Note: Descriptions are shown in the official language in which they were submitted.
CA 02470780 2004-06-11
G~IrASS ADHESION PRO1VIOTER
The present invention is directed towards a glass adhesion promoter or
composition.
More specifically, the invention is directed towards a copolymer useful in a
glass binding
s composition, wherein the copolymer has a carboxyl-functional moiety and a
substituted amide,
silanol, or amine oxide functional moiety. The copolymer is useful both as a
fiberglass binder
and in providing protective coatings on glass sheets.
Fiberglass insulation products generally consist of glass fibers bound
together by a
polymeric binder. The fibers are bound by spraying an aqueous polymer binder
onto matted
io glass fibers soon after the fibers are formed and while they are still hot.
This polymeric binder
accumulates at the junctions where the fibers cross each other, hvldin~g the
fibers together at
these points. The heat from the fibers vaporizes most of the water in the
binder. The fiberglass
binder should be flexible so that the fiberglass product can be compressed for
packaging and
shipping and later recover to its full vertical dimension when installed.
t5 In the past, fiberglass applications employed phenol-formaldehyde resins in
their binder
systems. These phenyl-formaldehyde compositions provided an excellent product
with
flexibility. However, due to environmemal and safety concerns formaldehyde-
free polymeric
binder systems were developed as a substitute for the phenol-formaldehyde
compositions. These
formaldehyde-free binder systems typically involve three parts. One part is a
polymer such as a
20 polycarboxyl, polyacid, polyacrylie, or anhydride that can be eopolymerized
with other
ethylenically unsaturated monomers. A second part is a cross-linker that is an
active hydrogen
compound, such as trihydric alcohol, triethsnol a»aine, beta-hydroxy alkyl
amides, or hydroxy
alkyl urea. The system can also include a catalyst or accelerator, such as a
phosphorous
containing compound or a fluoroborate compound. Still, these carboxyl-
containing polymers
2s and co-polymers show poor adhesion to glass fibers, resulting in insulation
that sags over time.
Accordingly, there is a need for alternative fiberglass binder systems that
provide the
performance advantages of phenol-formaldehyde resins in a formaldehyde-free
system. Further,
there is a need for a fiberglass binder composition having good adhesion to
glass fibers,
it is known to use a phosphorus-based catalyst for fiberglass sizing
fornnulations. While
3o the phosphorus-based catalysts lower the curing temperature, the addition
of inorganic salts such
as sodium hypophosphite adversely affect the water uptake of the finished
product_ While not
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CA 02470780 2004-06-11
being bound by theory, the inorganic salts introduced in to the insulation
system tend to absorb
moisture by a capillary mechanism. Accordingly, there is a need to minimize or
even eliminate
the inorganic salts (electrolytes) in this system. Additionally, there is a
need for a fiberglass
binder system and its associated resins) having improved water and humidity
resistance, and
that are not subject to the water absorption problems described above.
It has now been found that excellent adhesion to glass can be obtained by the
copolynnerization of a substituted amide, silanol, or amine oxide functional-
monomer with a
carboxyl-functional monomer. This copolymer also provides good adhesion to
silicon-based
materials such as glass sheets, thereby providing a protective coating to the
glass.
to In one aspect the present invention is directed towards a copolymer
composition having
one or more acid functional monomer units in an amount of about 30 to about
99.99 percent by
weight; monomer units selected from the group consisting of substituted amide
monomers,
silanol monomers, or amine oxide monomers in an amount of about 0.01 to about
30 percent by
weight; and one or more other ethylenically unsaturated monomer units in an
amount of about 0
1s to about 50 percent by weight, with the sum of all monomer weight
percentages that make up the
copolymer binder composition adding up to 100 percent.
The invention is also directed to a silicon-based substrate having directly
deposited
thereon this copolymer binder composition.
In another aspect, the present invention is directed towards a fiberglass
binding or sizing
z0 composition or formulation. This fiberglass binding composition includes a
polymer or
copolymer having at least one acid group, at least one carboxylic comonomer
and at least one
crosslinker.
In another aspect, the fiberglass binding composition includes a copolymer
having at
least one acid group derived from at least one acid monomer having the general
formula ()]
Ri R~
(1)
25 Ra R'
wherein R~ to R4 are independently hydrogen, methyl, carboxylic acid group or
CI-~COOH, alkyl
or aryl sulfonic acid and wherein the acid groups can be neutralized.
This fiberglass binding composition fiuther includes a hydrophobic comonomer
having
the general formula (II) -
CA 02470780 2004-06-11
R~
X
wherein RS is hydrogen, C,-C6 alkyl or Ci-C6 hydroxyalkyl, and X is either
mono or polycyclic
aromatic group or a substituted aromatic group (with RS being hydrogen or
methyl when X is
aromatic) or X is of the general formula (III) -
6
Wheheln R6 15 (independently of Rs) hydrogen, C,-Ca,, allryI, Cl-C~ alkoxy, C~-
C~, aminoalkyl,
G-Gi4 allcyl sulfonate, -0 alkyl, -OCO alkyl, NCO alkyl, carbocyclic,
heterocyclic, or C,-Cap
hydroxyalkyl; Y is O or N; and t is either 0 or 1. The fiberglass binding
composition also
includes a crosslinker.
t o It has now been found that addition of small amounts of hydrophobic
functionality can
overcome water absorption problems of fiberglass sizing formulations
containing inorganic salts.
In this respect, the invention is directed towards a resin containing
hydrophobically functional
comonomer. This hydrophobic fu:actionality can be introduced into the
copolymer by the
addition of hydrophobic comonomers. Alternatively, the hydrophobic
functionality can be
is introduced by adding hydrophobic emulsions as an additive. In another
aspect, surfactants are
beneficial to these fornnulations either as the hydrophobic additive or as a
stabilizer for the
hydrophobic emulsion additives. Alternatively, these hydrophobic emulsion
additives can be
stabilized by colloid stabilizers.
The present invention is further dirxtod towards an aqueous process for
producing
20 hydrophobic solution copolymers. This process includes adding an acid
functional monomer and
a hydrophobic monomer to an aqueous solution. An initiating aged is added to
the solution to
effect polymerization of the monomers. The monomers are then polymerized,
thereby forming
hydrophobic solution copolymers in the aqueous solution.
