Coatings for fiber strands, coated fiber strands, reinforced composites, assemblies and method of reinforcing the same

The present invention provides aqueous secondary coating compositions adapted to coat a sized fiber strand, the compositions including a urethane-containing polymer and a blend of a halogenated vinyl polymer and an elastomeric polymer. Another aspect of the present invention is a generally tubular assembly having a reinforcement coated with a primary layer of a sizing composition including a fiber lubricant which provides the assembly with an electrical resistance of greater than about 750 megaohms per 152.+-.13 millimeters of length of the assembly and a secondary layer including a halogenated vinyl homopolymer and a urethane-containing polymer. Another aspect of the present invention is a fiber strand formed from a thermoplastic or thermosetting material having a primary layer including a halogenated vinyl homopolymer and a urethane-containing polymer. The present invention also includes strands coated with the above-discussed coatings and polymeric composites and assemblies reinforced with the same.

FIELD OF THE INVENTION 
This invention relates generally to reinforcements for multilayered 
assemblies or composites and, more specifically, to fiber strands coated 
with (1) a blend of a halogenated vinyl polymer and an elastomeric polymer 
and (2) a urethane-containing polymer for reinforcing multilayered 
assemblies or composites. 
BACKGROUND OF THE INVENTION 
Reinforced multiple-ply hoses, for example those which are used to convey 
pneumatic fluids such as hydraulic oils, are often subjected to bending, 
twisting and physical environments which can cause deterioration of the 
hose materials and separation of the hose plies. Coatings on the 
reinforcement material can promote adhesion and compatibility between the 
reinforcement and the adjacent plies of the hose. 
U.S. Pat. No. 4,663,231 discloses an aqueous impregnating coating 
composition for glass fibers which includes an aqueous soluble, 
dispersible or emulsifiable elastomeric ethylene-containing interpolymer 
which has a glass transition temperature of around 0.degree. C. or less 
(see column 4, lines 38-54); one or more crosslinkable materials; a 
crosslinking controlling agent; wax, a plasticizer and a diene-containing 
elastomeric polymer. 
U.S. Pat. No. 4,762,750 discloses an aqueous impregnating coating 
composition for glass fibers which includes an aqueous soluble, 
dispersible or emulsifiable elastomeric polymer that is essentially free 
of any hydrocarbon diene functionality and essentially free of any 
chlorine functionality (see column 5, lines 58-63), such as elastomeric 
ethylene-containing interpolymers having a glass transition temperature of 
around 0.degree. C. or less (see column 6, lines 21-38), elastomeric 
polyurethanes, elastomeric silicones, fluororubbers, polysulfide rubbers, 
ethylene-propylene rubber or polyethers; a crosslinking material; and 
optionally a wax, plasticizer and diene-containing elastomeric polymer. 
There is a need for a coating for fiber reinforcements, such as glass fiber 
reinforcements, which provides adequate adhesion and compatibility between 
the reinforcement and adjacent materials, such as polyethylene or 
polyurethane hose plies, and superior performance characteristics such as 
high electrical resistance. 
SUMMARY OF THE INVENTION 
The present invention provides an aqueous secondary coating composition 
adapted to coat a fiber strand having thereon a primary layer of a sizing 
composition which is different from the secondary coating composition, the 
secondary coating composition comprising: (a) a blend of (1) a halogenated 
vinyl polymer; and (2) an elastomeric polymer, the blend being essentially 
free of a monoolefinic material; and (b) a urethane-containing polymer 
different from the elastomeric polymer. 
Another aspect of the present invention is a fiber strand having applied to 
at least a portion of a surface thereof a primary layer of a sizing 
composition and thereupon a secondary layer of an aqueous secondary 
coating composition different from the sizing composition, the secondary 
coating composition comprising: (a) a blend of (1) a halogenated vinyl 
polymer; and (2) an elastomeric polymer, the blend being essentially free 
of a monoolefinic material; and (b) a urethane-containing polymer 
different from the elastomeric polymer. 
Another aspect of the present invention is a fiber strand having applied to 
at least a portion of a surface thereof a primary layer of a sizing 
composition and thereupon a secondary layer of an aqueous secondary 
coating composition different from the sizing composition, the secondary 
coating composition comprising: (a) a blend of (1) a vinyl chloride 
copolymer; and (2) an acrylonitrile-butadiene copolymer, the blend being 
essentially free of a monoolefinic material; and (b) a urethane-containing 
polymer. 
Another aspect of the present invention is a reinforced polymeric composite 
comprising: (a) a fiber strand reinforcing material, at least a portion of 
a surface of the fiber strand reinforcing material having applied thereto 
a primary layer of a sizing composition and thereupon a secondary layer of 
an aqueous secondary coating composition comprising: (1) a blend of (i) a 
halogenated vinyl polymer; and (ii) an elastomeric polymer, the blend 
being essentially free of a monoolefinic material; and (2) a 
urethane-containing polymer different from the elastomeric polymer; and 
(b) a polymeric matrix material. 
The present invention also provides an aqueous secondary coating 
composition adapted to coat a fiber strand having thereon a primary layer 
of a sizing composition which is different from the secondary coating 
composition, the secondary coating composition comprising: (a) a 
halogenated vinyl homopolymer; (b) an elastomeric polymer; and (c) a 
urethane-containing polymer different from the elastomeric polymer. 
Another aspect of the present invention is an aqueous secondary coating 
composition adapted to coat a fiber strand having thereon a primary layer 
of a sizing composition which is different from the secondary coating 
composition, the secondary coating composition comprising: (a) a 
halogenated vinyl homopolymer; (b) a urethane-containing polymer; and (c) 
a wax material. 
Another aspect of the present invention is an aqueous secondary coating 
composition adapted to coat a fiber strand having thereon a primary layer 
of a sizing composition which is different from the secondary coating 
composition, the secondary coating composition comprising: (a) a 
halogenated vinyl polymer; and (b) a water soluble, emulsifiable or 
dispersible curable acrylic polymer. 
Another aspect of the present invention is a reinforced generally tubular 
assembly comprising: (a) a first layer formed from a polymeric material, 
the first layer having an inner surface and an outer surface; (b) a 
reinforcement layer having an inner surface and an outer surface, the 
inner surface of the reinforcement layer being positioned adjacent to the 
outer surface of the first layer, the reinforcement layer comprising an 
assembly of coated fiber strands having applied to at least a portion of a 
surface thereof a primary layer of a sizing composition and thereupon a 
secondary layer of an aqueous secondary coating composition different from 
the sizing composition, the sizing composition comprising: (1) a 
film-forming material; (2) a fiber lubricant adapted to provide the 
tubular assembly with an electrical resistance of greater than about 750 
megaohms per 152.+-.13 millimeters of length of the tubular assembly; and 
(3) a coupling agent; and the secondary coating composition comprising: 
(1) a halogenated vinyl homopolymer; and (2) a urethane-containing 
polymer; and (c) an outer layer formed from a polymeric material, the 
outer layer being positioned adjacent to the outer surface of the 
reinforcement layer to form a generally tubular assembly. 
Another aspect of the present invention is a fiber strand formed from a 
material selected from the group consisting of a thermoplastic material 
and a thermosetting material, the fiber strand having applied to at least 
a portion of a surface thereof a primary coating composition comprising: 
(a) a halogenated vinyl homopolymer; and (b) a urethane-containing 
polymer. 
The present invention also includes strands coated with the above-discussed 
coatings, polymeric composites and assemblies reinforced with the same and 
a method for reinforcing a generally tubular assembly.

DETAILED DESCRIPTION OF THE INVENTION 
The aqueous secondary coating compositions of the present invention are 
adapted to coat a fiber strand or roving having thereon a primary layer of 
a sizing composition, which is preferably at least partially dried. The 
coated fiber strands of the present invention are adapted to reinforce 
polymeric composites and multi-layered assemblies such as hoses. As used 
herein, the term "strand" means a plurality of individual fibers. The term 
"fibers" means a plurality of individual filaments. 
A fiber strand 10 of the present invention, shown in FIG. 1, has a primary 
layer of an essentially dried residue of a sizing composition 12 on at 
least a portion of its surface 14 to protect the surface 14 from abrasion 
during processing. As used herein, the terms "size", "sized" or "sizing" 
refer to the composition applied to the fibers immediately after formation 
of the fibers. Suitable sizing compositions for use in the present 
invention will be discussed in detail below. 
The term "secondary coating" 16 refers to a coating composition applied as 
a secondary layer over at least a portion of the primary layer of the at 
least partially dried sizing composition 12. The secondary coating 
composition is different from the sizing composition, i.e., the secondary 
coating composition (1) contains at least one component which is 
chemically different from the components of the sizing composition; or (2) 
contains at least one component in an amount which is different from the 
amount of the same component contained in the sizing composition. For 
example, the secondary coating composition can contain a thermoplastic 
polyurethane and the sizing composition can contain a chemically different 
thermosetting polyurethane. In another example, the secondary coating 
composition and sizing can each contain the same thermoplastic 
polyurethane but in different amounts. 
Broadly stated, the secondary coating compositions of the present invention 
are preferably aqueous-based and include components which are water 
soluble, emulsifiable or dispersible. The components of the secondary 
coating compositions can also be curable. 
As used herein, the term "water soluble" means that any of the components 
of the secondary coating composition are capable of being essentially 
uniformly blended and/or molecularly or ionically dispersed in water to 
form a true solution. See Hawley's Condensed Chemical Dictionary, (12th 
Ed. 1993) at page 1075, which is hereby incorporated by reference. 
The term "emulsifiable" as used herein means that any of the components of 
the secondary coating composition are capable of forming an essentially 
stable mixture or being suspended in water in the presence of an 
emulsifying agent. See Hawley's at page 461, which is hereby incorporated 
by reference. Non-limiting examples of suitable emulsifying agents are set 
forth below. 
The term "dispersible" means that any of the components of the secondary 
coating composition are capable of being distributed throughout water as 
finely divided particles, such as a latex. See Hawley's at page 435, which 
is hereby incorporated by reference. The uniformity of the dispersion can 
be increased by the addition of wetting, dispersing or emulsifying agents 
(surfactants), which are discussed below. 
As used herein, the term "curable" means (1) any of the components of the 
secondary coating composition are capable of being at least partially 
dried by air and/or heat; and/or (2) any of the components of the 
secondary coating composition, other components of the secondary coating 
composition and/or fibers are capable of being crosslinked to each other 
to change the physical properties of the component of the secondary 
coating composition. See Hawley's at page 331, which is hereby 
incorporated by reference. 
