Note: Descriptions are shown in the official language in which they were submitted.
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Primer Composition and
Bonding of Organic Polymeric Substrates
Field of the Invention
The present invention relates to a surface tre~tment or primer
composition that improves the adherence of materials such as adhesives, inks, and
coatings to organic polymeric substrates, particularly substrates made of organic
high polymers.
Back~round of the Invention
Many organic high polymers (i.e., large molecules, typically
greater than about 10,000 number average molecular weight, composed of repeat
units of low molecular weight species, for example, ethylene or propylene), suchas ethylene-propylene-diene terpolymer (EPDM) and ethylene-propylene rubber
(EPR), have surface energy characteristics that render them difficult to bond toadhesives, inks, and coatings, for PY~mple, using conventional bonding agents
and methods. Various proposals have been made to overcome these
disadvantages.
For example, compositions of styrene-ethylene/butylene-styrene
block copolymers and acrylic polymers in a solvent mixture for priming polymers
of low surface energy are known. These compositions improve the bonding of
pressure sensitive and structural adhesives to polymers of low surface energy.
Also, it is known that the receptiveness of rubbers, e.g.,
copolymer of styrene and but~(lienP (SBR) used for shoe soling, and other solid
high polymers is improved toward bonding with adhesives (e.g., solvent-based
polyurethane and polychloroprenes) by the chlorination of the surface with
solutions of halogen donors, such as trichloroisocyanuric acid and N,N-
dichlorobenzene sulfon~mide. This can be done, for example, by incorporating
the halogen donor into a primer or the adhesive itself. Typically, however,
solutions con~ g only halogen donors are effective only on substrates
cont~ining a high level of ethylenic unsaturation. Also, adhesive compositions,
.
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such as po1yulel1.ane adhesives, co~ ning a halogen donor, have limited
stability.
Primer compositions and adhesive compositions (e.g., hydroxy-
termin~ted polyurethane adhesives) that display improved adhesion to organic
5 high polymers having low levels of ethylenic unsaturation are known. Such
primer compositions typically contain halogen donors (e.g.,
dibromodimethylhydantion and trichoroisocyanuric acid) and aromatic
isocyanates (i.e., compounds in which isocyanate groups are directly ~tt~ç~led to
an aromatic carbon, such as in 4,4'-diphenylmethane diisocyanate). See, for
example, British Patent Application Nos. 1,458,007 (published December 8,
1976) and 1,460,043 (published December 31, 1976). However, such
compositions typically have shelf-lives of less than about 7 days. Thus, they
cannot be readily shipped as a one-part system because they must be mixed
shortly before use. In addition, the primed substrate, if exposed to W radiation,
15 will yellow and discolor due to the presence of the aromatic group in the
isocyanate compound, which is undesirable on white or clear rubber stock, for
example.
Many of these compositions, whether primer compositions or
adhesive compositions, require mechanical rough~ning or abrasion ofthe surface
20 of the substrate prior to or during application of the composition. However,
abrasion of the substrates, especially elastomers in the presence of the primer, is
not always easy or convenient for all applications and is sometimes wasteful of
prlmer.
Thus, there is a need for primer compositions and application
25 procedures which will effectively prime a variety of dirrel en~ substrates, especially
elastomers, for bonding. In addition, such primer compositions should possess a
long shelf-life, and after application, be stable to W radiation and high
temperature and humidity.
Summan of the Invention
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The present invention provides a primer composition comprising a
h~log~n donor compound, an aliphatic isocyanate-co.-l~inine compound, and an
organic solvent. In a plerel.ed embodiment, the primer composition comprises a
solution of: a hqlo~n donor compound selected from the group consisli"g of
5 1,3-dichloro-5,5-dimethylhydantoin, tetrachloroglycoluril, trichloroisocyanuric
acid, and cGmbil-dlions thereof; an aliphatic isocyanate-co..lAi~-;ng compound
selected from the group con.~icting of 1,6-heY~ntethylene diisocyanate, methylene
bis(4-cyclohexyl isocyanate), llh.l~lllyl he,~ll.Gll.ylene diisocyanate, isophorone
diisocyanate, y-isocyanatoprowl trimethoxysilane, and oligomers and
10 co...bh-alions thereof; and an organic solvent.