The present invention relates to a glass adhesion copolymer usefitl i,n a
fiberglass binder
2s composition arid having excellent adhesion to glass end other silicon-based
substrates. The glass
adhesion copolymer is formed by copolymerkation of one or more acid
ftanetlonal monomers
with one or more ethylenically unsaturated monomers. These unsaturated
monomers include
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CA 02470780 2004-06-11
substituted amide, silanol, or amine oxide functional-monomer. In one aspect,
the glass adhesion
copolymer includes di-substituted amide monomer units.
In one aspect, the one or mote acid monomers is at least a carboxylic acid
monomer used
in synthesizing the binder make up from about 30 to about 99.99 mole percent
of the copolymer.
s In another aspect, the ane or more acid monomers make up from about 50 to
about 99 mole
percent. In anther aspect, the one or more acid monomers make up from about 60
to about 95
mole percent of the copolymer,
The carboxylic acid monomer includes anhydrides that can form cuboxyl groups
in situ.
Examples of carboxylic acid monomers useful in forming the copolymer of the
invention include
1o acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, fumaric
acid, malefic acid, cinnanic
acid, 2-methylmaleic acid, itaconic acid, 2-methylitaconic acid, sorbic acid,
a ~-methylene
glutaric acid, malefic anhydride, itaconic anhydride, acrylic anhydride,
methacrylic anhydride. In
one embodiment the monomers are malefic acid, acrylic acid and/or methacrylic
acid. The
carboxyl groups can also be formed in s#u, such as in the case of isopropyl
esters of acrylates
~ 5 and methacrylates that forth acids by hydrolysis of the esters when the
isopropyl group leaves,
The acid monomer can include a sulfonic acid group such as 2-acrylamidomethyl
propane
sulfonic acid, styrene sulfonic acid, (meth)allyl sulfonic acid and
tmeth~llyloxybenzene sulfonic
acid. Mixtures of carboxylic acids and sulfonic acids can also be used.
The glass adhesion copolymer is synthesized from one or more substituted
amide, silanol,
2o or amine oxide- functional monomers. These functional monomers arc used at
a level of from
0,01 to 30 percent by weight, based on the total monomer. In another aspect
they are used at a
level of from 0.1 to 5 percent by weight. Substituted amide monomers include
those having the
formula (I1~:
R'
R9 C ' C -N (I~
Ra
2s wherein R' and Ra arc independently H, OhI, Ct.3~, alkyl, aryl, alkyl aryl
or hydroxyalkyl; and RQ
is Ii or CH3.
Examples of substituted amide monomers Include N-methylol acrylamidc, N-
ethanol
acrytamlde, N propanol acrylamide, N-methylol methacrylamide, N,N-
dimethylacrylamide,
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CA 02470780 2004-06-11
N,N-diethyl acrylamide, N-isopropyl acrylamide, N-hydroxyethyl acrylamide, N-
hydroxypropylacrylamide, N-octylacrylamide, N-laurylacrylamide, dimethyl
aminopropyl
(meth)acrylamide, and 1-vinyl-2-pyrrolidinone. 1n one aspect the substituted
amide is a di-
substituted amide such as N,N-dimethylacrylamide, and N,N-.diethylaerylamide.
The substituted
s amide monomer useful in the invention can also be a ring opening monomer
with the substituted
amide in the backbone of the monomer, wherein the monomer will copolymerize by
condensation or ring opening polymerization.
Examples of silanol monomers include vinyl trisisopropoxy silane, vinyl
trisethoxy
sifane, vinyl trismethoxy silane, vinyl tri(2-methoxyethoxy) silane, vinyl
methyl dimethoxy
io silane, y-methacryl oxypropyl trimethoxy silane, and vinyl triacetoxy
silane. These monomers
ate typically copolymerized with acrylic acid in water. They hydrolyze in sftu
forming silanol
linkages and liberating the eocresponding alcohol, which can then be distilled
off
In one embodiment, the amine oxide monomers are incorporated by copolymerizing
a
amine-containing monomer such as 2-vinylpyridine, 4-vinyl pyridine, or
dimethyl aminoethyl
~s methacrylate and subsequently oxidizing the amine functionality to the
amine oxide. In another
embodiment, the amine is oxidized to amine oxide prior to polymerization, and
the monomer is
then incorporated into the polymer.
The substituted amide and siianol functionallties can be introduced to the
polymer by
other means. For example, the silanol functionality can be incorporated by
using a chain transfer
zo agent such as y-mercaptopropyl trimethoxysilanc, Also, a polymer containing
acryl amide
groups can be funetionalized with dimethyl amine or another amine to give a
substituted amide
derivative. Copolymers of amino acids such as a copolymer of aspartic acid and
sodium
aspartate as disclosed in U.S. Patent Number 5,981,491 are useful. These
polymers contain
amide functionality in the backbone (available as Reactin AS 11 from Folia,
lnc., Birmingham,
25 AL). These copolymers also have irnide functionality. This imide
ftmctionality can be reacted
with an amine reagent such as diethanol amine to form a polymer with amide
side chains.
Copolymers from condensation and ring opening polymerization can also be used.
An example
of this is poly(2-ethyl-2-oxazolIne), wherein the substituted amide is in the
backbone of the
polymer.
3o Other ethylenically unsaturated monomers added at levels of up to about 50
weight
percent based on total monomers can also be optionally used to form the glass
adhesion
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CA 02470780 2004-06-11
copolymer. These monomers can be used to obtain desirable properties of the
copolymer in
ways known fn the art. Monomers can also be use to adjust the glass transition
temperature
{'T,~') of the copolymer to meet end-use application requicemcnts. Examples of
useful monomers
include (meth)acrylates, maleates, (meth)acrylamides, vinyl caters,
itaconates, styrenics,
acrylonitrile, nitrogen fimctionsl monomers, vinyl Caters, alcohol functional
monomers, and
unsaturated hydrocarbons.
Low levels of up to a few percent of crosslinking monomers can optionally be
used to
form the glass adhesion copolymer. The extra crosslinking improves the
strength of the bonding;
however, higher levels can be detrimental to the flexibility of the resultant
material. The
~o crosslinking moieties can be latent crosslinking where the crosslinking
reaction takes place not
during polyraerization but during curing of the binder. Chain-transfer agents
known in the art
can also be used to regulate chain length sad molecular weight. The chain
transfer agtnts can be
multifbnctlonal xo that star type polymers can be produced. The crosslinker
can be a polyol
andlor a polyamine.