In a preferred embodiment, the aqueous secondary coating composition of the 
present invention comprises a blend of (1) one or more halogenated vinyl 
polymers; and (2) one or more elastomeric polymers, the blend being 
essentially free of a monoolefinic material. As used herein, the terms 
"blend" or "polyblend" mean a uniform combination of (a) one or more 
halogenated vinyl polymers and (b) one or more elastomeric polymers. See 
Hawley's at page 157, which is hereby incorporated by reference. 
The halogenated vinyl polymer can be a homopolymer, copolymer or 
multipolymer formed by the polymerization of one or more types of 
halogenated vinyl monomers or preformed copolymers of the halogenated 
vinyl monomers. 
Non-limiting examples of preferred halogenated vinyl monomers for forming 
the halogenated vinyl polymer include vinyl chloride, vinyl fluoride, 
vinylidene chloride, vinylidene fluoride and mixtures thereof. Vinyl 
monomers of other halogens of group VIIA of the Periodic Table, such as 
bromine, iodine, astatine and mixtures thereof, can also be used. 
As used herein, the term "mixture" means a heterogeneous association of 
substances which cannot be represented by a single chemical formula and 
which may or may not be uniformly dispersed and can usually be separated 
by mechanical means. See Hawley's at page 788-789, which are hereby 
incorporated by reference. 
For information regarding methods for forming halogenated vinyl monomers, 
see Hawley's Condensed Chemical Dictionary, (12th Ed. 1993) at pages 
1215-1216 and Encyclopedia of Polymer Science and Technology, (1971) 
Volume 14 at pages 313-316, which are hereby incorporated by reference. 
Examples of polymerization methods for forming the halogenated vinyl 
polymer(s) from the halogenated vinyl monomer(s) include bulk 
polymerization in the presence of a free radical initiator, emulsion 
polymerization, suspension polymerization and solution and precipitation 
polymerization. For more information regarding methods for polymerizing 
halogenated vinyl monomers, see Kirk-Othmer, Encyclopedia of Chemical 
Technology, (2d Ed. 1970) Volume 21 at pages 369-377, which are hereby 
incorporated by reference. 
Examples of suitable halogenated vinyl polymers include polyvinyl chloride, 
polyvinyl fluoride, vinylidene chloride, vinylidene fluoride, mixtures 
thereof and copolymers thereof. Preferably, the halogenated vinyl polymer 
is polyvinyl chloride or a copolymer of polyvinyl chloride and vinylidene 
chloride. 
Such polymers can be emulsified with any conventional emulsifier well known 
to those skilled in the art and such as are discussed below. Non-limiting 
examples of useful emulsified halogenated vinyl polymers include VYCAR.TM. 
351, 352, 460X95, 575X43, 576, 577, 580X83, 580X158, 580X175, 590X4 vinyl 
chloride polymer and copolymer emulsions and YCAR.TM. 650X18 and 660X14 
vinylidene chloride copolymer emulsions, which are commercially available 
from B. F. Goodrich. 
For example, VYCAR.TM. 352 vinyl chloride copolymer emulsion has a glass 
transition temperature of about +69.degree. C., a specific gravity of 
1.16, a pH of about 10.3 to about 10.5, a surface tension of about 39 
dynes per centimeter, a Brookfield LVF viscosity of about 20 centipoise at 
25.degree. C. using Spindle No.1 at 60 revolutions per minute (rpm), an 
average total solids of about 57 weight percent and includes an anionic 
emulsifier, according to the supplier. 
Another example of a useful vinyl chloride copolymer emulsion is VYCAR.TM. 
580X83, which is plasticized with di-isodecyl phthalate and has a glass 
transition temperature of about +17.degree. C., a specific gravity of 
1.14, a pH of about 10.0, a surface tension of about 35 dynes per 
centimeter, a Brookfield viscosity of about 30 centipoise at 25.degree. C. 
using Spindle No. 2 at 60 rpm, an average total solids of about 56 weight 
percent and also includes an anionic emulsifier, according to the 
supplier. 
For more information regarding useful commercially available halogenated 
vinyl polymers, see "VYCAR.TM. Polyvinyl Chloride Emulsions", a Technical 
Bulletin of B. F. Goodrich Company (May 1994) at pages 2 and 13-17; 
"Textile Polymers and Chemicals Product Selection Guide" A Technical 
Bulletin of B. F. Goodrich Co. (May 1995) at pages 7-8; "BFGoodrich 
Emulsion Polymer Selection Guide", a Technical Bulletin of B. F. Goodrich 
Co. (1994); "Technical Data VYCAR.TM. 352", a Technical Bulletin of B. F. 
Goodrich Co. (August 1994); and "Technical Data VYCAR.TM. 580X83", a 
Technical Bulletin of B. F. Goodrich (August 1994), which are hereby 
incorporated by reference. 
Other materials which can be copolymerized with the halogenated vinyl 
polymer include vinyl esters such as vinyl acetate, acrylic esters such as 
methyl acrylate, ethyl acrylate and n-butyl acrylate, vinyl ethers such as 
cetyl vinyl ether or lauryl vinyl ether and maleic and fumaric esters. For 
more information, see Encyclopedia of Polymer Science and Technology, 
(1971) Volume 14 at pages 347-350 and 353-357, which are hereby 
incorporated by reference. 
One or more plasticizers for the halogenated vinyl polymer can be included 
in the aqueous secondary coating composition. Non-limiting examples of 
suitable plasticizers include phthalates (such as di-isodecyl phthalate, a 
preferred plasticizer, di-2-ethyl hexyl phthalate, diisooctyl phthalate); 
phosphates (such as trixylyl phosphate and tricresyl phosphate); esters of 
aliphatic dibasic acids (adipates such as dioctyl adipate); polyesters; 
and trimellitates, such as trioctyl trimellitate. See Encyclopedia of 
Polymer Science and Technology, Volume 14 (1971) at pages 396-397, which 
are hereby incorporated by reference. 
The amount of plasticizer can be about 10 to about 40 weight percent of the 
aqueous secondary coating composition on a total solids basis, and is more 
preferably about 20 to about 30 weight percent. 
The aqueous secondary coating composition of the present invention also 
comprises one or more elastomeric polymers. As used herein, "elastomeric 
polymer" is a polymer which is capable of recovery from large deformations 
quickly and forcibly and has the ability to be stretched to at least twice 
its original length and to retract very rapidly to approximately its 
original length when released. See Hawley's at page 455 and Kirk-Othmer, 
Volume 7 (1965) at page 676, which are hereby incorporated by reference. 
Suitable elastomeric polymers useful in the present invention for blending 
with the halogenated vinyl polymer include diolefins, such as 
polyisoprene, polybutadiene, polychloroprenes (neoprenes), 
styrene-butadiene copolymers, acrylonitrile-butadiene copolymers and 
styrene-butadiene-vinylpyridine terpolymers. Other elastomeric polymers 
useful in the present invention include fluoroelastomers, polysulfides, 
silicone rubbers, polyacrylates and polyurethanes which are different from 
the urethane-containing polymer discussed below. 
Preferably, the elastomeric polymer is a diolefin such as an 
acrylonitrile-butadiene copolymer or nitrile rubber. Suitable nitrile 
rubbers generally contain about 50 to about 82% butadiene. An example of a 
suitable acrylonitrile-butadiene copolymer is HYCAR G-17, which is 
commercially available from B. F. Goodrich Chemical Co. of Cleveland, 
Ohio. 
Polyisoprene is the main component of natural rubber. Suitable synthetic 
polyisoprene is commercially available from Shell Chemical Co. of Houston, 
Tex. Polybutadiene useful in the present invention generally has about 92 
to about 97% cis-1,4-polybutadiene. Suitable chloroprenes (neoprenes) are 
emulsion polymers of 2-chloro-1,3-butadiene. Suitable styrene-butadiene 
copolymers generally contain about 71 to about 77% butadiene. 
Suitable fluoroelastomers are rubbers containing fluorine, hydrogen and 
carbon, such as copolymers of vinylidene fluoride and 
chlorotrifluoroethylene (which are commercially available as Kel-F 
elastomers from Minnesota Mining and Manufacturing Co. (3M) of Minnesota) 
and copolymers of perfluoropropylene and vinylidene fluoride (which are 
commercially available from as VITON copolymers from E. I. duPont de 
Nemours & Co., Inc. of Wilmington, Del. and FLUOREL copolymers from 3M). 
Other useful fluoroelastomers include fluoroacrylates, fluoropolyesters, 
fluorinated silicones and fluorinated nitroso elastomers. 
Useful polysulfides include NOVOPLAS polysulfides which are commercially 
available from ICI Americas, Inc. of Wilmington, Del. 
Suitable polyacrylate elastomers are copolymers of alkyl acrylic acid 
esters, such as ethyl and butyl acrylates, and a crosslinking copolymer, 
such as acrylonitrile or a chlorinated vinyl derivative. 
Suitable silicone rubbers are siloxane polymers composed of a central chain 
of alternating silicon and oxygen atoms with alkyl or aryl groups attached 
to the silicon atoms. 
Suitable polyurethane elastomers can be formed by the condensation reaction 
of polyfunctional isocyanate-containing materials with linear polyesters 
or polyethers containing hydroxyl groups (polyols). Useful polyfunctional 
isocyanate-containing materials are difunctional isocyanates such as 
toluene diisocyanate, phenylene diisocyanate, dianisidine diisocyanate, 
diisocyanatodiphenyl methane, bis(p-phenyl isocyanate), bis(p-phenyl) 
methylene diisocyanate, bis(p-phenyl cyclohexyl) methylene diisocyanate, 
naphthalene diisocyanate, xylylene diisocyanate, tetramethylxylylene 
diisocyanate, cyclohexane diisocyanate, hexamethylene diisocyanate, 
isophorone diisocyanate and dicyclohexylmethane-4,4'diisocyanate. 
Useful linear polyesters containing hydroxyl groups can be formed by the 
reaction of ethylene or propylene glycol with adipic acid. Useful 
polyethers include polyoxy-1,4-butylene glycol, polyoxy-1,2-propylene 
glycol and polytetramethylene ether glycol. 
A non-limiting example of a suitable polyurethane elastomer is ESTANE, 
which is commercially available from B. F. Goodrich. 
Methods for forming suitable elastomeric polymers are well known to those 
skilled in the art and further discussion thereof is not believed to be 
necessary in view of the present disclosure. If more information is 
needed, see Kirk-Othmer, Volume 7 (1965) at pages 679-686 and 693-698 and 
Volume 17 (1968) at pages 543-544; Encyclopedia of Polymer Science and 
Technology, Volume 2 (1965) at pages 703-706 and Hawley's at page 942, 
which are hereby incorporated by reference. 
