Title of Invention

CONTINUOUS FILAMENTS MAT BINDER SYSTEM

Abstract A continuous filament glass mat (50) comprising: a mat of continuous glass filaments such as herein described and a binder applied to said mat, said binder including a phenolic compatible silane such as herein described and a polyvinyl acetate copolymer such as herein described.
Full Text CONTINUOUS FILAMENT MAT BINDER SYSTEM
TECHNICAL FIELD AND INDUSTRIAL
APPLICABILITY OF THE INVENTION
The present invention relates generally to continuous filament mats and more
specifically to a binder system for a continuous filament mat.
BACKGROUND OF THE INVENTION
Continuous filament mats are widely known and are used as one component in
fiber reinforced composite parts.
To make a fiber reinforced phenolic resin part having a continuous filament mat,
the continuous filament mat must first be produced. Traditionally, the continuous fiber
mat is produced by first introducing a sizing to the continuous glass fiber by known
methods. A polyester binder system is then introduced to the sized fiber using a curtain
coater or some similar technique to flood the glass fiber. The flooded sized fiber is then
dried in an oven to form the continuous filament mat. The mat and a glass roving(s) are
then subsequently wetted with a phenolic resin, typically by running the mat and roving
through a phenolic resin bath. The wetted mat and glass roving are then introduced into a
heated pultrusion die. The die shapes the mat and glass roving into a resin/glass composite
that is then cured to form a pultruded part.
One problem with known methods is that the polyester binder materials used to
form the continuous filament mats are not fully compatible with the phenolic resins that
form the resin matrix. This affects the performance of the composite part.
It is thus highly desirable to make a binder system that is fully compatible with the
phenolic resin bath, thereby forming fiber reinforced phenolic resin composite parts having
potentially superior performance characteristics.
SUMMARY OF THE INVENTION
One object of the invention is to make a binder system that is fully compatible with
the phenolic resin bath, thereby forming fiber reinforced phenolic resin composite part
having potentially superior performance characteristics.

The present invention uses a powdered bisphenol epoxy with a thermally active
crosslinking agent (dicyandiamide) dispersed into a flooding liquid preferably having a
non-ionic surfactant, a silane, a defoaming agent, and water. An organic acid is also added
for pH control. The powder binder and flooding liquid act as a system to bind the
multiplicity of glass fibers into a mat. As the powdered bisphenol epoxy and thermally
active crosslinking agent are compatible with the phenolic resin, as compared with
traditional unsaturated polyester binder systems which are not compatible, pultruded parts
having improved performance characteristics are realized.
In addition, the continuous filament mat formed in the above process could also be
used in an epoxy application using a prepreg type process to form a laminate material that
could be subsequently press molded to form a composite laminate part.
Other objects and advantages of the present invention will become apparent upon
considering the following detailed description and appended claims, and upon reference to
the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a schematic diagram of a process for making a continuous filament mat
according to a preferred embodiment of the present invention;
Fig. 2 is a schematic diagram for making a pultruded composite part from the
continuous filament mat of Fig. 1 according to a preferred embodiment of the present
invention; and
Fig. 3 is a schematic diagram for making an epoxy prepreg tape from the
continuous filament mat of Fig. 1 according to another preferred embodiment of the
present invention.
Fig. 4 is a schematic diagram depicting a urethane resin injection system according
to another preferred embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to Fig. 1, a preferred assembly process for forming a continuous
filament mat 50 is generally shown as 10. One or more strands of a continuous filament
fiber 12 are formed in a furnace 14 by melting a quantity of glass or other reinforcing
material, typically in the form of marbles, in a manner that is well known in the art. A