~s The copolymer is synthesized by known polymerization methods. These include
solution, emulsion, suspension and inverse emulsion polymerization methods. 1n
one aspect, the
polymer is formed by solution polymerization in an aqueous medium. The aqueous
medium can
be water or a mixed water/water-miscible solvent system such as a
waterlalcohol solution. The
polymeriration can be batch, semi-batch, or continuous. The polymers are
typically prepared by
2o free radical polymerization; however, condensation polymerization can also
be used to produce a
polymer containing the desired moieties. The monomers can be added to the
initial charge,
added on a delayed basis, or a combination of the two. Accordingly, the
present invention
includes an aqueous solution having the copolymer therein. In another aspect,
this aquoous
solution fi~rther includes a silanol moiety.
2s The architecture of the glass adhesion copolymer can be random, block,
star, or other
known polymer architcdure. Random polymers are preferred due to the economic
advantages;
however, other architectures could be useful in certain end uses. In one
aspoct, the copolymers
typically have weight-averaged molecular weights in the range of about 1,000
to about 300,000.
In another aspect, the copolymers have weight-averaged molecular weights in
the range of about
30 2,000 to about 15,000. In one aspect, the molecular weight of the copolymer
is in the range of
CA 02470780 2004-06-11
about 2,500 to about 10,000. In another aspect, the molecular weight of the
copolymer is in the
range of about 3,000 to about 6,000.
As previously noted, the copolymer binder exhibits very good adhesion to
silicon-based
substrates, As used herein, silicon-based substrates refer to any substrate
containing silicon
s atoms. Silicon-based substrates include glass in the form of sheets, fibers,
beads, and formed
objects; silicas, silicates, sand, clays and silicon microchip materials. If
SiOH or silanol groups
are present on the substrate, the copolymers of the invention adhere to the
substrate,
Accordingly, the present invention includes a silicon-based substrate having
deposited thereon
the copolymer binder composition. When the substrate is glass fibers, the
copolymer binder
o composition is provided at a level effective in binding the fibers together,
thereby forming a self
sustaining web.
In addition to its use as a fiberglass binder, particularly useful end uses of
the copolymer
include forming glass-protective coatings. Other uses include binders in
cements and other
building materials where sand is used as filler. The composition's bonding
with the sand leads to
~ s improved composite strength. The composition can also be used in adhering
materials to silicon
microchips or in adhering silicon microchips to other substrates. The
copolymer can partially or
completely cover one or more sides of the silicon-based substrate, or it can
contact the substrate
in one or more discrete points of contact.
Another end use of the glass adhesion copolymer is in fiberglass reinforced
composites.
2o Fiberglass is used as a reinforcement material in plastics, wall boards end
other such material.
However, the fiberglass often is not compatible in the plastic or gypsum that
it is added to. The
glass adhesion copolymer of this invention aids in making the fiberglass
compatible for use in
the plastic or other substrates. In this manner, at least part of the
copolymer adheres to the
f berglass while at least another part of the copolymer anchors in the plastic
or gypsum substrate.
2s Accordingly, fiberglass that has been treated with the glass adhesion
copolymer of the present
invention enhances the physical properties of composite materials such as
plastic, gypsum
concrete, wood andlor cloth when they are formed using this fiberglass.
In addition to the glass adhesion copolymer, the fiberglass binder composition
can
include a crosslinker. The sizing composition can be formulated with a
crosslinker typically
3o used in fiberglass binder compositions, such as hydroxyl, polyol, or
polyamine components.
Examples of useful hydroxyl compounds include trihydric alcohol; ~-hydroxy
alkyl amides;
CA 02470780 2004-06-11
polyols, especially those having molecular weights of less than 10,000;
ethanol amines, such as
triethanol amine; hydroxy alkyl urea; and oxazolidone. In one aspect, the
polyol is a material
containing two or more hydroxyl groups. Examples of polyols include but are
not limited to
glycerol, triethanolamine, pentaerythritol, hydroxy alkyl urea; oxazolidone,
poly vinyl alcohol,
polysaccharides like starches, guars and their derivatives, and combinations
thereof. In another
aspect the polyamine contains two or more amine groups. Examples of useful
amines Include
triethanol amine, diethylene triamine, tetratethylene pentamane, polyethylene
amine and
combinations thereof.
According to the present invention, compounds capable of forming hydrogen-
bonding
~o complexes with copolymer polycarboxyl-functional binders allow for
crosslinkang at lower
temperatures. These cmsslinking compounds can be used in conjunction with the
functional
copolymers of the present invention. They also can be used with polymer and
copolymers
currently used as fiberglass binders. They can further also be used in
combination with
conventional crosslinking compounds, Examples of hydrogen-bonding complexing
agents
~5 include polyalkylene glycol, polyvinyl pyrroladone, polyethylene amine, or
mixtures thereof 1n
one aspect, the polyalkylene glycol is polyethylone glycol.
The glass adhesion copolymer forms strong bonds without the need for a
catalyst or
accelerator. One advantage of not using a catalyst in the binder composition
is that catalysts
tend to produce films that can discolor andlor release phosphorous-containing
vapors. Still, an
2o accelerator or catalyst can be combined with the copolymer binder to
decrease cure time,
increase crosslinking density andlor decrease the water sensitivity of the
cured bindex. Useful
catalysts include those known in the art, such as alkali metal salts of a
phosphorous-containing
organic acid, e_g., sodium hypophosphate, sodium phosphate, potassium
phosphate, disodium
pyrophosphate, tetra-sodium pyrophosphate, sodium tripolyphosphate, sodium
2s hexametaphosphatc, potassium polyphosphate, potassium tripoIyphosphate,
sodium
trimetaphosphate, sodium tetrametaphosphate; fluouroborates; and mixtures
thereof. Useful
catalysts also include Lewis acids such as magnesium citrate or magnesium
chloride, Lewis
bases, or free radical generators such as peroxide. In one embodiment, the
catalyst is present in
the binder formulation in an amount of from about 0 tv about 2S percent by
weight based on the
3o copolymer binder. In another embodiment, the catalyst is present in an
amount of from about 1
to about 10 percent by weight based on the copolymer binder.
.g.