The halogenated vinyl polymer and elastomeric polymer can be blended by 
conventional blending equipment such as a mixer. The ratio of halogenated 
vinyl polymer to elastomeric polymer in the blend can be about 5:95 to 
about 99:1 based upon the weight of total solids of the blend, is 
preferably about 50:50 to about 95:5 and is more preferably about 70:30 to 
about 90:10. 
A non-limiting example of a useful commercially available blend of a 
halogenated vinyl polymer and an elastomeric polymer is VYCAR.TM. 552 
vinyl chloride copolymer and acrylonitrile-butadiene copolymer polyblend 
emulsion which is commercially available from B. F. Goodrich and has a 
glass transition temperature of about 4.degree. C., specific gravity of 
about 1.09, pH of about 10.3, a surface tension of about 36 dynes per 
centimeter, a Brookfield viscosity of about 17 centipoise at 25.degree. C. 
using a Spindle No. 1 at 60 rpm, about 55 weight percent average total 
solids and which includes an anionic emulsifier. See "VYCAR.TM. Polyvinyl 
Chloride Emulsions" at page 15 and "Technical Data VYCAR.TM. 552", a 
Technical Bulletin of B. F. Goodrich (August 1994), which is hereby 
incorporated by reference. 
Based upon the weight of the total solids of the aqueous secondary coating 
composition, the blend of the halogenated vinyl polymer and the 
elastomeric polymer generally comprises about 50 to about 99 weight 
percent of the aqueous secondary coating composition, preferably comprises 
about 70 to about 90 weight percent, and more preferably about 80 to about 
90 weight percent of the aqueous secondary coating composition. 
As used herein, "essentially free of monoolefinic materials" means that the 
blend preferably contains less than about 5 weight percent and more 
preferably less than about 1 weight percent of a monoolefinic material (an 
unsaturated aliphatic hydrocarbon having one double bond. See Hawley's at 
pages 851-852, which are hereby incorporated by reference). Examples of 
such monoolefinic materials include alkenes, such as ethylene and 
propylene. Most preferably, the copolymer is free of a monoolefinic 
material. 
The blend preferably has a glass transition temperature greater than zero 
.degree.C. as measured using a Differential Scanning Calorimeter (DSC), 
for example a Perkin Elmer Series 7 Differential Scanning Calorimeter, 
using a temperature range of about -55.degree. C. to about 150.degree. C. 
and a scanning rate of about 20.degree. C. per minute. 
In the preferred embodiment discussed above, the aqueous secondary coating 
composition also comprises a urethane-containing polymer which is 
chemically different from the elastomeric polymer, i.e., for example the 
urethane-containing polymer can be a thermosetting polyurethane and the 
urethane-containing polymer can be a chemically different thermoplastic 
polyurethane. In another example, the urethane-containing polymer can be a 
polyurethane formed from a polyether polyol and the elastomeric polymer 
can be a polyurethane formed from a polyester polyol. 
The phrase "urethane-containing polymer" as used herein means any polymer 
containing one or more units of the structure (I): 
##STR1## 
See Kirk-Othmer, Vol. 21 at pages 56-69, which are hereby incorporated by 
reference. As noted in Kirk-Othmer, Vol. 21 at page 57, the terms urethane 
and polyurethane are commonly used to refer to urethan and polyurethan, 
respectively. As used herein, the terms "urethane" and "polyurethane" are 
used to refer to "urethan" and "polyurethan", respectively. Such 
urethane-containing polymers can be elastomeric, thermoplastic or 
thermosetting, and either water soluble, or emulsifiable or dispersible 
with the use of an emulsifying or dispersing agent. 
Urethane-containing polymers are typically condensation products of a 
polyfunctional isocyanate-containing material such as are discussed above 
and a hydroxyl-containing material such as a polyether polyol or a 
polyester polyol and include, for example, WITCOBOND.RTM. W-290H, W-212 
and W-234 thermoplastic polyurethanes which are commercially available 
from Witco Chemical Corp. of Chicago, Ill. and RUCOTHANE.RTM. 2011L 
thermoplastic polyurethane latex, which is commercially available from 
Ruco Polymer Corp. of Hicksville, N.Y., which is preferred. 
An example of a useful thermosetting polyurethane is BAYBOND XW-110, which 
is commercially available from Bayer Corp. of Pittsburgh, Pa. A 
crosslinking agent can be included in the aqueous secondary coating for 
crosslinking such thermosetting polyurethanes which include reactive 
groups such as hydroxyl groups. Non-limiting examples of suitable 
crosslinking agents include melamine formaldehyde, blocked isocyanates 
such as Baybond XW 116 or XP 7055, epoxy crosslinking agents such as 
Witcobond XW by Witco Corp. and polyesters such as Baybond XP-7044 or 
7056. The Baybond products are commercially available from Bayer of 
Pittsburgh, Pa. The amount of crosslinking agent can be about 0.0001 to 
about 10 weight percent of the aqueous secondary coating composition on a 
total solids basis. 
Based upon the weight of the total solids of the aqueous secondary coating 
composition, the urethane-containing polymer(s) generally comprises about 
5 to about 50 weight percent of the aqueous secondary coating composition, 
preferably comprises about 10 to about 40 weight percent, and more 
preferably about 10 to about 20 weight percent of the aqueous secondary 
coating composition. 
In an alternative embodiment, the aqueous secondary coating composition 
comprises (1) one or more halogenated vinyl homopolymers (discussed 
above); (2) one or more elastomeric polymers (discussed above); and (3) 
one or more urethane-containing polymers (discussed above) different from 
the elastomeric polymers. Suitable homopolymers can be formed from the 
halogenated vinyl monomers discussed above by the methods mentioned above 
which are well known to those skilled in the art. Suitable elastomeric 
polymers and urethane-containing polymers also are discussed above. 
In another alternative embodiment, the aqueous secondary coating 
composition comprises (1) one or more halogenated vinyl homopolymers 
(discussed above); (2) one or more urethane-containing polymers (discussed 
above); and (3) one or more wax materials such as are discussed in detail 
below. An elastomeric polymer, such as are discussed above, can also be 
included in this aqueous secondary coating composition. 
In another alternative embodiment, the aqueous secondary coating 
composition comprises (1) one or more halogenated vinyl polymers, such as 
are discussed above; and (2) one or more water soluble, emulsifiable or 
dispersible curable acrylic polymer(s). This aqueous secondary coating 
composition can further comprise one or more elastomeric polymers which 
are preferably essentially free of a monoolefinic material and one or more 
urethane-containing polymers such as are discussed above. 
Suitable curable acrylic polymer(s) for this alternative embodiment can be 
homopolymers, copolymers or multipolymers and can be the addition 
polymerization products of one or more monomer components comprising one 
or more acrylic monomers, polymers and/or derivatives thereof (hereinafter 
"acrylic(s)"). The curable acrylic polymer and the halogenated vinyl 
polymer component can be present as a copolymer. 
Useful acrylic monomers include acrylic acid, methacrylic acid, derivatives 
and mixtures thereof. Other non-limiting examples of suitable acrylic 
monomers include esters of acrylic acid and methacrylic acid, such as 
acrylates and methacrylates, acrylamides, acrylonitriles and derivatives 
and mixtures thereof. Useful acrylics can have hydroxy and/or epoxy 
functionality. 
Useful esters of acrylic or methacrylic acid include straight chain or 
branched alkyl or hydroxyalkyl esters of acrylic or methacrylic acid. 
Useful alkyl esters can contain about 1 to about 24 carbon atoms, and 
preferably contain about 1 to about 18 carbon atoms. Non-limiting examples 
of useful alkyl esters include methyl (meth)acrylate, ethyl 
(meth)acrylates, propyl (meth)acrylates, butyl (meth)acrylates, pentyl 
(meth)acrylates, hexyl (meth)acrylates, heptyl (meth)acrylates, octyl 
(meth)acrylates, nonyl (meth)acrylates, decyl (meth)acrylates, dodecyl 
(meth)acrylates, tetradecyl (meth)acrylates, hexadecyl (meth)acrylates, 
ethylhexyl (meth)acrylates, lauryl (meth)acrylates, stearyl 
(meth)acrylates and 2-ethylhexyl (meth)acrylate. Suitable hydroxyalkyl 
esters include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl 
(meth)acrylate, 3-hydroxypropyl (meth)acrylate and hydroxybutyl 
(meth)acrylate. 
Non-limiting examples of other useful acrylic monomers include glycol 
acrylates such as ethylene glycol diacrylate, propylene glycol diacrylate, 
1,3-propanediol acrylate, 1,4-butanediol acrylate, 1,4-butanediol 
methacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 
1,3-butyleneglycol diacrylate and tetraethylene glycol diacrylate. A 
useful polyol acrylate is trimethylolpropane triacrylate. Useful epoxy 
functional acrylates include polyglycidyl acrylates and polyglycidyl 
methacrylates. Non-limiting examples of suitable acrylamides include 
methacrylamide, methylolacrylamide, and N-substituted derivatives thereof. 
Non-limiting examples of suitable acrylonitriles include acrylonitrile and 
methacrylonitrile. 
An addition polymerizable monomer or polymer can be polymerized with the 
acrylic. Non-limiting examples of addition polymerizable monomers which 
can be reacted with the acrylic include other vinyl monomers such as vinyl 
aromatics including styrene, vinyl toluene, alpha methyl styrene, 
halostyrenes such as chlorostyrene, and vinyl napthalene; dienes including 
butadienes such as 1,3-butadiene and 2,3-dimethyl-1,3-butadiene; isoprene; 
and chloroprene; vinyl acetates, block and graft copolymers thereof. Other 
useful addition polymerizable monomers include amides, such as n-methylol 
(meth)acrylamide; nitriles; pyrrolidones and olefins such as ethylene. 
Mixtures of any of the above addition polymerizable monomers are also 
useful. Preformed polymers of these monomers can also be addition 
polymerized with the acrylic polymer provided the preformed polymer has 
addition polymerizable unsaturation. 
Methods for polymerizing acrylic monomers with themselves and/or other 
addition polymerizable monomers and preformed polymers are well known to 
those skilled in the art of polymers and further discussion thereof is not 
believed to be necessary in view of the present disclosure. If additional 
information is needed, such acrylics and polymerization methods are 
disclosed in Kirk-Othmer, Vol. 1 (1963) at pages 203-205, 259-297 and 
305-307, which are hereby incorporated by reference. 
The number average molecular weight (Mn), as determined by gel permeation 
chromatography of the acrylic polymer, can be about 200 to about 200,000 
and is preferably about 30,000 to about 100,000. The glass transition 
temperature of the acrylic polymer can be about -40.degree. C. to about 
100.degree. C. and is preferably about zero.degree.C. to about 80.degree. 
