U.S. patent application number 10/868231 was filed with the patent office on 2005-12-15 for fatty amide composition for wet use chopped strand glass fibers.
Invention is credited to Barrick, William E., Lee, Jerry H. C., Weller, David E..
Application Number | 20050276960 10/868231 |
Document ID | / |
Family ID | 34972202 |
Filed Date | 2005-12-15 |
United States Patent
Application |
20050276960 |
Kind Code |
A1 |
Lee, Jerry H. C. ; et
al. |
December 15, 2005 |
Fatty amide composition for wet use chopped strand glass fibers
Abstract
A size composition containing one or more film forming agents,
at least one coupling agent, and a fatty amide lubricant
synthesized from a (poly)ethylene amine and a C.sub.5-C.sub.20
unsaturated fatty acid is provided. The fatty acid is preferably a
conjugated fatty acid and the (poly)ethylene amine is preferably
tetraethylenepentamine. The fatty amide lubricant may be modified
by maleinized rubber or carboxylated rubber. The size is
advantageously applied to glass fibers such as wet use chopped
strand glass and used to form roofing composites, such as shingles.
The fatty amide lubricant facilitates interfacial bonding between
the glass and asphalt through a vulcanizing mechanism. The
unsaturation of the fatty amide modifies the surface energy of the
glass fibers to make the glass more compatible with the asphalt,
enhances the compatibility between the glass and the asphalt, and
improves glass/asphalt interactions through the reduced interfacial
tensions.
Inventors: |
Lee, Jerry H. C.; (Columbus,
OH) ; Barrick, William E.; (Newark, OH) ;
Weller, David E.; (Newark, OH) |
Correspondence
Address: |
OWENS CORNING
2790 COLUMBUS ROAD
GRANVILLE
OH
43023
US
|
Family ID: |
34972202 |
Appl. No.: |
10/868231 |
Filed: |
June 15, 2004 |
Current U.S.
Class: |
428/292.1 |
Current CPC
Class: |
E04D 1/20 20130101; C03C
25/25 20180101; C03C 25/26 20130101; E04D 5/02 20130101; C03C 25/32
20130101; Y10T 428/249924 20150401 |
Class at
Publication: |
428/292.1 |
International
Class: |
D04H 001/00 |
Claims
Having thus described the invention, what is claimed is:
1. A sizing composition for glass fibers comprising: at least one
film forming polymer; one or more silane coupling agents; and a
fatty amide lubricant synthesized from a (poly)ethylene amine and
an unsaturated conjugated C.sub.5-C.sub.20 fatty acid.
2. The sizing composition of claim 1, wherein said (poly)ethylene
amine is selected from the group consisting of
tetraethylenepentamine, diethylenetriamine, tetraethylenetriamine,
ethylene diamine, diethylene triamine, triethylene tetramine and
pentaethylene hexamine.
3. The sizing composition of claim 2, wherein said one or more
silane coupling agents comprises an aminosilane coupling agent and
a vinyl silane coupling agent.
4. The sizing composition of claim 2, further comprising a member
selected from the group consisting of a secondary lubricant, a pH
adjuster, viscosity modifiers, biocides, glycols and glycol
ethers.
5. The sizing composition of claim 1, wherein said fatty amide
lubricant is modified by incorporating an elastomeric material.
6. The sizing composition of claim 5, wherein said elastomeric
material is selected from the group consisting of a maleinized
rubber and a carboxylated rubber.
7. The sizing composition of claim 1, wherein said at least one
film forming polymer is present in said sizing composition in an
amount of from 30-80% by weight of total solids, said one or more
silane coupling agents are present in said sizing composition in an
amount of from 5-30% by weight of total solids, and said fatty
amide lubricant is present in said sizing composition in an amount
of from 5-30% by weight of total solids.
8. A reinforced composite roofing material comprising a plurality
of glass fibers sized with a sizing composition including: at least
one film forming polymer; one or more silane coupling agents; and a
fatty amide lubricant which is the reaction product of a
(poly)ethylene amine and an unsaturated C.sub.5-C.sub.20 fatty
acid.
9. The composite roofing material as claimed in claim 8, wherein
said fatty acid is a conjugated fatty acid.
10. The composite roofing material as claimed in claim 8, wherein
said one or more silane coupling agents comprises an aminosilane
coupling agent and a vinyl silane coupling agent.
11. The composite roofing material as claimed in claim 8, wherein
said (poly)ethylene amine is selected from the group consisting of
tetraethylenepentamine, diethylenetriamine, tetraethylenetriamine,
ethylene diamine, diethylene triamine, triethylene tetramine and
pentaethylene hexamine.