CA 02470780 2004-06-11
The present invention further relates to fiberglass binder or siziwg
compositions or
formulations containing the copolymer binder described above. These fiberglass
sizing
compositions have excellent adhesion to the glass fibers. This good adhesion
between fibers
prevents the fibers from moving past each other and sagging over time.
s One of the major problems encountered wish current non-formaldehyde-based
resin
systems (herein referred to as conventional non-formaldehyde binder systems)
is their lack of
resistance to water and humidity. This lack of resistance results in sagging
of the insulation in
end use, which is detrimental to its insulating properties. While not being
bound by theory, it is
believed that the lack of water and humidity resistance is due, at least in
part, to the presence of
~o high amounts of inorganic salts in the system. Further, conventional
polycarboxylates used in
the binder system are extremely hydrophilic and tend to absorb large amounts
of water and
moisture.
The present invention overcomes this problem by use of a hydrophobic copolymer
in a
fiberglass sizing composition. This hydrophobic copolymer has at least one
acid group and a
is hydrophobic comonomer. The polymer portion having at least one acid group
is derived $om at
least one carboxylic monomer having the general formula (1) -
R' R=
R' R~
wherein R' to R' arc independently hydrogen, methyl, carboxylic acid group,
CH2COOH, or alkyl
or aryl sulfonic acids, and wherein the acid groups can be neutralized. This
acid monomer
20 includes acrylic acid, malefic acid, itaconic acid, 2~acrylamidomethyl
propane sulfonie acid,
styrene sulfonic acid, (meth)allyl sulfonic acid, (meth)allyloxybenzene
sulfonic acid and
combinations thereof.
The hydrophobic comonomer portion of the copolymer has the general formula
(iI) -
Rs
H X
25 wherein R3 is hydrogen, C,-C6 alkyl or C~-C6 hydroxyalkyl, and X is either
raono or polycyclic
aromatic group or a substituted aromatic group (with R~ being hydrogen or
methyl when X is
aromatic) or X is of the g~oral formula (Itn -
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CA 02470780 2004-06-11
~~-f -C~-.Y-~Rs (III)
wherein R8 is (indepertdcntly of R~ hydrogen, C~-C~ alkyl, C~-Cu alkoxy, C~-Cu
aminoalkyl,
G,-Cy~ alkyl sulfonate, -O alkyl, -OCO alkyl, -NCO alkyl, carboeyclic,
heterocyclic, or Cl-C2a
hydroxyalkyl; Y is 0 or N; snd t is either 0 or 1. This hydrophobic comonomer
constituent
includes, for example, methacrylic acid, methyl (meth) acrylate, ethyl (meth)
acrylate, t-butyl
(meth) acrylate, methyl (meth) acrylamide, ethyl (meth) acrylamide, t butyl
(meth) acrylamide,
vinyl acetate, vinyl pyrolidone, vinylpyridine, dimethylaminoethyl
{meth~crylate,
diethylaminoethyl(meth)aerylate, t-butylaminoethyl(meth)acrylate, dimethyl
amirropropyl
(meth)acrylate, dimethyl aminoethyl (meth)acrylamide, diethyl
aminoethyl(meth)acryiamide, t-
to butyl aminoethyl(meth)acrylamide, dimethyl atrtinopmpyl (meth)acrylanude,
polyethylene
glycol) tnethacrylate, C,x.~s adeohol ethoxylated methacrylate, Ci=-is a-
olefin, C~~.~s a-olefin
sulfonate, styrene sulfonate, vinyl formamide, vinyl methylether, styrene, or
a-methyl styrene.
Combinations of these monomers are also included. The hydrophobic group caa
also be
incorporated in to the polymer using a chain transfer agent. The chain
transfer agent can be long
is chain alcohol or long chain thiol or mercaptan. The latter can incorporate
hydrophobic thin Rlky1
groups in to the polymer.
In addition to the hydrophobic copolymer, the fiberglass siring composition
can include a
erasslinker. The sizing composition can be formulated with a crosslinker
typically used in
fiberglass binder compositions, such as hydroxyl, polyol, or polyarnine
components. >~,xamplcs
20 of useful hydroxyl compounds include trihydric alcohol; ~-hydroxy alkyl
amides; polyols,
especially those having molecular weights of less than 10,000; ethanol amines
such as trietharwl
amine; hydroxy alkyl urea; and oxawlidone. In one aspect, the polyol is a
material containing
two or more hydroxyl groups. Examples of polyols include but are not limited
to glycerol,
triethanolamine, pentaerythritol, hydmxy alkyl urea; oxazolidone, poly vinyl
alcohol,
2s polysaccharides like starches, guars and their derivatives, attd
combinations thereof. In another
aspect the polyamine contains two or more amine groups. Examples of useful
amines include
triethanol amine, diethylene triamine, tetratethylcne pentamine, polyethylene
imine and
combinations thereof. The sizing formulation can optionally further include a
catalyst or
accelerator.
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CA 02470780 2004-06-11
Alten,,stively, the Lack of water and humidity resistance in conventional nvn-
formaldehyde-based fiberglass binder systems can be overcome by adding a
hydrophobic
additive to the fiberglass binder composition. The hydrophobic additive can
include any water
repellent material. 1t can bo a hydrophobic emulsion polymer such as styrene-
aorylates,
ethylene-vinyl acetate, poly siloxanes, fluorinated polymers and polyesters.
The hydrophobic
additive can also be a surfactant. The surfactant itself can provide
hydrophobicity, or it can be
used to deliver a hydrophobic water insoluble material. The surfactant can be
non-ionic, anionic,
cationic or amphoteric, In one aspect, the surfactants are nonionic and/or
anionic. Nonionic
surfactants include, for example, alcohol ethoxylates, ethoxylated polyamines
and eth~oxylated
to polysiloxanos. Anionic surfactant9 include alkyl carboxylates and alkylaryl
sulfonates, a-olefin
sulfonates and alkyl ether sulfvnates.
The glass adhesion or hydrophobic copolymer, crosslinker and optiotaal
catalyst are
blended together to form the fiberglass binder composition. This binder
composition can
optionally be further formulated with one or more adjuvants, for example,
anti~xidsnts/
1s reducing agents, coupling agents, dyes, pigments, oils, fillers, thermal
stabilizers, emulsifiers,
coring agetrts, anti-nnigration aids, wetting agents, biocides, plasticizars,
anti-foaming agents,
waxes, flame-retarding agents, enzymes and lubricants. The adjuvants are
generally added at
levels of less than 20 percent based on the weight of the copolymer binder.