C. as measured using a Differential Scanning Calorimeter (DSC), for 
example a Perkin Elmer Series 7 Differential Scanning Calorimeter, using a 
temperature range of about -55.degree. C. to about 150.degree. C. and a 
scanning rate of about 20.degree. C. per minute. 
Preferably, the curable acrylic polymer is present in an emulsion including 
an emulsifying agent, suitable examples of which are discussed below. The 
curable acrylic polymer is preferably self-crosslinking, although external 
crosslinking agents can be included in the secondary aqueous coating 
composition for crosslinking the curable acrylic polymer with itself or 
other components of the secondary aqueous coating composition, as 
discussed below. The curable acrylic polymer can be cationic, anionic or 
nonionic, but preferably is anionic or nonionic. 
Non-limiting examples of useful acrylic polymers include Fulatex.RTM. 
materials which are commercially available from H. B. Fuller Co. of St. 
Paul, Minn. Useful FULATEX.RTM. materials include FULATEX.RTM. PN-3716G, a 
butyl acrylate and styrene copolymer and FULATEX.RTM. PN-3716L1, a butyl 
acrylate, styrene and butyl methyl acrylate copolymer. See PN-3716-K and 
PN-3716-L1 Technical Data Sheets of H. B. Fuller Co. (Jul. 25, 1994), 
which are hereby incorporated by reference. Other useful FULATEX.RTM. 
materials include FULATEX.RTM. PN-3716F, FULATEX.RTM. PN-3716H, 
FULATEX.RTM. PN-3716J and FULATEX.RTM. PN-3716K. 
Other useful curable acrylic polymers include self-crosslinking acrylic 
emulsions such as RHOPLEX.RTM. E-32, E-693, HA-8, HA-12, HA-16, TR-407 and 
WL-81 emulsions commercially available from the Rohm & Haas Company. See 
"Building Better Nonwovens", a Technical Bulletin of Rohm and Haas 
Specialty Industrial Polymers, (1994), which is hereby incorporated by 
reference. Also useful are the CARBOSET acrylic polymers which are 
commercially available from B. F. Goodrich Co. of Toledo, Ohio. 
Useful acrylic polymers include copolymers of acrylic monomers with vinyl 
compounds such as n-methylolacrylamide vinyl acetate copolymers and 
VINOL.RTM. vinyl acetate products which are commercially available from 
Air Products and Chemicals, Inc. of Allentown, Pa. 
Yet another suitable acrylic are ethylene acrylic acid copolymers such as 
MICHEM.RTM. PRIME 4990 or MICHEM.RTM. PRIME 4983HS, which are commercially 
available from Michelman Inc. of Cincinnati, Ohio. 
The acrylic polymer and halogenated vinyl polymer useful in this 
alternative embodiment can be present as a copolymer, as discussed above. 
Suitable copolymers include VYCAR.TM. 590X20, 460X46, 450X61, 460X45 and 
460X49 polyvinyl chloride-acrylic copolymers which are commercially 
available from B. F. Goodrich. 
The amount of the curable acrylic polymer(s) can be about 1 to about 50 
weight percent of the secondary aqueous coating composition on a total 
solids basis, preferably about 5 to about 40 weight percent, and more 
preferably about 10 to about 30 weight percent. 
The aqueous secondary coating compositions of the different embodiments 
discussed above can further comprise one or more thermoplastic 
film-forming materials chemically different from the components discussed 
above. 
Examples of suitable thermoplastic film-forming materials include 
polyolefins, polyesters, vinyl polymers, derivatives and mixtures thereof, 
to name a few. 
Non-limiting examples of useful polyolefins include polypropylene and 
polyethylene materials such as the polypropylene emulsion RL-5440, which 
is commercially available from Sybron Chemicals of Birmingham, N.J., and 
Polyemulsion Chemcor 43C30, which is commercially available from Chemical 
Corp. of America. Another example of a suitable polyolefin for use in the 
present invention is the high density polyethylene emulsion Protolube HD 
which is commercially available from Sybron Chemicals of Birmingham, N.J. 
Thermoplastic polyesters useful in the present invention include ethylene 
adipates (such as Desmophen 2000) and ethylene butylene adipates (such as 
Desmophen 2001KS), both of which are commercially available from Bayer of 
Pittsburgh, Pa. 
Non-limiting examples of useful vinyl polymers include Resyn 2828 and Resyn 
1037 vinyl acetate copolymer emulsions which are commercially available 
from National Starch, and other polyvinyl acetates such as are 
commercially available from H. B. Fuller and Air Products and Chemicals 
Co. of Allentown, Pa. Other useful vinyl polymers include polyvinyl 
pyrrolidones such as PVP K-15, PVP K-30, PVP K-60 and PVP K-90, each of 
which are commercially available from ISP Chemicals of Wayne, N.J. 
As mentioned above, the aqueous secondary coating composition can include 
one or more aqueous soluble, emulsifiable or dispersible wax materials. 
The wax material can be selected from vegetable, animal, mineral, 
synthetic or petroleum waxes, for example. Preferred waxes are petroleum 
waxes such as MICHEM.RTM. LUBE 296 microcrystalline wax, POLYMEKON.RTM. 
SPP-W microcrystalline wax and PETROLITE 75 microcrystalline wax which are 
commercially available from Michelman Inc. of Cincinnati, Ohio and the 
Petrolite Corporation of Tulsa, Okla., respectively. Generally, the amount 
of wax can be about 1 to about 10 weight percent of the aqueous secondary 
coating composition on a total solids basis, and preferably about 3 to 
about 5 weight percent. 
The aqueous secondary coating compositions discussed above can include one 
or more emulsifying agents or surfactants for emulsifying components of 
the secondary coating composition, such as the halogenated vinyl polymer. 
Non-limiting examples of suitable emulsifying agents or surfactants 
include polyoxyalkylene block copolymers, ethoxylated alkyl phenols, 
polyoxyethylene octylphenyl glycol ethers, ethylene oxide derivatives of 
sorbitol esters and polyoxyethylated vegetable oils. 
An example of a suitable polyoxypropylene-polyoxyethylene copolymer is 
PLURONIC.TM. F-108, which is commercially available from BASF Corporation 
of Parsippany, N.J. Examples of useful ethoxylated alkyl phenols include 
ethoxylated octylphenoxyethanol, phenoxy polyethyleneoxy(ethanol), 
phenoxy(ethyleneoxy)ethanol and nonyl phenoxy poly(ethyleneoxy)ethanol. An 
example of a commercially available ethoxylated octylphenoxyethanol is 
IGE CA-630 from GAF Corporation of Wayne, N.J. An example of a 
polyoxyethylated vegetable oil is EMULPHOR EL-719, which is commercially 
available from GAF Corp. A useful polyoxyethylene octylphenyl glycol ether 
is Triton X-100, which is commercially available from Rohm & Haas of 
Philadelphia, Pa. Tween 21 and 81, which are available from ICI Americas 
of Wilmington, Del., and TMAZ 81, which is available from PPG Industries, 
Inc., are examples of useful ethylene oxide derivatives of sorbitol 
esters. Other suitable emulsifying agents include NOVEPOX.TM. or Prox E 
117 non-ionic epoxide polyols, which are commercially available from 
Synthron, Inc. 
Generally, the amount of emulsifying agent can be about 0.01 to about 20 
weight percent of the aqueous secondary coating composition on a total 
solids basis, and is more preferably about 0.1 to about 10 weight percent. 
Fungicides, bactericides, anti-foaming materials and chlorine-removing 
catalysts can also be included in the aqueous secondary coating 
compositions discussed above. Examples of suitable bactericides include 
potassium cyanide and Biomet 66 antimicrobial compound, which is 
commercially available from M & T Chemicals of Rahway, N.J. Suitable 
anti-foaming materials are the SAG materials which are commercially 
available from OSi Specialties, Inc. of Danbury, Conn. and MAZU DF-136 
which is available from PPG Industries, Inc. A non-limiting example of a 
suitable catalyst for removing chlorine from the aqueous secondary coating 
composition is urea. The amount of fungicides, bactericides, anti-foaming 
materials and chlorine-removing catalysts can be about 1.times.10.sup.-4 
to about 5 weight percent of the aqueous secondary coating composition on 
a total solids basis. 
Water (preferably deionized) is included in the aqueous secondary coating 
compositions discussed above in an amount sufficient to facilitate 
application of a generally uniform coating upon the strand. The weight 
percentage of solids of the aqueous secondary coating compositions 
discussed above generally can be about 5 to about 50 weight percent. 
Preferably, the weight percentage of solids is about 10 to about 30 weight 
percent and, more preferably, about 20 to about 30 weight percent. 
The aqueous secondary coating compositions of the present invention can be 
prepared by any suitable method such as conventional mixing well known to 
those skilled in the art. Preferably the components discussed above are 
mixed together and the mixture is diluted with water to have the desired 
weight percent solids. 
The application of an aqueous secondary coating composition, such as one of 
those discussed above, to one or more fiber strand(s) will now be 
discussed generally. 
As shown in FIG. 1, the aqueous secondary coating composition 16 is applied 
as a secondary layer over a primary layer of an essentially dried residue 
of a sizing composition 12 which is present on at least a portion of the 
surface 14 of the fiber strand to protect the surface 14 from abrasion 
during processing. 
Suitable components for the sizing composition will now be discussed. 
Preferably the sizing composition is aqueous-based and can include 
film-formers such as starches, thermosetting materials and thermoplastic 
materials; lubricants; coupling agents; waxes; emulsifiers and water as 
components, to name a few. Non-limiting examples of suitable sizing 
compositions are disclosed in K. Loewenstein, The Manufacturing Technology 
of Continuous Glass Fibres, (3d Ed. 1993) at pages 237-289. 
Preferably the sizing composition comprises one or more fiber lubricants 
(discussed in detail below) such as ALUBRASPIN 226 and CATION X which 
provide a multilayered hose assembly (discussed in detail below) according 
to the present invention which has an electrical resistance of greater 
than about 750 megaohms per 152.+-.13 millimeters (6.+-.0.5 inches) of 
hose length. The test method for determining the electrical resistance of 
the hose assembly will be discussed below. 
A preferred starch-based sizing composition which includes CATION X 
lubricant is disclosed in U.S. Pat. No. 3,265,516. Another preferred 
sizing composition includes about 78 weight percent PLURACOL V-10 
polyoxyalkylene polyol (commercially available from BASF Wyandotte of 
Michigan); about 8 weight percent EMERY 6717 partially amidated 
polyethylene imine lubricant (commercially available from Henkel 
Corporation of Kankakee, Ill.) and about 14 weight percent A-1108 
aminosilane (commercially available from OSi Specialties, inc. of Danbury 
Conn.). 