12. The composite roofing material as claimed in claim 8, wherein
said fatty amide lubricant is modified with an elastomeric material
selected from the group consisting of a maleinized rubber and a
carboxylated rubber.
13. The sizing composition of claim 8, wherein said at least one
film forming polymer is present in said sizing composition in an
amount of from 30-80% by weight of total solids, said one or more
silane coupling agents are present in said sizing composition in an
amount of from 5-30% by weight of total solids, and said fatty
amide lubricant is present in said sizing composition in an amount
of from 5-30% by weight of total solids.
14. The composite roofing material as claimed in claim 8, wherein
said composite roofing material is in the form of an asphalt
shingle.
15. The composite roofing material as claimed in claim 9, wherein
said fatty amide lubricant modifies the surface energy of said
glass fibers and improves the compatibility of said glass fibers to
asphalt present in said asphalt shingle.
16. The composite roofing material as claimed in claim 8, further
comprising at least one member selected from the group consisting
of a secondary lubricant, a viscosity modifier, a pH adjusting
agent, a biocide, glycol and glycol ether.
17. A roofing shingle comprising: a mat formed of a plurality of
randomly oriented fibers sized with a sizing composition that
includes at least one film forming polymer, one or more silane
coupling agents, and a fatty amide lubricant, said fatty amide
lubricant being the reaction product of a (poly)ethylene amine and
an unsaturated C.sub.5-C.sub.20 fatty acid; and an asphalt coating
on at least a portion of one outer surface of said mat.
18. The roofing shingle of claim 17, wherein said fatty acid is a
conjugated fatty acid.
19. The roofing shingle of claim 17, wherein said (poly)ethylene
amine is selected from the group consisting of
tetraethylenepentamine, diethylenetriamine, tetraethylenetriamine,
ethylene diamine, diethylene triamine, triethylene tetramine and
pentaethylene hexamine.
20. The roofing shingle of claim 19, wherein said one or more
silane coupling agents comprises an aminosilane coupling agent and
a vinyl silane coupling agent.
21. The roofing shingle of claim 17, wherein said at least one film
forming polymer is present in said sizing composition in an amount
of from 30-80% by weight of total solids, said one or more silane
coupling agents are present in said sizing composition in an amount
of from 5-30% by weight of total solids, and said fatty amide
lubricant is present in said sizing composition in an amount of
from 5-30% by weight of total solids.
22. The roofing shingle of claim 17, wherein said fibers are glass
fibers and said fatty amide lubricant modifies the surface energy
of said glass fibers and improves the compatibility of said glass
fibers to said asphalt.
23. The roofing shingle of claim 17, wherein said fatty amide
lubricant is modified by incorporating an elastomeric material
during the synthesis of the fatty amide lubricant.
24. The roofing shingle of claim 17, wherein said fatty amide
lubricant modifies the surface energy of said glass fibers and
improves the compatibility of said glass fibers to said
asphalt.
25. The roofing shingle of claim 17, wherein unsaturated
hydrophobic tails on the synthesized fatty amide react with the
asphalt and crosslink the glass and the asphalt.
26. The roofing shingle of claim 17, further comprising a sulfur
catalyst to promote interfacial bonding between the glass and the
asphalt.
27. A method of forming a roofing shingle comprising the steps of:
forming a mat composed of randomly oriented glass fibers sized with
a sizing composition including: at least one film forming polymer;
one or more silane coupling agents; and a fatty amide lubricant,
said fatty amide lubricant being the reaction product of a
(poly)ethylene amine and a C.sub.5-C.sub.20 unsaturated fatty acid;
and applying a coating of asphalt on at least one surface of said
mat.
28. The method of claim 27, wherein said (poly)ethylene amine is
selected from the group consisting of tetraethylenepentamine,
diethylenetriamine, tetraethylenetriamine, ethylene diamine,
diethylene triamine, triethylene tetramine and pentaethylene
hexamine.
29. The method of claim 28, wherein said one or more silane
coupling agents comprises an aminosilane coupling agent and a vinyl
silane coupling agent.
30. The method of claim 27, wherein said fatty acid is a conjugated
fatty acid.
31. The method of claim 27, further comprising the step of: cutting
said mat into an appropriate shape and size of a roofing
shingle.
32. The method of claim 27, further comprising the step of: coating
said asphalt with protective granules.
33. The method of claim 27, further comprising the step of reacting
the unsaturated hydrophobic tails on the synthesized fatty amide
with the asphalt to crosslink the glass and the asphalt.