The binder
composition can also optionally include corrosion inhibitors. These corrosion
inhibitors include
2o tin compounds, for example, tin oxalate, thio areas and acetylinic
alcohols.
The fiberglass sizing composition can also be optionally formulated to include
one or
more additives for reducing leaching of glass. These additives include Zn
compounds such as Zn
carbonate and/or Zn sulfate. The additives can also include sodium silicate.
In one aspect, these
additives can reduce corrosion in metallic components.
2s The fiberglass sizing composition can further be optionally formulated to
include one or
more release additives. These release additives include silicone crud
fluorocarbon. Tho release
additives can function in reducing static. They can also function in reducing
resin buildup on
equipnnent. In one aspect, the release additives are added to the fiberglass
sizing composition.
In another aspect, the release additives are applied onto a substrate either
before or after
3o applications of the fiberglass sizing composition onto the substrate.
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CA 02470780 2004-06-11 j~
As the pH of the fiberglass sizing composition is increased, the amount of
neutralized
carboxylate groups generated in the polymer is increased. Grosslinking is
achieved if the acid
group in the polymer is protonated. Crosslinking cannot be attained through
any of the
neutralized carboxylic groups, especially if the ration is monovalent. 'This
increasing pH leads to
s lower crosslink density and degradation in physical properties. A lower pH
can be achieved by
using an organic acid such as malic, citric, salicylic, oxalic or tartaric
acid, or an inorganic acid
such as boric, sulfamic or sulfonic acid. Salts of boric acid can also be
used. In one aspect, the
pH of the fiberglass sizing composition is about 3.5 or less.
The present invention provides for an aqueous process for producing
hydrophobic
to solution copolymers. According to this process, one or more acid functional
monomers and one
or more hydrophobic monomers are added to an aqueous solution. An initiating
agent is added
to the solution to effect polymerization of the monomers. Polymerization can
occur at a
temperature of about 90°C or greater. With the polymerization of the
monomers a hydrophobic
solution copolymer is formed in the aqueous solution. The aqueous process can
also include
~s adding one or more chain transfer agents to the aqueous solution. In
another aspect, the aqueous
pmcess can also include adding one or more allylic or disubstituted acid
monomers to the
aqueous solution. The aIlylic or disubstituted acid monomer can be malefic
acid, sodium
methallyl sulfonate, or combinations thereof. In one aspect, the aqueous
process can also include
adding one or more neutralizing agents to the aqueous solution.
2o The fiberglass binder composition is useful for bonding fibmus substrates
to form a
formaldehyde-free non-woven material. The fiberglass binder composition is
especially useful
as a binder for heat-resistant non-wovens such as aramid fibers, ceramic
fibers, metal fibers,
polyrayon fibers, polyester fibers, carbon fibers, polyimide :fibers and
mineral fibers such as
glass fibers.
2s The copolymer binder composition is generally applied with a suitable spray
applicator to
a fiber glass mat as it is being formed so that the binder is distributed
nearly evenly throughout
the formed fiberglass mat. Typical solids are present in the aqueous solutions
in amounts of
about 5 to about 12 percent. The binder may also be applied by other means
known in the art,
including, but not limited to, airless spray, air spray, padding, saturating,
and roll coating: The
so residual heat from the fibers causes water to be volatilized from the
binder, and the high-solids
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CA 02470780 2004-06-11
binder-coated fiberglass mat is allowed to expand vertically due to the
resiliency of the glass
fibers.
The fiberglass mat is then heated to cure the binder. Typically, the curing
oven operates
at a temperature of from about 130°C to about 325°C. When
compounds that form hydrogcn-
bonding complexes with the copolymer binder are used, lower cure temperatures
of about 110°C
to about 150°C can be used. 1n one embodiment, the lower cure
temperature is about 120°C.
The fiberglass mat is typically cured in about 5 seconds to about 15 minutes.
In another aspect,
the mat is cured in about 30 seconds to about 3 minutes. Cure time depends on
both the
temperature and level of catalyst used.
to After curing, the fiberglass mat can be compressed for shipping. An
important property
of the fiberglass mat is that it returns to its full vertical height once the
compression is removed.
The copolymer binder produces a flexible film that allows the fiberglass
insulation to bounce
back after the roll is unwrapped and placed in walls and/or ceilings.
Fiberglass and other non-woven materials treated with the copolymer binder
composition
i s are useful as heat and/or sound insulation in the form of rolls or hafts;
as a reinforcing mat for
roofing and flooring products, ceiling tiles and flooring tiles; as a
microglass-based substrate for
printed circuit boards and battery separators; for filter stock and tape stock
and for
reinforcements in both non-cementatious and cementatious masonry coatings.
The present invention also provides for a fiberglass sizing composition having
a polymer
2o having at least one acid group derived from at least one carboxylic acid
monomer, one or more
crosslinkers, and one or more additives. The acid-group containing polymer
includes acxylic
acid. In another aspect, the acid-group containing polymer is the glass
adhesion copolymer
described supra. In one aspect, the acid-group containing polymer is the
copolymer described in
formula ()] supra. In another aspect, the acid-group containing polymer is
tire copolymer
zs described in formula (In supra. The crosslinkers can include one or more
polyols andlor
polyamines. In one aspect, the polyol contains 2 or more hydroxyl grnups.
Exemplary polyols
include glycerol, tniethanolamine, pentaerythritol, hydroxy alkyl urea,
oxazolidone, polyvinyl
alcohol, polysaccharide-like starches, guars and their derivatives, or
combinations thereof. In
another aspect the polyamine contains 2 or more amine groups. Exemplary
polyamines Include
3o triethanol amine, diethylene triamine, tetratcthylene pentarnlne, and
polyethylene imine or
combinations thereof
-13-
f .
CA 02470780 2004-06-11
The one or more additives of this three constituent fiberglass sizing
composition includes
corrosion inhibitors, hydrophobic additives, additives for reducing leaching
of glass, release
agents, acids for lowering pH or combinations thereof. In one aspect the one
or more additives is
at least one or more corrosion inhibitors. These corrosion inhibitors include
tin compounds such
as tin oxalate, thin areas, acetylinic alcohols and combinations thereof.
In another aspect the one or more additives is at least one or more
hydrophobic additives.