The present invention also provides a method for adhering two
substrates together and the article prepa. ~d according to this method. The
method involves: applying a primer composition to a surface of a first organic
polymeric substrate to provide a primed surface; wherein the primer composition
15 is preparable by combining components comprising a halogen donor compound,
an aliphatic iSocyanate-cont~ining compound, and an organic solvent; applying anadhesive to the primed surface or to a surface of a second substrate; and
positioning the surfaces of the first and second substrates together to form a
bond.
Another method of the present invention is a method of Çol ........... ing a
traction coating on an article comlJlisil-g an organic polymeric substrate. The
method involves: applying a primer composition to a surface of the organic
polymeric substrate to provide a primed surface; wherein the primer composition
is preparable by combinil-g components comprising a halogen donor compound,
25 an aliphatic isocyanate-cont~ining compound, and an organic solvent; and
applying a traction coating comprising a plurality of hard, inorganic particles to
the primed surface. Preferably, the step of applying a traction coating coml,.ises:
applying an adhesive to the primed surface to form an adhesive-coated primed
surface; and applying a plurality of hard, inorganic particles to the adhesive-
30 coated primed surface. Alternatively, the step of applying a traction coatingcoml),ises applying a sheet material having a plurality of hard, inorganic particles
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adhered thereto.
Also provided is an article comprising an organic polymeric
bsL-~te having at least one surface on which is coated a traction co~tinP~ The
traction coating is preparable by: applying a primer composition to a surface of5 the organic polymeric substrate to provide a primed surface; wherein the primer
composition is plepa,~ble by cc,mbinil-g components comprising a halogen donor
compound, an aliphatic isocyanate-co.~lA;~.;n~ compound, and an organic solvent;and applying a traction coating COnl~JI is;i~g a plurality of hard, inorganic particles
to the primed surface. The article is prere.~bly an article offootwear, such as a
10 shoe having an elastomeric sole, particularly an athletic shoe, or a boot.
As used herein, elastomer or elastomeric material is used in its
conventional manner to refer to a material with rubber-like characteristics, as
defined by Hawley's Condensed Chemical Dictionary, Eleventh Edition, 1987,
New York, NY. This inel~ldes materials that are capable of retracting quickly to15 ap,ol o~ ately their original length after being stretched to at least twice their
original length, such as therrnosetting polymer~ike natural and synthetic rubbers.
This also inrhldes materials such as uncrosslinked polyolefins that are
therrnoplastic, which may yield upon stretçl~ing
Brief Description of the D. 2,~. i"~
FIGS. I and 2 are a side view and bottom view, respectively, of a
shoe in accordance with the present invention.
FIG. 3 is a partially exploded view of a boot having a traction
coating on the exposed surface of the sole.
FIG. 3A is a traction coating on the exposed surface of the sole of
the boot of FIG. 3 .
Detailed D~s_.;vtion
The present invention provides primer compositions of a halogen
donor compound and an aliph~tic isocyanate-cor.~ g compound in an organic
solvent. Preferably, these components are subst~nti~lly unreactive ~i.e.,
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nonreactive) with each other. That is, although there may be weak interactions
between the components, such as hydrogen bonding interactions, for example,
there are no covalent or ionic bonds broken or formed to produce new species in
prere"~;d compositione Thus, preferably, the primer compositions are stable at
5 elevated te~l~pe,alules up to about 60~C for at least about 14 days, when stored in
a moisture-free envil olu..~nl. More p~ erel ~bly, they are stable at room
temperature (25-30~C) for at least about 1 month, and most plerelably at room
te"")c. a~ure for at least about 6 months, when stored in a moisture-free
environment. As used herein, '~stable" refers to a composition that does not
10 decompose, react, precirit~te, or significantly discolor during the specified time
when stored in a moisture-free environment. That is, the composition is
subst~nti~lly ~mçhA~ d after a period of time when stored in a moisture-free
en-,irc"u~enl. Herein, a "moisture-free environ...enl" is an envi,-,nr"e..l fromwhich subst~ntiAlly all ~tmosF-heric moisture has been removed. Typically, there15 is less than about 0.01% water in a "moisture-free env;.unn~enl," such as a
moisture-free solvent and/or a moisture-free atmosphere, as used herein.
