Note: Descriptions are shown in the official language in which they were submitted.
WO 9S/22576 PCT/US95/01914
2l~j8929
ADHESION SYSTEM
Background of the Invention
1. Field of the Invention
This invention relates generally to an adhesion system for use with
rubbers, synthetic elastomers and other unsaturated polymers, especially
for treating fibrous and non-fibrous materials and the resultant products
thereof, such as adhesive-treated fibers, yarns, fabrics and fibrous pro-
ducts useful as reinforcing agents and particularly to such reinforcing
agents incorporated in hoses, belts, tires, molded articles, rolls and the
like, as well as the resultant reinforced article.
2. DescriDtion of the Drior art
Reinforced rubber products such as tires, belts, hoses, molded
articles, rolls and the like have found wide spread use for many years.
These rubber products have generally been reinforced with fibrous mate-
rials in various forms such as continuous filament yarns, staple spun
filament yarns, woven fabrics, knitted fabrics and other structures in
order to give the rubber products the strength, flexibility and other
properties needed to perform their functions. Filament yarns can be built
into the composite structure by braiding, knitting, spiral wrapping and
other techniques.
Since the surface of these fiber structures are chemically different
from the rubber, the compatibility of the two materials generally has been
improved by an adhesive treatment to the fibrous material in order to pro-
WO 95122576 PCIIUS95/01914
~158~ 2-
vide the "ecessary adhesion of the two materials to allow the composite
structure to offer the desired advantages in properties.
The early rubber products generally included naturally occurring rub-
ber ~cis-1,~polyisoprene plus proteins, fatty acids, lipids and numerous
other naturally occurring chemicals) and s~lllllelic rubbersj such as poly-
isoprene (IR), polybutadiene (BR), styrene-butadiene copolymers (SBR),
acrylonitrile-butadiene copolymers (Nitrile or NR), and polychloroprene (CR
or Neoprene), reinforced with naturally occurring or regenerated cellulose
fibers (cotton and rayon).
One of the first and presently the most widely used adhesion treat-
ments for these products is RFL or Resorcinol-Formaldehyde-Latex. Al-
though there may still be some question over exactly how RFL imparts the
required adhesion between the fiber and the rubber, it has been widely
accepted that formaldehyde reacts with resorcinol to form methylol groups
which in turn react with the hydroxyl groups of cellulose so as to provide
bonding to the fiber. These methylol groups also react with specific
groups in the latex, which is an aqueous dispersion of a copolymer con-
taining rubber compatible sections such as acrylonitrile, butadiene,
chloroprene and/or styrene. A reaction of specific groups of the latex
polymer with the rubber is generally thought to occur during the vul-
canization of the rubber.
There are many different types of rubber compounds for the many
different types of rubber products. In addition to the specific type of
rubber or elastomeric polymer, there are a variety of other additives such
as accelerators, fillers, antidegradants, processing aids and the like
designed to provide the specific properties in the rubber product. Any of
these variables, including relative and absolute amounts as well as type,
can affect the adhesion of a particular treated fiber product and demand
WO 95122576 PCT/US95/01914
21~892~
changes in the particular ratio of R to F to L or type of L (latex polymer)
and other variables in the treating procedure.
Since the introduction of RFL adhesion treatments for fiber rein-
forced rubber products, changing demands for better properties and/or
new rubber products has necessitated chan~es in both the rubber materials
and the fibers. Accordingly, cotton and rayon have been increasingly
replaced by polyester fibers (polyethylene terephthalate and similar poly-
mers) and aramid fibers {poly(p-phenylene terephthalamide) (Kevlar~),
poly(m-phenylene isophthalamide), copolyterephthalamides of 3,~di-
aminodiphenyl ether and p-phenylenediamine (Technora~)}. These fibers
differ from the cellulosic fibers in that they have few if any groups on their
surface capable of reacting with the RFL and the fiber surface is generally
more crystalline and not as accessible. Modifications in the adhesive
treatments have been made to overcome this problem.
One of the most widely used modifications constitutes pre-activation
of the fiber surface, either by the fiber producer or during the adhesive
treatment. Pre-activated fibers, produced by the introduction of reactive
groups such as epoxides, for example, which form surface hydroxyls or
other corresponding reactive groups, are commercially available. The RF
portion of the RFL treatment then is thought to react with these surface
groups. Another modification is to employ a two step process in the adhe-
sive treatment of the fiber. A subcoat is first formed on the fiber surface
by treatment with an epoxy or isocyanate compound or a combination of
the two. This treatment can be by either a solution of the subcoat-forming
compound in an organic solvent such as toluene or in an aqueous suspen-
sion of the subcoat-forming compound. Since isocyanates are so reactive
with water, they are usually blocked with compounds which prevent their
reaction with water at ambient temperatures and which are subsequently
WO 95/22576 PCT/US95/01914
~,i589;~3; 4
released at high temperatures to yield free isocyanate groups. The RFL
treatment is then applied as a topcoat.
Natural and sy"ll-elic rubbers have been increasingly replaced by
synthetic materials which differ structurally from natural rubber even more
than the synthetic rubbers mentioned earlier. In response to the require-
ments of improved resistance to heat, ozone and other degrading agents,
these newer elastomers generally have fewer double bonds. In addition,
the double bonds that are present are usually less accessible and generally
in side chains rather than in the backbone. Some examples of these mate-
rials are EPDM (Ethylene-Propylene-Diene Monomer), chlorosulfonated
polyethylene (CSM or Hypalon~) and butyl (isobutylene-isoprenecopolymer
and halobutyl elastomers. Modifications in RFL lrealments to meet these
challenges have generally involved using a latex that is more compatible
with the elastomer. EPDM, chlorosulfonated polyethylene and similar
latexes are available. Although these latexes may offer some improved ad-
hesion over the synthetic rubber type latexes to the specific elastomer,
there are still disadvantages such as expense and stability of the specialty
latex and the desire for greater adhesion.
In addition to being less suited to the newer materials used in rubber
composites and specific rubber products, RFL treatments also encounter
present day environmental and safety problems. Formaldehyde presents
many safety and environmental problems in the preparation of the chemi-
cal treatment, the application of the l~eat~ent, heat curing of the treat-
ment, converting and handling of the treated yarn, and incorporation into
the rubber product. Disposal of water containing the formaldehyde, resor-
cinol, and latex components is becoming an increasingly complex problem.
Lastly, due to the polymer formation on the surface of the fiber by the RF
reaction, the RFL treated materials are generally stiff, more variable in
regard to uniformity of concentration of the polymer along the fiber mate-
wo 95/22576 2 1 ~ ~ ~ 2 9 PCTIUS95/01914
rial surface, and variable in regard to surface tackiness, causing process-
ing problems in the incorporation of the treated materials into rubber pro-
ducts.
Isocyanates and epoxides alone and with plasticizers have been
used as alternatives to RFL. These approaches generally do not give as
high adhesion as RFL but they may overcome some of the environmental,
safety and processing problems. In addition, a great deal of research has
been directed to adhesive systems based on polyisocyanates combined
with a variety of materials, one of which includes polyenes sometimes
terminated by groups having active hydrogens, e.g., hydroxy-terminated
polybutadienes. Such systems, along with others are exemplified in the
following patents.
In Japanese Patent 50087477 issued to Toshiyuki et al. in 1975,
bonding of polyester fiber is said to be improved by treating the fibers with
a mixture of a diisocyanate prepolymer with polymer or copolymer of a
mercapto-terminated halogen-containing polybutadiene derivative such as
polychloroprene in a molar ratio of x:y isocyanate group to polychloroprene
to give two terminal isocyanate groups plus a polyester containing at least
60% ethylene terephthalate linkages in organic solvents such as dimethyl-
formamide. The equivalent ratio of the isocyanate groups to the halogen-
containing butadiene and hydroxyl groups from the polyester was between
0.9 and 1.3, inclusive, with the ratio of hydroxyl groups to thiol groups
being between 0.5 and 2.0 inclusive.
East German Patent 1282913 B describes polyamide fibers bonded
to a rubber mat by placing a polyethylene sheet containing a little plasti-
cizer onto the rubber mat, coating with a solution of an isocyanate com-
pound and rubber in an organic solvent, spreading polyamide staple fibers
on top and pressing through a pair of rollers.
WO 95122576 PCT/US95/01914
2~ 5~9~9 - 6 -
Japanese Patent 49011877 issued to Shima et al. on March 20,
1974, describes poly(ethyleneterephthalate) orsimilar polyesters modified
with one or more unsaturated dicarboxylic acids, diols, or hydroxy-
carboxylic acids such as polybutadiene glycol, and a chain linking agent
such as diphenylmethane diisocyanate dissolved in nitrobenzene for one
hour at 150C to give a material for improved dyeability of polyester fiber
or improved adhesive properties of polyester tire cord.
Japanese Patent 46006358 issued to Shima et al. on February 17,
1971, describes polyester fibers and films treated with a polyester, an
isocyanate and/or an epoxide, and a modified polybutadiene (molecular
weight 300-10,000) that show improved adhesion to rubber and improved
dyeability .
Japanese Patent 4800835 issued to Shuna et al. on March 13,
1973, describes a polyurethane adhesive for tire cords prepared from the
reaction of a polyester, a carboxyl or hydroxyl group terminated polyene
and a polyisocyanate containing three isocyanate groups such as toluene
triisocyanate.
Henning et al. in U.S. Patent 4,870,129 issued on September 26,
1989, introduced an aqueous solution or dispersion adhesive using a poly-
urethane with carboxylate or sulfonate groups. The polyurethane is pre-
pared by reacting isocyanate groups (NCO) with hydroxyl groups (OH) at
a ratio range equal to 1.2 - 2.5 equivalents of NCO to 1.0 equivalents of
OH.
U.S. Patent 5,045,393 issued to Kumanoya et al. on September 3,
1991, introduced a method for providing a polyolefin resin substrate with
an adhesive coating using a hydroxyl hydrocarbon paint with a catalyst,
which promotes the isocyanate-hydroxyl reaction, and then coating the
primer film with a polyurethane prepolymer adhesive rich in isocyanate
groups.
wo 95n2s76 2 1 5 ~ 9 2 9 PCT~S95/01914
- 7 -
U.S. Patent 4,552,816 issued to Spahic et al. on November 12,
1985, describes a process for producing covalently bonded laminated
structures composed of polyurethane elastomer and vulcanizable rubber.
The joining layer is comprised of polyurethane segments, polyisocyanate
segments, and hydroxyl containing polybutadiene segments where cova-
lent bonds exist between polyurethane and polyisocyanate segments and
between the hydroxyl of the polybutadiene and the polyisoc~,ranate
segment. -
U.S. Patent 3,528,878 issued to Lubowitz on September 15, 1970,
describes a method for bonding rubber to fabric comprised of a polyfunc-
tional polydiene having either hydroxyl or carboxyl groups or both, a pre-
dominant amount of vinyl groups on alternate carbon atoms of the poly-
diene backbone, an organic co-reacting chain extender, and a peroxide
free radical initiator. A substituted diisocyanate is used as a chain
extender when the polydiene contains hydroxyl groups.
Japanese Patent 01 144471 issued to Iwase et al. in 1989 describes
compounds containing isocyanate-modified polybutadienes having an
average number molecular weight ~Mn) 500-20,000, polyols having Mn
150-50,000, and acid phosphates gave good adhesion to various plastics.
u.s. Patents 3,743,616 and 3,879,248 issued to Kest on July 3,
1973, and April 22, 1975, respectively, describe a new class of and
method for producing pressure sensitive adhesives for bonding to various
substrates (e.g., glass, metal, paper...). The adhesive consists of a
hydrocarbon polymer with at least 1.6 terminal active-hydrogen groups
and an equivalent weight of 500 or greater co-reacted with an organic co-
reactant having two or more reactive groups (U.S. Patent 3,743,616) or
an organic polyisocyanate (U.S. Patent 3,879,248) in situ on the substrate
web to give a pressure sensitive adhesive. In the practice of the invention,
sufficient co-reactant is used to provide a ratio of 0.75-1.20 co-reactant
WO 95122576 PCT/US95/01914
215~ 8-
groups to the total of functional groups present in the diene telechelic
polymer.
iapanese Patent 48022191 describes improvement in the adhesion
of polyester fibers to rubbers by using a l-eal~"ent comprised of a conju-
gated diene copolymer, havin~ a molecular weight of 300-10,000 and
2-35 mole percent arG",alic or pyridine ring and polyesters, plus polyiso-
cyanates, polyisocyanate derivatives, or polyepoxy compounds. In addi-
tion, a curing agent or accelerator is used in the presence of isocyanate
or epoxy compounds. The composition is such that the total solids pre-
sent contains one gram equivalent mole of aliphatic unsaturation per 1000
molecular weight. The diene copolymer is prepared by copolymerizing a
diene such as butadiene and isoprene with styrene, vinyl naphthalene, or
vinyl pyridine. An application for the treated fibers is as reinforcement for
tires and belts.
U;S. Patent 3,616,193 issued to Lubowitz et al. on October 26,
1971, describes polydiene resins, such as dihydroxyl terminated 1,2-poly-
butadiene, mixed with organic chain extenders, such as toluene diisocya-
nate, in the presence of a peroxide free radical initiator, such as dicumyl
peroxide, to form a liquid polymeric mixture. The polydiene prepolymer
is preferably reacted in equimolar proportions and strong deviations will
result in a less desirable product.
European Patent 358079 issued to Lawson et al. on March 14,
1990 introduced an adhesive system useful for bonding an uncured rubber
to a cured polyurethane. A fiber reinforced pad was coated with the reac-
tion product of a hydroxyl terminated polybutadiene and toluene diisocya-
nate in a solvent such as toluene; dried and coated with two coats of an
adhesive cement comprising of 50% diphenyl methane diisocyanate in
toluene, a glycidyl diether of tetrabromobisphenol in toluene, and a 37%
dispersion of p-nitrobenzene in xylene; covered with a natural tie gum; and
WO 9S/22576 PCT/US9S/01914
215~5g~
_ 9 _
covered with an uncured cord-reinforced cushion stock to form an example
composite pad.
U.S. Patent 4,091,195 issued to Vitek et al. on May 23,1978,
describes hot-melt adhesives from a number of polymers which have been
at least partially cross-linked. One adhesive comprised a homogenized
polybutadiene reacted with a polyisocyanate as a cross-linking agent and
adding a cross-linking accelerator. No specific molar or equivalent ratios
were given.
Japanese Patent 56136363 assigned to Mitsubishi Chemical Indu-
stries Co., Ltd. in 1981, describes a canvas fabric bonded to an EPDM
(ethylene-propylene-diene monomer) elastomer in the presence of hydroge-
nated hydroxyl terminated polybutadiene and diphenylmethane diisocya-
nate at 1.1 equivalents o-f isocyanate (NCO) to 1 equivalent of hydroxyl
(OH).
Japanese Patent 47042636 issued to Shima et al. in 1972, de-
scribes polyurethane adhesives for bonding polyester fibers to rubber
prepared from mixtures of polyols and a diisocyanate. Thus, polybutadiene
glycol, ethylene glycol, trimethylolpropane, 2,2'4,4'-tetra(tert-butyl)-
3,3'-di(hydroxyphenyl) methane, and diphenylmethane diisocyanate were
heated in solvent (3:7 dimethyl sulfoxide: nitrobenzene) 1.5 hours at
150C to give a reactive copolymer solution. A 1100 denier polyethylene
terephthalate fiber is immersed in the solution and heat-treated at 240C.
The fiber is mixed with natural rubber and vulcanized at 160C with
dicumyl peroxide to give a composite with adhesive strength 15.1 kg.
Japanese Patent 50161578, issued to Yamada et al. on December
27, 1975, describes treated non-continuous fibers with the reaction pro-
duct of a h~/droxyl-terminated polybutadiene with toluene diisocyanate and
E-caprolactam to improve adhesion and reinforce rubber.
WO 95/22576 PCT/US95/01914
2'~gZ - 10-
Czechoslovakian Patent 235735 issued to Smatlove et al. on
December 1, 1986, describes a method eliminating the use of solvents,
discoloration of the vulcanizate, and the direct handling of toxic
isocyanates. The compound is manufactured by adding to the rubber com-
pound blend 1-25% reaclion product of a hydroxyl terminated telechelic
prepolymer such as an OH-terminated oligomeric polybutadiene (MW
2500) with a diisocyanate such as diphenylmethane diisocyanate at a
molar ratio of OH: NCO equal to 1 :(1.5-4).
Japanese Patent 01304168 issued to Hata on December 7, 1989,
describes fibers treated with epoxides or isocyanates and then with
epoxide resins and hydroxyl or carboxyl containing polybutadiene rubber
before bonding and vulcanizing with organic peroxide containing rubbers
for adhesion.
Japanese Patent 03205473 issued to Mori et al. on September 6,
1991, shows adhesives useful in bonding polyolefins in automobile inte-
riors comprised of a main component containing a saturated hydroxyl
terminated polybutadiene or their reaction products with diisocyanates and
a curing component containing isocyanate terminated urethane prepoly-
mers from hydrogenated hydroxyl terminated po!ybutadiene and excess
polyisocyanates.
U.S. Patent 3,837,892 issued to Marzocchi on September 24,
1974, introduces a method for improving the bonding relationship be-
tween glass fibers and elastomeric materials. Part of the adhesive compo-
sition uses a polyurethane prepolymer containing free isocyanate groups
prepared by reacting excess polyisocyanate with a hydroxyl terminated
polybutadiene or similar compound at a ratio of equivalents isocyanate to
equivalents hydroxyl equal to at least 1.5, but preferably equal to
2.0 - 4Ø
WO 95t22576 PCT/US9S/01914
2158~329
- 11 -
U.S. Patent 3,941,909 issued to Schoen et al. on March 2, 1976,
introduces a process for improving the adhesive properties of ethylene -
propylene copolymers and terpolymers. The surface is treated with the
reaction of a rubber-like hydroxyl-containing alkadiene-derived polymer and
an organic diisocyanate at a ratio of 0.9 to 1.2 equivalents of isocyanate
to hydroxyl.
U.S. Patent 3,894,982 issued to Polaski on July 15, 1975 divulges
adhesive compositions of a polydiene and a polyfunctional aminoorgano-
silane which can be utilized for bonding vulcanizable elastomers to them-
selves as well as other substrates. The chain extended substituted poly-
alkadiene reaction reacts a polybutadienediol with a diisocyanate at a slight
molar excess isocyanate up to ten percent.
Japanese Patent 58217576 assigned to Sekisui Chemical Co., Ltd.
in 1983, introduces urethane adhesives comprised of a hydroxyl termi-
nated 1,2-polybutadiene (~ 90% 1,2-units), hydroxyl terminated 1,4-
polybutadiene (2 60% 1,4-units), polyisocyanate (0.6 c isocyanate/hy-
droxyl ratio c 1.2), aromatic or aromatic-aliphatic petroleum resin, and
plasticizer. The adhesive composition is mixed, coated on a polyvinyl
chloride sheet with some plaslicizer, and cured to give an adhesive tape.
World Patent 92/03500 to Drake et al. on March 5, 1992, dis-
closes adhesive rubber compounds exhibiting very strong adhesion to other
elastomers, plastics and a variety of subslrates. A film or spreadable
liquid of this adhesive is cured in contact with the substrates to be
adhered.