34. The method of claim 33, further comprising the step of
providing a sulfur catalyst to promote interfacial bonding between
the glass and the asphalt.
Description
TECHNICAL FIELD AND INDUSTRIAL APPLICABILITY OF THE INVENTION
[0001] The present invention relates generally to a sizing
composition for glass fibers, and more particularly, to a sizing
composition for wet use chopped strand glass fibers that contains a
fatty amide lubricant synthesized from a (poly)ethylene amine and
an unsaturated C.sub.5-C.sub.20 fatty acid. A composite roofing
material formed from a reinforcing fiber material sized with the
sizing composition is also provided.
BACKGROUND OF THE INVENTION
[0002] Glass fibers are useful in a variety of technologies. For
example, glass fibers are commonly used as reinforcements in the
building composite industry 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.
[0003] To form a roofing shingle, glass fibers are first formned 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 with the sizing
composition, they are packaged in their wet condition as wet use
chopped strand glass (WUCS).
[0004] The wet, chopped fibers are then dispersed in a water slurry
which may contain surfactants, viscosity modifiers, or other
chemical agents and agitated to disperse the fibers. The slurry
containing the dispersed fibers is then deposited onto a moving
screen where a substantial portion of the water is removed to form
a web. A binder is then applied, and the resulting mat is heated to
remove the remaining water and cure the binder. 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 through a bath of
molten asphalt to place a layer of asphalt on both sides of the mat
and fill in the interstices between the individual glass fibers.
The coated mat is then cut to an appropriate shape and size to form
the shingle.
[0005] Conventional sizing compositions for wet use chopped strand
glass typically contain a film-forming polymeric or resinous
component, a coupling agent, and a lubricant dissolved or dispersed
in a liquid medium. Unfortunately, such conventional size
compositions are not always compatible with the asphalt used to
coat the fibrous mats and form the roofing shingles. Such
incompatability may cause processing difficulties, and may result
in roofing shingles that have poor physical properties, such as
poor tear strength. Further, the amount of binder that is employed
in conjunction with the conventional sizing compositions may
significantly increase the cost of the roofing shingles.
[0006] Therefore, there exists a need in the art for an improved
sizing composition for use in wet use chopped strand glass fibers
that increases the compatibility of glass fiber mats to the asphalt
coatings on asphalt composite articles, that lowers manufacturing
costs, and that improves physical properties of the composite.
SUMMARY OF THE INVENTION
[0007] It is an object of the present invention to provide a sizing
composition for wet use chopped strand fibers that includes one or
more film forming agents, at least one coupling agent, and a fatty
amide lubricant synthesized from a (poly)ethylene amine and a
C.sub.5-C.sub.20 unsaturated fatty acid. The synthesized fatty
amide compound is formed of an amine-based hydrophilic midsection
with hydrophobic tails at either end. The hydrophobic tails are
preferably conjugated and contain a high degree of unsaturation. In
preferred embodiments, the (poly)ethylene amine is
tetraethylenepentamine and the fatty acid is a conjugated fatty
acid. The fatty amide lubricant may or may not be modified by an
elastomer such as a maleinized rubber or a carboxylated rubber
during the synthesis of the fatty amide lubricant. Secondary
lubricants, viscosity modifiers, pH adjusters, biocides, and
coalescents such as glycols and glycol ethers may also be included
in the sizing composition. The reinforcing fiber material may be
one or more strands of glass, natural fibers, carbon fibers, or one
or more synthetic polymers. In at least one exemplary embodiment,
glass fibers are sized with the sizing composition and packaged as
wet use chopped strand glass that is subsequently used to form
reinforced building or roofing composites such as shingles.
[0008] It is another object of the present invention to provide a
composite roofing material that is formed of a plurality of glass
fibers sized with a sizing composition that contains one or more
film forming agents, at least one coupling agent, and a fatty amide
lubricant synthesized from a (poly)ethylene amine and a
C.sub.5-C.sub.20 unsaturated fatty acid as described above.
[0009] It is a further object of the present invention to provide a
reinforced shingle product formed of a mat of randomly oriented
glass fibers sized with a sizing composition that includes one or
more film forming agents, at least one coupling agent, and a fatty
amide lubricant synthesized from a (poly)ethylene amine and a
C.sub.5-C.sub.20 unsaturated fatty acid as described above.
