US2006/032320
TABLE 2
Binder Com osition A (Control)
Components of Binder Com osition % by wei lit of the active solids
Bordon FG 472( ) 69.23
DL 490NA(') 10.87
W ater 19.90
(a) urea-formaldehyde resin (Bordon Chemical Co.)
(b) styrene butadiene rubber latex modifier (Dow Reichhold)
TABLE 3
Binder Composition B
Components of Binder Composition % by wei ht of the active solids
Bordon FG 472(a) 69.23
DL 490NA(') 10.87
Water 19.90
A-1100( ) 0.17
Acetic Acid 0.40
(a) urea-formaldehyde resin (Bordon Cheinical Co.)
(b) styrene butadiene rubber latex modifier (Dow Reichhold)
(c) y-amulopropyltriethosysilane (GE Silicones)
TABLE 4
Binder Composition C
Components of Binder Composition % by weight of the active solids
Bordon FG 472(a 69.23
DL 490NA(') 10.87
Water 19.90
A-1100' ) 0.43
Acetic Acid 0.40
(a) urea-formaldehyde resui (Bordon Chemical Co.)
(b) styrene butadiene rubber latex modifier (Dow Reichhold)
(c) y-aminopropyltriethoxysilane (GE Silicones)
TABLE 5
Binder Coin osition D
Coinponents of Binder Composition % by Nveight of the active solids
Bordon FG 472~a) 69.23
DL 490NA(b) 10.87
Water 19.90
Y-9669( ) 0.10
Acetic Acid 0.40
(a) urea-forinaldehyde resin (Bordon Cheniical Co.)
(b) styrene butadiene rubber latex modifier (Dow Reichhold)
(c) n-phenyl- y-aminopropyltrimethoxysilane (GE Silicones)
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TABLL 6
Binder Coni osition E
Coni onents of Binder Composition % by wei lit of the active solids
Bordon FG 472(') 69.23
DL 490NA(') 10.87
Water 19.90
A-1100( ) 0.17
Y-9660) 0.10
Acetic Acid 0.40
(a) urea-fornialdehyde resin (Bordon Clieznical Co.)
(b) styrene butadiene rubber latex modifier (Dow Reichliold)
(c) 7-aminopropyltrietlioxysilane (GE Silicones)
(d) n-phenyl- -y-aminopropyltrimethoxysilane (GE Silicones)
E-type chopped strand glass fibers sized with a conventional sizing
composition
containing one or more film forniing agents, at least one lubricant, and at
least one
coupling agent were foi7iied into chopped strand glass mats on a sheetfoi7ner
using Binder
Compositions A - E. The chopped strand glass fibers had a length of 7/8 of an
inch and a
percent moisture of 10.92%. A chopped strand mat using Binder Composition A
(Control)
was replicated to confirm the reproducibility of the foiming process and the
data for the
average of the two tests were used as data in Tables 7 and 8 for Binder
Composition A. 2
inch wide test specimens of the chopped strand mats containing Binder
Compositions A -
E were then evaluated for wet tensile strength on an Instron tensile testing
apparatus. Each
of the chopped strand mat samples were soaked in 180 F water for 10 minutes
prior to
testing for wet tensile strength. The test results are set forth in Table 7.
The chopped strand mat saniples using Binder Compositions A - E were then
formed into shinglets on an asphalt coating mimic line. The sliinglet samples
were tested
for tear strength in the cross machine direction (CD) on an Elmendorf tear
testing
apparatus according to the testing procedures set forth in ASTM D3462. The
results are
set forth in Table 8.