From the preceding description of the references, it is difficult to
make any generalization except to note that the art is extraordinarily
crowded with efforts to provide improved adhesives, even in a narrow
area defined by the combination of, for example, isocyanates in combina-
WO gsn2576 PCI/US9!j/01914
9 2~ 12 -
tion with a polymer having active hydrogen-containing end groups and
double bonds.
Objects of the Inve..t;c..
lt is an object of one aspect of the present invention to provide an
improved adhesion system for fibrous and related products, especially for
use as reinforcing materials in composite rubber products, as well as for
other uses where good adhesion is required.
An object of another aspect of the invention is to provide composi-
tions which may be used as part of, or as the total adhesion system.
An object of a further aspect of the invention is to provide articles
of manufacture, such as, for example, fabrics, fibers and sheets provided
with the adhesion system, as well as final products such as, for example,
hose, belts, tires, other mechanical rubber goods, and the like, reinforced
with the treated articles of this invention.
Upon further study of the specification and appended claims, fur-
ther objects and advantages of aspects of this invention will become
apparent to those skilled in the art.
Summary of the Inve.,tic.~
These and other objects are achieved through the adhesive system
of the present invention which comprise(s): (a) an isocyanate compound,
(b) one or more of a polyunsaturated polymer (or oligomer), hereinafter
referred to as "hydrocarbon polymer", where the backbone of such a
polymer comprises carbon-carbon bonds and which contains some carbon-
carbon double bonds or 9roups capable of forming some carbon-carbon
double bonds or otherwise can undergo free radical reaction and/or a
polyunsaturated polymer (or oligomer), hereinafter referred to as a
"heteroatom polymer", which has a heteroatom backbone, that is, the
WO 95/22576 PCTIUS95101914
215~92~
polymer backbone contains atoms other than, and bonded to, carbon, such
as oxygen, nitrogen and sulfur, which also contains unsaturated groups as
for the hydrocarbon polymer. Both of these types of polyunsaturated
polymers may contain active hydrogen functional groups which can react
with or have reacted with an isocyanate compound. These reactive
groups are usually terminal end groups, but they can also be along the
polymer backbone or off of side chains, and (c) a carrier for dissolving or
dispersing (a) and (b) and optionally other functions, especially when a
plasticizer is used as a carrier. Each of these components contributes,
- 10 either singularly or in combination with other components to achieving the
advantages of the invention. This adhesion system can be applied to fila-
ment yarns, fabrics and other fibrous materials and other products such
as films and sheets to impart improved adhesion of these articles to rub-
bers and synthetic elastomers and other unsaturated polymeric products
which are difficult to bond with existing treatments. In general, the
adhesion system can be used to join any type or form of material to
another material, whether it be the same or different.
The components of this invention either form a homogeneous solu-
tion or uniform dispersion which can be applied to the articles without the
use of emissive solvents and without pretreatments or separate treatments
and without adversely arrecling the articles in their processing and use
with the rubber materials or other unsaturated polymeric materials con-
taining carbon-carbon double bonds.
Isocyanate compounds are an essential part of this invention. These
compounds, which generally should contain two or more isocyanate
groups per molecule, apparently contribute to the adhesion improvements
of this invention in more than one way. Some of these isocyanate mole-
cules may react with the polyunsaturated polymers which are the second
component of this adhesion system. However, it has been surprisingly
WO 95/22576 PCT/US95/01914
8~ 4-
found that additional isocyanate compound, other than that which reacts
with the polyunsaturated polymer component, is necessary. Therefore,
very large molar ratios of the isocyanate compound to the polyunsaturated
polymers, which results in a lar~e excess of isocyanate groups over what
can react with the polyunsaturated polymer, are unexpectedly required in
order to obtain the adhesion improvements imparted by the adhesion
system of this invention.
The- molar ratio is calculated as the number of moles of isocyanate
groups to the number of moles of functional groups on the polyunsaturated
polymer capable of reacting with the isocyanate. The specific molar ratio
used may be dependent on the hydrocarbon polymer and/or heteroatom
polymer used, the monomers used to form the polymer(s), the type of
reactive groups in the polymer(s), the number of unsaturated groups in the
polymer(s) and the amount and type of isocyanate used, among other
things. However, at least about 1.5 times molar excess of isocyanate has
been found necessary to impart the improved adhesion of this invention in
the case of the hydrocarbon polymers with ratios such as 200 to 1 and
higher giving very significant adhesion improvements. The heteroatom
polymers generally give adhesion improvement at even higher molar ratios
than the hydrocarbon polymers. The combination of a hydrocarbon
polymer and a heteroatom polymer also allows higher molar ratios of
isocyanate groups of each polymer than with either polymer alone.
Specifically, the preferred adhesion system comprises excess
polyisocyanate molecules plus polyisocyanate reacted with isocyanate
reactive polyunsaturated compounds plus plasticizers.
The isocyanate compounds of this invention include, but are not
limited to, those defined by D.H. Chadwick and T.H. Cleveland in "Isocya-
nates, Organic", Kirk-OthmerEncyclopediaofChemicalTechnology, 3rd
Edition, Vol. 13, pp. 789-818, Martin Grayson - Editor, John Wiley &
WO 95t22576 PCT/US95/01914
` 215g~2~
- 15 -
Sons, New York, 1981. Preferred isocyanate compounds of this inven-
- tion include compounds which contain at least two isocyanate groups
and/or isocyanate equivalent ~roups. Preferred compounds include diiso-
cyanates, polyisocyanates, prepolymers containing urethane or amide link-
ages with free isocyanate groups and dimers, trimers, oligomers and
copolymers of isocyanates, such as those obtained from diisocyanates.
Compounds with isocyanate equivalent groups include those which have
their isocyanate groups blocked with a potentially fugitive blocking agent,
adducts and derivatives of compounds having isocyanate groups with
other reactive species such as biurets or isocyanurates, and compounds
which may not contain isocyanate groups or their derivatives but do
contain groups which react like isocyanates such as, for example,
carbodiimides and compounds which contain isothiocyanate groups.
Representative species suitable for use as at least one of the
isocyanate compounds in this invention include but are not limited to
toluene diisocyanate (TDI) ~2,4 and 2,6-isomers and mixtures), hexa-
methylene diisocyanate (HDI), meta-tetramethylxylylene diisocyanate,
bis(4isocyanatocyclohexyl)methane (hydrogenated MDI), (1,4-bisiso-
cyanatomethyl) cyclohexane, isophorone diisocyanate (IPDI), diphenyl-
methane 4,4'-diisocyanate (MDI), polymeric or oligomeric MDI or poly-
methylene polyphenyl isocyanate (either 2,4' or 4,4'-isomers or any
mixture of these), p-xylylene diisocyanate, toluene triisocyanate, the
biuret of hexamethylene diisocyanate, the adduct of TDI with trimethylol
propane, the trimer (isocyanurate ring) of TDI, HDI or a copolymer of the
two; the dimer of TDI; caprolactam, phenol, substituted phenol, butanone
oxime or similar oxime blocked TDI, HDI or other isocyanate or derivative
as described above, polycarbodiimide modified MDI and other isocyanates
and polyureas of TDI, 1,4-benzene diisocyanate, dianisidine diisocyanate,
1-chlorophenyl-2,4-diisocyanate, trimethylene diisocyanate, pentamethy-
WO 95/22576 PCT/US95/01914
~5~g~
- 16 -
lene diisocyanate, butylene-1,2-diisocyanate, butylene-1,4-diisocyanate,
xylene diisocyanate, 2,~cyclohexane diisocyanate, 1 ,4-cyclohexane diiso-
cyanate, 1 ,1 -dibutylether diisocyanate, 1 ,6-cyclopentane diisocyanate,
2,5-indene diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane
diisocyanate,1,1 2-diisocyanatododecane,1-isocyanato-3,3,5-l,imell,yl-5-
isoc~ana~o" ~elhyl-cyclol)e~ane~ 4,4'-diisocyanatodicyclohexylpropane-(2,2)
and other di or polyisocyanates containing free isocyanate groups.
The isocyanate compounds defined above may be mixed with com-
pounds that contain one isocyanate group which include, but are not
limited to dimethyl meta-isopropenyl benzyl isocyanate, hexyl isocyanate,
ortho, para or meta-tolyl isocyanate, 1,4-phenylene isocyanate, 1,4-
phenylene isothiocyanate, 4-methoxyphenyl isocyanate, 4-methoxyphenyl
isothiocyanate, p-cyanophenyl isocyanate.
Isocyanate compounds which contain two or more isocyanate
groups are preferred in this invention. The polymethylene polyphenyl
isocyanates or polymeric MDI, which are oligomers or polymers of MDI,
are particularly preferred. Polymethylene polyphenyl isocyanate (PMPPI)
is available from a number of sources such as BASF Corporation, Dow
Chemical USA and Miles Inc. (formerly Mobay) and several others. These
products are a mixture of the various possibilities which can be repre-
sented by the following formula, giving five different compounds in terms
of "n" in that formula and two major isomers, 2,4' and 4,4'.
O = C = N-CH2(-AR-CH2-)n--AR-N = C = O
N=C=0
Where AR is a phenyl group and n = 0 to 4.
These mixtures, which generally contain about 50% n = 0 product
(MDI), have an isocyanate functionality ranging from greater than 2.0 to
about 3.0 or higher (MDI = 2.0) and have an isocyanate content of about
30 to about 33%. Reactive group functionality, such as isocyanate func-
WO 95/22576 PCT/US95/01914
21S892~
- 17-
tionality, refers to the average number of reactive groups per molecule or
- moles reactive groups/mole of compound. Even though these compounds
contain more than two isocyanate groups, they surprisingly do not form
excessive crosslinks or insoluble materials, even when mixed with other
reactive components of this invention within a carrier. For example, the
Desmodur series of Miles Inc. varies according to the following Table:
TYPICAL
PERCENT 'rYPlCAL TYPICAL
L E V ~ un TYPE ISOCYANATE FU _ I I KrJ lTY VISCOSN ~' ISOMER
0 VKS-2 33 20 65% 4,4'&
35% 2,4'
VKS-4 32.5 2.4 40 65% 4,4' &
35% 2,4'
VKS-5 32.4 57 65% 4,4' &
1 5 35% 2,4'
VKS-18 31 2.75 180 65% 4,4' &
35% 2,4'
VK-5 32.5 2.3 50 95% 4,4' &
5% 2,4'
VK-18 31.5 2.7 180 95% 4,4' &
5% 2,4'
VK-70 31 2.8 700 95% 4,4' &
5% 2,4'
VK-200 30.6 3.0-3.3 2000 95% 4,4' &
5% 2,4'
Although all of the polymethylene polyphenyl isocyanates will yield
improved adhesion in this invention, the Desmodur VKS-18 and Desmodur
VK-18 polymethylene polyphenyl isocyanates are preferred for their
balance of adhesion improvement and treating solution stability. Not wish-
ing to be bound by theory, with all other characteristics being equal, the
increased branching of the 2,4'-isomer appears to offer better treating
solution stability and better processing.
The second component of this invention comprises one or more of
a polymer and/or oligomer which contains more than one unsaturated
WO 95/22576 PCTIIJS9S/01914
2 ~i a~ ~ 18 -
group or carbon-to-carbon double bond unit either in the backbone or as
side chains or other groups capable of forming unsaturated groups or
otherwise undergoing free radical reaction or other such reaction to cross-
link or otherwise react with rubber and other polymer molecules during
rubber vulcanization or similar processes, such as but not limited to
chlorosulfonated polyethylene, which may lose S02 during vulcanization
or cure to develop unsaturated groups ~Paul R. Johnson, p. 787 in Martin
Grayson/Executive Editor, Kirk-Othmer Encyclopedia of Chemica/ Tech-
nology, 3rd Edition, Vol. 8, Wiley-lnterscience, New York) and similar
polymers as described in Volume 8. The polyunsaturated polymer general-
ly has at least one active hydrogen functional group per molecule, gene-
rally as a terminal group but possibly along the polymer chain or attached
to side chains, such as hydroxyl, carboxyl, amine, thiol, hydroxyl amine
and other active hydrogen functional groups which may react with the
isocyanate groups in the treating solution and/or on the treated article.
These polyunsaturated polymers may be either (a) the hydrocarbon poly-
mers, usually made by a free radical chain polymerization (addition
polymerization) or (b) the heteroatom polymers, usually made by conden-
sation or step-reaction poly."eri~lion.
Typical of the first type of polymers or hydrocarbon polymers,
which can have atoms other than hydrogen connected to the carbon atoms
in the polymer backbone, are homopolymers or copolymers of polyene or
diene monomers including but not limited to butadiene, isoprene, chloro-
prene, 2,3-dimethylbutadiene, 2,4-hexadiene, ethylidene norbornene,
1,4-hexadiene, dicyclopentadiene, cyclopentene and the like, which
upon polymerization leave a double bond or unsaturated group in the chain
or as side chain. The copolymers include copolymers of the diene mono-
mers with each other or vinyl monomers such as isobutylene, ethylene,
propylene, butene, vinyl ethers and the like, with vinyl substituted aro-
WO ssn2s76 Pcrlussslolsl4
215~929
- 19 -
matic compounds such as, for example, styrene, vinyl toluene, vinyl
pyridine, or with acrylic monomers such as, for example, acrylonitrile,
acrylic and methacrylic acids, amides and esters or with any other unsatu-
rated monomers capable of polymerizing with the polyenes or dienes.
The hydrocarbon polymers of this invention typically should have at
least one and preferably on the average at least about three or five and
more preferably about 10 repeat units or carbon-carbon double bond units
capable of undergoing free radical addition. The limiting factor on the high
side of repeat units of the diene monomers, and any comonomers in-
cluded, is to preferably maintain the hydrocarbon polymer in a liquid state
or to maintain solubility or dispersibility of the hydrocarbon polymer in the
other components of this invention. Corresponding molecular weight
values for these degree of polymerization ranges would depend on comon-
omers included in the polymer. A preferred range of average degree of
polymerization is from about 10 to about 100. An even more preferred
average degree of polymerization is about 15 to about 75 and especially
about 30-50, which is represented in polybutadiene Poly bd~ R45HT, a
commercial product from Atochem North America, Inc. (Poly bd~ is a
trademark of Atochem North America). This commercial polymer is a
liquid, hydroxyl-terminated homopolymer of butadiene with a number
average molecular weight of about 2800, polydispersity (Mw/Mn) of 2.5
(so Mw ~ 7000), a viscosity of about 5000 mPa-s at 30C, a specific
gravity of about 0.901 at 30C and an iodine number of about 400 and
glass transition temperature (Tg) of -75 C. The predominant configuration
of this polymer is about 60% trans, 20% cis and 20% vinyl as repre-
sented by the following formula:
H0-[-(CH2-C = C-CH2-)02-(-CH2-CH-)0.2-(-CH2-C = CH
H H CH = CH2 H CH2~)0.~]n~0H
where n = 50.
WO 95122576 PCTIUS95/01914
5~8~zg - 20-
The hydroxyl value of this preferred hydrocarbon polymer is about 0.86
meq/g with a hydroxyl number of about 48.2 mg KOH/g, representing a
hydroxyl functionality in the range of 2.4 to 2.6. Another preferred
hydroxyl-terminated hydrocarbon polymer is Poly bd R20LM from
Atochem. This polymer has a degree of polymerization of about 25, a
number average molecular weight of about 1230, with a polydispersity
value (Mw/Mn) of 2.0, a viscosity of about 2600 mPa-s at 23C, a
hydroxyl value of about 1.8 meq/g, representing a hydroxyl functionality
in the range of 2.4-2.6 glass transition temperature (Tg) of approximately
2.5.
Terminal or other groups in the hydrocarbon polymer which can
react with the isocyanate component of this invention, other than
hydroxyl groups, include but are not limited to carboxylic acid, thiol,
amine, as well as other groups which will react with isocyanate groups.
One example of a polymer with carboxyl groups along the chain is the
adducts of, for example, maleic anhydride with polybutadiene and other
polymers as described by Drake and Labriola in WO 92/03500.
Amine terminal groups are generally more reactive than hydroxyl-
terminal groups and can, in some cases, give more insoluble products and,
in such cases, can be combined with selected plasticizers and other
components of this invention to give usable treating solutions.
Although a reactive group functionality of around 1.0 to 3.0 func-
tional groups per polymer molecule is preferred and about 1.9 to about 2.6
functional groups per polymer molecule is more preferred, the improved
adhesion of this invention should be obtained with polymers having a reac-
tive group functionality of as low as 0.1 or even lower, or higher than
3.0, with the selection of the proper components of this invention. In
fact, some of the hydroxyl groups of these hydrocarbon polymers, such
as Poly bd R45HT, can be reacted so that non-isocyanate reactive groups,
WO 95/22576 PCT/~JS95/01914
- 21 21j`8929
such as, for example, acrylate, vinyl, phenyl, alkyl and the like, are
present. In the case of where the functionality is below one, some poly-
mer molecules may not react with the isocyanate groups, but they still
may contribute to adhesion improvements by physical entanglements or
other mechanisms. In the case of functionalities significantly below 1.0,
the actual molar ratio of NC0 to actual reactive group will increase
significantly and may even approach infinity.
Some of the double bonds of the hydrocarbon polymers of this in-
vention can be further reacted either before or after the polymer's reaction
with isocyanate, such as being epoxidized or oxidized, for example.
Representative of such polymers include but are not limited to Poly bd 600
and 605 Resins from Atochem North America.
It has also been discovered that phenyl terminated polybutadiene
combined with the isocyanate compound and plasticizer has yielded good
adhesion. In such a case, where phenyl or other non-reactive hydrocarbon
functinoal group is used, some reactive groups may have been introduced
in some manner and the molar ratio of isocyanate groups to active hydro-
gen groups will exceed 200:1 may even greatly exceed 200:1 and may
even approach infinity. Without wishing to be bound by an explanation,
the phenyl-terminated polybutadienes employed in the examples may have
had hydroxyl groups since they were subject to atmospheric conditions for
several years without the protection of antioxidants.
Typical of the heteroatom polymers of this invention are unsaturated
polyesters, polyamides, polyurethanes, and polyethers, where eitherat
least one of the difunctional dicarboxylic acids, isocyanates, epoxides or
methylol condensates and/or at least one of the difunctional alcohols,
thiols or amines involved in the polymerization reaction have double bonds
or unsaturated groups. These polymers will usually have active hydrogen
groups, which will react with the isocyanate compounds of this invention,
WO 95/22576 PCI/US95/01914
22 -
as terminal groups and even as side groups, if polyfunctional monomers
are used. The nature of these terminal reactive groups will be dependent
on the molar ratio and of the two reactants whether the active hydrogen
groups were hydroxyl, amine or thiol or a combination thereof.
The polyester and polyamide polymers can be made by reacting un-
saturated dicarboxylic acids, or their derivatives such as, for example,
anhydrides, esters, acid chlorides, amic acids, amides and the lil~e with
diols, in the case of polyesters, and with diamines, in the case of
polyamides. The dicarboxylic acids can be aromatic as well as aliphatic,
and they preferably have at least one double bond, preferably a carbon to
carbon unconjugated double bond.