[0010] An advantage of the synthesized fatty amide lubricant is its
built-in reactivity with asphalt when forming an asphalt roofing
product. Covalent bonding between the glass and the asphalt may be
established through a vulcanizing mechanism in which the
unsaturated hydrophobic tails on the synthesized fatty amide react
with the asphalt in the presence of sulfur at an elevated
temperature and crosslink the glass and the asphalt. This
interfacial bonding results in increased mechanical performance and
improved tear strength in the composite article formed from fibers
sized with the inventive sizing composition.
[0011] A further advantage of the synthesized fatty amide lubricant
is that the high hydrophobicity and low surface energy of the
hydrophobic tails on the fatty amide lubricant enhances the
compatibility between the glass and the asphalt during the
formation of asphalt roofing products and improves glass/asphalt
interactions through the reduced interfacial tensions.
[0012] 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.
DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS OF THE INVENTION
[0013] Unless defined otherwise, all technical and scientific terms
used herein have the same meaning as commonly understood by one of
ordinary skill in the art to which 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. It is to be noted that the phrases "size composition",
"sizing composition", and "size" are used interchangeably
herein.
[0014] The present invention relates to sizing compositions for wet
use chopped strand glass fibers. The sizing composition includes
one or more film forming agents, at least one coupling agent, and a
fatty amide lubricant synthesized from a (poly)ethylene amine and a
C.sub.5-C.sub.20 unsaturated fatty acid. The fatty amide lubricant
may or may not be modified by an elastomer. Conventional
lubricants, viscosity modifiers, pH adjusters, biocides, and
coalescents such as glycols and glycol ethers may also be included
in the sizing composition.
[0015] The film forming polymer component of the sizing composition
may be any suitable polymer that can be dispersed or dissolved into
an aqueous medium and which will coalesce to form a film when the
sizing composition has been dried. In addition, the film former is
desirably chosen to have compatibility with the matrix resin in
which the sized glass fibers will be used. Examples of film forming
agents for use in the size composition include polyester polymers,
polyurethanes, acrylic polymers, vinyl polymers, mixtures of such
polymers, copolymers of the corresponding monomers, carboxylic acid
or anhydride modified polyolefins, cellulose, polyvinyl alcohols
(PVA), and mixtures thereof. In a preferred embodiment, the film
forming polymer is a polyvinyl alcohol, and in an even more
preferred embodiment, the film forming polymer is a partially
hydrolyzed polyvinyl alcohol having approximately 87-89% hydrolysis
and a low to intermediate molecular weight. Examples of suitable
polyvinyl alcohols for use in the size include Celvol 203, 205, and
325 from Celanese Chemicals. The film forming agent or agents may
be present in the size composition in an amount of approximately
30-80% by weight of dry solids.
[0016] In addition, the sizing composition contains one or more
coupling agents. Preferably, at least one of the coupling agents is
a silane coupling agent. Silane coupling agents function to enhance
the adhesion of the film forming polymer to the glass fibers and to
reduce the level of fuzz, or broken fiber filaments, during
subsequent processing. Examples of silane coupling agents which may
be used in the size composition may be characterized by the
functional groups amino, epoxy, vinyl, methacryloxy, ureido,
isocyanato, and azamido.
[0017] Suitable silane coupling agents for use in the size include,
but are not limited to, .gamma.-aminopropyltriethoxysilane
(A-1100), n-trimethoxy-silyl-propyl-ethylene-diamine (A-1120),
.gamma.-glycidoxypropyltrimethoxysilane (A-187),
.gamma.-methacryloxyprop- yltrimethoxysilane (A-174),
n-.beta.-aminoethyl-.gamma.-aminopropyltrimeth- oxysilane (A-1120),
methyl-trichlorosilane (A-154), methyl-trimethoxysilane (A-163),
.gamma.-mercaptopropyl-trimethoxy-silane (A-189),
.gamma.-chloropropyl-trimethoxy-silane (A- 143),
vinyl-triethoxy-silane (A-151), vinyl-tris-(2-methoxyethoxy)silane
(A-2171), vinyl-triacetoxy silane (A-188), octyltriethoxysilane
(A-137), methyltriethoxysilane (A-162), methyltrimethoxysilane
(A-1630), Silquest RC-1 vinyl silane, and Silquest RC-2 sulfur
silane. All of the silane couplings agents listed herein are
Silquest products available from GE Silicones. Preferably, the size
composition contains both an aminosilane coupling agent and a vinyl
silane coupling agent. The coupling agent or agents may be present
in the sizing composition in an amount of from 5-30%, and
preferably, in an amount of from 10-20% by weight of the dry
solids.