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TABLE 7
Chopped Strand Mat Properties
Binder ginder Binder Binder Binder
Comp. A Comp. B Comp. C Comp. D Comp. E
(Control)
LOI (%) 19.05 16.86 17.57 17.98 19.32
Basis Weiglit 2.06 2.05 1.98 1.97 1.97
Dry Tensile Stren h(Ib/2in) (nID) 91.5 85.0 84.0 75.0 83.0
Hot Wet Tensile Stren li (lb/2in) 27.3 42.1 44.8 37.1 41.5
Retention of Stren h%) 29.9 49.5 53.3 49.5 50.0
Change (%) in wet tensile strength 65.6 78.3 65.6 67.2
froin Binder Com . A (Control)
Amount of Silane in Binder Comp. 0.00 0.20 0.50 0.20 0.40
(% diy solids basis)
TABLE 8
Tear Strength Shinglet
Binder Binder Binder Binder Binder
Comp. A Comp. B Comp. C Comp. D Comp. E
(Control)
Tear Strengtli (g) (CD) 994.5 1064 1072 1083 1026
Change ( /o) in tear strength fi=oin 1,0 7.8 8.9 3.2
Binder Comp. A (Control)
As shown in Table 7, the chopped strand mats formed with inventive Binder
Compositions B - E demonstrated a marked improvement in wet tensile strength
over the
cutTent state of the art. As discussed above, an estimate of the long terni
perforinance of
shingles is detei7nined in the industiy by determining the hot wet tensile
strength of the
chopped strand mats forming the shingles. It is believed that high hot wet
tensile strength
perfoimaiice of the chopped strand mat is related to better long teim
perfoi7nance of the
shingle. The results set forth in Table 7 illustrates that the chopped strand
mats formed
with the inventive binder compositions had outstanding wet tensile strengths
compared to
the current state of the art (Binder Composition A). Thus, it is believed that
shingles
formed from chopped strand mats foimed utilizing the inventive binder
composition
would have improved long teim performance.
In addition, this improvement in the hot wet tensile strengths of the chopped
strand
mats is achieved without a decrease in the shingle tear strength, as shown in
Table S. This
result is an unexpected feature since the addition or increase of a coupling
agent in a size
foi7nulation for chopped glass fibers commonly results in a reduction in the
shingle tear
strength.
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Examnle 2: Hot Tensile Strengths of Chopped Strand Glass Mats and
Shinalets Formed With Two-Part Inyentive Binder Comnositions
E-type chopped strand glass fibers sized with a conventional sizing
composition
containing one or more film forming agents, at least one lubricant, and a
coupling agent
were formed into chopped strand glass mats on a sheetformer using Binder
Compositions
A, B, and D set fortll in Tables 2, 3, and 5 respectively. The chopped strand
glass fibers
had a length of 1 1/4 inches and a percent moisture of 13.22%. A chopped
strand mat
using Binder Composition A (Control) was replicated to confirtn the
reproducibility of the
forming process and the data for the average of the two tests were used as
data in Tables 9
and 10 for Binder Composition A. 2 inch wide test specimens of the chopped
strand mats
containing Binder Compositions A, B, and D were then evaluated for wet tensile
strength
on an Instron tensile testing apparatus. Each of the chopped strand mat
samples were
soaked in 180 F water for 10 minutes prior to testing for wet tensile
strength. The test
results are set forth in Table 9.
The chopped strand mat samples using Binder Compositions A, B and D were then
formed into shinglets on an asphalt coating mimic line. The shinglet saniples
were tested
for tear strength in the cross machine direction (CD) and machine direction
(MD) on an
Elmendorf tear testing apparatus according to the testing procedures set forth
in ASTM
D3462. The shinglet samples were also tested for dry tensile strength in the
machine
direction (MD) on an Instron tensile testing apparatus. The results are set
forth in Table
10.
TASLE 9
Chop ed Strand Mat Properties
Binder Binder Binder
Comp. A Comp. Comp.
(Control) B D
LOI (%) 18.29 19.04 18.31
Basis Weight 1.89 1.91 1.86
Diy Tensile Stren h(Ib/2ui) (MD) 110.5 112.0 107.0
Hot Wet Tensile Strength (lb/2in) 45.7 57.7 51.6
Retention of Stren h(%) 41.4 51.5 48.2
Cliange (%) ui wet teiisile strength from Binder Comp. A 24.4 16.4
(Control)
Amount of Silane in Binder Com .(% diy solids basis) 0.00 0.20 0.20
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TABLE 10
Teat= Stren li Shin let
Binder Binder Binder
Comp. A Comp. Comp.