As discussed above the sizing composition can include one or more starches 
including those prepared from potatoes, corn, wheat, waxy maize, sago, 
rice, milo and mixtures thereof, such as National 1554 (a high viscosity, 
low amylose crosslinked potato starch) and Hi-Set 369 starches which are 
commercially available from National Starch and Chemical Corp. of 
Bridgewater, N.J. and Amaizo starches which are commercially available 
from American Maize Products Company of Hammond, Ind. 
Examples of suitable thermoplastic and thermosetting film-forming materials 
for use in the sizing composition include acrylic polymers, alkyds, 
polyepoxides, phenolics, polyamides, polyolefins, polyesters, 
polyurethanes, vinyl polymers, derivatives and mixtures thereof, to name a 
few. 
Fiber lubricants useful in the present sizing composition include cationic, 
non-ionic or anionic lubricants and mixtures thereof. Generally, the 
amount of fiber lubricant can be about 1 to about 15 weight percent of the 
sizing composition on a total solids basis, preferably about 3 to about 12 
weight percent, and more preferably about 5 to about 10 weight percent. 
Non-limiting examples of such fiber lubricants include amine salts of fatty 
acids (which can, for example, include a fatty acid moiety having 12 to 22 
carbon atoms and/or tertiary amines having alkyl groups of 1 to 22 atoms 
attached to the nitrogen atom ), alkyl imidazoline derivatives (such as 
can be formed by the reaction of fatty acids with polyalkylene 
polyamines), acid solubilized fatty acid amides (for example, saturated or 
unsaturated fatty acid amides having acid groups of 4 to 24 carbon atoms 
such as stearic amide), acid solubilized polyunsaturated fatty acid 
amides, condensates of a fatty acid and polyethylene imine and amide 
substituted polyethylene imines, such as EMERY.RTM. 6717, a partially 
amidated polyethylene imine commercially available from Henkel Corporation 
of Kankakee, Ill. and Alubraspin 226, which is commercially available from 
PPG Industries, Inc. 
Useful alkyl imidazoline derivatives are CATION X, which is commercially 
available from Rhone Poulenc of Princeton, N.J. and Alubraspin 261, which 
is available from PPG Industries, Inc. Other useful lubricants include 
Alubraspin 227 silylated polyamine polymer lubricant which is manufactured 
by PPG Industries, Inc., RD-1135B epoxidized polyester which is 
commercially available from Borden Chemical of Louisville, Ky., CIRRASOL 
185A fatty acid amide, KETJENLUBE 522 partially carboxylated polyester 
which is commercially available from Akzo Chemicals, Inc. Of Chicago, Ill. 
and PROTOLUBE HD high density polyethylene emulsion which is commercially 
available from Sybron Chemicals of Birmingham, N.J. 
The sizing composition can further comprise one or more coupling agents 
such as organo silane coupling agents, transition metal coupling agents, 
amino-containing Werner coupling agents and mixtures thereof. These 
coupling agents typically have dual functionality. Each metal or silicon 
atom has attached to it one or more groups which can react or 
compatibilize with the fiber surface and/or the components of the aqueous 
secondary coating composition. As used herein, the term "compatibilize" 
means that the groups are chemically attracted, but not bonded, to the 
fiber surface and/or the components of the sizing composition, for example 
by polar, wetting or solvation forces. Examples of hydrolyzable groups 
include: 
##STR2## 
the monohydroxy and/or cyclic C.sub.2 -C.sub.3 residue of a 1,2- or 1,3 
glycol, wherein R.sup.1 is C.sub.1 -C.sub.3 alkyl; R.sup.2 is H or C.sub.1 
-C.sub.4 alkyl; R.sup.3 and R.sup.4 are independently selected from H, 
C.sub.1 -C.sub.4 alkyl or C.sub.6 -C.sub.8 aryl; and R.sup.5 is C.sub.4 
-C.sub.7 alkylene. Examples of suitable compatibilizing or functional 
groups include epoxy, glycidoxy, mercapto, cyano, allyl, alkyl, urethano, 
halo, isocyanato, ureido, imidazolinyl, vinyl, acrylato, methacrylato, 
amino or polyamino groups. 
Functional organo silane coupling agents are preferred for use in the 
present invention. Examples of useful functional organo silane coupling 
agents include 3-aminopropyldimethylethoxysilane, 
gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, 
beta-aminoethyltriethoxysilane, 
N-beta-aminoethyl-aminopropyltrimethoxysilane, 
gamma-isocyanatopropyltriethoxysilane, vinyl-trimethoxysilane, 
vinyl-triethoxysilane, allyl-trimethoxysilane, 
mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, 
glycidoxypropyltriethoxysilane, glycidoxypropyltrimethoxysilane, 
4,5-epoxycyclohexyl-ethyltrimethoxysilane, ureidopropyltrimethoxysilane, 
ureidopropyltriethoxysilane, chloropropyltrimethoxysilane, and 
chloropropyltriethoxysilane. 
Preferred functional organo silane coupling agents include amino silane 
coupling agents, such as A-1100 and A-1108, each of which are commercially 
available from OSi Specialties, Inc. of Tarrytown, N.Y. The organo silane 
coupling agent can be at least partially hydrolyzed with water prior to 
application to the fibers, preferably at about a 1:1 stoichiometric ratio 
or, if desired, applied in unhydrolyzed form. 
Suitable transition metal coupling agents include titanium, zirconium and 
chromium coupling agents. Non-limiting examples of suitable titanate 
coupling agents include titanate complexes such as Ken-React KR-44, KR-34 
and KR-38; suitable zirconate coupling agents include Ken React NZ-97 and 
LZ-38, all of which are commercially available from Kenrich Petrochemical 
Company. Suitable chromium complexes include Volan which is commercially 
available from E. I. duPont de Nemours of Wilmington, Del. The 
amino-containing Werner-type coupling agents are complex compounds in 
which a trivalent nuclear atom such as chromium is coordinated with an 
organic acid having amino functionality. Other metal chelate and 
coordinate type coupling agents known to those skilled in the art can be 
used herein. 
The amount of coupling agent can be 1 to about 5 weight percent of the 
sizing composition on a total solids basis, and is preferably about 2 to 
about 3 weight percent. 
The sizing composition can further comprise one or more organic acids in an 
amount sufficient to provide the sizing composition with a pH of about 4 
to about 6. Suitable organic acids include mono- and polycarboxylic acids 
and/or anhydrides thereof, such as acetic, citric, formic, propionic, 
caproic, lactic, benzoic, pyruvic, oxalic, maleic, fumaric, acrylic, 
methacrylic acids and mixtures thereof, which are well known to those 
skilled in the art and are commercially available. 
The sizing composition can also include other components such as 
crosslinking agents, emulsifiers and waxes discussed above. The amounts of 
such components used in the sizing composition are similar to the amounts 
set forth above for the secondary coating composition and can be 
determined by a skilled artisan without undue experimentation. 
The primary layer of the sizing composition and secondary layer of the 
secondary coating composition are applied to fibers, strands, yarns or the 
like of natural or man-made materials. Fibers believed to be useful in the 
present invention and methods for preparing and processing such fibers are 
discussed at length in the Encyclopedia of Polymer Science and Technology, 
Vol. 6 (1967) at pages 505-712, which is hereby incorporated by reference. 
Suitable natural fibers include those derived directly from animal, 
vegetable and mineral sources. Suitable natural inorganic fibers include 
glass and polycrystalline fibers, such as ceramics including silicon 
carbide, and carbon or graphite. 
The preferred fibers for use in the present invention are glass fibers, a 
class of fibers generally accepted to be based upon oxide compositions 
such as silicates selectively modified with other oxide and non-oxide 
compositions. Useful glass fibers can be formed from any type of 
fiberizable glass composition known to those skilled in the art, and 
include those prepared from fiberizable glass compositions such as 
"E-glass", "A-glass", "C-glass", "D-glass", "R-glass", "S-glass", and 
E-glass derivatives that are fluorine-free and/or boron-free. Preferred 
glass fibers are formed from E-glass. Such compositions and methods of 
making glass filaments therefrom are well known to those skilled in the 
art and further discussion thereof is not believed to be necessary in view 
of the present disclosure. If additional information is needed, such glass 
compositions and fiberization methods are disclosed in K. Loewenstein, 
"The Manufacturing Technology of Glass Fibres", (3d Ed. 1993) at pages 
30-44, 47-60, 115-122 and 126-135, which are hereby incorporated by 
reference. 
Non-limiting examples of suitable animal and vegetable-derived natural 
fibers include cotton, cellulose, natural rubber, flax, ramie, hemp, sisal 
and wool. Suitable man-made fibers can be formed from a fibrous or 
fiberizable material prepared from natural organic polymers, synthetic 
organic polymers or inorganic substances. As used herein, the term 
"fiberizable" means a material capable of being formed into a generally 
continuous filament, fiber, strand or yarn. 
Suitable man-made fibers include those produced from natural organic 
polymers (regenerated or derivative) or from synthetic polymers such as 
polyamides, polyesters, acrylics, polyolefins, polyurethanes, vinyl 
polymers, derivatives and mixtures thereof. 
Non-limiting examples of useful polyamide fibers include nylon fibers such 
as are commercially available from E. I. duPont de Nemours and Company of 
Wilmington, Del., polyhexamethylene adipamide, polyamide-imides and 
aramids such as KEVLAR.TM., which is commercially available from duPont. 
Thermoplastic polyester fibers useful in the present invention include 
those formed from polyethylene terephthalate (for example DACRON.TM. which 
is commercially available from duPont and FORTREL.TM. which is 
commercially available from Hoechst Celanese Corp. of Summit, N.J.) and 
polybutylene terephthalate. FIRESTONE 3401 polyester fiber, which is 
commercially available from Firestone of Akron, Ohio, is a preferred fiber 
for use in the present invention. 
Fibers formed from acrylic polymers believed to be useful in the present 
invention include polyacrylonitriles having at least about 35% by weight 
acrylonitrile units, and preferably at least about 85% by weight, which 
can be copolymerized with other vinyl monomers such as vinyl acetate, 
vinyl chloride, styrene, vinylpyridine, acrylic esters or acrylamide. A 
non-limiting example of a suitable acrylic polymer fiber is ORLON.TM., 
which is commercially available from duPont. 
Useful polyolefin fibers are generally composed of at least 85% by weight 
of ethylene, propylene, or other olefins. 
Fibers formed from vinyl polymers believed to be useful in the present 
invention can be formed from polyvinyl chloride, polyvinylidene chloride 
(such as SARAN.TM., which is commercially available from Dow Plastics of 
Midland, Mich.), polytetrafluoroethylene, and polyvinyl alcohol (such as 
VINYLON.TM., a polyvinyl alcohol fiber which has been crosslinked with 
formaldehyde). 