[0018] The sizing composition also contains a fatty amide lubricant
synthesized from a (poly)ethylene amine and an unsaturated
C.sub.5-C.sub.20 fatty acid such as linoleic acid or oleic acid. In
addition, vegetable-based unsaturated fatty acids such as, but not
limited to, Agri-Pure 130 (Cargill, Inc.) and Agri-Pure 150
(Cargill, Inc.) may be used to synthesize the fatty amide
lubricant. Preferably, the unsaturated fatty acid is a fatty acid
containing conjugated double bonds such as linoleic acid, Edenor
UKD 5010 (Cognis Corp.), Edenor UKD 5020 (Cognis Corp.), and
EdenorUKD 6010 (Cognis Corp.). Non-exclusive examples of
(poly)ethylene amines that may be used to form the fatty amide
lubricant include tetraethylenepentamine (TEPA), diethylenetriamine
(DETA), tetraethylenetriamine (TETA), ethylene diamine, diethylene
triamine, triethylene tetramine, and pentaethylene hexamine. In
preferred embodiments, the (poly)ethylene amine is
tetraethylenepentamine. The synthesized fatty amide compound is
formed of an amine-based hydrophilic midsection with hydrophobic
tails at either end. The hydrophobic tails are preferably
conjugated and contain a high degree of unsaturation. The fatty
amide lubricant may be present in the size in an amount of from
5-30% by weight of the dry solids, and more preferably in an amount
of from 10-20% by weight of the dry solids.
[0019] The fatty amide lubricant may be modified with an elastomer
by incorporating a maleinized rubber or a carboxylated rubber
during the synthesis of the fatty amide lubricant. Incorporating
hydrophobic rubbers or elastomers in the synthesized fatty amide
aids in reducing the surface energy of the glass fibers and in
enhancing interactions between glass and asphalt. In addition, the
elastomers may serve as an energy buffer or barrier to dissipate
the energy passed between the high modulus rigid glass and low
modulus soft asphalt when asphalt roofing products are subjected to
an impact force. Examples of suitable maleinized rubbers include
adducts of maleic anhydride and polybutadiene and adducts of maleic
anhydric and polybutadiene styrene copolymers. The maleinized
rubber or carboxylated rubber may be present in an amount of 5-40%
by weight of the fatty amide lubricant, and even more preferably in
an amount of from 10-30% by weight of the fatty amide
lubricant.
[0020] In addition to the synthesized fatty amide lubricant, the
size composition may also contain a secondary lubricant to
facilitate manufacturing. The secondary lubricant may be any
conventional lubricant such as, but are not limited to,
water-soluble ethyleneglycol stearates (e.g., polyethyleneglycol
monostearate, butoxyethyl stearate, and polyethylene glycol
monooleate), ethyleneglycol oleates, ethoxylated fatty amines,
glycerine, emulsified mineral oils, organopolysiloxane emulsions,
stearic ethanolamide (sold under the trade designation Lubesize
K-12 (Alpha/Owens Corning)), Stantex G-8145 (Cognis Corp.), SF-8275
(Cognis Corp.), and Emery 6760 (Cognis Corp). The secondary
lubricant may be present in the size in an amount of from 0-10% by
weight of the dry solids.
[0021] Optionally, the sizing composition may contain a viscosity
modifier such as a polyacrylamide, a hydroxyethyl cellulose, or a
polyamine viscosity modifier. Specific examples of viscosity
modifiers include Nalco 7530 (ONDEO Nalco), 01PF067 (ONDEO Nalco),
Superfloc C-507 (Cytec Industries, Inc.), Superfloc MX 40 (Cytec
Industries, Inc.), Superfloc MX 80 (Cytec Industries, Inc.), and
Superfloc SD-2065 (Cytec Industries, Inc.). The viscosity modifier
acts as a secondary dispersant in the size composition. The
viscosity modifier may be present in the sizing composition in an
amount of from 0-5% by weight of the dry solids.
[0022] In addition, the size composition may optionally include a
pH adjusting agent such as acetic acid, citric acid, sulfuric acid,
or phosphoric acid in an amount sufficient to adjust the pH to a
desired level. The pH may be adjusted depending on the intended
application, or to facilitate the compatibility of the ingredients
of the size composition. Preferably, the sizing composition has a
pH of from 3-6, and more preferably a pH of from 4-5.
[0023] Further, the size may optionally contain conventional
additives such as dyes, oils, fillers, thermal stabilizers,
anti-foaming agents, anti-oxidants, dust suppression agents,
wetting agents, and/or other conventional adjuvants. In addition,
the size may include coalescents such as glycols and glycol ethers
to aid in fiber storage stability and/or biocides such as Amerstad
250 (Ashland Chemicals) and Nalco 9380 (ONDEO Nalco).