Primer compositions according to the present invention typically
effectively modify the surface of an organic polymeric substrate (e.g., substrates
made of organic high polymers, which can be synthetic or natural) for improved
20 adhesion of an adhesive, an ink, or other coating. They also p, t;fel ably have
relatively long shelf-lives and preferably do not significantly discolor upon
exposure to UV light. Such primers are typically effective on a wide variety of
organic polymeric sub~lales having low surface energies, thereby rendering them
adherent to an adhesive, an ink, or other co~ting This allows for improved
25 ~dhes;on to other organic polymeric substrates or other nonpolymeric substrates,
such as glass, metal, ceramic, and the like, using a variety of adhesives.
Further, such primers are generally particularly effective on
organic polymeric substrates COI-~ Ail~;ng some degree of ethylenic unsaturation.
For example" ~hesion of adhesives, inks, co?ting~ and the like, to substrates,
30 particularly elastomers co.~ g ethylenic unsaturation such as polybutadiene,
polychloloprene, polyisoprene, natural rubber, isobutene-isoprene copolymer
. , . .. . . .... ~ ..
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styrene-butadiçne copolymer, styrene-butadiene-styrene block copolymers, and
the like, can be improved using primers according to the present invention. Also,
adhesion of such materials to substrates that contain low levels of, or no ethylenic
unsaturation, such as ethylene-propylene-diene terpolymer, ethylene-propylene
5 rubber, butyl and bromobutyl rubber, can also be improved by the primer
compositions of the present invention. Significantly, other substrates, such as
polyethylene vinyl acetate foams and polyurethane rubber or foams, as well as
other organic high polymer substrates such as synthetic and natural leather,
polyester, polyamide, and plasticized polyvinyl chloride, are also effectively
10 primed for adhesive bonding using the primers according to the present invention.
The surface of the organic polymeric substrates can be mechanically roughened,
prior to priming, to enhance adhesion, although this is not a requi- el~enL.
Suitable halogen donor compounds for making primers according
to the present invention are well known in the art (see, e.g., U.S. Pat. No.
3,991,255 (Blaskiewicz et al.). Such materials are referred to in the art as
"halogen donor compounds" typically because it is believed that such materials
"donate" a halogen atom to an unsaturated moiety in the substrate, although thisis not a nec~esqry requi.~,...enl for the present invention. Classes of such
compounds inchlde, but are not limited to, N-monohalogenated aromatic
20 sulfon~m:des, N,N-dihalo~nqted aromatic sulfonamides, wherein sulfonamide
nitrogen is bonded to two atoms of chlorine, bromine, or iodine and the sulfonylsulfur is bonded directly to the aromatic nllclel~.c; and saturated N-halogenated
heterocyclic amides, wherein the carbonyl carbon is situated in the ring with the
carbonyl carbon being bonded to two N-halogenated nitrogen atoms both of
25 which also reside on the heterocyclic ring. Examples of such compounds include
1,3-dichloro-5,5 dimethylhydantoin, tetrachloroglycoluril, and
trichloroisocyanuric acid. Various combinations of such materials can be used.
They may be prepared by methods well known in the art or obtained from
co,."..el cial sources. Chlorine donors such as trichloroisocyanuric acid (which is
30 available, for t;Aa""Jle, under the trade rlecign~tion "ACL 90 PLUS" from
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Occid~nt~l Chemical Corporation of Dallas, TX) are pl e~e~ ~ ~d since they are
more economical and available than are bromine or iodine donors.
~ lirh~tic isocyanate-cQl~t~ining compounds useful in making
p. hll~l ~ according to the present invention are those in which the isocyanate
5 (-NCO) groups are directly att~hed to aliphatic carbons. Thus, although not
typically prere~,ed, the aliphatic isocyanate-co~-~A~ g compounds may include
aromatic moieties. Preferably, the alirhatic isocyanate-cont~inine compounds do
not contain any aromatic moieties. Thus, the aliphatic isocyanate-co~ -g
compounds may include uns&lu,~lion, ~Ithough saturated materials are typically
10 prefe"ed. Furthermore, pr~ ed aliphatic isocyanate-cont~ining compounds are
subst~nti~lly nonreactive with the halogen donor compounds.