Further examples of fiberizable materials believed to be useful in the 
present invention are fiberizable polyimides, polyether sulfones, 
polyphenyl sulfones; polyetherketones, polyphenylene oxides, polyphenylene 
sulfides, polyacetals, synthetic rubbers or spandex polyurethanes such as 
LYCRA.TM., which is available from duPont. 
It is understood that blends or copolymers of any of the above materials 
and combinations of fibers formed from any of the above materials can be 
used in the present invention, if desired. 
Another aspect of the present invention is shown in the alternative 
embodiment of FIG. 2, in which the fiber strand 100 is formed from a 
thermoplastic material and/or a thermosetting material such as those 
discussed above, which preferably is a polyester, and has applied to at 
least a portion of a surface thereof a primary coating composition 102 
comprising a homopolymer of a halogenated vinyl monomer, such as polyvinyl 
chloride, and a urethane-containing polymer, such as a thermoplastic 
polyurethane, in amounts such as are disclosed above. The primary coating 
composition 102 can also include any of the other secondary coating 
components, lubricants and/or coupling agents discussed above. The primary 
coating composition 102 can be applied without diluting with water or in 
an aqueous form by any of the methods discussed below. 
The present invention will now be discussed generally in the context of 
glass fiber strands. However, one of ordinary skill in the art would 
understand that the aqueous secondary coating compositions of the present 
invention are useful for coating any of the fibers discussed above. 
Suitable apparatus and methods for processing glass fiber strands will be 
discussed below. For further information, see Loewenstein (3d Ed.) at 
pages 165-172 and 219-222, which are hereby incorporated by reference. 
The primary layer of sizing can be applied in many ways, for example by 
contacting the filaments with a static or dynamic applicator, such as a 
roller or belt applicator, spraying or other means. The sized fibers are 
preferably dried at room temperature or at elevated temperatures. The 
dryer removes excess moisture from the fibers and, if present, cures any 
curable sizing or secondary coating composition components. The 
temperature and time for drying the glass fibers will depend upon such 
variables as the percentage of solids in the sizing composition, 
components of the sizing composition and type of glass fiber. For example, 
the forming package can be dried in an oven at a temperature of about 
104.degree. C. (220.degree. F.) to about 160.degree. C. (320.degree. F.) 
for about 10 to about 24 hours to produce glass fiber strands having a 
dried residue of the composition thereon. The sizing composition is 
typically present on the fibers in an amount between about 0.1 percent and 
about 5 percent by weight after drying. 
The fibers are gathered into strands and the secondary layer of the 
secondary coating composition is applied over the primary layer in an 
amount effective to coat or impregnate the portion of the strands. The 
secondary coating composition can be conventionally applied by dipping the 
strand in a bath containing the composition, by spraying the composition 
upon the strand or by contacting the strand with a static or dynamic 
applicator such as a roller or belt applicator, for example. The coated 
strand can be passed through a die to remove excess coating composition 
from the strand and/or dried as discussed above for a time sufficient to 
at least partially dry or cure the secondary coating composition. The 
method and apparatus for applying the secondary coating composition to the 
strand is determined in part by the configuration of the strand material. 
Preferably, the secondary coating composition is applied to the strands by 
passing the strands through a bath or dip of the secondary coating 
composition and exposing the fibers to elevated temperatures for a time 
sufficient to at least partially dry or cure the secondary coating 
composition. The strand can be "opened up" just before entering the 
secondary coating composition bath by passing it over a bar or other 
spreading device which acts to separate the individual fibers from one 
another. This spreading of the fibers from one another results in a more 
thorough impregnation of the strand with the composition. Preferably, a 
die is used to remove excess coating. 
The strand is preferably dried after application of the secondary coating 
composition in a manner well known in the art. For example, the coated 
strand can be at least partially dried in air at room temperature (about 
25.degree. C.) or alternatively in a furnace or oven, preferably above 
232.degree. C. (450.degree. F.), to speed the curing process and evaporate 
the water. A particularly suitable dryer is that disclosed in U.S. Pat. 
No. 5,197,202, which is hereby incorporated by reference. 
The average diameter of the strand is preferably about 0.25 millimeters 
(about 0.010 inches) to about 3.05 millimeters (about 0.120 inches), and 
more preferably about 0.51 millimeters (about 0.020 inches) to about 2.03 
millimeters (about 0.08 inches). 
In an alternative embodiment, a tertiary layer of a tertiary coating 
composition can be applied to at least a portion of the secondary layer, 
i.e., such a fiber strand would have a primary layer of sizing, a 
secondary layer of the secondary coating composition and a tertiary, outer 
layer of the tertiary coating. 
The tertiary coating is different from the sizing composition and the 
secondary coating composition, i.e., the tertiary coating composition (1) 
contains at least one component which is chemically different from the 
components of the sizing and secondary coating composition; or (2) 
contains at least one component in an amount which is different from the 
amount of the same component contained in the sizing or secondary coating 
composition. 
For example, the tertiary coating composition can contain a thermoplastic 
polyurethane and the sizing and secondary coating can contain chemically 
different thermosetting polyurethanes. In another example, the tertiary 
coating, secondary coating and sizing can each contain the same 
thermoplastic polyurethane but in different amounts. 
The tertiary coating can be formed from one or more thermoplastic 
film-forming materials such as polyolefins, polyesters, vinyl polymers and 
mixtures thereof, such as are discussed in detail above. Preferably, the 
tertiary coating contains a urethane-containing polymer such as 
WITCOBOND.RTM. W-290H thermoplastic polyurethane or RUCOTHANE.RTM. 2011L 
thermoplastic polyurethane latex. The tertiary coating can also include 
conventional stabilizers and other modifiers known in the art of such 
coatings. 
The fiber strands discussed above can be used in a wide variety of 
applications, but are preferably used as reinforcements for reinforcing 
multilayered assemblies, such as multi-ply hoses, or polymeric matrix 
materials, such as polymeric thermoplastic materials and polymeric 
thermosetting materials. 
The reinforced multilayered assembly is preferably generally tubular, 
although the multilayered assembly can have any shape desired. The 
generally tubular assembly 20, shown in FIGS. 3 and 4, comprises a first 
layer or tube 22 formed from a polymeric matrix material, such as the 
thermoplastic and thermosetting polymeric matrix materials which are 
discussed below. Preferably, the tube 22 is formed from polyethylene. The 
tube 22 has an inner surface 24 and an outer surface 26, the inner surface 
24 preferably being generally smooth, although the inner surface 24 can 
have surface irregularities such as protrusions or ridges, if desired. 
The tube 22 is positioned adjacent to, and preferably in contact with a 
reinforcement layer 28 comprising an assembly 30 of fiber strands 10 
having applied thereto a primary layer of a sizing composition 12 and 
thereupon a secondary layer of an aqueous secondary coating composition 16 
according to the present invention as discussed in detail above. 
The assembly 30 of the reinforcement layer 28 is preferably a generally 
tubular braid 32 (shown in FIGS. 3 and 4), although the assembly 30 can be 
in the form of a mesh or woven fabric 34 (shown in FIG. 5) or knit fabric 
36 which is shown in FIG. 6. 
Methods for forming a braided material are well known to those skilled in 
the art. For further information, see Textile Terms and Definitions, The 
Textile Institute (9th Ed. 1991) at pages 35-36. The braid 32 can include 
about 5 to about 1000 strands, and preferably about 36 strands. The 
thickness 40 of the braid 32 is preferably generally equal to the diameter 
of a strand. 
The fabric 34, 36 can be formed using the coated strands of the present 
invention as warp strands 44 and/or weft strands 46. The warp strands 44 
can be twisted prior to secondary coating by any conventional twisting 
technique known to those skilled in the art, for example by using twist 
frames. Generally, twist is imparted to the strand by feeding the strand 
to a bobbin rotating at a speed which would enable the strand to be wound 
onto the bobbin at a faster rate than the rate at which the strand is 
supplied to the bobbin. Generally, the strand is threaded through an eye 
located on a ring which traverses the length of the bobbin to impart twist 
to the strand, typically about 0.5 to about 3 turns per inch. 
The warp strands 44 and weft strands 46 are used to prepare the reinforcing 
fabric 34, 36. The reinforcing fabric 34, 36 can be formed by knitting or 
weaving depending upon such factors as the number of warp strands and 
desired density or width of the fabric. A suitable knit reinforcing fabric 
36 can be formed by knitting using any conventional knitting machines well 
known to those skilled in the art such as a Liba knitting machine or a 
crochet-type knitting machine which is commercially available from Comez. 
The reinforcing fabric can alternatively be formed by weaving using any 
conventional loom, such as a shuttle loom, air jet loom, rapier loom, or 
other weaving machine. A needle-type loom, such as is commercially 
available from Muller, is another example of a suitable loom. 
The knit construction can be a loop stitch in which the weft strand 46 does 
not penetrate the warp strand 44, but rather loops to knit adjacent warp 
strands, as shown in FIG. 6. It is understood that other knitting styles 
well known to those skilled in the art, such as crochet, can be used to 
form the reinforcing fabric 36. The weave construction can be a regular 
plain weave or mesh 34 (shown in FIG. 5), although any other weaving style 
well known to those skilled in the art, such as a twill weave or satin 
weave. 
Preferably, the reinforcing fabric 34, 36 includes about 5 to about 50 warp 
strands 44, and more preferably about 12 to about 24 warp strands 44. It 
is preferred that the reinforcing fabric 36 has about 3 to about 25 picks 
per centimeter (about 1 to about 15 picks per inch) of the weft strand 46. 
The reinforcement layer 28 has an inner surface 48 and an outer surface 50, 
the inner surface 48 of the reinforcement layer 28 being positioned 
adjacent to, and preferably in contact with, the outer surface 26 of the 
first layer 22. 
The assembly 20 comprises a second layer 52 formed from a thermoplastic 
polymeric material such as are discussed below for the matrix material, 
and is preferably formed from a polyurethane. The second layer 52 is 
positioned adjacent to, and preferably in contact with, the outer surface 
50 of the reinforcement layer 28 to form the generally tubular assembly 
20. 
One skilled in the art would understand that the first and/or second layers 
22, 52 can be preformed and positioned adjacent to the reinforcement layer 
28 or formed in situ by coating the inner surface 48 or outer surface 50, 
respectively, of the reinforcement layer 28 with the selected matrix 
material. 
Also, multiple first layers, multiple reinforcement layers and/or multiple 
second layers of different materials can be included in the assembly. 