ng composition 18 is introduced to the one or more strands of fiber 12. The sizing
composition 18 preferably contains a phenolic compatible silane and a lubricant that is
introduced to the fiber 12 by roll application, dipping, flooding or by any other method that
is known in the art. A preferred composition of the sizing composition 18 is listed below
in Table 1.
The sized fibers 12 are then formed together into one continuous strand 13 by a
pair of pulleys 14A and 14B. The continuous strand 13 may also be split into a multiple
number of bundles or splits (n=2-30), and is hereinafter referred to as continuous strand 13
for ease of description. The continuous strand 13 is placed onto a moving belt 16. The
continuous strand 13 is then moved along the moving belt 16 and flooded with continuous
filament mat ("CFM") binder slurry 24. The CFM binder slurry 24 comprises a powdered
polymer binder material with a thermally active cross-linking agent dispersed in water
with a small percentage of phenolic compatible silane. An antifoaming agent and
dispersant are also typically added to the slurry. A preferred composition of the slurry is
listed below in Table 2.
The CFM binder slurry 24 that is formed is then delivered from a sump tank 26 to a
curtain coater 28 wherein the mixture floods the continuous strand 13. The excess liquid is
removed from the strand 13 by suction. The strands 13 are then transferred to an oven 15
for moisture removal and curing and then pressed in a plurality of presses 16 to form a
binded filament mat 50. Preferably, the oven 15 is set between approximately 450-520
degrees Fahrenheit. Upon exiting, the binded filament mats 50 are then slit by a slitter 30,
cut to a preferred size by a cutter 32, and rolled onto a cardboard tube 34. The binded
filament mats 50 rolled onto the cardboard tube 34 are loaded with the CFM binder in a
range of 4-8% of the dry total weight of the binder and matting.
The binded mats 50 that are formed above are then available to be combined with a
plurality of glass rovings 52 to form a composite phenolic pultruded part 60. This is
depicted in Fig. 2. First, the mats 50 and a plurality of glass rovings 52 are dipped through
a phenolic bath 54. The phenolic bath 54 that is used is well known in the art and is
compatible with the mats 50 having the CFM binder. For example, one preferred phenolic
pultrusion resin for use in the phenolic pultrusion bath 30 is Georgia Pacific's 289D17
phenolic resin.

The mats 50 and rovings 52 are then introduced into a heated pultrusion die 56.
The heated pultrusion die 56 cures the resin/glass composite into composite part 60. The
time and temperature within the heated pultrusion die 56 are to ensure that the composite
part 60 formed is fully cured. Preferably, the temperature within the heated pultrusion die
56 is between approximately 375 and 450 degrees Fahrenheit and the time is sufficient to
ensure a fully cured part.
In an alternative embodiment, the phenolic bath 54 may be replaced with a
urethane resin injection system 74, as shown in Fig. 4. The urethane resin injection system
includes an injector box 76 for injecting resin onto the mats and rovings prior to them
entering the pultrusion die 56. Resin is supplied from a resin mixing box 78 which is
typically connected to a metering pump (not shown) from which the resin components are
fed from one or more supply pumps (not shown).
The urethane resin composition, like the phenolic resin composition, is compatible
with the CFM binder contained within the mat 50. The curing temperature for the
urethane composite part formed within the heated pultrusion die 56 is typically lower than
that of the phenolic composite part 56, with preferred temperatures between approximately
250 and 350 degrees Fahrenheit.
In an alternative preferred embodiment, as shown in Fig. 3, an epoxy type prepreg
70 may be produced from the mats 50 formed above. In this process, the fibers 12 are run
through the sizing composition 18 and the CFM slurry bath 24 to form the binded mat 50
as described above in Fig. 1. The mats 50 are then dipped in an epoxy bath 62 and
prestaged in an oven 64 to form the epoxy prepreg 70. Preferably, the oven 64 is set for
between 300 and 400 degrees Fahrenheit and the line speed is set sufficient to cure the
epoxy prepreg, typically around 5-10 minutes. The layers of the epoxy prepreg 70 are then
pressed together in a press 66 to form a composite part 72. This composite part 72 may be
used in a wide variety of applications such as electrical laminates that are well known in
the art.
One preferred example of an epoxy bath 62 that may be used in the present
invention is discussed in Tables 1 and 2 of G.A. Hunter's 1988 Article "Pultruding Epoxy
Resin", presented at the 43rd Annual Conference sponsored by The Society of Plastics
Industry, Inc., which is herein incorporated by reference.
Mat and Roving Material