The isocyanate-cont~ining compound can be in the form of
monomers, oligomers, or polymers, as long as there are available (i.e., unreacted)
isocyanate groups. Exampl~- of such aliphatic isocyanate-cont~ining compounds
15 include monomers such as 1,6-h~ a~elhylene diisocyanate, methy~ene bis(4-
cyclohexyl isocyanate), l~h,l~llylh~Y~methylene diisocyanate, isophorone
diisocyanate, y-isocyanatopropyl trimethoxysilane, dimer acid diisocyanate,
xylene diisocyanate, benzene-1,3-bis(1-isocyanato-1-methylethyl), and benzene-
1,4-bis(1-isocyanato-1-methylethyl), oligomers of aliphatic isocyanate monomers,20 and polyrners or prepolymers (i.e., reaction products) of aliphatic isocyanates
with active hydrogen co~ ni~-g compounds. Of these, isophorone diisocyanate,
y-isocyanatopropyl trimethoxysilane, and oligomers and combinations thereof are
prere" ed. Oligomers of aliph~tic isocyanates, such as the trimer of isophorone
diisocyanate (which is available, for example, under the trade design~tion
25 "VESTANAT T1890E" from H~lls America, Inc. of Piscataway, NJ), are
particularly p,~re"~d because they are less volatile and therefore less toxic than
monomeric isocyanates.
The reaction products of aliphatic isocyanates with active
hydrogen-con~ e compounds are suitable if they contain unreacted isocyanate
30 groups. Plefe"ed such materials are subst~nti~liy unreactive with the halogendonor compound and the organic solvent. Any of the above-listed aliphatic
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isocyanates can be used to make such materials. Eka...ples of active hydrogen-
conlAi~ -g compounds include ethylene glycol, 1,4-butanediol, 1,6-h~ ne(liol,
I,;",cll-ylol p,opane, pentaerythritol, and 1,4-cyclohexane dimethanol. Polyester
and polycarbonate polyols are also useful. The reaction products of aliphatic
S isocyanates with active hydrogen-cor.l;.;..; ~g compounds that contain ethylenic
unsaturation or other functional groups that react with the halogen donor
compounds may be useful, but are not prel~.led. For eY~rnrle, prepolymers of
polytetramethylene oxide polyether, polypropylene oxide polyether, or
polyethylene oxide polyether polyols with an aliphatic isocyanate, such as
10 isophorone diisocyanate, are typically not prefel . ed as they may react with the
halogen donor compound, particularly trichloroisocyanuric acid. Mixtures of the
aliphatic isocyanate monomers, oligomers, and/or prepolymers have also been
found to be useful.
Any of a wide range of organic solvents may also be used,
15 includine, for example, aliphatic esters, aliphatic hydrocarbons, and halogen~ted
aromatic or aliphatic hydrocarbons. Preferably, the organic solvent is an aliphatic
solvent (e.g., aliphatic hydrocarbons, aliphatic esters, and halogenated aliphatic
hydrocarbons). Ex~,nples inclllde, but are not limited to, ethyl acetate, butyl
~cet~te, trichloroethylene, cyclohexane, heptane, andbe~zol-inuoride. Mixtures
20 of such solvents can be used. r~ ef~. ably, the solvent is subst~nti~lly nonreactive
with the halogen donor compounds and the aliphatic isocyanate-co..~ g
compounds. Solvents such as ketones are not prefe. led since they react with thehalogen donor to form chlorinated by-products, thereby decreasing the shelf
stability and efficacy of the primer solutions. A p~fe- I ed solvent is a mixture of
ethyl acetate and cyclohexane in weight ratios of about 95 :5 to about 5 :95, and
more preferably about 80:20 to about 20:80 (ethyl acetate to cyclohexane).