(Control) B D
Tear Stren li O(CD) 1759 1733 1706
Tear Strength ()(MD) 1343 1223 1317
Total Tear Stren IZ 3101 3068 30S4
Clian e(%) in tear stren h from Binder Com . A(Control) -1.1 -0.5
Tensile Stren hO(MD 239 263.0 268.0
Chan e(% ui Tensile Stren li from Binder Com . A (Control) 10.0 12.1
As shown in Tables 9 and 10, the inclusion of a coupling agent in Binder
Compositions B and D improved the hot wet tensile retention of the chopped
strand mats
with little impact on the tear strength. In addition, as illustrated in Table
10, the inclusion
of a coupling agent in the inventive binder compositions used in foi7ning the
chopped
strand mats demonstrated a positive and significant effect on the shingle diy
tensile
strength (MD) with a minimal and statistically insignificant change in the
total tear
strength. This improvement in the diy tensile strength will pei7nit
manufacturers to run
their shingle production lines at a faster rate with less tearing or "break
up" of the shingles.
As a result, an increase in productivity may be achieved by the inclusion of a
coupling
agent or agents to the chopped strand mat during the wet-laid process.
Example 3: Hot Tensile Strengths of Chopped Strand Glass Mats and
Shinglets Formed With Two-Part Inventive Binder Compositions
E-type chopped strand glass fibers sized with a conventional sizing
composition
contaiiiing one or more film foiming agents, at least one lubricant, and at
least one
coupling agent were fonned into chopped strand glass mats on a sheetformer
using Binder
Coinpositions A, B, and D set forth in Tables 2, 3, and 5 respectively. The
chopped strand
glass fibers had a length of 1 1/4 inches and a percent moisture of 13.69%. A
chopped
strand mat using Binder Composition A (Control) was replicated to confirm the
reproducibility of the foi-ining process and the data for the average of the
two tests Nvere
used as data in Tables 11 aiid 12 for Binder Composition A. Wet tensile
strength of the
chopped strand mats were deterinined according to the procedure set forth in
EYainple 2
above. The test results are set forth in Table 11. Shinglet samples were then
formed and
tested for tear strength in both the machine direction (MD) and in the cross
machine
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direction (CD) and diy tensile strength as described in Example 2 above. The
results are
set forth in Table 12.
TABLE 11
Chopped Strand Mat Pro erties
Binder Binder Binder
Couip. A Coinp. Comp.
(Control) B D
LOI %) 18.7 19.65 17.81
Basis Wei lit 1.88 1.80 1.92
Diy Tensile Stren h(lb/2.in) MD) 112.0 105.5 108.0
Hot Wet Tensile Stren h(lb/2in) 57.5 68.3 59.6
Retention of Strength (%) 51.3 65.0 55.1
Cllange (%) in wet tensile sti-ength from Binder Comp. A 26.7 7.4
(Control)
Amount of Silane in Binder Com .(% diy solids basis) 0.00 0.20 0.20
TABLE 12
Tear Strength Shinglet
Binder Binder Binder
Coinp. A Coinp. Comp.
(Control) B D
Tear Sh=eno-th (g) (CD) 1801 1715 1839
Tear Strength (g) (NID 1416 1182 1331
Total Tear Strength 3217 3244 3230
Change (%) in tear strength from Buider Comp. A(Control) 0.8 0.4
Tensile Sh=en hO(MD) 221.0 251 239.0
Change (%) in Tensile Strength from Binder Comp. A 13.6 8.1
(Coiih=ol)
As shown in Tables 11 and 12, the inclusion of a coupling agent in the
inventive
binder compositions improved the hot wet tensile retention of the chopped
strand mats
with little impact (minimal impact) on the tear strength. In addition, as
illustrated in Table
12, the inclusion of a coupling agent in Binder Compositions B and D used to
foim the
chopped strand mats demonstrated a positive improved effect on the shinglet
dry tensile
strength (MD). As discussed above in Example 2, improvement in the tensile
strength of
the shingle will permit manufacturers to run their shingle production lines at
a faster rate
with less tearing or "break up" of the shingles. As a result, an increase in
productivity may
be achieved by the inclusion of a coupling agent or agents to the chopped
strand mat
during the wet-laid process.
The invention of this application has been described above both generically
and
with regard to specific embodiments. Although the invention has been set forth
in what is
believed to be the preferred embodiments, a wide variety of alternatives known
to those of
24
CA 02617777 2008-02-01
WO 2007/024683 PCT/US2006/032320
skill in the at-t can be selected within the generic disclosure, including by
way of example,
using this invention in the process of forming a continuous filatnent mat, a
diy laid mat, or
any other fibrous mat having a similar binder system. The invention is not
otherwise
limited, except for the recitation of the claims set forth below.