[0024] The balance of the size composition is composed of water. In
particular, water may be added to dilute the aqueous sizing
composition to a viscosity that is suitable for its application to
glass fibers and to achieve the desired solids content. The sizing
composition may contain up to approximately 99.5% water.
[0025] The size composition may be applied to strands of glass
formed by conventional techniques such as by drawing molten glass
through a heated bushing to form substantially continuous glass
fibers. Any type of glass, such as A-type glass, C-type glass,
E-type glass, S-type glass, or modifications thereof, is suitable
for use as the fiber material. For example, in one modification of
E-type glass, the boron oxide is replaced by magnesium oxide. Such
a glass is commercially available from Owens Coming Fiberglass
Corporation under the trade name Advantex.RTM..
[0026] Alternatively, the sizing composition may be applied to
strands of one or more synthetic polymers such as polyester,
polyamide, aramid, and mixtures thereof. The polymer strands may be
used alone as the reinforcing fiber material, or they can be used
in combination with glass strands such as those described above. As
a further alternative, natural fibers may be used as the
reinforcing fiber material. The term "natural fiber" as used in
conjunction with the present invention to refers to plant fibers
extracted from any part of a plant, including, but not limited to,
the stem, seeds, leaves, roots or bast. Examples of natural fibers
suitable for use as the reinforcing fiber material include cotton,
jute, bamboo, ramie, hemp, flax, and combinations thereof. Carbon
fibers may also be used.
[0027] The size composition is preferably applied to the fibers
such that the size is present on the fibers in an amount of from
about 0.02 to about 0.50 percent by weight based on the total
weight of the fibers, and even more preferably in an amount of from
about 0.05 to about 0.30 percent by weight. This can be determined
by the loss on ignition (LOI) of the WUCS fibers, which is the
reduction in weight experienced by the fibers after heating them to
a temperature sufficient to burn or pyrolyze the organic size from
the fibers. The size composition may be applied to fibers having a
diameter of from about 6-23 microns, with fibers of from about
11-20 microns in diameter being more preferred.
[0028] The sizing composition may be applied to the fibers in any
conventional maimer using any conventional applications such as by
spraying or drawing the fibers to be sized across a rotating or
stationary roll wet with the sizing composition. The size
composition is preferably applied to the fibers in an amount
sufficient to provide the fibers with a moisture content of from
about 10% by weight to about 15% by weight of the WUCS fibers.
[0029] In preferred embodiments, glass fibers are sized with the
sizing composition and packaged as wet use chopped strand glass
that is subsequently used to form reinforced building or roofing
composites such as shingles. For example, the sized glass fibers
are chopped while wet and dispersed into a water slurry which may
contain surfactants, viscosity modifiers, or other chemical agents.
The slurry containing the dispersed fibers is then deposited onto a
moving screen where a substantial portion of the water is removed.
Next, a binder (e.g., a urea formaldehyde binder or a
polycarboxylic acid based binder) is applied, and the resulting mat
is dried to remove the remaining water and cure the binder. The
formed non-woven mat is an assembly of randomly oriented,
dispersed, individual glass filaments. The mat may be dried by in
any conventional manner, such as by passing the mat through an
oven. Asphalt is then applied to the dried/cured mat in any known
manner, such as by passing the mat through a bath containing an
asphalt mix that may include molten asphalt, fillers, and
optionally sulfur to place a layer of asphalt on at least one side
of the mat and fill in the interstices between the individual glass
fibers. The asphalt-coated mat is then cut to the appropriate shape
and size to form a shingle. 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.
[0030] The synthesized fatty amide is designed not only to function
as a lubricant and a dispersant, but also to interact with the
asphalt in the asphalt mix. Thus, one advantage provided by the
fatty amide is its built-in reactivity with other components. For
example, covalent bonding (e.g., interfacial bonding) between the
glass and the asphalt can be established through a vulcanizing
mechanism in which the unsaturated hydrophobic tails on the
synthesized fatty amide react with the asphalt in the presence of
sulfur at an elevated temperature and crosslink the glass and the
asphalt. In this reaction, the sulfur acts as a catalyst. The
interfacial bonding between the glass and the asphalt increases the
mechanical strength of the resulting composite article.