Examples of dicarboxylic acids, and their derivatives as described
above, for heteroatom polymers of this invention include but are not
limited to maleic, itaconic, citraconic, fumaric, trans-3-hexene-dioic
acids, anhydrides and acid chlorides; 1-cyclopentene-1,2-dicarboxylic
anhydride; alkenyl substituted succinic anhydrides and the like. These
unsaturated dicarboxylic acids can be mixed with saturated or other dicar-
boxylic acids which do not undergo free radical addition, such as, for
example, succinic, phthalic, terephthalic, trimellitic acid and similar acids
as long as there are enough reactive double bonds in the resulting polymer
to give the desired adhesion. The same applies to unsaturated or satu-
rated acids having more than two carboxyl groups as long as the solubility
or dispersibility in the other components of this invention is maintained.
Either the saturated or unsaturated dicarboxylic acids or their derivatives
or a mixture of the two can be reacted with unsaturated polyols and/or
polyamines.
The heteroatom polymers of this invention can vary widely in regard
to average degree of polymerization or number of repeat units of unsatu-
rated units. The upper limit will generally be dictated by the desire to
WO 95/22576 PCT/US95/01914
, 215892~
maintain a liquid state or solubility in plasticizers or solvents, but pre-
ferably will be about 30 repeat units and more preferably about 20 repeat
units. The lower limit should bé more than one repeat unit of unsaturated
units and preferably at least three or five repeat units and more preferably
at least eight repeat units.
The polyhydroxy compounds should contain at least two hydroxyl
groups, with the preferred group being diols. Particularly preferred diols
are sterically hindered 2,2,~tri~1Ower)alkyl pentane-1,3-diols, especially
2,2,4-tri-(C,-C3)-alkylpentane-1,3-diol, although other diols, even those
containing other functional groups or aromatic hydrocarbon components
or further reacted additional hydroxyl groups, should be suitable in the
polyunsaturated polycarboxyls of this invention. Representative diols,
both saturated and unsaturated, include but are not limited to: 2,2,4-
trimethyl-1,3-pentanediol, neopentyl glycol, 1,3-butanediol, 1,4-butane-
diol, 2,4-dimethyl-2-ethyl-1,3-hexanediol, 1,6-hexanediol, 1,5-hexane-
diol, 5-hexene-1,2-diol, 2-butene-1,4-diol, 3-cyclohexene-1,1-dimetha-
nol, hydroxyl-terminated butadiene, isoprene, chloroprene and the like
homopolymers and copolymers, 7-octene-1,2-diol, 5-norbornene-2,2-di-
methanol, cis-3,5-cyc!ohexadiene-1,2-diol, ethylene glycol, propylene
glycol, diethylene glycol, polyethylene glycol, polypropylene glycol,
2,2'-thiodiethanol, 1,3-propane diol, 2-methyl-1,3-propane diol, resor-
cinol, 1,3-dihydroxynaphthalene, cyclohexane dimethanol, 3-allyloxy-
1,2-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2,3-dihydroxypropyl-
acrylate and methacrylate, N,N'-(1,2-dihydroxyethylene)bisacrylamide,
dihydroxycinnamic acid, 2,4-dihydroxybenzoic acid dihydroxyfumaric acid
and similar diols and combinations of any of these diols. Triols and higher,
such as glycerol, lr~ lylol propane and pentaerythritol can be used, but
crosslinking and insolubilization may result, so blends of polyols with diols
may be useful. Polyamines, such as 1,6-diaminohexane, p-phenylene-
WO 95/22576 PCT/US95101914
2~89~g - 24-
diamine, 1,3-pentanediamine, 2-methylpentamethylenediamine, 1,2-
diaminocyclohexane and 1 ,2-diamino-2-methylpropane, amine terminated
butadiene, isoprene, chloroprene and the like homopolymers and copoly-
mers, and disulfides, such as 1,6-hexanedithiol, dithioerythritol, 1,4-
butanedithiol, 2,3-butanedithiol, thiol terminated butadiene, isoprene,
chloroprene homopolymers and copolymers and the like can also be used
to give polyamides or polythiol esters. Combinations of polyols, poly-
amines and polythiols or even compounds containing combinations of
these functional groups on the same molecule, as well as other functional
groups such as carboxylic acids, can also be used. Mixed group com-
pounds, such as ethanol amine, 2-mercaptoethanol, 3-amino-1-propanol,
6-amino- 1 -hexanol, 2-(2-aminoethoxy)ethanol and 2-(2-aminoethylamino)-
ethanol, can also be used to give, for example, a polymer containing
both amide and ester groups.
Other heteroatom polymers contemplated by this invention are poly-
mers formed by the reaction of polyreactive compounds other than poly-
carboxylic acids and their derivatives with the active hydrogen containing
compounds as described above. Examples of such polyreactive com-
pounds include, but are not limited to polyisocyanates, as defined under
component a) of this invention, polyepoxides, such as ethylene and poly-
ethylene glycol diglycidyl ether, propylene and propylene glycol diglycidyl
ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, the
glycidyl ester ether of p-hydroxy benzoic acid, 1,6-hexanediol diglycidyl
ether, bisphenol A diglycidyl ether, allyl glycidyl ether, o-phthalic acid
diglycidyl ester, terephthalic acid diglycidyl ester, hydroquinone diglycidyl
ester, an unsaturated high molecular weight dicarboxylic acid diglycidyl
ester sold as Denacol EX-1 1 14 from Nagase Chemicals, Ltd., dibromo neo-
pentyl glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylol-
propane polyglycidyl ether and other similar compounds, and polymethylol
WO 9S122576 PCT/US95/01914
- 25 - 215~9~
compounds and their derivatives, such as methylolated methylated and
other alkylated methylol melamines, ureas, cyclic ureas, phenols, and re-
sorcinol and other such polyfunctional compounds capable of reacting with
active hydrogen groups.
In the adhesion system of this invention, some of the isocyanate
compound of component a) presumably reacts with the reactive groups of
the polyunsaturated polymer component. This reaction product, which is
also a component of the adhesion system of this invention, is preferably
formed in situ in the treating solution and/or on the treated article by
adding the large excess of isocyanate compound to the polyunsaturated
polymer or polymers and the carrier component and then applying this mix-
ture to the treated article However, this reaction product can be formed
separately and added to the additional isocyanate component and carrier
and even additional polyunsaturated polymer of either type if advanta-
geous This can be done for either type of polyunsaturated polymer, either
alone or together.
Especially surprising is the fact that a combination of the two types
of polyunsaturated polymers, i.e., the hydrocarbon polymers and the
heteroatom polymers, gives beKer adhesion in most cases than either
polymer alone Indeed, the combination of these two types of polymers,
particularly polybutadiene diol and poly(2,2,4-trimethyl-1,3-diol maleate),
in combination with the polyisocyanates and plasticizers of this invention
appear to be preferred
The third component of this invention is the carrier, which can per-
form several functions for the adhesion system of this invention One
function is to serve as a solvent for dispersing or solubilizing the other two
components and for other plasticizers or other additives Indeed, ordinary
solvents such as, for example, toluene, xylene and other aromatic hydro-
carbons, ketones, e g., acetone, methyl ethyl ketone and methyl iso-
WO 95/22576 PCT/US95101914
a~9 26-
butyl ketone, esters, e.g., ethyl acetate and butyl acetate; tetrahydro-
furan (THF) and other ethers, mineral spirits, 1,1,1-trichloroethane and
other chlorinated and chlorofluorinated and fluorinated solvents, 2-(1-
methoxy)propyl acetate, nitrobenzene, nitriles, such as acetonitrile,
adiponitrile and pentenenitrile, dimethyl formamide, dimethyl sulfoxide,
N-methyl pyrrolidone, alkanes, hexane, mineral oil, paraffin oil,
naphthenic oil, sulfonated oils and similar oils, mono- and polyglycols and
their mono- and di-esters and ethers and related materials and combina-
tions of any of the above can be used as a carrier, either alone or in
combination with each other or with plasticizers, to impart improved adhe-
sion to the treated material. Water can also serve as a carrier if the other
components of this invention are emulsified or dispersed in it. The
isocyanate may also have to be blocked to prevent premature reaction with
water, depending on the time and application methods involved.
It is, however, generally preferred to use a plasticizer as a carrier
because it can also perform other functions, as well as generally impart
better adhesion with the other two components than a solvent functioning
as a carrier. In addition to functioning as a solvent or a dispersing agent
and a viscosity modifier, the plasticizer or plasticizer combination can
affect the surface of the material to be treated so that the isocyanate com-
pounds and any polymer forming from them, either by reaction with the
polyunsaturated polymer or with water or both, may be able to better pen-
etrate the surface of the material to be treated and become better attached
to it, either physically by molecular entanglement, and/or chemically by
making more reactive end groups of the material to be treated accessible.
The plasticizer, by nature of its general hydrophobicity, can also function
to protect the isocyanate groups so that they do not react with water
either in the air, in solution or on the treated article, as rapidly. The plasti-
cizer or plasticizer combinations can also affect the surface of the rubber
WO 95/22576 PCT/US95/01914
215892~
- 27 -
where it contacts the fibrous material or related article by softening, swell-
ing or other mechanism, to make a more physically compatible interface
to facilitate any chemical reactions between the rubber and chemically
l-lzaled fibrous ",aterial surface.
Another important function of the plasticizer can be to modify the
surface of the lreatelJ filament yarns or fibrous materials for processing.
For example, the higher alkyl adipate and phthalate esters can impart
softness and lubricity to the treated article while more hydrophilic esters,
particularlyphosphates, can impart antistatic properties. Finally, a very
significant advantage of the plasticizer is that it, or a combination of
plasticizers can perform all of the above functions, including acting as a
carrier for the isocyanate and unsaturated oligomer or polymers and any
reaction products thereof without having to be disposed of or reclaimed as
a solvent, either aqueous or nonaqueous, would have to be. The plastici-
zer(s) stays with the treated material and then with the rubber material
once it is formed. This feature saves energy from eliminating the need to
remove a solvent from the treated material and possibly recovering and/or
purifying the solvent and eli~inales environmental contamination by
release of a solvent to the atmosphere during removal or recovery or upon
disposal of a solvent which cannot be recovered.
These plasticizers should be liquid, soluble or dispersible in other
components of the mixture, or soluble or dispersible in a solvent that is
compatible with the other components. Liquid plasticizers which can help
solubilize other components of the mixture are particularly preferred.
Plasticizers constitute a broad class of chemical compounds. A
chemical is generally classified as a plasticizer if it modifies the physical
properties of a plastic or related material, including rubber or synthetic
elastomers. This modification of the physical properties is again quite
broad and includes a variety of uses such as modification to change vis-
WO 95n2576 PCT/US95/01914
~5~$~9 28-
cosity, flexibility, strength, improve the workability during fabrication and
even extend the natural properties of the plastic or rubber. Plasticizers are
routinely added to rubber compounds to modify their properties. Such
broad classes as organic and inorganic esters and amides (mono and poly-
carboxylic acids, phosphoric acid, sulfuric and sulfonic acid and other
acids, alkylandaromatic), hydrocarbonsandhalogenated, epoxidizedand
other modified esters and hydrocarbons encompass plasticizers. If a com-
pound does not fall into the broad chemical class just described and still
modifies the physical properties of a plastic or rubber material, it functions
as a plasticizer. Also, one class of chemicals may function well as a plasti-
cizer for certain plastics or rubbers, but may have little or no effect on the
properties of other plastics or rubbers. For example, various silicones may
be excellent as plaslickers for silicone polymers and rubbers but may have
no plasticizing effect on more hydrophilic rubbers and plastics.
A chemical is classified as a plasticizer for the purpose of this inven-
tion if it is classified as a plasticizer by the general definition above, in the
general chemical literature or by the technical literature or advertisements
of a supplier, if it is conventionally known as a plasticizer or if it has
swelling, softening or other effect on the physical properties of the fiber
or other material to be l~eated or the rubber or other polymeric material to
be adhered to.
In regard to choosing plasticizers for the adhesive system of this
invention, the effect of the plasticizer on the particular rubber and fiber,
which structurally is a combination of plastic and rubber domains or
regions, or similar material to be treated and bonded is thought to play a
significant role. However, other factors, such as the ability to dissolve
the other components, both as added to the treating formulation and as
may be formed in situ, either by reacting with each other or with other
species such as water in the air, its viscosity, its volatility and its effect
WO 95/22576 PCI~/US9S/01914
2~ 9~
- 29 -
on processing of the treated fibrous or related material in its incorporation
or preparation for incorporation into the particular composite structure and
other efrec~s are also thought to be important. It has been found that
combinations of two or more plasticizers can be quite beneficial in the
formulations of this invention. These plasticizers may modify the different
rubber and plastic materials in different ways and/or may contribute in
some or all of the other factors described above. Particularly preferred
plasticizers are the common alkyl esters of adipic, phthalic and terephtha-
lic, sebacic, azelaic, glutaric, oleic, pelargonic, lauric and similar acids.
Even more preferred are straight and branched chain dioctyl adipate,
dioctyl terephthalate, dioctyl phthalate and alkyl mixtures and variations
of these compounds, such as, but not limited to di(2-ethylhexyl) adipate,
di(2-ethylhexyl) phthalate, di(2-ethylhexyl) terephthalate, di(n-octyl)
adipate, di(n-octyl) phthalate, di(n-octyl) terepthalate, di(isooctyl) adipate,
di(isooctyl) phthalate, di(isooctyl) terephthalate, di(C7 1,-alkyl) adipate,
di(C7."-alkyl) phthalate, di(C7"-alkyl) terephthalate, diisobutyl adipate,
mixed C~"-alkyl phthalates, diundecyl phthalate, dinonyl adipate, di(n-
decyl adipate), (n-decyl, n-octyl) adipate, and (2-ethylhexyl, n- octyl)
adipate. Specialty plasticizers, such as phosphate esters (tributoxyethyl
phosphate, tricresyl phosphate and the like), dibutoxyethyl phthalate, N-n-
butylbenzene sulfonamide, and the like, can be mixed with these basic
plasticizers to enhance solubility, viscosity and specific properties of the
treated article and the rubber product. Plasticizers with reactive groups,
such as but not limited to dibutyl maleate, dioctyl maleate, polyethylene
glycol monopelargonate, polyethylene glycol mono- and dioleate, and tri-
alkyl citrates can also be used and may offer certain advantages.
The polyunsaturated polymers of this invention do not impart any
significant adhesion when applied to the article alone in solvent or with
plasticizer. Some adhesion, depending on the particular elastomer and
WO 95/22576 PCT/US95/01914
2l~5~9 - 30 -
other components of the rubber compound can be imparted by application
of the isocyanate alone to the article. Generally, even more adhesion can
be imparted by applying the polyisocyanate in conjunction with a plasti-
cizer or combination of-plasticizers. The magnitude of the adhesion can
be varied by the choices of plastici~r and to some extent the polyisocya-
nate, and is also quite dependent on the type of rubber compound. In
general, the combination of isocyanates and plasticizers may give signifi-
cant adhesion improvements in regard to natural and the older synthetic
rubbers, but the adhesion systern of this invention will give improved
adhesion to these rubbers as well as the newer more difficult to bond to
synthetic elastomers such as EPDM, chlorosulfonated polyethylene (CPM)
and butyls.
Not wishing to be-bound by theory, the isocyanate compounds,
the polyunsaturated polymers and plasticizers of this adhesive system pro-
bably perform a number of functions in arrecli,.9 the improved adhesion to
rubber compounds. Each of these components contributes, either singu-
larly or in combination with other components, to achieving the advan-
tages of the invention. For example, in regard to the isocyanate com-
pounds and the polyunsaturated polymers, the isocyanate groups cannot
only react with the terminal or other reactive groups of the unsaturated
oligomers and polymers, reactive groups on the fiber or related material
surface and possibly even reactive groups in the matrix rubber compound
but also with water in the atmosphere. The reaction of water with an
isocyanate group gives an unstable acid (R-NH-C(O)-OH) which loses car-
bon dioxide to give an amine end group (R-NH2 + CO2). This amine group
can then react with other isocyanate groups to form amide linkages which
can form polyamides on the fiber or related article surface. These poly-
amides can make the surface of the fiber or related material more uniform
by filling in cavities, giving better physical interaction and contact with the
WO 95122576 2 I 5 8 ~ 2 ~ PCTIIJS95/01914
- 31 -
rubber surface so that better bondin~ can take place. At the same time,
this forming polyamide is and has interacted with the polyunsaturated
polymer, certainly physically and even chemically if the polyunsaturated
polymer has reactive terminal or side groups that can react with the iso-
cyanate groups of the formin~ polyamides. The plasticizers can facilitate
this activity by physically interacting with the polymer molecules of the
fiber or similar article, particularly on the surface, to make them more
accessible. By forming such a matrix on the surface of the fiber or related
material, the double bonds of the polyunsaturated polymer may be in a
better position to interact with the double bonds of the rubber or synthetic
elastomer material, particularly with those less accessible double bonds
such as in EPDM, during the vulcanization process.
In the vulcanization process, double bonds of the rubber or synthe-
tic elastomer are connected with each other by a free radical mechanism
using sulfur or sulfur compounds or peroxides or other materials so that a
crosslinked, less liquid and elastic material is formed. See Vulcanization
of Elastomers, Ed. G. Aleger and l.J. Sjothun, Rinehold Pub. Co. (1964).
Not wishing to be bound by theory, it is believed that by using the unique
combinations of th`is invention, the double bonds of the polyunsaturated
polymer can participate in this crosslinking reaction, bonding the surface
of the treated fibrous material or related article to the rubber. These
double bonds can be made more accessible by the action of the
plasticizers on the fiber surface and particularly the rubber, particularly
under the heat conditions of the vulcanization process, to make the
unsaturated groups from the rubber and fiber more accessible to each
other. This result can not only give the greatly improved adhesion values
shown in the following examples but can also give better adhesion to meet
the ever increasing demands modern technology places on rubber products
in regard to retention of adhesion upon exposure to very high tempera-
WO 95122576 PCI/US95/01914
2~58~ 32-
tures, dynamic adhesion where the rubber product is exposed to contin-
uous flexing and other mechanical stress which can otherwise break any
physical adhesion between the fibrous material or related article to the
matrix rubber.
The above reasoning may explain the very surprising result that little
improvement in adhesion is obtained if the ratio of isocyanate groups to
reactive groups of the polyunsaturated polymer is low so that the amount
of free isocyanate compound present on the surface of the treated fibrous
material or related product is very low. If one considers that the
accessibility of the double bonds may be different in the two different
types of polymers used in this invention, the above reasoning may also
explain the other surprising result that the use of two different types of
polyunsaturated polymer can give better adhesion than just one.
The present invention provides significant flexibility to a chemist in
the field in tailoring the adhesion needed to meet the rigorous demands im-
posed on rubber products now and in the future. The teachings of the
chemical choices of the present invention can be used to obtain optimum
adhesion by routine experimentation by consideration of the article to be
treated and the formulation of the rubber compound in terms of rubber
polymer or synthetic elastomer type and amount; filler type and amount;
accelerator type and amount; and other additives.