Primer compositions according to the present invention include
the arol~.,.e.,lioned components in ~nountc sl.fficient for providing improved
adhesion of an ink, an adhesive, and/or other coating to high organic polymeric
substrates. Prefe,ably, the halogen donor compound is present in an amount of
about 0.5% to 10% by weight, and more plt;rel~bly about 1.5% to about 5% by
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weight, based on the total weight of the primer composition. r, cfcrably, the
aliphatic isocyanate-co~ g compound is present in an amount of about 1% to
about 15% by weight, and more p. ere- ~bly about 1% to about 10% by weight,
based on the total weight of the primer composition. The organic solvent is
S preferably present in the primer composition in an amount of at least about 75%
by weight, based on the total weight of the composition.
Primer compositions according to the present invention may
further include additives. These includç for example, coupling agents such as
silane coupling agents, adhesion promoting agents such as chlorinated polyolefins
(e.g., chlorinated polypropylene), and acid scavengers such as aliphatic epoxy
resins. Typically, the additives are present in the primer compositions in an
amount to provide the desired effect. Preferably, they do not exceed about 10%
by weight, based on the total weight of the primer composition.
Primer compositions according to the present invention are
typically homogeneous solutions, although this is not a neCpss~ry re~uirement.
They may be applied to a substrate using a ~ariety of techniques inchlrling
dipping, spraying, brushing, rotogravure coating, as well as Meir rod and knife
co~ting The primer is typically dried before the adhesive, ink, or other coatingmaterial is applied. A particularly preferred method involves meçh~nically
abrading the surface ofthe substrate, brushing on the primer, and allowing it todry, prior to adhesive bonding.
The adhesives, inks, and other coating materials that demonstrate
improved adhesion to primed organic high polymers (i.e., substrates coated with
the primer compositions according to the present invention) can be thermosetting,
Ihclllloplastic, and hybrid materials. The terrn hybrid as used herein refers tocon.bina~ions of two or more di~renl types of materials (e.g., adhesives) as well
as two or more polymers suitable for forming adhesives, inks, and other coating
materials. Typically, the material coated on the primed organic high polymers are
adhesives.
Thermosetting adhesives are generally formed by addition
polymerization. Ex~tnples of thermosetting adhesives include polysulfides,
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silicones, polyesters, polymetl.~l-es epoxies, anaerobic and aerobic acrylics,
radiation curable polymers and v!llcs~ni7ing rubbers. Thermosetting adhesives
typically cure by heat, catalysts or light or moisture activation. After curing,thermosetting adhesives are generally insoluble (i.e., the adhesive will not dissolve
in an organic solvent or water) and infusible (i.e., the adhesive will not flow when
heated).
Therm~plq~tic adhesives are soluble and fusible materials.
Examples of thermoplastic adhesives include vinyl adhesives (e.g., polyvinyl
chloride, polyvinyl butyral, polyvinyl alkyl esters and ethers and vinyl-acetate-
ethylene copolymer adhesives, acrylic adhesives, and polyurethane adhesives), hot
melt adhesives, cellulosic adhesives, and asphalt-based adhesives. Thermoplasticadhesives may be in the form of emulsions, solutions, or solids.
When the primer composition is applied to a substrate, it is
typically allowed to dry prior to application of the coating, typically an adhesive.
The adhesive may include components that react with the aliphatic isocyanate-
CG~ i"i"g compound. Forexample, polyurethane-based adhesivesand epoxy-
based adhesives may react with the aliphatic isocyanate-cont~ining compounds.
ln order to increase the rate of reaction between the aliphatic isocyanate and the
polyurethane adhesive, a catalyst may be added to the adhesive, although this isnot required. E~r~mp'es of such catalysts include dialkyltin dicarboxylates,
mixtures of dialkyltin dicarboxylates and trialkyltin oxides, metal acetyl
acetonates, metal carboxylates, mixtures of metal acetyl acetonates and tertiaryamines, and the like.
Primer compositions according to the present invention may be
used in the m~mlfactllre of any of a wide variety of articles, such as footwear,particularly footwear with elastomeric co~,ponents such as athletic shoes, as well
as tennis rackets, and roofing l"ell.b.~i~es. They are also suitable for bonding two
organic polymeric substrates together, or one such substrate to a variety of other
substrates such as those conts ining metal, glass, ceramic, wood, and the like.