These hydrophobic additives can include a water repellent material. In another
aspect, the
hydrophobic additives can include a hydrophobic emulsion polymer. The
hydrophobic emulsion
polymer can be, for example, styrene-acrylates, ethylene-vinyl acetate, poly
siloxancs,
to fluorinated polymers, polyesters or combinations thereof. In another aspect
the ocsr or more
hydrophobic additives can include one or more surfactants. These surfactants
can provide
hydrophobicity to the composition. A,t least one of the surfactants can
deliver a hydrophobic
water insoluble material. In one aspect the surfactant is nonionic, anionic,
cationic or
amphoteric. In another aspect the surfactant is nonionic or anionic. Examples
of the nonionic
~ 5 surfactant include alcohol ethoxylates, ethoxylated polyamines,
ethoxylated polysiloxanes or
combinations thereof. Examples of the anionic surfactant include alkyl
carboxylates and
allcylaryl sulfonates, a-olefin sulfonates, allrylether sulfonates or
combinations thereof.
In one embodiment, the one or more additives of the three constituent
fiberglass sizing
composition include at least one or more additives for reducing leaching of
glass. These
20 leaching reduction additives can include Zn compounds. Examples of such Zn
Compounds
include Zn carbonate andlor Zn sulfate. These one or more leaching reduction
additives can also
include sodium silicate. In one aspect, these leaching reduction additirres
can reduce corrosion in
metallic components.
In another embodiment, the one or more additives of the three constituent
fiberglass
25 sizing composition include at least one or more release additives. These
release additives can
function in reducing static. The release additives can also function in
reducing buildup of the
resin on equipment. l:,xamples of release additives include silicone or
fluorocarbon.
The following examples are presented to further illustrate and explain the
present
invention and should not be taken as limiting in any regard.
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CA 02470780 2004-06-11
COPOLYMER COMPOSITIONS
A reactor containing 200 grams of water sad 244 gins of isopropanol (C3Ha0)
was
heated to 85°C. A monomer solution containing 295 grams of acxylic acid
(C31-LO~ and 4.1
grams of N,N-dimethyl acrylamlde was added to the reactor over a period of 3,0
hovers. An
initiator solution containing 15 grams of sodium gersulfate (NaZS20a) in 100
grains of deionized
water was simultaneously added tv the reactor over a period of 3.5 hours. The
reaction product
wss bald at 85°C for an additional hour. The isopmpanol was then
distilled using a Dean-Stark
1o trap.
A reactor containing 200 grams of water and 244 grams of isopropanol was
heated to
85°C. A monomer solution containing 295 grams of acrylic acid and S
grams of vinyl tri-
~s isoprogoxy silane (available as Coat 0 SiI~ 1706 from CrE Silicones,
Wilton, Connecticut, US)
was added to the reactor over a period of 3.0 hours. An initiator solution
comprising of 15 grams
of sodium persulfate in 100 grams of deioniz~ed water was simultaneously added
to the reactor
over a period of 3.5 lmurs. 'The reaction product was held at 85°C for
an additional hour. The
isopropanol was then distilled using a Dean-Stark trap. The isopropoxy silane
attaches to the
2o copolymer via the vinyl linkage. However, it hydrolyzes during the reaction
to form silanol
groups and isopropanol. The isopropanol formed is distilled with the rest of
the isopropanol
added to the initial charge. Additional water is added to the reaction to
dilute it to 50 % solids.
25 A reactor containing 200 grams of water and 2~4 grams of isopropanol was
heated to
85°C. A monomer solution containing 29S grains of acrylic avid and S
gams of vinyl triethoxy
silane (available as Siiquestm A-151 Shane from GE Silicones, Wilton,
Connecticut, US) was
added to the reactor over a period of 3.0 hours. An initiator solution
comprising of 15 grams of
sodium pe~sulfate in 100 grams of deionized water was simultaneously added to
the reactor over
3o a period of 3.5 hours. The reaction product was held at 85°C for an
additional hour. The
isopropanol was then distilled using a Dean-Stark trap. The vinyl triethoxy
silane attaches to the
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CA 02470780 2004-06-11
copolymer via the vinyl linkage. However, it hydrolyzes during this reaction
to form silanol
Groups and ethanol. The ethanol formed is distilled with the rest of the
isopropanol added to the
initial charge, Additional water is added to the inaction to dilute it to 50
percent solids.
s ~XAMP~E 4
A reactor containing 200 grams of water and 244 grams of isopropanol was
heated to
85°C. A monomer solution containing 295 grams of acrylic acid and 5
grams of 4-vinylpyridine
was added to the reactor over a period of 3.0 hours. An initiator solution
comprising of 1 S grams
of sodium persulfate in I00 grams of deionized water was simultaneously added
to the reactor
io over a period of 3.5 hours. The reaction product was held at 85°C
for an additional hour. The
isopropanot was distilled using a Dean-Stark trap. The vinyl pyridine moiety
was then oxidized
to amine oxide by treating the polymer with hydrogen peroxide in the presence
of sodium
molybdate (NazMoO4 ~ 2Hi0).
is E~' 1',E5
The test procedure for adhesion to glass is as follows. A 10 percent polymer
solution is
sprayed onto glass microscope slides. A polyr~ner film forms on each slide
with evaporation of
the water from the solution. The glass slides are weighed lxfore and aftex the
films are
developed. The slides are then soaked in a 1,0% NaOH solution for 10 minutes
and then dried.
zo The effectiveness of the adhesion to glass can be measured either by the
amount of polymer still
on the glass slides, ar by analyzing the amount of polymer redissolved in the
1.0% NaOH
solution.
TAB l,E 1
Exam Pal mer le Pol mer description Adhesion
le sam to leas
5a AlcosperseA Homopoiymer of acrylicnone
802 said
from Alco ica
Cherri
5b Example Copolym~r of acrylic good
1 acid wrld N,N
dimeth la amide
5c Example Copolymer of acrylic Excellent
2 aGd and
vin I tri8 silenol
5d Example Copolyrrrdr of acryNcF~ccellant
3 acid and
vin I tris si>anol
Se Fxsrnple Copolymer of acrylic
4 acid 4-
vin I ridine-N-oxide
-16-
CA 02470780 2004-06-11
EXAMPLE 6
A reactor containing 300 grams of water and 244 grams of isopropanol was
heated to
85°C. A monomer solution containing 295 gams of acrylic acid and 40
grams of methyl
methacrylate and 4 gams of vinyl methoxy silane was added to the reactor over
a period of 3.0
hours. An Initiator solution comprising of 15 grains of sodium persulfate in
100 gams of
deionized water was simultaneously added to the reactor over a period of 3.5
hours. The reaction
product was held at 85°~ fox an additional hour, The isopropanol was
then distilled using a
Dean~Stark trap, The vinyl methoxy silane is attached to the copolymer via the
viny) linkage.