Although the treated fibrous materials and related materials of the
invention give their best performance in imparting greatly improved adhe-
sion to EPDM and other difficult to adhere to rubbers, they generally give
improved adhesion to any given rubber compound, without changing any
of the variables in the compounding formulation. Such changes, although
they may enhance the adhesion, may not be possible because the vari-
ables of the rubber compound formulation may be set by the end use de-
mands of the rubber product. Such changes are generally not necessary
WO 95/22576 PCT/US95/01914
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- 33 -
for the materials of the invention to impart their improved adhesion and
other benefits. However, if one does have flexibility in changing some of
the variables in the compound formulation, the adhesive systems of the
present invention are believed to generally give their best adhesion per-
formance with higher concentrations of rubber polymer and accelerator in
the matrix.
In particular, the adhesion system of this invention works especially
well with rubber compounds and materials which are very difficult to bond
with the conventional adhesive treatments. For example, rubber com-
pounds filled with carbon can be more difficult to obtain good adhesion to
reinforcements than with rubber compounds filled with minerals and clay.
Reinforcement materials treated with the adhesive system of this invention
give significantly improved adhesion to rubber compounds filled with
carbon.
A wide variety of materials may be treated with the adhesive system
of the invention by any of the common methods of application of chemi-
cals to that particular article. One of the most preferred applications of the
adhesive system of this invention is to treat filament yarns used as rein-
forcement particularly in hose, but also in conveyor belts, drive belts,
tires, molded articles, and other mechanical rubber goods. The adhesive
system of this invention can be applied to the yarns by a variety of tech-
niques but are most preferably applied by a kiss roll technique where a roll
is rotated in a solution to be applied and becomes coated continuously
with that solution. The filaments are then passed over the surface of the
kiss roll, at different angles and speeds to control the amount of solution
applied, to pick up the solution from the roll and to be wound onto a new
package. Another preferred technique is to use a metering pump to pump
the solution through a tube, at a precise rate controlled by the metering
pump, to an applicator such as a slot, where the yarn runs through, with
WO 95/22576 PCT/US95/01914
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a hole in the slot to allow the liquid to be absorbed by the yarn as it moves
- through.
If no solvent is included in the adhesive system, the yarn does not
have to be dried to remove the solvent. Also, the treated yarn does not
have to undergo extensive and high temperature heat trealn,enls to cause
the lreal~-,ent to be errecli~e. In fact, the treated yarn, i,"",eJiately after
lredl"-ent, can be wound onto tubes for further processing for their in-
tended use. These tubes may be given a heat treatment by placing them
in an oven for a particular time and temperature, preferably at about
200F for about 3 to 4 hours. This heat treatment may allow the chemi-
cals to better penetrate the surface of the yarn to give better processing
and less removal of the treatment chemicals as the yarn passes over
various surfaces in subsequent unwinding and winding operations and as
the yarn passes over various surfaces in its incorporation into hoses and
other mechanical rubber goods.
In many situations, however, no heat treatment is required to
effect improved adhesion, as particularly shown in Example 70. This ease
of treatment gives the materials of this invention especially significant
advantages over conventional RFL traal"~ents which must be, in the case
of a plel~ealment with isocyanate, dried or cured at temperatures generally
over 400F and dried again to remove water from the RFL treatment and
must be cured at temperatures generally above 350F to effect the
reactions of the resorcinol with formaldehyde and that product with the
latex and the fiber.
Also, RFL treated yarns, probably because of their water solvent,
must be dried before winding onto tubes. If RFL treated yarns were
wound directly onto tubes and then dried, the resulting yarn would be
very sticky and very difficult, if not almost impossible, to unwind and
would be very uneven in regard to amount of material on the yarn. In fact,
WO 95/22576 PCT/US95/01914
2l58g~
- 35 -
uneven treatment, due to a combination of factors including uneven dry-
ing and uneven reaction along the yarn, is common with RFL treatments,
adversely affecting processing of the yarn into hose or other product
incorporation steps and resulting in variable adhesion. Furthermore,
conventional RFL treated yarns are generally stiff, probably due to the
extensive polymer formation on the surface of the yarn. On the other
hand, the treated yarns of this invention can be varied as required to be
stiff, soft-or intermediate, depending on the choice of plasticizers in the
system.
The amount of isocyanate compound applied to the fibrous material
or related article can vary widely. Since isocyanate compounds having
from as low as about 1 wt.% to over 50 wt.% isocyanate (NCO) content
are available, the amount of isocyanate compound applied to the fibers is
expressed herein in terms of isocyanate groups. Generally about 0.05 to
about 10 wt.% of isocyanate groups or N=C=O groups, based on the
weight of fiber, should be applied to the fiber and preferably from about
0.2 to about 2.0 wt.% and more preferably from about 0.5 to about 1.25
wt.%-
Related to the amount of isocyanate compound on the treated fiber
is the amount of isocyanate compound and polyunsaturated polymer in the
treating solution. The adhesion system treating solution consists of from
about 1 to 75 and preferably from about 5 to about 50 and more prefera-
bly from about 10 to about 35 parts by weight of the isocyanate contain-
ing compound and about 0.5 to 50 parts and preferably 1 to 20 and more
preferably 1 to 10 parts per weight of the polyunsaturated polymers,
maintaining the ratios of isocyanate groups to polyunsaturated polymer
reactive terminal or side groups as stated below in this summary, with the
remainder of the solution being plasticizer. The amount of isocyanate
compound in the treating solution is very dependent on the isocyanate
WO 95/22576 PCT/US9S/01914
2~ 36-
content of the particular compound. The ranges given above were for
compounds with about 30 to 33% isocyanate content. This solution can
be applied to the fibrous or related article at a pickup of from about 1 to
over 100% on the weight of the solution to treated article and preferably
from about 3 to about 25 wt.% and more preferably from~ about 6 to 18
wt. % and even more preferably from about 10 to about 1 5 wt. % and even
more preferably from about 11 to 12 wt.%. Amounts outside these
ranges are also acceptable.
The amount of plasticizer on the treated fibrous material or related
article can generally vary from none to as much as the material will accept.
However, for EPDM and other difficult to bond elastomers, the combina-
tion of plasticizer, polyunsaturated compound, and polyisocyanate is
necessary to give adhesion. These adhesion values are quite high, gene-
rally increasing with the amount of polymer in the compound. A range of
about 2 to about 12% by weight of plasticizer on the treated fibrous
material or related articles is generally preferred with about 6 to about
10% being most preferred. Related to the amount of plasticizer on the
treated article is the amount of plasticizer in the treating solution. Lower
viscosity liquid plasticizers are preferred in larger amounts for ease of
handling and applying the treating solution and for solubilizing the other
components. Generally plasticizers, either singularly or in combination,
should constitute about 10 to 90 parts by weight per 100 parts of the
treating solution. The preferred range is 60 to 80 parts by weight per 100
parts of the treating solution.
Surprisingly, it has been found that very large molar ratios of isocy-
anate groups to reactive groups of the polyunsaturated polymers such as
hydroxyl give the best adhesion results. Although there are references in
the literature of the reaction of isocyanate containing compounds with
hydroxyl terminated polybutadienes, the real concept of this invention has
WO 95/22576 PcrluS95/01914
21S8g29
- 37 -
been overlooked. These combinations are always in equal amounts or with
only relatively small excesses of isocyanate groups to hydroxyl groups.
Surprisingly, it has been found that large excesses of polyisocyanates to
polyunsaturated compounds impart hi~her adhesions to the hard to bond
to synthetic elastomers such as EPDM. This is demonstrated by the
examples herein such as Examples 38H-38N from Table 10. The propor-
tion of reacted and unreacted isocyanate is calculated for Examples 38H-
38N to clearly illustrate the significance of excess polyisocyanate used.
It also appears that higher amounts of polyunsaturated polymers, especial-
Iy if the isocyanate content is held constant or reduced, can give less
adhesion improvements in some situations.
Amount Amount Amount %
Des .,Gdur Poly bd ~.rea.,t~.d U~.r~.act~.d
VK-5 R45HTRatio of GramsGrams Des .. Gdur Des .~GJur
Example (9) 19) NCO/OH OH C=C VK-5 (9) VK-5 (9)
38H i 7.20 1.60100 0.020.70 17.03 99.0%
381 17.20 3.2050 0.091.40 16.86 98.0%
1 5 38J 17.20 6.3025 0.092.76 16.52 96.1 %
38K 17.20 15.80 10 0.226.92 15.50 90.1 %
38L 17.20 31.80 5.0 0.4513.93 13.79 80.2%
38M 17.20 63.20 2.5 0.8927.69 10.42 60.6%
38N 3.70 13.50 2.6 0.195.92 2.25 60.9%
It appears that the actual adhesion imparting combination is excess poly-
isocyanate molecules plus polyisocyanate partially reacted with reactive
polyunsaturated compounds.
Improved adhesion under this invention can be obtained with 2.5 to
1 or higher moles of isocyanate (N = C =0) to hydrocarbon polymer reac-
tive groups. However, the higher molar ratios of isocyanate to hydro-
carbon polymer reactive groups are generally preferred, namely from 5:1
or 10:1 to about 100:1, 200:1, 750:1, 1500:1, 3000:1 or higher and
WO 95122576 PCI/US95/01914
~ ~5~9 ~ - 38 -
particularly from about 25: 1 to 200: 1 and more particularly 50: 1 to 100: 1.
The same relationship applies in regard to the amount of heteroatom
polymer where even higher ratios of isocyanate to polymer end or reaction
groups appear to be preferred. Although a range as low as 1: 1 and higher
can be used in this invention, the range of about 25:1 or about 50:1 to
350:1 isocyanate to polymer reactive groups is generally preferred.
When the two polymers are used together with the isocyanate,
then the ratio of isocyanate to reactive group for each polymer should
generally increase so that a more preferred range would be about 25:1 to
about 250: 1 for the isocyanate to hydrocarbon polymer reactive group and
about 50 to 1 to about 750 to 1 for the isocyanate to heteroatom polymer
terminal or reactive group when both polymers are used.
The polyunsaturated polymer used in the adhesion system of this
invention can also be expressed in terms of the amount of carbon-carbon
double bonds on the treated articles. In that the polyunsaturated polymer can
vary greatly in terms of unsaturation, such an expression is best done in
wt.% of carbon-carbon double bonds on the treated article. It has been
found that a tota! of polyunsaturated polymers as low as 0.034 wt. %, based
carbon-carbon double bonds, on the weight of the treated article, provides
a significant improvement in adhesion. Even lower amounts, such as 0.0075
wt.%, can be expected to provide adhesion improvements. The lower limit
for the effective amount of carbon-carbon double bonds will depend on the
specific rubber compound used, particularly in regard to variables such as the
type of polymer, the amount of polymer and the amount of filler in the
rubber compound to be adhered to.
Other materials may also be added to the adhesion system of this in-
vention to perform other functions. One example is the addition of a free
radical initiator or generator to facilitate bonding to the rubber and other
polymers. This free radical initiator or generator will even preferably react
WO 95/22576 PCT/US95/01914
39 21~89~
with the other components of the adhesion system of this invention, either
isocyanate or terminal or side groups on either polyunsaturated polymer.
Such compounds include, but are not limited to, amine, hydroxyl and car-
boxyl terminated azo and peroxide compounds such as 2,2'-azobis~2-methyl-
N-(2-hydroxyethyl)propionamide, 2,2'-azobis(2-amidinopropane)dihydro-
chloride, 4,4'-azobis(4-cyanopentanoic acid), dehydroxy azobenzene and
similar compounds. Non-reactive free radical initiators or generators such as
azo, peroxide and sulfide and sulfur compounds known in the art of initiating
free radical polymerization and in the rubber vulcanization process. Other
crosslinking agents such as polyepoxides, melamine-formaldehyde adducts
and their ethers, urea and urea derivative-formaldehyde adducts and their
ethers, phenol-formaldehyde adducts and their ethers, resorcinol-
formaldehyde adducts and their ethers, and other crosslinkers known in the
art can be added. Furthermore, coupling agents such as but not limited to
vinyl, mercapto, .nell,ac,~/l, amino, ureido and epoxy silanes may be
added. These chemicals can react with the components of the adhesion sys-
tem of this invention through some groups and either chemically or physical-
ly, or both, with the ~aated fibers and related articles, especially fibers withvery inactive surfaces such as glass, metals and ceramics, and with the rub-
ber and other polymers, and especially with fillers such as silica and other
minerals. Such fillers and even carbon can be also added to the components
of the adhesion system of this invention. Extenders, such as naphthenic and
hydrocarbon oils, when they do not function as a solvent or a plasticizer can
also be added as well as other functional materials well known to those
skilled in the art.
The treated yarns can be incorporated into hoses or other mechanical
rubber goods by braiding, spiral wrapping or knitting processes and other
conventional techniques. The treated yarns can also be converted to fabrics
and other fibrous articles, which can be incorporated into mechanical rubber
WO 9S/22576 PCT/US95/01914
2~ 9 - 40 -
goods and related articles or be bonded directly to rubber sheets, by knitting,
weaving or non-woven techniques. It is in these converting processes that
the invention can be better utilized by selecting plasticizers, isocyanates and
unsaturated oligomers or polymers to optimize processing in these conversion
steps. Woven, non-wovenorknittèd fabrics, films orsheets, consisting of
polymers the same as or similar to those used in filaments, yarns or fibers,
can be treated by padding, coating or other well known techniques to be
incorporated into rubber composites or bonded to rubber sheets.
The treated fibrous materials of the invention can be incorporated into
a variety of rubber products by a variety of conventional methods, as well
as by unconventional methods. Although the simplest method of reinforcing
may be a rubber to fibrous or related material bond, either with the fibrous
material wrapped around the rubber material as in a hose or a tube
or with the fibrous material next to the rubber material in a sheet-like
assembly such as in conveyor belts or the like, any type of structure such
as but hot limited to rubber-fibrous material-rubber, rubber-fibrous
material-rubber-fibrous material, rubber-fibrous material-rubber-fibrous
material-rubber and so on is contemplated for the adhesion system of this
invention. Such assemblies can be used for the many types of hoses,
tubes and related articles, including but not limited to automotive hoses
such as brake hoses, power steering hoses, coolant hoses and the like,
washingmachinehoses, gardenhoses, firehoses, gasolinehoses, weld-
ing hoses, oil suction hoses, optical cables, electrical cables and the like.
Such assemblies can also be used for the many other types of rubber pro-
ducts including but not limited to conveyor belts, automotive and other
drive belts such as V belts, "stiff" cord belts and the like, automotive and
other vehicle tires including but not limited to tractors, "off-the-road"
vehicles, airplanes, motorcycles, bicycles, wheelchairs and the like,
rubber reinforced fabrics, pads, molded articles, geotextiles such as pond
and land fill liners, silt and erosion control, filtration media for French
drains and the like, tank liners, tank insulation matting, roofing mem-
WO 95/22576 PCI`tUS95/01914
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- 41 -
branes, cow and other animal mats, vibrational damping pads, air
inflated shock absorbing units, reinforced rubber bags for various gas and
liquid collection and other composite articles such as rods, masts, bars
and the like.
The adhesion system of this invention can also be used as described
above to impart adhesion to products containing polymers other than the
rubber polymers, as long as these polymers are capable of bonding with
the components of the adhesion system of this invention in the same
manner as the rubber polymers. More particularly, non-rubber polymers
which contain carbon-carbon double bonds or groups which are capable
of producing such double bonds or groups which can react with the free
radical producing agents or other vulcanizing or crosslinking agents should
have increased adhesion with articles treated with the adhesive system of
this invention. Such polymers can include but are not limited to unsatu-
rated polyesters, unsaturated polyamides, unsaturated polythioesters,
polynorbornenes, unsaturated polyethers, randomly unsaturated polyole-
fins, non-rubber copolymers such as acrylic and methacrylic acid, ester
and amides, alkyl vinyl ethers and other vinyl monomers such as styrene,
vinyl pyridine, vinyl pyrrolidone and the like containing diene units and the
like.
In addition to bonding to the various polymers described above, the
adhesion system of this invention can even bond to itself, either alone or
in combination with a rubber or non-rubber polymer. This bonding can be
facilitated by the addition of bonding agents, either from an external
application or by an internal application as described elsewhere in this
summary. Such bonding can be in composite articles with very little
matrix material, such as but not limited to sail masts, golf clubs, fishing
rods, automotive and airplane assemblies, rocket nozzles and the like
where high strength fibers and fabrics and other articles made from these
WO 9S/22576 PCT/US9S/01914
42-
fibers such as carbon, ~lass, ceramic, and organic aramid, high strength
polyolefin and others as described below are aligned very closely in a
matrix.
It is envisioned that any or~anic or inorganic fiber or related material
can be treated with oG~-,pounds of this invention. Organic fibers include,
but are not limited to, polyester ~polyethylene terephthalate, polybutylene
terephthalate, polycyclohexanedimethanolterephthalate, and related poly-
mers), nylon 6, nylon 66 and other nylons, cotton, rayon, Tencel~,
Lyocel cellulosic fibers, Mewlon~, Kuralon~ and other polyvinyl alcohol
fibers, Nomex~, Kelvar~, Twaron~ and Technora~ aramid fibers, poly-
benzimidazole (PBI) fibers, polypropylene, polyethylene and other poly-
olefin, ultra high strength polyolefins, polyphenylene sulfide wool, silk,
ramie, flaxandblendsandmixturesthereof. Inorganicfibersinclude, but
are not limited to carbon, glass, metal and ceramic fibers and blends and
mixtures thereof and with organic fibers. Exact formulations of the various
components of the invention, such as amount of isocyanate compound
and plasticizer type can be o~ ed for particular fibers or classes of
fibers.
The treated yarns and other materials of the invention should give
improved adhesion when incorporated into a wide variety of rubber pro-
ducts consisting of all of the natural and synthetic rubber and synthetic
elastomers and thermoplastic elastomers as described in Martin Grayson/
Executive Editor, Kirk-Othmer Encyclopedia of Chemical Technology, 3rd
Edition, Vol. 8, Wiley-lnterscience, New York; and Maurice Morton - Editor,
Rubber Technology, 2nd Edition, Van Nostrand Reinhold Co. (1973); N.P.
Cheremisinoff, Elastomer TechnologyHandbook, CRC Press Inc. ~1993).
Such rubber-like polymers include, but are not limited to, natural rubber
(NR), polyisoprene (IR) and copolymers of isoprene, polybutadiene (BR),
styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR) and
WO 95122576 2 1 S ~ PCI'IUS95/01914
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other copolymers of butadiene, polychloroprene (CR) and copolymers of
chloroprene, ethylene propylene diene comonomers (EPDM), ethylene
propylene rubber (EPM), chlorinated polyethylene (CPE), chlorosulfonated
polyethylene (CPM), butyl rubber (BR), chlorobutyl (CBR), bromobutyl
rubber (BBR), hydrogenaled nitrile-butadiene rubber (HNBR), crosslinke
polyethylene (XPE), silicone rubber (VMQ), fluorosilicone rubber (FVMQ),
epichlorohydrin rubber (EC0), tetrafluoroethylene-propylene copolymer,
and polyvinyl chloride (PVC) and blends and mixtures of the above with
each other and with other polymers.