[0031] In addition, the nitrogens present in the hydrophilic
amine-based mid section of the synthesized fatty amide, once
neutralized with an acid, become cationic nitrogens. These cationic
nitrogens may then form ionic bonds with the anionic charge of the
glass fibers which helps to anchor the fatty amide lubricant onto
the glass fibers.
[0032] Another advantage provided by the fatty amide is that the
fatty amide modifies the surface energy of the glass to make the
glass more compatible with the asphalt. The high hydrophobicity and
low surface energy of the hydrophobic tails on the fatty amide
lubricant enhances the compatibility between the glass and the
asphalt and improves glass/asphalt interactions through the reduced
interfacial tensions. Thus, the new fatty amide also acts as an
adhesion promoter.
[0033] Having generally described this invention, a further
understanding can be obtained by reference to certain specific
examples illustrated below which are provided for purposes of
illustration only and are not intended to be all inclusive or
limiting unless otherwise specified.
EXAMPLES
Example 1
Synthesis of a Conventional Lubricant--Lubesize K-12
[0034] Lubesize K-12 is a conventional lubricant that is an adduct
of tetraethylenepentamine (TEPA) and stearic acid. It has no degree
of unsaturation. The ingredients used to synthesize Lubesize K-12
are set forth in Table 1.
1 TABLE 1 Weight (g) % of Total Charge Stearic Acid 125.00 63.98
Tetraethylepetamine 46.75 23.93 (TEPA) Acetic Acid 23.62 12.09
Total 195.37 100.00
[0035] Table 2 illustrates a 1 kg charge based on the ingredients
set forth in Table 1.
2 TABLE 2 Weight (g) % of Total Charge Stearic Acid 639.80 63.98
Tetraethylenepentamine (TEPA) 239.3 23.93 Acetic Acid 120.9 12.09
Total 1000.00 100.00
[0036] The stearic acid was charged and melted at 200.degree. F.
under a light nitrogen blanket. Once all of the stearic acid was
melted, it was agitated under a nitrogen blanket. When the
temperature was controlled at 200.degree. F., the heat was removed.
Tetraethylenepentamine (TEPA) was then slowly added from a dropping
funnel. After an exotherm peak, the heating was resumed. Once all
of the TEPA was added, the temperature was raised as fast as the
foaming permitted. At approximately 380.degree. F., it was
determined that approximately 50% of the distillate had been
removed. At this time, the nitrogen blanket was removed and a low
nitrogen sparge was applied.
[0037] After the low nitrogen sparge was applied, heat was again
applied towards a maximum temperature of 480.degree. F. until the
distillate stopped. Once the distillate had stopped, the reaction
mixture was cooled to a temperature of approximately
160-170.degree. F. by ambient air. The total distillate removed
from the stearic acid and TEPA was determined to be approximately
12% of the total charge. Acetic acid was then added over a period
of approximately 15 minutes. A slight exotherm of approximately
10.degree. F. was noted as the acetic acid was added. After all of
the acetic acid was added, the mixture was agitated for
approximately 10 minutes and then poured onto release paper where
it was permitted to cool and solidify.
[0038] The final product at 1% in water had a pH in the range of
4.5-5.0. In addition, the final product prior to acid
neutralization had a residual acid value of 0.4% and a
non-detectable iodine value. The solidified product was determined
to be Lubesize K-12.
Example 2
Synthesis of an Unsaturated Fatty Amide Lubricant Containing
Conjugated Diene Structure
[0039] The experiment set forth in Example 1 was repeated except
that stearic acid was replaced with linoleic acid on an equivalent
basis. The linoleic acid used was Emersol 315 linoleic acid from
Cognis Corp. The finished product prior to acid neutralization had
a residual acid value of 0.29% and an iodine value of 24.8. The
iodine value of Emersol 315 linoleic acid was 27.4. It was
determined that approximately 90.5% of the unsaturation in the
fatty acid was maintained in the synthesized product.
Example 3
Synthesis of an Unsaturated Fatty Amide Lubricant Containing No
Conjugated Diene Structure
[0040] The experiment set forth in Example 1 was repeated except
that stearic acid was replaced with oleic acid on an equivalent
basis. The oleic acid used was Emersol 213 oleic acid from Cognis
Corp. The synthesized product prior to acid adjustment had a
residual acid value of 0.18% and an iodine value of 21.8. The
iodine value of Emerson 213 oleic acid was 24.3. It was determined
that approximately 90% of the unsaturation in the fatty acid was
maintained in the synthesized product.