Primer compositions according to the present invention are
particularly useful in the mqnllf~Gture of footwear with elastomeric soles, such as
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athletic shoes. Rere,~ing to Figures 1 and 2, an athletic shoe 20 is shown, which
has upper 22, optional midsoles 24 and 25, and sole (or outsole) 26. In the
m~mlfncture of athletic shoes 20, for example, the primer composition is appliedby spraying, brushing, or wiping to the ~ttacllment side of a rubber sole 26.
Typically, the solvent is removed by evaporation (e.g., air drying) to form a
primed surface. The primed surface of the sole 26 is then treated in the
conventional manner by applying adhesive, preferably a polyurethane adhesive. Ifthe adhesive is solvent based, the solvent is allowed to evaporate. The upper
portion 22, and optionally the midsoles 24 and 25, of the shoe 20 may be coated
with the same or a di~lenl adhesive and any solvent allowed to evaporate.
When the adhesives have dried, the sole 26, and optional midsoles 24 and 25, andupper 22 are bonded in a conventional manner, typically with heat reactivation of
the adhesive co~tings. For example, the adhesive on the sole may be reactivated
at about 80~C and the sole applied to the upper, which may or may not have been
heat reactivated. The assembly is then treated in a manner known in the art, such
as using a press at an elevated pressure.
rlition~lly, for enhanced traction, the exposed surface of the
sole 26 of the shoe 20 may be coated with a primer composition according to the
present invention. A layer of adhesive may be coated thereon and a plurality of
hard, inorganic particles 28 coated on the layer of adhesive to form a traction
co~ting Alternatively, an adhesive-coated sheet ~e.g., paper or polymeric sheet
material) having hard, inorganic particles adhered thereto can be adhered to theprimed surface of the sole forming a traction co~ting The adhesive used in the
p~ep~alion of a traction coating can be any of the adhesives desclil,ed above orother binders typically used in the abrasives industry.
The exposed surfaces of the soles of many types of footwear can
be coated with a primer composition according to the present invention and a
traction coetin~ Traction co~tingS are particularly suitable on shoes, such as
athletic shoes, and boots, such as overshoes, hip-waders, etc. Referring to
Figures 3 and 3A, a boot 30 is shown having a boot body 32 secured to a sole 34.The exposed surface 36 ofthe sole 34 is coated with a primer composition, a
~, . . . .
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layer of adhesive, and a plurality of hard, inorganic particles to form a traction
coating 36A and 36B (Figure 3A). This traction coating can be on the entire
e,.~,osed surface of the sole 34 or it can be on selectecl portions of the exposed
surface of the sole for a particular application, such as on the front and rear
portions only, as shown in Figure 3A.
Hard, inorganic particles, typically have irregular surfaces and
suffi~ient hard,~ess to provide improved g~ipping characteristics as described in
U.S. Patent No. 5,038,500 (Nicholson), the disclosure of which is incorporated
herein by rtference. Preferably, the particles are made of an inorganic compoundhaving a Mohs hardness of at least about 7, and more preferably, having a Mohs
hardness of at least about 9. Examples of some typical hard, inorganic particlesfor use in the traction coating include fused ~lllminum oxide, heat treated
minllm oxide, white fused aluminum oxide, black silicon carbide, green silicon
carbide, tit~n: um diboride, silica, ~ilic~te~ boron carbide, tl.~ ten carbide,
titanium carbide, silicon nitride, ceria, zirconia, titania, diamond, cubic boron
nitride, garnet, fused ~ min~ zirconia, sol gel derived alumina particles and the
like. Examples of sol gel derived ~lllmin~ particles can be found in U. S. Pat. Nos.
4,314,827 (T çitheieer et al.), 4,623,364 (Cottringer et al.); 4,744,802 (Schwabel),
4,770,671 (Monroe et al.); 4,881,951 (Wood et al) and 5,366,523 (Rowenhorst
et al.). The diamond and cubic boron nitride hard, inorganic particles may be
monocrystalline or polycrystalline. The pref~l . ed inorganic particles are metal
oxides (e.g. ~IIlmin~), metal carbides (including silicon carbide), metal borides and
metal nitrides. In one ple~lled mode, silicon carbide is p,~r~l-ed due to the
spectral appea-~nce ofthe silicon carbide particles.