Improved adhesion to rubber can be obtained with a variety of rub-
ber compounds, with variables in the rubber compound maybe affecting
the absolute adhesion values but not affecting the result of the improved
adhesion by the adhesion system of this invention. There are many types
of rubber compounds, formulated with major or minor changes to achieve
specified properties in the final rubber product. Examples of some rubber
formulators who supply various rubber compound to mechanical rubber
goods manufacturers and other rubber processors are Burke Rubber,
Cadillac Rubber, Colonial Rubber and Kleen-Tex. Examples of some hose,
belt, tire and other mechanical rubber goods manufacturers are Cooper
Industrial Products, Dana Corporation, Dayco Products Inc., Gates
Rubber Company, The Goodyear Tire and Rubber Company, HBD Indus-
tries, Parker-Hannifin Corporation and Plumley Industries. Some of these
manufacturers also formulate their own rubber compounds.
Without further elaboration, it is believed that one skilled in the art
can, using the preceding description, utilize the present invention to its
fullest extent. The following preferred specific embodiments are, there-
fore, to be construed as merely illustrative, and not limitative of the
remainder of the disclosure in any way whatsoever.
In the foregoing and in the following examples, all temperatures are
WO 95/22576 PCT/US95/01914
5~
set forth uncorrected in degrees Celsius and unless otherwise indicated,
al! parts and percentages are by weight.
The entire disclosures of all applications, patents and publications,
cited above and below, are hereby incorporated by reference.
WO 9S/22576 PCT/US9S/01914
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- 45 -
E X A M P L E S
- EXAMPLE 1
As a control and as a gerieral procedure for the following examples,
A.C.S. certified toluene was applied by a slot applicator to 1000 denier,
1.5 TPI polyester continuous filament yarn (AKZO Diolen Type 174S) and
wound onto 6 3/4" lon~, 1 1 /2" inside diameter paper tubes on a direct
drive winder at a speed of about 90 yards per minute. A Masterflex peri-
staltic pump using #14 Viton tubing was used to deliver the treating solu-
- tion to the yarn at a rate of 1.23 grams toluene per minute to give a
pickup of the solution on the yarn of 12 wt. % . After about 1000 to 1100
yards of yarn were wound, the tube was removed from the winder. After
about four to twelve hours under ambient conditions, the tube was placed
in a walk-in oven at 200F for 220 minutes followed by a 20 minute cool
down cycle to about 120F. The tubes were then removed from the
oven about four hours later and allowed to cool and condition at ambient
conditions before testing.
EXAMPLE 2
Example 1 was repeated exceptthat the treating solution was 20.75
parts by weight of toluene added to 79.25 parts by weight of dioctyl
terephthalate (Kodaflex~ DOTP, Kodaflex~ is a trademark of Eastman
Chemical Company).
The treating solution was made by adding the toluene to the dioctyl
terephthalate and mixing until homogenous. The mixing was done by us-
ing a stirring bar and a magnetic stirrer. A stirring rod was used if the
magnetic stirrer was not sufficient in producing a homogeneous solution.
WO 95/22576 PCTIUS95/01914
ag~ 46-
EXAMPLE 3
- Example 2 was repeated exceptthat the treating solution was 20.74
parts of toluene added to 79.25 parts dibutyl phthalate (Kodaflex DBP
from Eastman Chemical-Company).
EXAMPLE 4
Example 2 was repeated except that the treating solution was 20.75
parts of toluene added to 79.24 parts dioctyl adipate (di-2-ethylhexyl
adipate) (Kodaflex DOA from Eastman Chemical Company).
EXAMPLE 5
Example 2 was repeated except that the treating solution was 13.0
parts of tolylene-2,4-diisocyanate (Eastman Chemical Company #06590P,
CAS #584-84-9) added to 87.0 parts toluene.
EXAMPLE 6
Example 5 was repeated except that the treating solution was 12.59
parts of hexamethylene diisocyanate (Eastman Chemical- Company
#06735, CAS #822-06-0) was added to 87.41 parts of toluene.
EXAMPLE 7
Example 5 was repeated except that the treating solution was 19.19
parts of polymethylene polyphenyl isocyanate with approximately 32.5%
isocyanate content and an approximate viscosity of 40 centipoise
(Desmodur VKS-4 from Miles Inc.) added to 80.90 parts of toluene. Then
0.39 parts toluene was added to the mixture to obtain a 19.1 % solution.
WO 95/22576 PCI/US9S/01914
47 2 ~ 9 2 9
EXAMPLE 8
Example 7 was repeated except that 19.1 parts of Desmodur VK-5
from Miles Inc. (polymethylene polyphenyl isocyanate with approximately
32.5% isocyanate content and an approximate viscosity of 50 centipoise)
was added to 80.9 parts of toluene.
EXAMPLE 9
Example 7 was repeated except that 20.0 parts of Desmodur VK-18
from Miles Inc. (polymethylene polyphenyl isocyanate with approximately
31.5% isocyanate content and and an approximate viscosity of 180
centipoise) was added to 80.0 parts of toluene.
EXAMPLE 10
Example 7 was repeated except that 20.0 parts of Desmodur
VKS-18 from Miles Inc. (polymethylene polyphenyl isocyanate with
approximately 31 % isocyanate content and an approximate viscosity of
180 centipoise) was used in place of Desmodur VK-18.
EXAMPLE 11
Example 7 was repeated except that 21.9 parts of Desmodur VK-70
from Miles Inc. (polymethylene polyphenyl isocyanate with approximately
31 % isocyanate content and and an approximate viscosity of 700
centipoise) was added to 78.1 parts of toluene.
EXAMPLE 12
Example 7 was repeated except that 23.97 parts of Desmodur
VK-200 from Miles Inc. (polymethylene polyphenyl isocyanate with approx-
imately 30.6% isocyanate content and and an approximate viscosity of
2000 centipoise) was added to 76.00 parts of toluene.
WO 95n2576 PCT/US95/01914
48 -
EXAMPLE 13
All treated continuous yarn fiber samples in these examples were
evaluated for adhesion properties by winding each treated sample from its
wound tube onto 4" wide masking tape (Anchor) wrapped around, with
adhesive side up, a rotatable stainless steel drum that had replaced the
standard flat plate on a Serriplane manufactured by Alfred Suter, Inc., so
that three 1 1/3" wide fiber samples, either the same or different yarn
samples, were put on one tape. Each yarn sample was wound so that
there was no overlapping of filaments and no space between adjacent fila-
ments. This drum was 6" long, of 6" diameter and had one thin slot
across the length. The tape containing the three wound yarn samples was
then removed from the drum by cutting across the slot on the drum with
a razor blade. The 4" wide tape containing three samples was then cut
into four 4" lengths.
Two clean 4" X 8 1/2" pieces of an unvulcanized compounded rub-
ber, which had been milled to a specified thickness, were placed side by
side touching to form a 8" x 8 1/2" square centered on a 1 o" x 10" alumi-
num plate. This plate had been preheated to the vulcanization temperature
for the specific rubber compound. A 1 " X 9" strip of aluminum foil was
placed on the outside edge of each 4" x 8 1/2" piece of compounded rub-
ber. Two fiber tape sections containing three fiber samples each were
then placed fiber side down on each 4" X 8 1/2" rubber pad so that the
fibers were perpendicularto the aluminum foil and about one inch of their
length covered the aluminum foil strip. The top 10" X 1 o" aluminum plate
which had also been preheated to the vulcanization temperature for the
specific rubber compound was placed on top of the samples so that a
sandwich of top plate, tape, yarn samples, rubber compound and bottom
plate was formed. This sandwich was then placed in a PHI model # 02 38
C-X7 hydraulic press at the vulcanization temperature for the specific
WO 95/22576 PCT/US95/01914
21~8~2~
- 49 -
rubber compound for the specified time for that particular compound at
3200 Ibf. The pad was removed after cure and allowed to cool and condi-
tion at ambient conditions for 16 to 24 hours. After conditioning, each
pad was cut into six 1" X 4" strips by measuring 3/16" from the edge of
the tape of the first strip, cutting the first one inch strip, measuring 3/16"
to the second sample, cutting the second one inch strip, and so on. The
aluminum foil strip, which functioned to give a starting separation be-
tween the yarn samples and the rubber compound, was removed from
each strip and discarded. If the foil could not be removed, it was left in
the strip.
Each 1" x 4" composite strip was tested on a Lloyd -500 tensile
machine. The distance from the lower jaw to the upper jaw was set at
one inch. Each sample strip was then placed horizontally in the tensile
tester with the fiber side being attached to the upper jaw and the rubber
side being attached to the lower jaw. The tester was set to a traversing
speed of two inches per minute and started. The mean and maximum load
required to separate the fiber from the rubber was determined by a compu-
ter attached to the tester. After each adhesion pull was complete, each
pad was inspected for the mode of separation and the length of separa-
tion. Fiber-to-rubber separation means that the separated area showed
mainly fiber with no or only a few small pieces of rubber adhered. Rubber-
to-rubber separation means that the separated area showed mainly rubber
with no or only a few fibers visible. Mixed fiber-to-rubber and rubber-to-
rubber separation means that there were significant amounts of both fiber
and rubber adhered to fiber in the separated area. A shorter separation
length was observed to show increased difficulty in separating the yarn
and rubber sections, indicating higher adhesion. Shorter separation
lengths were usually accompanied by stretching of the rubber. In cases
where duplicate tests with the same yarn and same rubber compound
WO 95/22576 PCT/US95/01914
50 -
were made, each of the above parameters were averaged and reported in
the table.
EXAMPLE 14
The ~reated yarn samples from Examples 1 through 12 were tested
for adhesion properties according to the procedure of Example 13. A
carbon filled EPDM compound used in commercial hoses milled to a thick-
ness of about 0.060 inches was the rubber compound used. The vulcani-
zation conditions were 325F for 30 minutes at 3200 PSI pressure. The
data in Table 1 was obtained which shows that yarn treated with only the
separate components of the adhesion system of this invention exhibit low
adhesion to the rubber.
WO 95122576 PCrlUS9S/019~4
2~58~2.
~ ~ ~ ,. o o
G D n n n n 8 n n n n~ c
~ n C C C C C D n n n .x x
K o N Oo~q ~ ~ r~ ~t tl~ cn U~ --
S _ o o _ _ ~ ~ ~ ~ ~ ~ U~
J
, .
a
C ~~D Oa~ ~D
O u~ ~ o.a~ I~ _ r~ ~ _ ~ ~ u
O O O O O -- <~
O
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o ~ ~ ~ o
o U ~ U
n LJ r. n I L~
>
.. . . . . . . . . .
Z
r~ G
~U ES~ (~Eæ)
WO 95/22576 PCT/US95/01914
- 52 -
E~AMPLE 15
Example 14 was repeated except that a different carbon filled EPDM
compound used in cG"""ercial hoses milled to a thickness of about 0.100
to 0.120 inches was used. The vulcanization conditions were 320F for
25 minutes at 3200 PSI pressure. The results are shown in Table 2.
Wo 95/22576 2 1 :3 8 9 2 ~ PcrrUs95/0l9l4
5 3
_ ~ E
~ ' E O a~ ~ a~ u~ ~ ~ ~t et
~ D D D DD D D D D D
C~ D D D DD D D D D D
I-- G t~ C ~
O O O OO O O O O O
IL D D D DD D D D D D
._ ~ _ 0~ ~o a~
J _ _ _ _ --o _
o ~ ~ a~
J _ O O O OO O --
C ~ - ~
O ~-- I -- --c
~ -- ~ .C C~ .C ~D .~ _ ~ ~ ~ O ~ a~ ~ O C~ g
o ._ t~ , O,_ O ,_ u~ ,_, c 1~ c c~
~ ._ _ __ y _ v _ y _ v
.o ,~oC~ to~ ~o oo, o_ o, o,
O "O C c C ~ C _C >` ~ C O C O C O C O
- E c ~ ~ ~ E
o z ~ ~ ~ ~ ~ 6 ~ ~ ~ ~ ~ ~ ~
E
SUBSTI~UrE SHEEr (Rl ILE 26)
WO 95/22576 PCI~ S95101914
3 54
The data in Table 2 shows that yarn treated with only the separate
components of the adhesion system of this invention also exhibit the same
Iow adhesion to a different EPDM rubber as in Table 1.
EXAMPLE 16
Example 7 was repeated with the exception that the treating
solution was 20.0 parts of Desmodur VKS-18 added to a solution of 75.0
parts dioctyl terephthalate (Kodaflex DOTP from Eastman Chemical
Company) and 5.0 parts toluene.
EXAMPLE 17
Example 2 was repeated except that the treating solution was 95.0
parts of toluene added to 5.0 parts hydroxyl terminated-1,3-butadiene
homopolymer (CAS# 69102-90-5) having a number average molecular
weight of approximately 2,800, a hydroxyl number of 0.83 meq/g, and
an unsaturation of 20% cis-1,4, 60% trans-1,4, and 20% vinyl-1,2,
(Poly bd R45HT from Atochem North America).
EXAMPLE 18
Example 2 was repeated except that the treating solution was 75.0
parts dioctyl terephthalate (Kodaflex DOTP from Eastman Chemical Com-
pany) added to 5.0 parts hydroxyl terminated-1,3-butadiene homopolymer
from Example 17 and 20.0 parts of toluene.
EXAMPLE 19
Example 17 was repeated except that the treating solution was
20.0 parts Desmodur VKS-18 added to a solution of 5.0 parts of the
hydroxyl terminated-1,3-butadiene homopolymer dissolved in 75.0 parts
25 toluene.
WO 9S122576 PCTIUS95/01914
2158~29
- 55 -
EXAMPLE 20
Example 19 was repeated except 75.0 parts dioctyl terephthalate
replaced the toluene.
EXAMPLE 21
The treated yarn samples from Examples 16 through 20 were tested
for adhesion properties according to the procedure of Example 13. The
same EPDM compound from Example 14 but milled to a thickness of
approximately 0.100 to 0.120 inches was used. The vulcanization condi-
tions were 325F for 30 minutes at 3200 PSI pressure. The results are
shown in Table 3.
WO 95/22~76 PCT/US95/01914
5 6
C E ..
~ E~ c~ ~ o
,
DD
D '' D
~ D D D ~: G
,0 o O, O
DD
l,L D D D ~ ~
E ~ _ ~ ~ ~ ~ ~D
Q~ o,o ~ ~~ ~
_ J -- ~
U' C _
~ ~ ~ ^ ~D O O
~ 5 ~ o o ~ ~
X ~D N
q~ ~ c -- ~ C ~
'~ I ~ .o ~ ,o ~ , .~,
~ .C D C CI D I D
~ ~ 8 ~ 1~ ~ ~" ~ ~ c ~" ~ --
E O ~ ~,_ O ~
X CD 1~0 a~ o
LLI _ _ _ _ ~
SUBSTlTUrE SHEE~ (RULE 26)
WO 95/22576 2 1 ~ ~ 9 2 9 PCI`/US9S/01914
- 57 -
The data in Table 3 shows that yarn treated with the combination
of components consistent with the adhesion system of this invention (Ex-
amples 19 and 20) exhibits significantly improved adhesion in terms of
higher mean and maximum loads, failure type and shorter pull length, to
the EPDM rubber compared to other compositions.
EXAMPLE 22
The treated yarn samples from Examples 16 through 20 were
tested for adhesion properties according to the procedure of Example 13.
The same EPDM compound from Example 15 was used. The vulcanization
conditions were 320F for 25 minutes at 3200 PSI pressure. The results
are shown in Table 4.
WO 9S122576 PCTIUS95101914
2~ 58-
" E ~ ~
J _ ~t
D ~ ' 8 D
D D D GD~ GD~
I-- G G G O O
; -- _ -- _
IL D D D GD~ D
E ~ ,~ ~n
~ 8 ~ tD 1~ ~ t CD
m~ 8 ~, co a~ ~ u~ ~
~,5 J _ N O -- ~ 0
~ U~ X .~ X
,~ ~ ~ O ~ O
C~ c c o C ~ I D I D
O ~ C O 1-- ~ -- C ~ ~ C
Q) D D 1-- ~'E ~ ~ E
E o ~ o ,~ o ~ ~ ~ o ~" ~ o ~"
K CD 1~ 0 O) O
SUBSTllUrE S~EET (RULE 26~
WO 95122576 PCT/US95/01914
2~892~
- 59 -
The data in Table 4 shows that yarn treated with a combination of
components consistent with the adhesion system of the present invention
(isocyanate, carrier (plasticizer/solvent) and polyunsaturated polymer)
exhibits even more improvement in adhesion to a different EPDM rubber
5 than in Table 3.
EXAMPLE 23
The treated yarn samples from Examples 16 through 20 were tested
for adhesion properties according to the procedure of Example 13. A com-
mercial EPDM compound used in commercial hoses, similar to that used
in Example 21 but containing less EPDM and more filler was used. It also
was milled to a thickness of approximately 0.100 to 0.120 inches. The
vulcanization conditions were 325F for 30 minutes at 3200 PSI pressure.
The results are shown in Table 5.
WO 95/22576 PCI`/US95/01914
6 0
~ C E
D Q ~17 D D
~_ o ~ Cl:
0 D D D D D
Ir C C G cr:
o o ~ o ~ o
5 ~ e _ ~ ~ _ _
e~5 o D . ~ ~ O N
~ O F I ~ I ~ C ~ ~ C ~ ~
E
S~IBSTITUTE SHEET ~RUEE 26)
WO 95122576 PCT/US95/01914
2 ~ 2 ~
- 61 -
The data in Table 5 also shows that yarn treated with the
combination of components consistent with the adhesion system of the
present invention (isocyanate, carrier (plasticizer/solvent) and
polyunsaturated polymer) exhibits the highest adhesion to the EPDM
rubber compared to other combinations.
EXAMPLE 24
Example 2 was repeated with the exception that the treating
solution used was 20.0 parts of toluene added to 80.0 parts of the
mixture of 80% bis(2-ethylhexyl) terephthalate (dioctylterephthalate
(DOTP) CAS# 6422-86-2) and 20% poly(2,2,4-trimethyl-1,3-pentanediol
maleate) (CAS# 250-5-65-8) (Kodaflex PA-6 from Eastman Chemical
Company).
EXAMPLE 25
Example 24 was repeated with the exception that the treating solu-
tion used was 20.0 parts of toluene added to a mixture of 75.0 parts of
the mixture of 80% bis(2-ethylhexyl) terephthalate and 20% poly(2,2,4-
trimethyl-1,3-pentanediol maleate) and 5.0 parts of the hydroxyl termi-
nated polybutadiene used in Example 17.
EXAMPLE 26
Example 24 was repeated except that the treating solution was
20.0 parts of Desmodur VKS-18 added to a solution of 75.0 parts of the
mixture of 80% bis(2-ethylhexyl) terephthalate and 20% poly(2,2,4-
trimethyl-1,3-pentanediol maleate) mixed with 5.0 parts toluene.
WO 95/22576 PCTtUS9StO1914
&~ 62-
EXAMPLE 27
Example 25 was repeated except that the treating solution was
20.0 parts of Desmodur VKS-18 added to a solution of 37.5 parts of
dioctylterephthalate (DOTP) (CAS# 6422-86-2) and 37.5 parts of the
mixture of 80% bis(2-ethylhexyl) terephthalate and 20% poly(2,2,4-
trimethyl-1,3-pentanediol maleate) mixed with 5.0 parts of the hydroxyl
ter-,-inatecl polybutadiene (Poly bd R45HT).
EXAMPLE 28
The treated yarn samples from Examples 24, 25, 26 and 27 were
tested for adhesion properties according to the procedure of Example 13.