The mat 50 material is preferably a continuous filament glass fiber material. This
may include s-type glass fibers or e-type glass fibers, and other commercially available
glass fibers that are well known in the art. In the preferred embodiment of the present
invention, e-type glass is used.
The roving 52 material is also preferably a continuous filament glass fiber material.
This may include s-type glass fibers or e-type glass fibers, and other commercially
available glass fibers that are well known in the art. In the preferred embodiment of the
present invention, e-type glass is used. In addition, the method for making the glass roving
material may include any method that is well known in the art.
Sizing composition
The sizing composition 18 is made by mixing a phenolic compatible silane in
water. The pH of the resultant mixture is then adjusted to between 4 and 6 by adding an
acid such as acetic acid. One preferred silane that may be used is a gamma-aminopropyl
trimethoxy silane such as Witco-OSI's A-1100. At least one lubricant is added to the
resultant mixture and the pH is once again adjusted to between 4 and 6 using acetic acid.
Two preferred lubricants are Cirrosol 185AE and 185AN, each manufactured by ICI
America. Cirrosol 185AE is a octanoic (caprylic) acid-tetraethylene pentamine condensate
solubulized with acetic acid, while 185AN is a (pelargonic) acid-tetraethylene pentamine
condensate solubulized with acetic acid. A preferred sizing composition 18 is shown
below in Table 1:


CFM Binder Slurry
Current binder materials use unsaturated polyester binders that have shown
unacceptable performance in phenolic pultrusion systems. It is believed that the polyester
binders do not provide a compatible interface with the phenolic binder resins. The CFM
binder system of the present invention solves this problem by providing a compatible
interface.
The CFM binder slurry 24 is prepared by dispersing a powdered polymer resin
having a thermally active cross-linking agent into the liquid portion of the slurry 24. One
preferred powdered polymer resin having a thermally active cross-linking agent is a
bisphenol type epoxy resin with a thermally active dicyandiamide cross-linking agent such
as Pretex 110, manufactured by Reichold. The powdered polymer is fed at a constant flow
rate to deliver the concentration above. This material is fed into a sump tank with high
agitation to keep the powder dispersed in the flooding liquid.
One or more non-ionic surfactants are typically added as a dispersant and as a
defoamer. Preferably Triton X-100 (Union Carbide, a division of Dow Chemical, Danbury
,CT) is used as the surfactant and Foamex AD-300 (Rhodia Inc., Cranbury, NJ) is used as
the defoamer. Also, a phenolic compatible silane is added to the resultant mixture.
Preferably, this silane is Witco-OSFs A-1100 silane. Finally, the pH is adjusted to between
4 and 6 using acetic acid.
The composition contains the following materials with the preferred ranges: 0 to
about 6 percent by weight cross-linking agent; 0 to about 5 percent by weight nonionic
surfactant; 0 to about 3 percent by weight acetic acid; 0 to about 3 percent by weight
silane; and 0 to about 3 percent by weight defoamer. Water is added to bring the total
percent by weight of the composition to 100%.
Table 2 discloses an example of the prepared binder slurry as well as the most
preferable ranges of materials added to the binder slurry.


Alternatively, another preferred composition of the CFM binder can be used.
Surprisingly, it has been determined that a polyvinyl acetate copolymer (PVAC/Silane
copolymer) provides a more compatible interface for phenolic resin systems. The PVAC is
added prior to the delivery to the sump tank.
In the present invention, Vinamul 25-1037 PVAC copolymer (Vinamul Polymers,
Woodruff, SC) is preferably used. Other alternative compositions include QRXP 1629A
(Rohm & Haas, Philadelphia, PA), a polycarboxylic acid/polyhyrdric alcohol and Vinamul
25-028A (Vinamul Polymers, Woodruff, SC), a self-crosslinking acrylic copolymer. The
composition is made as described above; however, a cross-linking agent is not added. The
composition contains the following materials with the preferred ranges: 0 to about 10
percent by weight PVAC copolymer; 0 to about 5 percent by weight nonionic surfactant; 0
to about 3 percent by weight acetic acid; 0 to about 3 percent by weight silane; and 0 to
about 3 percent by weight defoamer. Water is added to bring the total percent by weight of
the composition to 100%.
Table 3 discloses an example of the prepared binder slurry as well as the most
preferable ranges of materials added to the binder slurry.


While the invention has been described in terms of preferred embodiments, it will
be understood, of course, that the invention is not limited thereto since modifications may
be made by those skilled in the art, particularly in light of the foregoing teachings.