However, it hydrolyzes during the reaction to form silanol groups and
methanol. The methanol
io formed is distilled with the isopropanol added to the initial charge.
Additional water is added to
the reaction to diluto it to 50% solids.
EXAMPLE 7
A reactor containing 300 grams of water and 244 grams of isopropanol was
heated to
i5 85°C. A monomer solution containing 295 grates of acrylic acid and
60 grams of methyl
methacrylate was added to the r~eaetor over a period of 3.0 hours. An
initiator solution
comprising of 15 grams of sodium persulfate in 100 grams of deionized water
was
simultaneously added to the reactor over a period of 3.5 hours. The reaction
product was held at
85°C for an additional hour. The isopropanol was then distilled using a
Dean-Stark trap.
20 Additional water is added to the reaction to dilute it to 50% solids.
EXAMPLE 8
A reactor containing 300 grams of water and 244 grams of isopropanol was
heated to
2s 85°C. A monomer solution containing 295 grams of acrylic acid and 20
grates of styrene and 4
grates of vinyl ethoxy silane was added to the reactor over a period of 3.0
hours. An initiator
solution comprising of 15 grams of sodium persulfate in 100 grams of deionized
water was
simultaneously added to the reactor over a period of 3.5 hours. The reaction
product was held at
85°C for an additional hour. The isopropanol was then distilled using a
Dean-Stark trap. The
3o vinyl ethoxy silane is attached to the copolymer via the vinyl linkage.
However, it hydrolyzes
during the reaction to form silanol groups and ethanol. The ethanol formed is
distilled with the
-17-
CA 02470780 2004-06-11
isopropanol added to the initial charge. Additional water is added to the
reaction to dilute it to
50% solids.
EXAMPLE 9
s A reactor containing 300 grams of water and 244 grams of isopropanol was
heated to
$5°C. A monomer solution containing 295 grams of acrylic acid and 30
granns of styrene was
added to the reactor over a period of 3.0 hours. An initiator solution
comprisung of 15 grams of
sodium persulfate in 100 grams of deionized water was simultaneously added to
the n,.actor over
a period of 3.5 hours. The reaction product was held at 85°C for an
additional hour. The
1o isopropanol was then distilled using a Dean-Stark trap. Additional water is
added to the reaction
to dilute it to 50% solids.
~X~LE 10
Aqueous process for producing a hydrophobically modified copolymer -
is 300 g of water, 42 grams of malefic anhydride and 0.025 grams of ferrous
ammonium
sulfate hexahydrate was heated in a reactor to 95°C. A mixture of 280 g
of acrylic acid and 23.7
g of styrene were added to the reactor over a period of four hours. At the
same time, a solution
of 12.0 g of sodium persulfate, 75 grams of 35% hydrogen peroxide solution in
100 g of water
was added to the reactor over a period of 4.5 hours. The temperature of the
reactor was
20 maintained at 95°C for two hours, after which a clear light yellow
solution of the polymer was
obtained.
FIBERGLASS SIZING FORMULATION EXAMPLES
z5 SAMPLE 11
Fiberglass sizing composition having hydrophobic copolymer -
' nts Wt
Polymer of Example 7 20
Triethanol amino 5
38 Water 75
-18-
CA 02470780 2004-06-11
EXAMPLE 12
Fiberglass sizing composition having hydrophobic copolymer with a glass
adhcsion
moiety -
In 'ents Wt
Polymer of Example 6 20
Glycerol 4
Water 76
EXAMPLE 13
Fiberglass sizing composition having a surfactant as a hydrophobic additive -
ie Wt
Polymer of Example 9 20
Triethanolamine 5
C~Z_,5 alcohol with 7 moles ofethoxylation (su~rf'actant) 10
i 5 Water 65
LE 14
Fiberglass sizing composition having hydrophobic copolymer with a glass
adhesion
moiety and a corrosion inhibitor
2o In ' Wt
Polymer of Example 6 20
Glycerol 4
Tin oxalate (corrosion inhibitor) 1
Water 76
L1r I S
Fiberglass sizing composition having hydrophobic copolynner -
In ' is ° o
Polymer of Example 7 20
3o Triethanol amine 5
Tartaric acid (to lower pH) 10
Water 65
-19-
CA 02470780 2004-06-11
EXAMP
Fiberglass sizing composition having acrylic acid homopolymer and hydrophobic
copolymer as an additive -
lQg~,edients
Wt %°~a
s Polymer of Example 7 2
Starch 5
Homopolymer of acrylic acid (available as Alcosperse~ 602A
from Alco Chemical, Chattanooga, Tennessee, US) 20
Water 73
EXAMPLE 17
Fiberglass sizing composition having acrylic acid homopolymer and hydrophobic
emulsion copolymer as an additive -
jn~redient t
Ethylene vinyl acetate copolymer (available as Resyn~ 1971 from
Vinamul Polymers, Enoree, South Carolina, US) 2
Glycerol 5
Homopolymer of acrylic acid (available as Alcosperse~ 602A
from Alto Chemical, Chattanoo~s, Tennessee, US) 20
2o Water 73
EXAMPLE :~~
Fiberglass sizing composition having acrylic acid homopolymer and hydrophobic
emulsion copolymer as an additive -
IIl r~ Wt °/a
Organosilicone (available as Dow Coming~ 2-9034 from
Dow Corning, Midland, Michigan, US) 2
Glycerol 5
Homopolymer of acrylic acid (available as Aquatreat~ 900A
from Alco Chemical, Cha#anooga, Tennessee, US) 20
Water 73
-20-
CA 02470780 2004-06-11
EXAMPLE 19
Fiberglass sizing composition having acrylic acid homopolymet and hydrophobic
copolymer as an additive -
TI1 1811t o 0
s Sodium methyl sileonate (available as Dow Corning 772 from
Dow Corning, Midland, Michigan, US) 1
Triethanol amine 8
Homopolymer of acrylic acid (available as Alcosperse~ 602A