The same carbon filled EPDM compound from Example 15 was used. The
vulcanization conditions were 320F for 25 minutes at 3200 PSI pressure.
The results are shown in Table 6.
~ ~ ~ ~ PCT/US95/01914
WO 95/22576 ~C ] ~ ,~ 9
~ E
:
o D 8
LL X D D D
E c~
X _ ~ _ 0 ~)
D 'J W D -- ~ ~D
~u -- , - o ~ " ~ C C ~ U
- ~ C ~E L C ~ --U E :~ ~ ~ o
-
SUBSTllUrE S~EET ~RULE 2~
WO 95/22576 PCT/US95/01914
z~C ~ 64 -
The data in Table 6 shows that yarn treated with the combination
of components consistent with the present invention (isocyanate, carrier
(plaslici~er/solvent) and polyunsaturated polymers) exhibit higher adhesion
to the EPDM compound compared to the other combinations of compo-
nents and that mixtures of hydroxy-terminated polybutadiene and poly-
maleate ester provided treated yarns with the highest adhesion to the
EPDM compound.
EXAMPLE 29
Thetreated yarnsamples from Examples 16, 17, 18, 19, 20,
24, 25, 26 and 27 were tested for adhesion properties according to the
procedure of Example 13. A carbon filled neoprene compound used in
commercial hoses milled to a thickness of about 0.100 to 0.120 inches
was the rubber compound used . The vulcanization conditions were 325 F
for 30 minutes at 3200 PSI pressure. The results are shown in Table 7.
WO 9S/22576
2I~ tf~ PCI/lJSg5~01914
6 ~
~, E ~ o o
0: D D a ~ D`
e ~ ~ e C~ D
~ D D D X D D D X
E ~ _ o~
5 o _ c
C -- _ ~ ~, o ~ o O
_ c W 1~ c a
X ~ _ C
~_ ~o ~o ~ o S ~, 5 c
E ~ e ~
u, ~ ~ ~ I ~ '" t- ~ ~ ~ uJ u, ' o
X ~ I~ ~ O ~ C~ r~
SU8STITUIE S~IEE~ ~RULE 26)
WO 95/22576 PCT/US95/01914
66 -
The data in Table 7 shows that yarn treated with the conventional
adhesion system of isocyanate and plasticizer (Example 16) gives higher
adhesion to neoprene, one of the older synthetic rubbers, than to EPDM,
one of the more difficult to adhere to synthetic elastomers (Table 6) but
the adhesion system of this invention (Examples 19, 20, 26 and 27)
gives the same or higher adhesion than the conventional adhesion system
on neoprene.
EXAMPLE 30
Example 19 was repeated except that the treating solution used
was 13.06 parts of tolylene-2,4-diisocyanate (from Example 5) added to
a mixture of 5.02 parts Poly bd R45HT (from Example 17) added to 81.99
parts toluene.
EXAMPLE 31
Example 30 was repeated except that the treating solution used
was 12.59 parts of hexamethylene diisocyanate (from Example 6) added
to a mixture of 5.01 parts Poly bd R45HT added to 82.39 parts toluene.
EXAMPLE 32
Example 30 was followed except that the treating solution used
was 19.10 parts of Desmodur VK 5 (from Example 8) added to a mixture
of 5.01 parts Poly bd R45HT added to 75.89 parts toluene.
EXAMPLE 33
Example 32 was followed except that the treating solution used
was 20.01 parts of Desmodur VKS-18 (from Example 10) added to a
mixture of 4.99 parts Poly bd R45HT added to 74.99 parts toluene.
WO 95/22576 PCT/US95/01914
- 67 - ~15~9~
EXAMPLE 34
Example 32 was followed except that the treating solution used
was 21.91 parts of Desmodur VK-70 (from Example 11) added to a
mixture of 4.99 parts Poly bd R45HT added to 73.09 parts toluene.
EXAMPLE 35
Example 32 was followed except that the treating solutiori used
was 24.01 parts of Desmodur VK -200 (from Example 12) added to a
mixture of 4.99 parts Poly bd R45HT added to 71.00 parts toluene.
EXAMPLE 36
The treated yarn samples from Examples 30 through 35 were tested
for adhesion properties according to the procedure of Example 13. The
same carbon filled EPDM compound milled to the same thickness as in
Example 14 was used. The vulcanization conditions were 325F for 30
minutes at 3200 PSI pressure. The results are shown in Table 8.
WO 95122576 PCI/US95/01914
68
E ~ ~ ~ ~ ~ c~
iL 2
D D D D
~ ~
~ X XX ~ ~ D D D
~X ~ ^ ~ ~ o o ~ ~
n~ o D . I~ O
5 J e
00
uJ ' ~ a)
~S 5 ~
~ ~ c _ co c 8 c
.' ~ C ~ ~y ~y ~ ~ ~
C; ~ ~ D~ D ~ D
~ E t~E gE ~ E Q
o X X X ~
c.C I .C I ,C E C E C E C c
D C ~-,o o C ~ ~ X >
O ~ ;~ O O O-- o I
-
X O
SU~ I jE S~ (~
WO gsn2576 PCT/US95/01914
~15~9
- 69 -
The data in Table 8 shows that significant adhesion to EPDM is
exhibited by yarn lrealecl with adhesion systems of this invention where
a solvent is used as the carrier component.
E)CAMPLE 37
The lrealed yarn samples from Examples 30, 31, 32, 34 and 35
were tested for adhesion properties according to the procedure of Example
13. A carbon filled chlorobutyl compound used in commercial hoses milled
to a thickness of about 0.100 to 0.120 inches was the rubber compound
used. The vulcanization conditions were 310F for 40 minutes at 3200
PSI pressure. The data in Table 9 was obtained.
WO 9S122576 PCTIUS95/01914
_
E
8 o O
,o, . o . o
IL D ~o X D 0
E ~ u~
CS, ~ C"
C~ o o
C y ' V ' V '
o O 0 x X ' E ~ E o E o
2 '~ e 2~e ' ~ 2 E , e
X O
Sl~l~U~ESI~ (~iJiE2t)
WO 95122S76 2 I S ~ ~ 2 ~ PCr'US95'0l9l4
- 71 -
The data in Table 9 shows that significant increase in adhesion to
the chlorobutyl rubber is exhibited by yarn treated with adhesion systems
of this invention where a solvent is used as the carrier.
E~CAMPLE 38
Table 10 shows a comparison of a solvent as a carrier versus a
plasticizer as a carrier over a range of molar ratios of isocyanate to termi-
nal groups of hydrocarbon polymer. In this Table, the amount of Poly bd
R45HT specified was added to either the amount of toluene as a solvent-
carrier or the amount of di-2-ethylhexyl adipate (Kodaflex DOA) as speci-
fied in Table 10. After stirring as in Example 2 to obtain a homogeneous
solution, the amount of Desmodur VK-5 as specified in Table 10 was
added and the resulting mixture again made homogeneous and applied to
the Type 174S polyester yarn as in Example 1. The treated yarns were
tested for adhesion by the procedure of Example 13 using the same carbon
filled EPDM compound as in Example 15. The vulcanization conditions
were 320F for 25 minutes at 3200 psi. The adhesion results for the
varying ratios are shown in Table 10.
In Table 10, the molar ratios of isocyanate (NCO) to hydroxyl group
(OH) were calculated using Desmodur VK-5 (from Example 8) with a
32.5% isocyanate content and Poly bd R45HT (from Example 17) with a
hydroxyl value of 0.83 meq OH/g and a calculated hydroxyl number (OH#)
of 46.563 meq KOH/g by calculating equivalent ratios and translating to
molar ratios by the following equations:
Equivalent Weight, EW = grams/equivalents
EW = 4202/%NCO ; Formula Weight NCO = 42.02 9
EW = 56,100/OH# ; Formula Weight KOH = 56.1 9
Hydroxyl Value = meq OH/g
OH# = meq OH/g x meq KOH/meq OH x 56.1 mg KOH/meq KOH
WO 9S122576 PCT/US95/01914
2~S~ 9 72-
Equivalent Ratio (NCO/OH) = Equivalents NCO/Equivalents OH =
(grams NCO/EWNCO)l(grams OH/EWOH)
Molar Ratio (NCOIOH) = Moles NCOlMoles OH = eq NCO/eq OH
x mole NCO/eq NCO x eq OH/mole OH
Sample calculation for Example 38H
OH#R45HT = (0.83 meq OH/g) x (meq KOH/meq OH) x (56.1 mg
- KOH/meq KOH)
grams Poly bd R45HT = 1.60
grams Desmodur VK-5 = 17.20
EWR45HT = 56,100/(0.83 x 56.1)
EWVK-5 = 4202/32.5
Equivalent Ratio (NCO/OH) =
[(17.20 g)/(4202/32.5)geq1]/[(1.60g)/(56,100/(0.83 x 56.1))geq~']
Equivalent Ratio (NCO/OH) = 0.1330319eq NCO/0.0013278eq OH
Molar Ratio (NCO/OH) = [0.1330319eq NCO/0.0013278eq OH] x
[mole NCO/eq NCO] x [eq OH/mole OH]
Molar ratio (NCO/OH) = 100 mole NCO/mole OH
WO 95122576 PCT/US95/01914
2 1 5 8 ~ ~ r9
~ ~ E O ~ ~ ~ ~' 5
:~ ~ c ~ c ~
o ~ 8 o ~ " g ~
~ ~ o _ ~ ~ ~ u~ q u) o _ ~
;~5 r ~ , n o o ~ o ~n ~ OD 10
o F ~ ~ $ o ~ ~ o -- o o
o oOOOO~D~ O
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, ~ ~ ,~ o ~ _ ~ o o o o o o o o
O. ~ ~n 0. ~
C ~ O r~ _ ~q o -- o _ ~ ~ _ ~ O
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~S 0 0 ~D 0 0 0 0 0 3 0 0 0 Z0
WO 95122576 PCT/US95/01914
- 74 -
~15~9~9
EXAMPLE 39
The concept of the effect of the molar ratio of isocyanate groups
to reactive groups on the polybutadiene diol from Example 38 is
demonsl(aled further in Table 11 using a different isocyanate (Desmodur
VK-18) and using a ~laslici~er (dioctyl terephthalate or Kodaflex DOTP).
The method of solution preparation, yarn lreal.~ent, yarn heat treatment
and testing was the same as in Example 38. Examples 39A through 39F
used the same EPDM compound and vulcanization conditions as in
Example 38. Examples 39G through 39L used a specially prepared EPDM
compound which had been milled to about 0.100 to about 0.120 inches
thickness. The vulcanization conditions for Examples 39G through 39L
were 330F for 30 minutes at 3200 Ibs. pressure.
Table 11 not only demonstrates again the unexpected advantage of
higher adhesion with an excess of isocyanate compound present in the
treating solution of the novel adhesion system, but also shows that a
higher weight percent concentration of isocyanate groups on the treated
article gives higher adhesion at the same ratio of isocyanate groups to
butadiene polymer reactive terminal groups (Examples 39H through 39L
versus Examples 39B through 39F).
WO 95/22576 PCT/US95/01914
~ ~ 2 1 ~2~
o E
z E ~ ~t ~ ~ ~ ~ ~ ~ ~ ~ ~ ,q
, ~ .
W o _ _, _ _ _ _ _ _ o _ , _ ,C _, _ _
C ~ D ~ ~ n~ n ~c n~ ~ D n n ~ ~o ~ ~ D n ~ x n n .x
2 _ ~ ~o ~ ~ o
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~ ~ _ ~ ~ ~ o m o~
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WO 95122576 PCI/US95/01914
76-
EXAMPLE 40
Following Example 1 in United States Patent Number 3,941,909
issued to Schoen et al., 150 ml of toluene was added to a beaker contain-
ing 39.16 grams of hydroxyl terminated polybutadiene (Poly bd R45HT
Resin as in Example 17). The hydroxyl terminated polybutadiene was
completely dissolved in the toluene usin~ a magnetic stirrer and stirring rod
as in Example 2. While this solution was stirring, 6.10 grams of to~ylene-
2,4-diisocyanate [TDI] (as in Example 5) were added and the mixture
stirred for approximately two minutes after complete addition of the TDI.
This solution was then transferred to a round bottom flask, 8-10
Boileezers boiling chips ~available from Fisher Scientific] were added, an
Allihn condenser was connected, and the flask was placed in a heating
mantle. At a medium power setting, the mixture was heated to refluxing
temperature over a period of 20 minutes, the solution was maintained at
a slight reflux 115-25 drops per minute) for 1 hour. After refluxing for 1
hour, the flask was removed from heat, stoppered, cooled slightly with
a damp cloth for approximately 5 minutes, and immersed in cool water.
At ambient temperature, the mixture was transferred to a closed
container.
EXAMPLE 41
Example 40 was repeated except 5.89 grams of hexamethylene di-
isocyanate (as in Example 6) replaced the tolylene-2,4-diisocyanate.
EXAMPLE 42
Example 40 was repeated except 10.89 parts of polymethylene
polyphenyl isocyanate (Desmodur VK-5 as in Example 8) replaced the
tolylene-2,4-diisocyanate. The mixture gelled before the solution could be
applied to fiber and was remade for fiber treatment in Example 45.
WO 95/22576 PCT/US95/01914
215~929
EXAMPLE 43
Example 40 was repeated except 13.08 parts of Desmodur VK-18
(from Example 9) replaced the tolylene-2,4-diisocyanate. The mixture
showed signs of gellin~ after 17 minutes at slight reflux and gelled while
l,ansrerring from the distilling flask.
EXAMPLE 44
Example 40 was repeated except 14.25 parts of Desmodur VK-70
(from Example 11) replaced the tolylene-2,4-diisocyanate. The solution
gelled after 45 minutes at slight reflux.
EXAMPLE 45
Examples 40, 41 and 42 were applied to 2000 denier, 1.5 TPI
polyester continuous filament yarn (AKZO Diolen Type 174S) by slot appli-
cator as in Example 19 at a rate to give 2.8% solids add-on of the prepoly-
mer. The solution from Example 42 had gelled within six days after trans-
ferring from the reaction flask so a fresh solution was made, using the
quantities in Table 12 at approxil,lately double the amount used in Example
42, and applied approximately 15 hours after transferring from the reac-
tion flask. Observation of the remade solution from Example 42 indicated
that it began to gel approximately 72 hours after being transferred from
the reaction flask. The treated packages were heat-treated and condi-
tioned as in Example 1. The yarns were tested for adhesion as in Example
13 using the same carbon filled EPDM (Ethylene-Propylene-Diene Mono-
mer) compound milled to the same thickness as in Example 23. The vul-
canization conditions were 325F for 30 minutes at 3200 PSI pressure.
The results shown in Table 12 were obtained.
WO 95/22576 PCT/US95/01914
7 ~
~, E
J
lu oo o
~ ,~
,¢ & & &
o o o
e
0
.c~ 1`
~e
C~
~ > o
¢~ -- --
~S O ~ ~ o>
G ¢
l_
O O~
O --
~ !D .
Z ~
~ .
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WO 95t22576 PCI'IUS95/01914
2ls892~
- 79 -
The data in Table 12 shows that yarn treated only with a pre-
polymer of an unsaturated polymer and polyisocyanate in toluene consis-
tent with U.S. Patent 3,941,909 exhibits poor adhesion to the EPDM
elasto".er.
EXAMPLE 46
Solutions from Examples 40 and 42 were used in preparation of
Examples 46A through 46H. Each solution was applied to 2000 denier,
1.5 tpi, polyester continuous filament yarn (AKZ0 Diolen Type 174S~ as
in Example 1 at rates sufficient to give the respective pick-up levels below.
The samples were heat-treated and conditioned as in Example 1 and tested
as in Example 13 using the same carbon filled EPDM compound as used
in Example 23 milled to a thickness of about 0.100 to 0.120 inches. The
vulcanization conditions were 325F for 30 minutes at 3200 PSI pressure.
The results are shown in Table 13.
WO 95122576 PCI'/US95/01914
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ilUllltS~(~Eai~
WO 95122S76 PCT/US95/01914
81 215892,.~J
The data in Table 13 shows that the addition of plasticizer alone to
the pre-reaction products of Examples 40 and 42 did not provide treated
yarns with high adhesion to the EPDM elastomer, while the addition of
plaslici~er and polyisocyanate to the pre-reaction product did provide
l~ealecl yarns with high adhesion to the EPDM elastomer.
This further demonsL-ates that excess of isocyanate beyond that
needed to react with the hydroxyl terminated polybutadiene gives
significantly improved adhesion.
EXAMPLE 47
Solutions from Examples 40 and 42 were remade and used as Ex-
amples 47A and 47B. For Examples 47C through 47F, a master batch
solution was prepared by adding 372.12 9 dibutyl phthalate lavailable from
Eastman Chemical Company as Kodaflex~ DBP (CAS# 84-74-2)],218.72 9
of a mixture of C7 - Cll dialkyl phthalate esters [available from BASF
Corporation as Palatinol~ 711 P], and 59.14 9 of a petroleum based naph-
thenic neutral oil lavailable from Macmillan Petroleum (Arkansas) Inc. as
Coastal Pale Oil] to a half gallon container. The container was stoppered,
and the mixture was shaken for one minute. Example solutions 47C and
47D were prepared by adding a specific amount of isocyanate (see Table
14) to a specific amount of master batch solution (see Table 14) and stir-
ring into solution using a magnetic stirrer. After each solution was mixed
thoroughly and appeared homogeneous (~3 minutes), the solution was
ready to be applied. Example solutions 47E and 47F were prepared by dis-
solving Poly bd R45HT Resin from Atochem North America (as in Example
17) in a specific amount of master batch solution (see Table 14). Once a
homogeneous solution was obtained, a specific amount of isocyanate was
added (see Table 14) and stirred into solution using a magnetic stirrer.
Samples were mixed and ready to be applied the same as Examples 47C
and 47D.
WO 95/22576 PCT/US95/01914
- 82 -
~,~LS~ 9
TABLE 14
Examph - p~ ~Iy Type ~UO~f~ ~t~ T~pe Poly bd R45HT Pl-; ~r Type
[Parts Used] [Parts Used] [Parts Used] [Parts Used]
47A Ite."ade solution None None None
as in Example 40
usin~ twice the
in~redients
47B Remade solution None None None
as in Example 42
usin~ twice the
inoredients
47C None Tolylene-2,4- None Dibutvl Pl,ll-aldl~
Diisocyanate ~47.8]
[16.5] C,-C1l Dialkvl
Phthalate2 [28.1]
NNO3 [7.6]
47D None Desmodur VK-5 None Dibutyl Pl,Ll,alale [16.5] [47.8]
C,-C11 Dialkyl
Phthalate [28.1 l
NN0 [7.6]
47E None Tolylene-2,4- 8.0 Dibutvl Pl,ll,alalc:
Diisocyanate [43.2]
[16.5] C7-C11 Dialkyl
Pl,ll,alale [25.4]
NN0 [6.9]
47F None Desmodur VK-5 8.0 Dibutvl Pl.ll,alala [16.5] [43.2]
C,-C1l Dialkyl
Phthalate [25.4]
NNO [6.9]
1 Kodaflex~ DBP from Ea~ an Chemical Company
2 Palatinol~ 711 P from BASF Corl,o,.,lion
3 NN0 = Naphll,el~ c Neutral Oil
WO 95/22576 PCI/US95/01914
2158~2~
EXAMPLE 48
The solutions in Example 47 were applied to 2000 denier 1.5 tpi,
polyester continuous fila"~e~l yarn (AKZ0 Diolen Type 1 74S) as in Exam-
ple 1 except solutions 47A and 47B were applied at a different rate suffi-
cient to ~ive a pick-up of 2.8 percent solids on the fiber. The treated
fibers were heat lrealed as in Example 1. The treated fibers were tested
as in Example 13 using the same carbon filled EPDM compound as used
in Example 23 milled to a thickness of about 0.100 to 0.120 inches. The
vulcanization conditions were 325 F for 30 minutes at 3200 PSI pressure.