WE CLAIM:
1. A continuous filament glass mat (50) comprising:
a mat of continuous glass filaments such as herein described; and
a binder applied to said mat, said binder including a phenolic compatible
silane such as herein described and a polyvinyl acetate copolymer such
as herein described.
2. The continuous filament glass mat as claimed in claim 1, comprising a
non-ionic surfactant, a defoamer such as herein described, water and
an organic acid.
3. The continuous filament glass mat as claimed in claim 2, wherein said
organic acid is acetic acid and wherein the pH of the binder is
maintained between approximately 4 and 6.
4. The continuous filament glass mat as claimed in claim 1, wherein said
phenolic compatible silane comprises a gamma-aminopropyl trimethoxy
silane.
5. A method for making a continuous filament glass mat (5), the method
comprising the steps of:
providing at least one continuous glass filament fiber (12);
applying a sizing composition such as herein described (18) to each of
said at least one continuous glass filament fiber;

forming said at least one continuous glass filament fiber into a continuous
fiber strand (13);
applying a CFM binder (24) to said continuous fiber strand, said CFM
binder comprising a phenolic compatible silane and a polyvinyl acetate
copyolymer binder;
drying and curing (15) said CFM binder on said continuous fiber strand; and
pressing (16) said continuous fiber strand having said CFM binder to form the
continuous filament mat.
6. The method as claimed in claim 5, wherein said dried CFM binder
comprises between 4 and 8% of the total weight of said continuous
filament mat.
7. The method as claimed in claim 5, wherein said at least one continuous
filament fiber comprises at least one continuous e-type glass such as
herein described filament fiber.
8. The method as claimed in claim 5, wherein the pH of said sizing
composition and said CFM binder slurry is between approximately 4 and 6.
9. The method as claimed in any of claims 5 to 8 including the steps of:

slitting (30) said continuous filament glass mat to a desired size and
shape;
pulling at least one of said continuous filament mats and at least one
continuous filament roving (52) through a phenolic resin bath (54);
and
molding and curing said continuous filament mat and said at least one
continuous fiber roving within a heating pultrusion die (56) to form a
pultruded composite part.
10. The method as claimed in claim 5 comprising the steps of:
slitting (30) said continuous filament glass mat to a desired size and
shape to form a continuous filament mat (50);
pulling at least one of said continuous filament mats and at least one
filament roving (52) through a urethane resin injection system (74); and
molding and curing said continuous filament mat and said at least one
continuous fiber roving within a heated pultrusion side (56) to form a
pultruded composite part.

A continuous filament glass mat (50) comprising: a mat of continuous glass
filaments such as herein described and a binder applied to said mat, said binder
including a phenolic compatible silane such as herein described and a polyvinyl
acetate copolymer such as herein described.

Documents:

1674-kolnp-2004-granted-abstract.pdf

1674-kolnp-2004-granted-assignment.pdf

1674-kolnp-2004-granted-claims.pdf

1674-kolnp-2004-granted-correspondence.pdf

1674-kolnp-2004-granted-description (complete).pdf

1674-kolnp-2004-granted-drawings.pdf

1674-kolnp-2004-granted-examination report.pdf

1674-kolnp-2004-granted-form 1.pdf

1674-kolnp-2004-granted-form 18.pdf

1674-kolnp-2004-granted-form 2.pdf

1674-kolnp-2004-granted-form 3.pdf

1674-kolnp-2004-granted-form 5.pdf

1674-kolnp-2004-granted-pa.pdf

1674-kolnp-2004-granted-reply to examination report.pdf

1674-kolnp-2004-granted-specification.pdf


Patent Number 231335
Indian Patent Application Number 1674/KOLNP/2004
PG Journal Number 10/2009
Publication Date 06-Mar-2009
Grant Date 04-Mar-2009
Date of Filing 08-Nov-2004
Name of Patentee OWENS CORNING
Applicant Address ONE OWENS CORNING PARKWAY, TOLEDO, OH
Inventors:
# Inventor's Name Inventor's Address
1 LANE ADRIAN C P.O. BOX 0304, ALEXANDRIA PA 16611
2 ANTLE JEFFREY L 17550 FM 2590 CANYON, TX 79015
PCT International Classification Number C08J 7/04
PCT International Application Number PCT/US2003/14933
PCT International Filing date 2003-05-12
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/380580 2002-05-15 U.S.A.