The present invention also includes a method of reinforcing a generally 
tubular assembly. The method comprises (a) forming a generally tubular 
braid having an inner surface and an outer surface as discussed above, the 
braid comprising a plurality of coated fiber strands of the present 
invention; (b) positioning a tube formed from a polymeric material within 
the braid adjacent the inner surface of the braid; (c) coating the outer 
surface of the braid with a thermoplastic material to form an outer layer 
upon the braid; and (d) heating the tube and outer layer to adhere to the 
braid and form a reinforced generally tubular assembly. Preferably the 
outer layer is extruded onto the braid. 
Another method for reinforcing a generally tubular assembly comprises (a) 
forming a generally tubular braid having an inner surface and an outer 
surface as discussed above, the braid comprising a plurality of coated 
fiber strands of the present invention; (b) coating the inner surface of 
the braid with a first polymeric material to form an inner layer; and (c) 
coating the outer surface of the braid with a second polymeric material to 
form an outer layer, as discussed above. The inner and outer layers can be 
laminated to the braid. 
To determine the resistance of a predetermined length of the hose assembly, 
a 152.+-.13 millimeters length of hose is capped on its exposed ends to 
prevent the entry of moisture into the interior of the hose assembly. The 
hose assembly is exposed to air having a relative humidity of at least 85% 
at 19.degree. C..+-.2.degree. C. (75.degree. F..+-.5.degree. F.) for a 
period of 168 hours. 
After exposure, the surface moisture is removed from the hose assembly. One 
end of the hose assembly is attached to a source of 60 Hertz sinusoidal, 
37.5 kilovolts (rms) of electricity. The other end of the hose assembly is 
connected to ground through a 1,000-100,000 ohm resistor. A suitable 
alternating current (AC) voltmeter such as are well known to those skilled 
in the art is connected across the resistor with a fully shielded cable. 
For a five (5) minute period, 37.5 kilovolts of electricity are applied to 
the specimen and the maximum current observed over the period is 
determined. Leakage in excess of 50 microamperes over the entire length of 
the hose is not desirable, i.e., the hose assembly preferably has a 
resistance of greater than about 750 megaohms. 
As discussed above, the coated fibers of the present invention are also 
useful for reinforcing thermoplastic or thermosetting polymeric matrices. 
Non-limiting examples of suitable polymeric thermoplastic matrix materials 
include polyolefins such as polyethylene, extended-chain polyethylene, 
polypropylene, polybutene, polyisoprene, and polypentene, polymethyl 
pentene, polytetrafluoroethylene and neoprene; polyamides, thermoplastic 
polyurethanes and thermoplastic polyesters such as are discussed above, 
vinyl polymers such as polyvinyl chloride, polyvinylidene chloride 
(saran), polyvinyl fluoride, polyvinylidene fluoride, ethylene vinyl 
acetate copolymers and polystyrenes; derivatives and mixtures thereof. 
Thermoplastic elastomeric materials useful as matrix materials in the 
present invention include styrene-butadiene rubbers, styrene-acrylontrile 
(SAN) copolymers, styrene-butadiene-styrene (SBS) copolymers and 
acrylonitrile-butadiene-styrene (ABS) copolymers. 
Further examples of useful thermoplastic materials include polyimides, 
polyether sulfones, polyphenyl sulfones, polyetherketones, polyphenylene 
oxides, polyphenylene sulfides, polyacetals, polyvinyl chlorides and 
polycarbonates. Also included as suitable thermoplastic materials are any 
of the above thermoplastics which are modified by an unsaturated monomer. 
Matrix materials useful in the present invention can include thermosetting 
materials such as thermosetting polyesters, vinyl esters, epoxides 
(containing at least one epoxy or oxirane group in the molecule, such as 
polyglycidyl ethers of polyhydric alcohols or thiols), phenolics, 
aminoplasts, thermosetting polyurethanes, derivatives and mixtures 
thereof. 
Other components which can be included with the polymeric matrix material 
and reinforcing material in the composite are, for example, colorants or 
pigments, lubricants or process aids, ultraviolet light (UV) stabilizers, 
antioxidants, other fillers, and extenders. 
The fiber strand reinforcing material can be dispersed in the matrix by 
hand or any suitable automated feed or mixing device which distributes the 
reinforcing material generally evenly throughout the polymeric matrix 
material. For example, the reinforcing material can be dispersed in the 
polymeric matrix material by dry blending all of the components 
concurrently or sequentially. 
The polymeric matrix material 112 and strand 110 can be formed into a 
composite 114, shown in FIG. 7, by a variety of methods which are 
dependent upon such factors as the type of polymeric matrix material used. 
Thermosetting polymeric matrix materials can be cured by the inclusion of 
crosslinkers in the matrix material and/or by the application of heat, for 
example. Suitable crosslinkers useful to crosslink the polymeric matrix 
material are discussed above. The temperature and curing time for the 
thermosetting polymeric matrix material depends upon such factors as the 
type of polymeric matrix material used, other additives in the matrix 
system and thickness of the composite, to name a few. 
Reinforced polymeric composites can be formed from the polymeric matrix 
material, reinforcing material and any other desired components in a 
variety of ways. For example, for a thermosetting matrix material, the 
composite can be formed by compression or injection molding, pultrusion, 
filament winding, hand lay-up, spray-up or by sheet molding or bulk 
molding followed by compression or injection molding. For a thermoplastic 
matrix material, suitable methods for forming the composite include direct 
molding or extrusion compounding followed by injection molding. Useful 
extrusion equipment includes single or twin screw extruders commercially 
available from Werner Pfleiderer and Welding Engineers, respectively. 
Methods and apparatus for forming the composite by the above methods is 
discussed in I. Rubin, Handbook of Plastic Materials and Technology (1990) 
at pages 955-1062, 1179-1215 and 1225-1271, which are hereby incorporated 
by reference. 
The method according to the present invention for reinforcing a polymeric 
matrix material comprises: (1) applying to a sized fiber strand 
reinforcing material the above aqueous secondary coating composition; (2) 
drying the aqueous secondary coating composition to form a substantially 
uniform coating upon the reinforcing material; (3) dispersing the 
reinforcing material in the polymeric matrix material; and (4) at least 
partially curing the polymeric matrix material to provide a reinforced 
polymeric composite in a manner such as is discussed in detail above. 
The present invention will now be illustrated by the following specific, 
non-limiting examples. 
EXAMPLE 1 
A six gallon mixture of the aqueous sizing composition of Table 1 was 
prepared, applied as a primary layer to single strand bundles (1600 
filaments per strand) and four strand bundles of H-15 E-glass fibers and 
the bundles were wound onto individual forming packages in a manner 
similar to that discussed above in the specification. The weight of sizing 
composition on the fibers after drying the forming package at a 
temperature of about 100.degree. C. for about 10 hours was about 0.7 
weight percent. 
TABLE 1 
______________________________________ 
Sizing Component Weight Percent of Component 
______________________________________ 
PLURACOL V-10 polyoxyalkylene 
78 
polyol.sup.1 
EMERY 6717 partially amidated 
8 
polyethylene imine lubricant.sup.2 
A-1108 aminosilane.sup.3 
14 
______________________________________ 
Samples A1 (single strand) and A2 (four strand) were prepared by coating 
the above strands with a secondary layer of the secondary coating 
composition set forth in Table 2 below. Corresponding Controls A1 and A2 
were prepared from the sized strand without secondary coating. 
TABLE 2 
______________________________________ 
Secondary Coating Component 
Weight of Component (grams) 
______________________________________ 
VYCAR .TM. 552 polyvinyl chloride/ 
12,000 
nitrile rubber copolymer latex.sup.4 
Rucothane 2011L polyurethane.sup.5 
2362 
urea 20 
MAZU DF-136 defoamer.sup.6 
12 
deionized water 10,000 
______________________________________ 
.sup.1 PLURACOL V10 polyoxyalkylene polyol is commercially available from 
BASF Wyandotte of Michigan. 
.sup.2 EMERY 6717 partially amidated polyethylene imine lubricant is 
commercially available from Henkel Corporation of Kankakee, Illinois. 
.sup.3 A1108 aminosilane is commercially available from OSi Specialties, 
Inc. of Danbury, Connecticut. 
.sup.4 VYCAR .TM. 552 polyvinyl chloride/nitrile rubber copolymer latex i 
commercially available from B. F. Goodrich of Cleveland, Ohio. 
.sup.5 RUCOTHANE .RTM. 2011L thermoplastic polyurethane latex is 
commercially available from Ruco Polymer Corp. of Hicksville, New York. 
.sup.6 MAZU DF136 defoamer is available from PPG Industries, Inc. 
The secondary aqueous coating composition was applied to the sized glass 
fibers by drawing the glass fibers through a bath of the coating and a die 
to remove excess coating, such that the loss on ignition (LOI) of the 
coated glass strand was about 14 percent. The diameter of the passage 
through the die for the strand samples prepared was about 0.56 millimeters 
(0.022 inches). 
Evaluation of Sample A1 for Electrical Resistance at 37.5 kilovolts: 
A hose assembly was prepared by braiding thirty-six of the above Sample A1 
strands to form a generally tubular reinforcement layer having a thickness 
generally equal to a single layer of strand. The reinforcement layer was 
coated with an inner layer of polyethylene about 1 millimeter thick and an 
outer layer of polyurethane about 1 millimeter thick. A 152.4 millimeter 
(six inch) length of the hose assembly was evaluated for electrical 
resistance by the method discussed in detail above using 37.5 kilovolts. 
The electrical resistance of this sample was less than 750 megaohms. 
According to this test protocol, this hose assembly did not pass the test 
standards for this particular end use application as a pneumatic hose, 
however this assembly can be useful for other hose assembly or 
reinforcement applications. 
EXAMPLE 2 
Samples B1 and B2 were prepared by coating single strands of K-18 (800 
filaments per strand having a twist of 1 turn per 3 inches) and G-37 (400 
filaments per strand having a twist of 1 turn per 4 inches), which are 
commercially available as 610 product.sup.7 from PPG Industries, Inc. of 
Pittsburgh, Pa., respectively, with a secondary layer of the secondary 
coating composition set forth in Table 2 above. Controls B1 and B2 were 
prepared from the corresponding sized 610 product strands without 
secondary coating. 
FNT 7 The 610 product is produced according to U.S. Pat. No. 3,265,516 and 
includes about 60 weight percent of about a 5:1 mixture of NATIONAL 1554 
and AMAIZO 2213 starches; about 25 weight percent ECLIPSE 102 oil; about 
10 weight percent MACOL E-300 polyethylene glycol, which is available from 
PPG Industries, Inc.; and less than 5 weight percent each of TMAZ 81 
emulsifier which is also available from PPG industries, diglycol 
monostearate, CATION X lubricant and CHEMTREAT CL-2141 biocide, the 
commercial sources of which are discussed above in the specification. 