Example 4
Synthesis of a Rubber Modified Unsaturated Fatty Amide
[0041] The experiment set forth in Example 1 was repeated except
that the stearic acid was replaced with 90% of Emersol 315 linoleic
acid (Cognis Corp.) and 10% Ricon 130MA13 maleinized polybutadiene
(Sartomer) on a weight basis. The synthesized product prior to acid
neutralization had a residual acid value of 0.21% and an iodine
value of 27.7. The iodine value of the raw mixture of linoleic acid
and maleinized polybutadiene prior to the condensation reaction was
36.3. It was determined that 76.3% of the unsaturation in the fatty
acid was retained in the synthesized product.
Example 5
Synthesis of a Polybutadiene Styrene Copolymer Rubber Modified
Unsaturated Fatty Amide
[0042] The experiment set forth in Example 1 was repeated except
that the stearic acid was replaced with 90% of Emersol 315 linoleic
acid (Cognis Corp.) and 10% Ricon 184MA6 maleinized polybutadiene
styrene rubber (Sartomer) on a weight basis. The iodine content of
the starting raw mixture of linoleic acid and polybutadiene styrene
rubber prior to the condensation reaction was 32.2. The synthesized
product prior to acid neutralization had a residual acid value of
0.25% and an iodine value of 30.7. It was determined that
approximately 95.3% of the unsaturation of the fatty acid was
maintained in the synthesized product.
Example 6
Comparison of Lubesize K-12 and Unsaturated Fatty Amide Lubricant
Containing Conjugated Diene Structure
[0043] Fiber samples were coated with sizing compositions
containing the fatty amides prepared in Examples 1 and 2 above. The
sized fiber samples were formed into roofing mats on a sheet
former. The mat samples were then converted to lab shingle samples
by coating the mats with an asphalt mix containing 0%, 0.2%, or
0.8% post-added elemental sulfur. The results are summarized in
Table 3.
3TABLE 3 Sulfur Content 0% 0% 0.2% 0.2% 0.8% 0.8% Lab Shingle CD
Total CD Total CD Total Property Tear Tear Tear Tear Tear Tear
Example 1 saturated 1324 2278 1356 2519 1243 2335 amide (control)
Example 2 conjugated 1510 2617 1554 2841 1649 2958 amide
(inventive) Improvement In Tear 14.0% 14.9% 14.6% 12.8% 32.7% 26.7%
Strength Note: CD cross direction Tear strengths were measured on
an Elmendorf Tear Strength Tester following the procedure set forth
in ASTM D-3462 Units for tear strength are in grams
[0044] The performance improvement data in this Example shows that
a lab shingle formed from fibers sized with a sizing composition
containing a fatty amide synthesized from TEPA and a conjugated
fatty acid had improved tear strength with or without external
sulfur in the asphalt coating formulation. Although not wishing to
be bound by theory, it is believed that the increased performance
in the sizing compositions when no sulfur was added was due to the
higher hydrophobicity and reduced surface energy of the glass
surface by the inventive fatty amide. It is also believed that the
reduction of the surface energy improves interactions between the
glass and the asphalt added to form the lab shingle.
Example 7
Comparison of Lubesize K-12 and Unsaturated Fatty Amide Lubricant
Containing No Conjugated Diene Structure
[0045] Fiber samples were coated with sizing compositions
containing the fatty amides prepared in Examples 1 and 3 above. The
sized fiber samples were formed into roofing mats on a sheet
former. The mat samples were then converted to lab shingle samples
by coating the mats with an asphalt mix containing 0% and 0.2%
post-added elemental sulfur. The results are summarized in Table
4.
4TABLE 4 Sulfur Content 0% 0% 0.2% 0.2% Lab Shingle CD Total CD
Total Property Tear Tear Tear Tear Example 1 saturated amide 1324
2278 1356 2519 (control) Example 3 non-conjugated amide 1440 2606
1470 2691 (inventive) Improvement In Tear Strength 8.8% 14.3% 8.4%
6.8% Note: CD = cross direction Tear strengths were measured on an
Elmendorf Tear Strength Tester following the procedure set forth in
ASTM D-3462 Units for tear strength are in grams
[0046] The performance improvement data in this Example shows that
a lab shingle formed from fibers sized with a sizing composition
containing a fatty amide synthesized from TEPA and a non-conjugated
unsaturated fatty acid had improved tear strength with or without
external sulfur in the asphalt coating formulation.
[0047] The invention of this application has been described above
both generically regard to specific embodiments. Although the
invention has been set forth in what ed to be the preferred
embodiments, a wide variety of alternatives known to those of he
art can be selected within the generic disclosure. The invention is
not otherwise except for the recitation of the claims set forth
below.
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