The traction coating will typically comprise a distribution of
particle sizes of the hard, inorganic particles. These distributions may be a
narrow distribution or a broad distribution, depending upon the end application.The mean particle size ofthe hard, illolg~lfJc particles can range from about 0.2
mm to about 5 mm, p-efe.~bly from about 0.3 mm to about 2.5 mm, and more
preferably from about 0.5 mm to about 1.5 mm. The particle size ofthe hard,
inorganic particle is typically measured by the longest dimension of the hard,
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ino,~,ànic particle. It is generally pl~"ed that the traction coating contain atleast 50% by weight of the hard, inorganic particles that have a particle size
greater than about 50 m ~ on~elers and more pleîel~bly greater than about 100
~iclomele~. In some in~ ces it is pr~relled that the traction coated hard,
h~ol~3dnlc particles having a particle size less than about 7500 miclo"l.,tt;l~, and
more pl efel ably less than about 6000 micrometers. Thus, the traction coating
should preferably not contain particles greater than about 7.5 mm, and more
preferably, not greater than about 6 mm.
The hard, inorganic particle may be randomly shaped. In many
in~Al-ces, very large hard, inorganic particles are crushed or broken into smaller
pieces to form smaller size particles. Subsequently, these smaller hard, inorganic
particles are screened to the desired particle size distribution. In some in.ct~nces,
it is plerelled that the randomly shaped hard, inorganic particles have a more
elongate shape, rather than a blocky shape. Alternatively, the hard, inorganic
particle may have a shape associated with it. Examples of such shapes include
rods, triangles, pyramids, cones, solid spheres, hollow spheres and the like. For
example, methods to make shaped sol gel derived alumina particles are further
described in U.S. Pat. Nos. 5,009,676 (Rue et al.), 5,090,968 (Pellow), 5,201,916
(Berg et al.), and 5,366,523 (Rowenhorst et al.).
It is also with the scope of this invention to use diluent particles,
coated along side of the hard, inorganic particles. In some inst~ncçs~ these
diluent particles may accomplish one ofthe following goals: (1) reduce the cost
of the traction co~tine; (2) reduce the weight of the traction co~ting; (3) improve
traction; or (4) increase cushion. F.~ of diluent particles include metal
carbonates (such as calcium ca,l.onale (chalk, calcite, marl, travertine, marble and
linnestone), calcium m~necium carbonate, sodium carbonate, m~gnçci~lm
carbonate), metal sulfates (such as calcium sulfate, barium sulfate, sodium sulfate,
minum sodium sulfate, ~lllminum sulfate), gypsum, ~ mimlm trihydrate,
graphite, metal oxides (such as calcium oxide (lime)) and metal sulfites (such as
c~lci~n sulfite), metal particles (tin, lead, copper and the like) and the like. The
.. ~ , . .. . . . . . .
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diluent particles may have e~.c~ lly the same particle size as the hard, inorganic
particles or the two particle size distributions may be di~el e.lt.
The traction coating may also contain a mixture of two or more
dirre~ t;nl hard, inorganic particles. Conversely, the traction coating may comprise
5 a uniform mixture of hard, illOl'galliC particles and diluent particles. Alternatively,
the traction coating may contain a layer of diluent particles and a layer of hard,
inorganic particles present over the diluent particles.
The hard, inorganic particles may also be present in the form of an
agglomerate; this agglomerate is a particulate of a plurality of individual hard,
10 inorganic particles bonded together by an agglomerate binder. The abrasive
agglomerates may be irregularly shaped or have a predetermined shaped. The
abrasive agglomerate may utilize an organic binder or an inorganic binder to bond
the hard, inorganic particles together. Examples of organic binders include
phenolic binders, epoxy binders, acrylate binders, urea formaldehyde binders and15 the like. Examples of inorganic binders include vitreous binders, silicate binders,
frit binders, metal binders and the like. Exanlples of how to make such
agglomerates co~ g hard, inorganic particles can be found in the following
U.S. Pat. Nos. 4,652,275 (Bloecher et al.), 4,799,939 (Bloecher et al.) and
5,500,273 (~Iolmes et al.). These agglomerates of cont~ining hard, inorganic
20 agglomerates should have a particle size less than about 5 mrn, typically less than
about 2.5 mm and preferably less than about 1.5 mm.