The results are shown in Table 15.
WO 95122576 PCT/US9S/01914
J~
-
fi
.
~- o ~ c~
J
.
.
-- -- ~ a
J ~ ~) ~ Q
~ _ D D -- r
- Q c' D D ~ ~ ~
~ ~ J CL
a~ O O O ~: ~
~ ~ D
LL D D Q ~ ~ D
-- -- -- a, --
J
D
O ~ C
E
-- X
D CD C~ o
J
Q ~ m t ~
SluU~t SR~ (FilliE 26)
WO 95/22576 PCT/US95/01914
2~5~29
- 85 -
The results in Tables 12, 13 and 15 support the results in
Tables 10 and 11 that an excess of isocyanate groups above that amount
of isocyanate groups that may react with the terminal hydroxyl groups of
the butadiene polymers, or isocyanate groups that may be involved in
such a reac~ion product by the reaction of another isocyanate group on the
same molecule is necessAry to achieve the adhesion improvements of this
invention and that the addition of prepolymers, as are found in the prior
art, of isocyanate containing compounds with polybutadiene diols, alone
to an article to be bonded to rubber will not yield the adhesion improve-
ments contemplated by this invention.
EXAMPLE 49
The following adhesion samples were tested as in Example 13
using solutions47A, 47B, 47C, 47D, 47E, and 47F with thefollowing
differences. The compound used was the same carbon filled EPDM com-
pound as used in Example 23 milled to a thickness of about 0.100 to
0.120 inches. The vulcanization conditions were 325F for 30 minutes
at 3200 PSI pressure. The untreated yarn (AKZ0 174S polyester yarn) for
Example 48 was wound on the tape as in Example 13. Four 3 15/16" x
3 15/16" tape sections were used per adhesion press, along with four 1 n
x 3 15/16" sections of aluminum foil. Four rubber compound sections
were cut, 3 15/16" x 3 15/16" each, per adhesion press. Each 3 15/16
x 3 15/16" rubber section was weighed and then coated with a different
solution from Example 47 using a soft bristle paint brush. The brush was
cleaned with toluene after each solution application. After each rubber
section was coated, it was set aside for fifteen minutes and reweighed.
A different mold was used which consisted of a top and a bottom 10" x
10" flat aluminum plate (1/4" thick each) plus a middle 10" x 10" alumi-
num plate (3/4" thick) with four 4" x 4" cutouts and eight 4" x 4" plates
WO 95/22576 Pcrluss5/ol9l4
~Lr ~ 9~ 86
(3/8" thick each) arranged and preheated to the specific compound vul-
canization temperature in the hydraulic press. The samples were tested
as in the general procedure in Example 13 with the noted exceptions. The
data in Table 16 was obtained. This data shows that low adhesion is ob-
tained with solutions 47A-47F when applied to the rubber instead of the
yarn.
TABLE 16
Weight of coaffn~
on the mbber sec- Maximum Pull
~on after 15 Mean LoadLoad Len~
Example minutes (~) ~Ibf.l(Ibf.) Failure Type Imm)
47A 0.31 2.72 3.22 Fiber to Rubber 40
47B 0.46 2.39 3.47 Fiber to Rubber 46
15 47C 0.23 0.75 1.51 Fiber to Rubber 35
47D Ø25 2.50 3.39 Fiber to Rubber 44
47E 0.21 1.68 2.02 Fiber to Rubber 44
47F 0.25 2.87 3.96 Fiber to Rubber 41
EXAMPLE 50
The results of increased adhesion obtained by the combination of
a large excess of isocyanate groups to terminal hydroxyl groups of
polybutadiene of Examples 38 and 39 were explored in more detail with
other terminal groups of butadiene polymers.
The hydroxyl terminated polybutadiene in Examples 50C and 50G
was the previously used and described Poly bd R45HT Resin (Example 17)
from Atochem North America. The carboxyl terminated polybutadiene in
Examples 50D and 50H was compound number 525 from Scientific Poly-
mer Products, Inc. This polymer had a number average molecular weight
of approximately 4500, a weight average molecular weight by GPC of
WO 95/22576 PCT/US95/01914
2~5~2~
- 87 -
approximately 18,000, and a functionality of 1.9. The phenyl terminated
polybutadiene in Examples 50E and 501 was compound number 443 from
Scienliric Polymer Products, Inc. This polymer had a number average
mGlecular weight of approxi~ately 3400, a weight average molecular
weight by GPC of approxi",ately 8,442, and 99% unsaturation (25%
vinyl-1,2; 45% trans-1,4; 25% cis-1,4). The acrylate terminated poly-
butadiene in Examples 50F and 50J was Poly bd 300 Resin from Atochem
North America, which is said to be the esterification reaction product of
Poly bd R45HT with acrylic acid, with about one of the terminal hydroxyls
remaining free and the other terminal group being the acrylate ester.
In Examples 50C through 50F, a molar ratio of about 50 to 1 or
higher of NCO to terminal group for the various polybutadienes was used,
giving a very large excess of polymethylene polyphenyl isocyanate
~Desmodur VK-18). In Examples 50G through 50J, the molar ratio was
much lower than in Example 50C through 50F, giving much less excess of
polymethylene polyphenyl isocyanate (Desmodur VK-18). The amount of
each different terminated butadiene polymer used in Table 17 was based
on calculations of molar ratios of 50 to 1 and 2.5 to 1 moles of NCO to
OH for the hydroxyl te~ inated polybutadiene in Example 50C. In the case
of the other polymers in Table 17, the amounts used were based on
maintaining the same amount of double bond equivalents for each different
terminated polymer, as these were in the hydroxyl terminated
polybutadiene (Poly bd R45HT) at the 50 to 1 molar ratio, since at the
time it was thought that some of these polymers should not react with the
isocyanate groups. However, as explained above, that may not be the
case, so Table 17 is expressed in terms of molar ratio of NCO to known
reactive group except in the case of the phenyl terminated polybutadiene,
where the ratio is expressed in terms of NCO to phenyl group, assuming
two phenyl groups, on each polymer molecule. The phenyl terminated
WO 95122576 PCIIUS95/01914
88 -
polybutadiene actually was said to be made by an initiator system that
should give two phenyl terminal groups with no reactive groups being
present. I lov~/~ ./er, it is possible that an unknown amount of hydroxyl
groups were formed on the polymer molecules by oxidation of the poly-
5 butadiene double bonds. It was said that the polymer was several yearsold, contained no antioxidants, was eYposed to the al",os~,here and was
manufactured for the purpose of oxidative polyn,eri,alion.
The plaslici~er dioctyl terephthalate (Kodaflex DOTP) completed
the formulation. The yarns were treated as in Example 1 and tested for
adhesion by the procedure of Example 13 using the carbon filled EPDM
compound and the vulcanization conditions as in Example 38. The
adhesion results for the varying ratios are shown in Table 17.
WO 95/22576 PCT/US95/01914
8 ~ 2i5~92~
~ ~ E ~ 5
o o o o
G 111 G ~ D W ~ Q ~ G Q G G
" ~ _ ~ ~ ~ ~ C O
O ~ ~ --
O ~ ~ ~ i ~ O ~ O r~
z
~ O ~ O O O O O O O O
t
Ul o ~ ~ o ,`
o
~ ~ e.L U. ~ O ~ . U
o ~G O 1
~ i a O
o o r~ .) _ _
;~ lU o o o g o o o o o o
WO 9S/22576 PCI~/US9S/01914
,g 90
The data in Table 17 shows that polyunsaturated polymers with
phenyl, hydroxyl, carboxyl and acrylate terminal groups can provide yarns
which exhibit high adhesion to the EPDM elastomer.
In Table 17, the molar ratios of isocyanate to polymer terminal
group were calculated usin~ DEs,-,oJur VK-18 (from Example 9) with a
31.5% isocyanate conle~l as in Example 38. In the case of carboxyl,
phenyl, and acrylated terminated polybutadienes, the following formula
was used to calculate equivalent weight (EW):EW = Molecular Weight
(Mn)/Functionality. A functionality of 2.0 was used for the phenyl-
terminated polybutadiene, and a functionality of 1.0 was used for the
acrylated polybutadiene.
EXAMPLE 51
Example 50 was further expanded to demonstrate the effect of dif-
ferent polymers of butadiene with various terminal end groups. Poly-
methylene polyphenyl isocyanate as Desmodur VKS-18 was used at
17.2% in each of the solutions in Example 51. The plasticizers dioctyl
adipate (DOA as Kodaflex DOA from Eastman Chemical Company) and
C7-C1, dialkyl phthalate (Palatinol~ 711P, Palatinol~ is a trademark of
BASF Corporation) completed the formulation. The amount of Palatinol
711P was 25.0% in each of the treating solutions while the amount of
Kodaflex DOA varied as indicated in Table 18. The solutions were made
by making two premixes. Premix "A" consisted of the specified amount
of the designated isocyanate added to the specified amount of Palatinol
711P or the plasticizer(s) which replaced it in that particular experiment
and stirring with a magnetic stirrer until a homogeneous solution resulted.
Premix "B" was formed by adding the Kodaflex PA-6 to the hydroxyl
terminated polybutadiene and then adding the Kodaflex DOA, or the
WO 95n2s76 Pcrrus9slol9l4
~8~2~
- 91 -
plasticizers which repl~ced it in that particular experiment. The mixture
was then stirred with a magnetic stirrer until a homogeneous solution was
obtained. The solutions were then mixed and stirred using the magnetic
stirrer and applied to yarn as in Example 1.
The Poly bd R20LM Resin from Atochem North America in Example
51C has been dEscribed earlier. The Poly bd 605 Resin from Atochem
North America in Example 51 D is an epoxidized polybutadiene diol with an
epoxy equivalent weight of about 260, an oxirane oxygen content of
about 6.5%, a hydroxyl value of about 2.7 meq/g, a viscosity of about
250 P at 25C, a microstructure of 15% cis, 55% trans and 30% vinyl
and a number average molecular weight of approximately 1400. The Poly
bd 600 Resin from Atochem North America in Example 51 E had an epoxy
equivalent weight of about 460, an oxirane oxygen content of about
3.5%, a viscosity of about 55 P at 25C, a microstructure of 15% cis,
55% trans and 30% vinyl and a number average molecular weight of
approximately 1400. The carboxyl terminated polybutadiene in Example
51F was compound number 524 from Scientific Polymer Products, Inc.
This polymer had a number average molecular weight of approximately
4000, a weight average molecular weight by GPC of approximately
17,000, and a functionality of 1.9. The carboxyl terminated polybuta-
diene in Example 51 G was compound number 525 from Scientific Polymer
Products, Inc., described in Example 50. The carboxyl terminated
polybutadiene in Example 51 H was compound number 526 from Scientific
Polymer Products, Inc. This polymer had a number average molecular
weight of approximately 4000, a weight average molecular weight by
GPC of approximately 16,000 and a functionality of 1.9. The acrylate
terminated polybutadiene in Example 511 was Poly bd 300 Resin, de-
scribed in Example 50. The vinyl (acrylate) terminated acrylonitrile/
butadiene copolymer in Example 51J was compound number 516 from
WO 95122576 PCT/US95/01914
? ~) `
Scientific Polymer Products, Inc. This polymer had a number average
- molecular weight of approxi~-~alely 2000, an acrylonitrile content of about
16.2%, a vinyl equivalent weight of about 1,100, a Brookfield viscosity
of about 250,000 cps at 27C and an acrylic vinyl content of about 3.8%
and a functionality of 1.9. The vinyl (acrylate) terminated acrylonitrile/
butadiene copolymer in Example 51K was compound number 522 from
Scientific Polymer Products, Inc. This polymer had a number average
molecular weight of approximately 2500, an acrylonitrile content of about
16.5%, a vinyl equivalent weight of about 1,400, a Brookfield viscosity
of about 225,000 cps at 27C and an acrylic vinyl content of about 3.0%.
The solutions were made up as in Example 38 and applied to yarn as in Ex-
ample 1 but a 3.3 TPI polyester was used. The treated yarns were tested
for adhesion by the procedure of Example 13 using a different carbon filled
EPDM compound used in commercial hoses which had been milled to a
thickness of 0.100 to 0.120 inches. The vulcanization conditions were
315F for 45 minutes at 3200 psi. The adhesion results for the varying
ratios are shown in Table 18.
WO 9S/22S76 PCT/US95101914
9 ~ .8.~ 2 ~
J ~--
z E ~ " 0 ~ o co
G G t~
I LU ~ Ul ~ ~ O O
m m m m m m ~
~' G G~ ~ ~ ~ ~ G G
G X G G G U- LU X m X ~ X
m s s ~L m m m ~L s
5 0 c,~ a~ 't 0 ~ 0 ~ O - '`~
~ ~S-- N ~ ~ D 0 _ o 00
5 ~ _
6 c,~~ ~ ~ . ~ ~ a~
~ Z,
J~
-- o cn ~ 0 o~
X X X X X X ~ X ~ X
Z o ~ O O 0~ 0~ 0 0 0 JO JO JO
5 3 r G ~,X ~ ~ m G G G G C~
~ ZZZ Z ZZZZ ~ J
w ~ ~ ul w
c a O ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
zo oooo o oooo ~
z ~ ~ ~ ~ ~ ~ ~ o_ ~tm ~m
m ~ uJ ~ ~ I _ ~ Y
I _ _ _ _ _ _ _ _
WO 95/22576 PCI~/US95/01914
- 94 -
~,~sag~ v
EXAMPLE 52
The three basic components of this invention - isocyanate, plasti-
cizer, and polyunsaturated polymer - were applied in various combinations
in two step applications versus a one step application. This example indi-
cates that better adhesion is obtained if the isocyanate is applied with the
plasticizer, that the isocyanate and the potenlially reactive hydroxyl termi-
nated polybutadiene do not have to be applied at the same time and that
there is no apparent benefit in a two step application versus a one step
application. Each of the solutions in each application was made by the
general procedure of Example 38. Toluene was added to each solution in
each application to compensate for the 12% pickup to maintain the proper
amount of each component on the yarn. Dioctyl terephthalate (Kodaflex
DOTP) was the plasticizer used. The treated yarns were evaluated for ad-
hesion properties by the procedure of Example 13 using a specially formu-
lated carbon filled EPDM compound which had been milled to a thickness
of approxi,nately 0.100 to 0.120 inches. The vulcanization conditions
were 330F for 30 minutes at 3200 psi. The results are shown in Table
19.
WO 95122576 PCI/US95/01914
21.~g29
9 5
uJ E ~ ~ o (D ~ m
G 1~ 1 g G m G mG m g G m u~ LU
~ 1- IL G 1~ ~ !S ~ m ~ m ~ m ~ x x m m x X
s O m
~s ~ ~ ~ a~ ~ -- O ~0 _ ~ _
~5 ~ ~ m ~ m o m
S _ ~ ~ o u o
J z
O _ ~L ~ O a~
O G Z 1~ ~D 1~ 1~ 0 1~ ~0 r~ 1` 1~ 10
Ul
~ Z ~ S Ul
O m m m ~ r~ ~ m m r~ m m m m
0 5-- 0 0 o. u~ ~ 0 ~ 0 ~ ~ ~
t O ~ _ -- r~ _ _ q -- r~ _ ~ O
m m T d d m o d ~ ~ ,O
d ' -- , ' d ~ a O ,, O
~ ~_ o O O d . ~ m _ O d~- . o _ G . O O O d Z Z O
. _
~ E E T - . D E _ o _ ~
O O d To o n T
O O O ~ d m d m d ~ d D d D D
UJ . . . . . O d ' - d d ~
-- O O ~ o o c~ C
. ~ . O . O
~: m ~ O ~ ~ ~ I _ _ y
S(~STIME SH~E~ ~RULE ~6)
WO 9S/22S76 PCT/US9S/01914
g~ 96-
EXAMPLE 53
The treated yarns from Example 52 were also evaluated for adhe-
sion by the same procedure as used in Example 52 with the same chloro-
butyl compound underthe same vulcanization conditions as in Example 37.
The results are shown in Table 20.
Tables 19 and 20 show that there is no advantage in adhesion in
applying an isocyanate prelreal~ent to the polyester yarn, as is done with
RFL l~eal~,ents, with the adhesion system of this invention (Examples C
and D versus Examples K and L). The results in Tables 19 and 20 also
indicate that the isocyanate should be dissolved or dispersed in the
plasticizer when it is applied to the article as opposed to separate
applications and preferably with or before the third component (poly-
unsaturated polymer) in order to obtain the adhesion improvements con-
templated by this invention (Examples I and J versus Examples A, B, E,
F, G and H) and that the addition of all three components in the same
solution or dispersion is the best way to achieve the adhesion improve-
ments of this invention.
WO 95122576 PCT/US95/01914
9 7 2158929
c, E
~ ~ ~ ~ C ~ ~ C C tl: ~ tl: 11: ~ ~
' t- x x~ m m m m x x x m m m m m m m m m m
;~ ~ s s t G ~ 5 S 1~ CC G ~
S c~ O
X ~t
z ~ ~ ~ ID U -- O
-
Z ~ In -- 0 ~ _ ~ 0
Z 1~ Q 1~ 1
o S ~
--~t O - ~
~ O O ~ ~ ~ ~ r~ ~ ~ ~ r7
I--`'C O G
o ~ O O o IOD IOD O 11~ 0 10 U UO~
~_o~
d ` O
o ~ ~ ~ O o
Z o d ~_ o . ZC O d
~ O ~ a , ; ~ ~ Z o
s ~ ~ ~ O~ O ~ ~ E E
0 0 0 d d ,~ " d d d ,d~ d d _ ~_
G ~ ~ G -- O . G . O . O . G . G
s
~ t m ~ o lu IL ~ I _ -~ y J
SUBSTITUTE SHEET (RULE 26)
WO 9S122576 PCT/US95/01914
'19 - 98 -
EXAMPLE 54
The effect of the isocyanate groups on the treated yarn was
studied by exposing treated yarn to three different moisture conditions.
Isocyanate groups are quite reactive to water, so varying moisture condi-
tions should ~ive some indication of the role that the isocyanate group
plays in regard to adhesion properties and in interaction with the other
cG,.,ponents. Yarn was Irealed with four different formulations containing
some or all of the basic components of this invention. The four different
treal--,ents were isocyanate only, isocyanate plus plasticizer, isocyanate
plus hydroxyl terminated polybutadiene and isocyanate plus hydroxyl termi-
nated polybutadiene plus plasticizer. Each of these four different yarns
were exposed to three different moisture conditions.