Relative Electrical Resistance of Samples and Controls 
The electrical resistance of strands of the above Samples and Controls, as 
well as the electrical resistance of uncoated Firestone 3401 polyester 
strand (Control C) and Firestone 3401 strand coated with the secondary 
coating of Table 2 (Sample C) was determined by applying 60 volts of 
direct current (DC) electricity to one inch long bundles of 60 strands of 
each of the above Samples and Controls. The averages for electrical 
resistance of ten runs for each Sample and Control are presented in Table 
3 below. 
TABLE 3 
______________________________________ 
Example Average Resistance (megaohms) 
______________________________________ 
Sample A1 656 
Control A1 30,100 
Sample A2 412 
Control A2 30,500 
Sample B1 4410 
Control B1 126,000 
Sample B2 7510 
Control B2 135,00 
Sample C 2640 
Control C 379,000 
______________________________________ 
As shown in Table 3 above, while Samples A1, A2, B1 and B2 have the same 
secondary coating, Samples B1 and B2, which are coated with a starch-based 
sizing composition prepared according to U.S. Pat. No. 3,265,516, have 
relatively higher values of electrical resistance as compared to Samples 
A1 and A2, which are coated with the sizing of Table 1. It is believed 
that the improved electrical resistance of Samples B1 and B2 can be 
attributed at least in part to the lubricant in the sizing composition 
(CATION X alkyl imidazoline reaction product of tetraethylene pentamine 
and stearic acid) over Samples A1 and A2 which include EMERY 6717 
partially amidated polyethylene imine lubricant in the sizing composition. 
The sized strands coated with the secondary coating composition of Table 2 
were believed to provide improved adhesion when laminated to the inner and 
outer layers of the hose assembly discussed above. 
EXAMPLE 3 
The aqueous sizing composition of Table 1 was applied as a primary layer to 
double strand bundles and four strand bundles of H-15 E-glass fibers and 
the bundles were wound onto individual forming packages and dried as 
described in Example 1 above. 
Samples D1 (double strand) and D2 (four strand) were prepared by coating 
the above strands with a secondary layer of the secondary coating 
composition set forth in Table 4 below having about 35 weight percent 
solids. Corresponding Controls D1 and D2 were prepared from the sized 
strand without secondary coating. 
TABLE 4 
______________________________________ 
Secondary Coating Component 
Weight of Component (grams) 
______________________________________ 
VYCAR .TM. 576 polyvinyl chloride 
12,136 
emulsion.sup.8 
RHOPLEX E-32 acrylic emulsion.sup.9 
3750 
PETROLITE 75 wax.sup.10 
1500 
MAZU DF-136 defoamer.sup.11 
10 
urea 15 
deionized water 750 
______________________________________ 
.sup.8 VYCAR .TM. 576 polyvinyl chloride emulsion plasticized with 
di2-ethyl hexyl phthalate is commercially available from B. F. Goodrich o 
Cleveland, Ohio. 
.sup.9 RHOPLEX E32 acrylic emulsion is commerically available from Rohm 
and Haas Company of Philadelphia, PA. 
.sup.10 PETROLITE 75 wax is commercially available from Michelman Inc. 
.sup.11 MAZU DF136 defoamer is available from PPG Industries, Inc. 
The secondary aqueous coating composition was applied to the sized glass 
fibers by drawing the glass fibers through a bath of the coating and a die 
to remove excess coating, such that the loss on ignition (LOI) of the 
coated glass strand was about 14 percent. The diameter of the passage 
through the die for the strand samples prepared was about 0.81 millimeters 
(0.032 inches) for Sample D1 and Control D1 and about 1.1 millimeters 
(0.044 inches) for Sample D2 and Control D2. 
EXAMPLE 4 
The aqueous sizing composition of Table 1 was applied as a primary layer to 
four strand bundles of H-15 E-glass fibers and the bundles were wound onto 
individual forming packages and dried as described in Example 1 above. 
Samples E1 and E2 were prepared by coating the above strands with a 
secondary layer of the secondary coating composition set forth in Table 5 
below having about 37 weight percent solids. Corresponding Controls E1 and 
E2 were prepared from the sized strand without secondary coating. 
TABLE 5 
______________________________________ 
Secondary Coating Component 
Weight of Component (grams) 
______________________________________ 
VYCAR .TM. 590X20 polyvinyl chloride/ 
16,000 
acrylic copolymer emulsion.sup.12 
MAZU DF-136 defoamer.sup.13 
20 
urea 20 
deionized water 2700 
______________________________________ 
.sup.12 VYCAR .TM. 590X20 polyvinyl chloride/acrylic copolymer emulsion i 
commercially available from B. F. Goodrich of Cleveland, Ohio. 
.sup.13 MAZU DF136 defoamer is available from PPG Industries, Inc. 
The secondary aqueous coating composition was applied to the sized glass 
fibers by drawing the glass fibers through a bath of the coating and a die 
to remove excess coating, such that the loss on ignition (LOI) of the 
coated glass strand for Sample E1 and Control E1 was about 14 percent for 
the diameter of the passage through the die of about 1.1 millimeters 
(0.044 inches) and the LOI for Sample E1 and Control E1 was about 16.3 for 
the diameter of the passage through the die of about 1.17 millimeters 
(0.046 inches). 
EXAMPLE 5 
The aqueous sizing composition of Table 1 was applied as a primary layer to 
two strand and four strand bundles of H-15 E-glass fibers and the bundles 
were wound onto individual forming packages and dried as described in 
Example 1 above. 
Samples F1 (two strand) and F2 (four strand) were prepared by coating the 
above strands with a secondary layer of the secondary coating composition 
set forth in Table 6 below having about 40 weight percent solids. 
Corresponding Controls F1 and F2 were prepared from the sized strand 
without secondary coating. 
TABLE 6 
______________________________________ 
Secondary Coating Component 
Weight of Component (grams) 
______________________________________ 
VYCAR .TM. 590X20 polyvinyl chloride/ 
16,000 
acrylic copolymer emulsion.sup.14 
RHOPLEX E-32 acrylic emulsion.sup.15 
2416 
PETROLITE 75 wax.sup.16 
556 
MAZU DF-136 defoamer.sup.17 
20 
urea 20 
deionized water 3200 
______________________________________ 
.sup.14 VYCAR .TM. 590X20 polyvinyl chloride/acrylic copolymer emulsion i 
commercially available from B. F. Goodrich of Cleveland, Ohio. 
.sup.15 RHOPLEX E32 acrylic emulsion is commerically available from Rohm 
and Haas Company of Philadelphia, PA. 
.sup.16 PETROLITE 75 wax is commercially available from Michelman Inc. 
.sup.17 MAZU DF136 defoamer is available from PPG Industries, Inc. 
The secondary aqueous coating composition was applied to the sized glass 
fibers by drawing the glass fibers through a bath of the coating and a die 
to remove excess coating, such that the loss on ignition (LOI) of the 
coated glass strand for Samples F1 and F2 and Controls F1 and F2 was about 
15 percent for the diameter of the passage through the die of about 0.81 
millimeters (0.032 inches). 
EXAMPLE 6 
The aqueous sizing composition of Table 1 was applied as a primary layer to 
four strand bundles of H-15 E-glass fibers and the bundles were wound onto 
individual forming packages and dried as described in Example 1 above. 
Sample G (four strand) was prepared by coating the above strands with a 
secondary layer of the secondary coating composition set forth in Table 7 
below having about 40 weight percent solids. Corresponding Control G was 
prepared from the sized strand without secondary coating. 
TABLE 7 
______________________________________ 
Secondary Coating Component 
Weight of Component (grams) 
______________________________________ 
VYCAR .TM. 552 polyvinyl chloride/ 
16,000 
nitrile rubber copolymer latex.sup.18 
MAZU DF-136 defoamer.sup.19 
15 
urea 18 
deionized water 6000 
______________________________________ 
.sup.18 VYCAR .TM. 552 polyvinyl chloride/nitrile rubber copolymer latex 
is commercially available from B. F. Goodrich of Cleveland, Ohio. 
.sup.19 MAZU DF136 defoamer is available from PPG Industries, Inc. 
The secondary aqueous coating composition was applied to the sized glass 
fibers by drawing the glass fibers through a bath of the coating and a die 
to remove excess coating, such that the loss on ignition (LOI) of the 
coated glass strand for Sample G and Control G was about 16.7 percent for 
the diameter of the passage through the die of about 1.17 millimeters 
(0.046 inches). 
EXAMPLE 7 
The aqueous sizing composition of Table 1 was applied as a primary layer to 
a one strand bundle of H-15 E-glass fibers and the bundle was wound onto 
individual forming packages and dried as described in Example 1 above. 
Sample H (one strand) was prepared by coating the above strands with a 
secondary layer of the secondary coating composition set forth in Table 8 
below having about 40 weight percent solids. Corresponding Control H was 
prepared from the sized strand without secondary coating. 
TABLE 8 
______________________________________ 
Secondary Coating Component 
Weight of Component (grams) 
______________________________________ 
VYCAR .TM. 580X83 polyvinyl chloride 
16,000 
emulsion.sup.20 
MAZU DF-136 defoamer.sup.21 
12 
urea 18 
deionized water 6000 
______________________________________ 
.sup.20 VYCAR .TM. 580X83 polyvinyl chloride emulsion which is plasticize 
with diisodecyl phthalate is commercially available from B. F. Goodrich o 
Cleveland, Ohio. 
.sup.21 MAZU DF136 defoamer is available from PPG Industries, Inc. 
The secondary aqueous coating composition was applied to the sized glass 
fibers by drawing the glass fibers through a bath of the coating and a die 
to remove excess coating, such that the loss on ignition (LOI) of the 
coated glass strand for Sample H and Control H was about 19 percent for 
the diameter of the passage through the die of about 0.66 millimeters 
(0.026 inches). 
From the foregoing description, it can be seen that the present invention 
provides secondary coatings for fiber strands having improved adhesion to 
inner or outer layers of a hose assembly or a polymeric matrix, such as 
polyurethanes. The present invention provides a simple, economical hose 
assembly having one or more of the following performance characteristics 
such as high tensile strength, high modulus of elasticity, resin 
compatibility, dielectric properties to provide electrical resistance, 
environmental stability and cost effectiveness. The present invention also 
provides a hose assembly having good tensile and compressive strength 
which is capable of withstanding the rigorous environment to which such 
hose assemblies are subjected. 
It will be appreciated by those skilled in the art that changes could be 
made to the embodiments described above without departing from the broad 
inventive concept thereof. It is understood, therefore, that this 
invention is not limited to the particular embodiments disclosed, but it 
is intended to cover modifications which are within the spirit and scope 
of the invention, as defined by the appended claims.