from Alco Chemical, Chattanooga, Tennessee, US) 20
t 0 Water 71
~~Q
Fiberglass sizing composition having acrylic acid homopolymer and hydrophobic
emulsion copolymer as an additive
15 1n Wt
Styrene-acrylate emulsion (available as ltAp 810NA from The Dow
Chemical Company, Midlsnd, Michigan, US) 5
Glycerol 8
Homopolymcr of acrylic acid (available as Aquatreat~ 900A
2o from Alco Chemical, Chattanooga, Tennessee, US) 18
Water 68
ALE 21
Fiberglass sizing composition having an anionic surfactant as a hydrophobic
additive -
2s In lent
Polymer of Example 9 20
Triethanol amine 5
C,ms alcohol with 3 moles of ethoxylation sulfate (surfactant) 10
water 6s
-21-
CA 02470780 2004-06-11
EXAMPLE 22
Fiberglass sizing coraposition having hydrophobic emulsion copolymer -
insredient t %
Styrene-acrylate emulsion (available as Joncryl~ 90 from Johnson
s Polymer, Stwtevant, Wisconsin, US) 20
Glycerol 8
Watcr 72
EXAMPLE 23
io Fiberglass sizing composition having acrylic acid homopolymer and,
hydrophobic
emulsion copolymer as an additive -
ei t
Methacrylic acid-ethylacrylate copolymer (available as Alcogum~ L15
from Alto Chemical, Chattanooga, Tennessee, US) 5
a 5 Glycerol 8
Homopolymer of acrylic acid (available as Aquatreat~ 900A
flbm Alto Chemical, Chattanooga, Tennessee, US) 18
Water 68
zo E3~AMPL,~24
Molecular modeling was used to calculate solubility parameters of a copolynner
of acrylic
acid and co-styrene (7.5 mole %), The solubility parameter provides! in Table
2 below gives an
estimate of the water solubility of the copolymer,
2s ~'ASr~z
Material pH Mole% Na acrylateSolubility
parameter
Joules/cc ~n
Acrylic acid - 3 5 27.63
co-styrene
?.5 mole
Acrylic acid - 4 33 43.13
co-styrene
(7.3 mole
Pol lie acid 4 0 46.2
Pol st rene ~ ~ - 20,
~
Water ~ - 47.96
The data indicates that golyacrylic acid is very water soluble since its
solubility
parameter is close to that of water. The data indicate that the styrene
copolymer with acrylic acid
_22.
CA 02470780 2004-06-11
is less water soluble. In fact, at ply 3 it is extremely hydrophobic since its
solubility parameter is
close to that of polystyrene which is insoluble in water. Therefore,
fiberglass sized using an
acrylic acid-styrene copolymer will be very water repellent. .
s E7~AMPLE 25
Molecular modeling was used to calculate solubility parameters of various
copolymers of
acrylic acid at pH 3. The copolymers modeled and their associated solubility
parameters arc
provided below in Table 3 -
TA~LE 3
Copolymer Mole % Solubility parameter
comonomer Jouleslcc tn
Water - 48
Ac lie acid - lie acid 30 35
Ac lie acid -meth 1 10 30
laic
Ac lie acid - st ne 7.5 28
Pol st a 20
to
The data indicates that acrylic acid copolymers with styrene, methyl
methaerylate and
methacrylic acid arc very hydrophobic.
i5 Hydrophobic proptrties of acrylic acid - methyl methaerylate copolymer
compared to
homopolymer of acrylic acid -
TABLE 4
Solution A Solution B
ams ams
Polymer of 1~aCample 20 -
b (Copolymer
of acrylic acid and
methyl
methaa late
Homo 1 er of ac llc - 20
acid
Sodium h ho 'te - 3
Triethanol amine 7 7
Water 73 73
zo The solutions detailed in Table 4 above were prepared. Solutions A and 13
were sprayed
on to fiber glass mats. The mats were curod in an oven at 200°C for 2
minutes. These mats were
-23-
CA 02470780 2004-06-11
then put in to humidity chamber at 40°C and 90°Yo humidity for 1
hour. The moisture uptako aver
an hour was measured as the percent weight gain of the mat, provided in Table
5 below,
TABLE 5
Solution Pol mer % moisture
a a
A Polymer of Example 6 (Copolymer40
of
lic acid and meth 1 mcthac
late
H Homopolymer of acrylic acid60
catalyzed
with sodium h o hoe bite
s
The data indicate that hydrophobic copolymers of this invention absorb far
less moisture
than a homopolymer of acrylic acid catalyzed using sodium hypophosphite. This
can be
attributed to the fact that the inorganic material gent from sodiwn
hypophosphite will
absorb moisture and have a negative impact on the fiber glass mat properties.
~o
FX.~LE 27
Fiberglass sizing composition having a surfactant as a release agent
Polymer of Example 9 20
t 5 Triethanolamine S
Dioctylester of sodium sulfosuccinic acid {available as
Aerosolm OT 100 from Cytec Industries, West Pat~son, NJ) 1
Water 74
zo EXAMPLE 28
Fiberglass sizing composition having a silicone as a release agent -
In ' t ~~° o,
Polymer of Example 9 20
Triethanolamine 5
25 Silicone emulsion of a 350 cs dimethyl polysiloxa~ fluid (available as
SWS-231 from Wacker Chemical Corp., Adrian,1VQ) 1
Water 74
-24-
CA 02470780 2004-06-11
~xAMPLE z9
Fiberglass sizing corinposition having an addiGvc to minimize glass leaching -
In ~t
Polymer of Example 9 24
TriethanoIamine 5
ZnC03 2
Water 73
1;XAMPLE 30
o Fiberglass sizing composition having an acid for pH control -
Wt~/u
Polymer of Example 9 20
Tricthanolamine 5
Boric acid 2
i5 Water 73
EXAMPLE 31
Fiberglass sizing composition having an acid corrosion inhibitor -
2o Polymer of Example 8 20
Triethsnolamine 5
Borate ester corrosion inhibitor (available as Monacor BE
from Uniqema, Peterson, NJ) Z
Water 74
2s
~XAM~E 32
Fiberglass sizing composition having an acid corrosion inlubitor/prevention of
glass
leaching agent -
3o Polymer of Example 7 20
Triethanolarnine 5
Sodium Silicate (SiOs/NazO) (available as IVY Sodiwn Silicate from the
PQ Corporation, Borwyn, PA) I
Water 74
-25-