The first moisture condition was to minimize exposure of the
treated yarns to water by immediately securing the package of wound
yarn, after treatment with its particular formulation, in a Polyethylene Zip-
Lock bag, flushed with nitrogen and sealed. The package of treated yarn
was removed from the bag and immediately placed in the oven for the heat
treatment as in Example 1. After removal from the oven, the package was
allowed to cool for one hour and then returned to the bag. The bag was
flushed with nitrogen and sealed. The package of treated yarn was not re-
moved from the sealed bag until it was tested as in Example 13.
The second moisture condition was, immediately after the initial
treatment with the specific formulation as in Example 1, to repeat the
treating step with water as the treating solution. The rewound package
was then heat treated as in Example 1.
The third moisture condition was to follow Example 1 with each
of the four different formulations except to retreat each treated yarn as in
Example 1 with water approximately eight hours after completing the heat
cycle as in Example 1. Each of the twelve different treated yarns were
WO 9Sn2576 PCT/US9S/01914
21S892~
99
tested for adhesion by the procedure of Example 13 using the same EPDM
- rubber compound and vulcanization conditions as used in Example 14 ex-
cept that the rubber compound was milled to a thickness of 0.100 to
0.120 inches. The results are shown in Table 21.
WO 95/22576 PCI/US95/01914
,9 1~
ul E~ o
J E~r ~ ~ ~ ~ ~ q ~ r7
o o o o o o o
Ul D D n ~ D D D D D D D
Ic O ~: _ _ _ O o
X DD .r~ D D D D D D ~ D
~-- ~O ~ 0 0 ~ ~ 0
X ~ ~~ U~ ~ O ~q
0_0"7 0 ~ o ~ ~ m
N~ 0 U) _ri 0 ~ ",
~ .
~ ~ o ' o ' ' o
~ O a ' r ~ ~ ~
~~ $ ~ 0 - ~ o O ~ _ o
D * -- D O o , , o D
~j ~3 D--o -- D O D -- o o
" '~o~ ~ ~ ~ ~ ~o
,_ ~ o s o ~ o o ~ ~ . - s
E , Z _ _ E ,
o, -- -- o . -- -- o . -- -- o .
o ~C
X X X . X ~ ~o
O O O O o o O o ~ O ~O ~ O ~ O ~ O
. . . . . . . . . - . . . .
O
u
m ~ c~ m ~ ~
SU~lUUlt ~,Er (~iE a6~
WO 95/22576 PCI/US95/019~4
21~5~
- 101 -
The data in Table 21 indicates that water applied to the yarn con-
taining the components of this invention, either applied before or after a
heat lreal-"ent, has no detrimental effect on adhesion to rubber. This re-
sult further indicates that the adhesion improvement, which appears to
require excess isocyanate ~roups applied to the yarn (Examples 38 and 39)
may not be necessa~ily errecled by the isocyanate groups themselves but
possibly by some reaction product of the isocyanate groups, such as with
water from the ambient air.
EXAMPLES 55, 56, 57, 58, 59, 60, 61, 62, 63 and 64
Tables 22, 23, 24, 25, 26, 27, 28, 29, 30 and 31 contain
data from Examples 55-64, respectively. Examples 55-64 demonstrate the
invention with different combinations of different isocyanates, different
plasticizers, polybutadienediol, andpoly~2,2,~trimethyl-1,3-pentanediol
maleate) on different fibers. The treating solutions were made by making
two premixes as in Example 51. In Examples 58-64, the two solutions
were metered separately by two peristaltic pumps at the proper ratio into
a pan containing a kiss roll. The filament yarns were then passed over the
kiss roll, which was geared to give a pickup of 11.5% and wound by
direct drive winders on tubes as in Example 1 except that fu118" diameter
packages were made. The wound tubes were then heat treated as in Ex-
ample 1. The solution in the pan was replenished as necessary by the
metering pumps, which were activated by a float device. The pickup was
determined by comparing the weights of the average of three each of 30
meter skeins of freshly treated yarn with dry untreated yarn. The percent
pick up was calculated by the formula: 100 times (Average Treated Weight
minus Average Untreated Weight) divided by (Average Untreated Weight).
In Examples 55D, 55K and 56F, the Desmorapid LA was added
to the "B" solution after all of the other components were mixed. In
WO 95n2576 PCT/US95/01914
9~ 102 -
Example 55F, the KP-140~ (Tri-butoxy ethyl Phosphate) (KP-140~ is a
trademark of FMC) repl~ced Palatinol 711 P in the mixing procedure. In
Example 55G, the Plasthall0 DIBA diisobutyl adipate (Plasthall~ is a
trademark of The C.P. Wall Co.) replaced Palatinol 711 P while in Example
551, the Kodaflex DBP replaced Kodaflex DOA.
Example 55J had Cymel~ 303 and Cycat~ 600 added to Premix B.
Cymel~ and Cycat~ are re~istered tradcl, larks of American Cyanamid Com-
pany. Cymel~ 303 is hexamethylmelamine, and is a crosslinking agent for
polymers containign carboxyl, hydroxyl or amide groups. Cycat~ 600 is
an aromatic sulfonic acid catalyst for Cymel~ 303.
Example 55 (Table 22) used Polyvinyl Alcohol 1200 Denier 2.5 TPI
Mewlon filament yarn from Unitika, Japan. The compound used was a
carbon filled EPDM used in commercial hoses. This compound had been
milled to a thickness of 0.100 to 0.120 inches. The vulcanization con-
ditions were 320F for 25 minutes at 3200 psi.
Example 56 (Table 23) used Nomex 1200 Denier 2.0 TPI filament
yarn from Du Pont Fibers. The compound used was the same carbon filled
EPDM with the same vulcanization conditions used in Example 54. This
compound had been milled to a thickness of 0.100 to 0.120.
Example 57 (Table 24) used 840/3 5.0 TPI Nylon filament yarn
from Akzo Fibers. The compound used was a carbon filled chlorinated sul-
fonated polyethylene (Hypalon) used in commercial power steering hoses.
This compound had been milled to a thickness of 0.100 to 0.120 inches.
The vulcanization conditions were 315F for 30 minutes at 3200 psi.
Examples 58, 60, 61, 62 (Tables 25, 27, 28 and 29) used
1000/1 1.5 TPI Polyester Filament yarn type 174S from Akzo Fibers.
Examples 59 and 63 (Tables 26 and 30) used 2000/1 1.5 TPI Polyester
Filament yarn type 174S from Akzo Fibers. Example 64, Table 31, used
1300/1 3.3 TPI Polyester filament yarn type 174S, as above. In Examples
WO 95/22576 PCT/US9S/01914
2158~2~
- 103-
58, 60 and 61, the yarns were wound from the 8" diameter package
from the treating step onto 5 1 /4" diameter cones using a Leesona Model
50 winder. In Examples 59, 62 and 63, the yarns were wound from the
8" diameter package from the treating step after heat treatment onto 7"
diameter cones usin~ a Leesona Model 50 winder. In Examples 64A, B,
C and E (Table 31), the yarns were wound from three 8" diameter treater
packages from the treating step onto one 5~ long tube (two ends up) using
a Leesona Model 50 winder for subsequent use on a braider. The three
ends (two separate yarns) would then be pulled off of the braider package
together for incorporation into a hose. In each of the examples in Table
31, one of these two ends, or yarns, was tested as described in the
Table. The yarn in Example 64D was wound from one 8" diameter treater
package onto one 5" long braider tube or package (one end up).
All of the treated yarns as described above were tested for adhe-
sion by the procedure of Example 13. The rubber compound and vulcani-
zation conditions used in Example 58 were exactly the same as in Example
21. The rubber compound used in Example 59 was a carbon filled chloro-
butyl rubber which had been milled to a thickness of 0.100 to 0.120
inches. The vulcanization conditions were 320F for 25 minutes. The
rubber compound used in Example 60 was a carbon filled nitrile/PVC (poly-
vinyl chloride) blend rubber which had been milled to a thickness of 0.100
to 0.120 inches. The vulcanization conditions were 325 F for 30
minutes. The rubber compound used in Example 61 was a carbon filled
neoprene rubber which had been milled to a thickness of 0.100 to 0.120
inches. The vulcanization conditions were 325F for 30 minutes. The
rubber compound used in Example 62 was a carbon filled chlorobutyl rub-
ber which had been milled to a thickness of 0.100 to 0.120 inches. The
vulcanization conditions were 310F for 40 minutes. The rubber com-
pound used in Example 63 was a carbon filled natural rubber which had
WO 95122576 PCT/US95/01914
04-
been milled to a thickness of 0.100 to 0.120 inches. The vulcanization
conditions were 350F for 5 minutes. The rubber compound and vulcani-
zation conditions used in Example 64 were exactly the same as for
Example 23. The data in Tables 55-64 demonst~ales that various yarns
l,aated with adhesion systems of this invention which contain both hy-
droxy terminated polybutadienes and polymaleate esters show high adhe-
sion to many rubbers and elastomers and when applied to different
polymeric materials.
WO 95/22576 2 1 ~ 8 PCT/US95/01914
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WO 95/22576 PCr/US95/01914
- 115 2~ 92
EXAMPLE 65
The amounts of each of the three components of this invention on
the fiber were varied by varying the amount of each component in the
treating solution and by varying the pick-up of the treating solution on the
yarn. Akzo Type 174S 1000/1 1.5 TPI polyester yarn was treated by the
procedure of Example 19. The treated yarns were tested for adhesion by
the procedure of Example 13. The rubber compound was the same carbon
filled EPDM as used in Example 15 with the same vulcanization conditions.
High adhesion of the treated yarns to the carbon filled EPDM is obtained
for the various formulations and amounts of the adhesion system on the
yarn. The results are shown in Table 32.
.,
WO 95/22576 PCI~/US95/01914
Q~9~ 1 16
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WO gsn2576 PCI/US95/01914
9 ~ F9,
- 117-
EXAMPLE 66
Akzo Type 1 74S (unactivated) (Examples 66A-66F1 1 000/l 1 .5 TPI
and AkzoType 164S (pre-activated) (Examples 66G-66L) 1000/1 1.5 TPI
polyester yarns were treated with each of the solutions of Table 33 by the
procedure of Example 19. Each solution in Table 33 contained 20.0% by
weight Desmodur VK-18 in addition to the ingredients listed in Table 33.
Examples which do not add to 100 percent contained toluene to make up
the difference. The treated yarns were tested for adhesion by the
procedure of Example 13. The rubber compound was the same carbon
filled EPDM as used in Example 15 with the same vulcanization conditions.
WO 95/22576 PCI~/US95/01914
~?9 118
.
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WO 95/22576 PCI/US95/01914
2f ~
- 119-
EXAMPLE 67
A variety of isocyanates and isocyanate derivatives were applied
to 1000 denier 1.5 Akzo Type 174S polyester yarn by the procedure of
Example 19. Mondur CD in Examples 67A and 67C is a carbodiimide
modified diphenylmethane 4,4'-diisocyanate (MDI) from Miles, Inc.
Desmodur N-3200 in Example 67D is a hexamethylene diisocyanate based
biuret from Miles, Inc. Desmodur N-3300 in Example 67E is the trimer of
hexamethylene diisocyanate to form an isocyanurate ring. The Desmodur
E-21A in Example 67F is a higher molecular weight polyurethane pre-
polymer, based on MDI containing reactive isocyanate groups. The
treated yarns were tested for adhesion by the procedure of Example 13.
The rubber compound was the same carbon filled chlorobutyl rubber as
used in Example 37 with the same vulcanization conditions. The results
are reported in Table 34 which shows that a variety of isocyanates and
isocyanate derivatives can be used in the adhesion system of this invention
to provide treated yarn with high adhesion to the chlorobutyl rubber.
~,
WO 95122576 PCT/US95/01914
~ 120
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WO 95/22576 PCTIUS9S/01914
- 121 - 2'I 5 ~2,~
EXAMPLE 68
The poly maleate ester used in the previous examples was studied
more extensively by cG,--parin~ the commercial mixture (Kodaflex PA-6
from Easll,-an Chem c~ mpany) ~Examples 68A and 68D), which is
approximately 80/20 by wei~ht of a mixture of bis(2-ethylhexyl)-
terephthalate (CAS# 6422-86-2) to poly~2~2~lri",elh~ 3-pentanediol
maleate) ~CAS# 25085-65-8), with a laboratory prepared mixture of
approximately 80/20 by weight of a mixture of bis~2-ethylhexyl)-
terephthalate as Kodaflex DOTP from Eastman Chemical Company with
poly(2,2,4-trimethyl-1,3-pentanediol maleate) prepared in the laboratory by
the procedure of Example 1 of U.S. Patent 3,466,264 issued to Eastman
Kodak Company (Hagemeyer, Jr. et al.) on September 9, 1969 ~Examples
68B and 68E). Also, Example 68C in Table 35 uses a laboratory prepared
mixture of approximately 80/20 by weight of a mixture of bis(2-ethylhexyl)
adipate as Kodaflex DOA from Easln,an Chemical Company with the same
poly(2,2,4-trimethyl-1,3-pentanediol maleate) prepared in the laboratory.
In Example 68C, the 20 parts of the lab made poly(2,2,4-trimethyl-1,3-
pentanediol maleate) was dissolved in 80 parts Kodaflex DOA. This solu-
tion (12.5 parts) was then added to the mixture of Poly bd R45HT and
43.3 parts of the Kodaflex DOA listed in Example 68C of Table 35. The
various formulations in Table 35 were applied to 1000 denier 1.5 Akzo
Type 174S polyester yarn by the procedure of Example 55. The treated
yarns were tested for adhesion by the procedure of Example 13. The
rubber compound in Table 35 was a different carbon filled chlorinated
sulfonated polyethylene (Hypalon) than was used in Example 57. This
rubber compound was milled to a thickness of 0.100 to 0.120 inches.
The vulcanization conditions were 325F for 30 minutes at 3200 PSI. The
results are reported in Table 35.
WO 95/22576 PCI/US95/01914
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WO 95122576 PCTtUS95/01914
- 123- 2
EXAMPLE 69
Example 69 expands on Examples 50 and 51 by showing the
effect of different terminal ~roups of butadiene polymers combined with
the polymaleate ester component. The polyester used, method of appli-
cation and l-lell-od of testin~ was the same as in Examples 50 and 51. A
mineral filled EPDM rubber colY)pound, milled to a thickness of 0.100 to
0.120 inches, used to make commercial hoses was used in the adhesion
testing. The vulcanization conditions were 325F for 30 minutes. The
results are shown in Table 36.
WO 95/22576 PCT/US95101914
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EXAMPLE 70
Table 37 demonstrates a significant advantage of this invention in
regard to energy require,-~enls. No heat treatment is required to impart the
adhesion improve.-.e.-ts at various molar ratios of isocyanate to hydrocar-
bon polymer. This table further demonslrales the uniqueness of the inven-
tion in regard to the molar ratio of isocyanate to hydrocarbon polymer
requirements and the advantage of the addition of a plasticizer.
All solutions were applied to 1000/l 1 .5TPI polymers Type 174S
from Akzo fibers as in Example 1 except for heat treatment as noted in
Table 37. The treated fibers were tested for adhesion as in Example 13
using the same carbon filled EPDM rubber as in Example 14 milled to a
thickness of 0.100 to 0.120 inches. The vulcanization conditions were
the same as in Example 14.
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EXAMPLES 71. 72 AND 73
Other polyunsaturated polyesters were made in the lab as in Exam-
ple 68 by substituting 1,6-hexanediol for 2,2,4-~i",elhyl-1,3-pentanediol
(Examples 74E and 74F) and by substitutin~ itaconic anhydride for maleic
anhydride (Examples 71D and 72D). Ex.,.l~ s 71C and 72C have a
change in the molar ratio of the maleic anhydride and 2,2,4-trimethyl-1,3-
pentanediol. All solutions were made by the procedure of Example 68 and
applied to 1000/1 1.5 TPI Akzo Type 174S polyester yarn as in Example
68 and tested for adhesion as in Example 13. Examples 71 and 73 used
the same carbon filled Hypalon compound and vulcanization conditions as
in Example 57. Example 72 used the same carbon filled EPDM compound
and vulcanization conditions as in Example 15. The results for Examples
71, 72 and 73 are shown in Tables 38, 39 and 40, respectively.
EXAMPLE 74
Table 41 shows the effect of different types of polymers and
terminal groups on adhesion with a Hypalon (chlorinated sulfonated
polyethylene) compound. The effect of the polymaleate ester with the
isocyanate and plasticizer on this compound should be noted. All
treatments were applied to the same yarn and by the same procedure as
in Example 19. The adhesion was tested as in Example 13. The same
carbon filled Hypalon compound and vulcanization conditions from Example
68 was used.
In Table 41, the molar ratios of isocyanate to polymer terminal
group were calculated as in Example 50. In the case of polymaleate ester,
an acid number of 3.16 meqKOH/g for Kodaflex PA-6 was used to
calculate an equivalent weight (EW) using the following formula:
EW = 56,100/Acid Number.
WO 95/22576 PCI/US95tO1914
9 - 128-
EXAMPLE 75
The versatility of this adhesion system was examined by applying
the solutions in Examples 75A, 75B, 75C and 75D each to a 0.005 inch
thick 6" x 6" sheet of polyesler film. A clean 6" x 6" preweighed sheet
taped on one side usin~ the masking tape from Example 13, was evenly
coated, on the unlaped side, with each example solution by means of a
soft bristle brush. The samples were weighed i"-",ecliately after coating,
and a pick-up was determined using the formula: 100 x (wet weight-dry
weight)/~dry weight). Each coated sheet was placed in an oven at 93C
for 220 minutes and removed and allowed to cool at ambient temperatures
before adhesion testing. Four 1 " x 3 15/16" sections of aluminum foil
were cut to allow the film to be separated from the rubber when testing
using the general procedure in Example 13 with the noted exceptions. A
3 15/16" x 3 15/16" section was cut from each 6" x 6" sheet and tested
using the mold from Example 49. The same EPDM compound from Exam-
ple 14 was used except milled to a thickness of 0.100 to 0.120 inches.
The vulcanization conditions were 325F for 30 minutes at 3200 psi. The
results are shown in Table 42.
EXAMPLE 76
Table 43 summarizes the invention by comparing two commercial
adhesive treated polyester yarns (RFL and Non-RFL) used for hose re-
inforcement (both on Akzo Type 1 74S 1500 Denier 1.5 TPI polyester) with
a preferred embodiment of this invention in respect to adhesion yarn
processing and solution stability (also on 1500 denier 1.5 TPI Akzo Type
1 74S polyester yarn). All three yarns had been wound on cones for pro-
cessing into hoses. The same carbon filled EPDM compound and vulcani-
zation conditions from Example 15 was used in Example 76. This pre-
ferred embodiment of this invention was applied to yarn as in Example 58.
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The results in Table 43 show significantly improved adhesion is obtained
from yarn lrea~ed with the preferred adhesion system over commercial
yarns.
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The preceding examples can be repeated with similar success by
substituting the generically or specifically described reactants and/or
operating conditions of this invention for those used in the preceding
examples.
From the fore~oin~ description, one skilled in the art can easily
ascertain the essential characteristics of this invention, and without
departing from the spirit and scope thereof, can make various changes
and modifications of the invention to adapt it to various usages and
conditions .