Objects and advantages of this invention are further illustrated by
the following examples, but the particular materials and amounts thereof recitedin these examples, as well as other conditions and details, should not be construed
25 to unduly limit this invention. All parts and pe~ce~ ges are by weight unless otherwise indic~ted
E~camples
Examples 1-6, ComParative E~amples A-D, and Control I: Stability of
30 Compositions
Pl epal alion and Stability of Example 1
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A solution cG~ isillg 2% trichloroisocyanuric acid, which is a
halogen donor compound, and 2% isophorone diisocyanate trimer (i.e., the trimer
of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate), which is available as
70% isophorone diisocyanate trimer in butyl acetate under the trade desi~n~tion
"VESTANAT T1~9OE" from Huls Arnerica, Incorporated, Piscataway, NJ, was
prepared as follows. A 20 ml amber colored glass vial was dried at 120~C for 30
mi~nltes~ capped, and cooled. Ethyl acetate was dried over molecular sieves
(Type 4A, Grade 514 available from W.R. Grace and Company, Davison
Ch~m;~~l Division, R~ltimore, MD) to remove residual water. The cap from the
vial was removed, 14.4 grams ofthe dried ethyl acetate were added to the vial,
followed by the additions of 0.3 gram of trichloroisocyanuric acid and 0.3 gram
of the 70% isophorone diisocyanate trimer solution. A~er the addition of the
isophorone diisocyanate trimer solution the vial was again capped.
The composition in the vial was placed in a 60~C oven and
monitored daily for formation of insoluble cyanuric acid and/or a color change,
which was an indication that the trichloroisocyanuric acid had reacted with the
isocyanate. Even after 21 days, the solution of Example l r~ ined colorless
with no appa~en~ plecip;l~te formation.
Preparation and Stability of Example 2
The composition of Example 2 was prepared as described in
Example 1 except meta-tetramethylxylene diisocyanate, which is available under
the trade desi~n~tion "M-TMXDr' from Cytec Industries Incorporated of West
Patterson, NJ, was used in place of the 70% isophorone diisocyanate trimer
solution. The composition in the vial was placed in a 60~C oven and monitored
daily for formation of insoluble cyanuric acid. Even a~er 21 days, the solution
rem~ined colorless with no apparenl precipitate formation.
Plepa~lion and Stability of Example 3
The composition of Example 3 was prepared as described in
Example 1 except isophorone diisocyanate, which is available under the trade
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~ci~n~tion "VESTANAT IPDI" from Huls America, Incorporated of
Piscataway, NJ, was used in place of the 70% isophorone diisocyanate trimer
solution. The composition in the vial was placed in a 60~C oven and monitored
daily for formation of insoluble cyanuric acid. Even after 21 days, the solutionS re~ ed colorless with no app~e.ll precip;late formation.
P~ el~a~lion and Stability of Example 4
The composition of Example 4 was prel)&~ ~;d as deswibed in
Example 1 methylene bis(4-cyclohexyl isocyanate), which is available under the
10 trade desi~nqtion "DESMODUR V~' from Bayer Corporation of Pittsburgh, PA,
was used in place of the 70% isophorone diisocyanate trimer solution. The
composition in the vial was placed in a 60~C oven and monitored daily for
formation of insoluble cyanuric acid. Even after 21 days, the solution r~m~ined
colorless with no appale--l plècipilate formation.
Pl~pa~lion and Stability of ExamPle S
The composition of Example 5 was prepared as described in
Example 1 except an isophorone diisocyanate polyester prepolymer, which is
available under the trade de~i~n~tion "ASN-540 M" from Air Products and
20 Chemicals, Incorporated of Allentown, PA, was used in place of the 70%
isophorone diisocyanate trimer solution. The composition in the vial was placed
in a 60~C oven and monitored daily for formation of insoluble cyanuric acid.
Even after 21 days, the solution ~ ined colorless with no appare..l precipitate
formation.
P~pa.~lion and Stability of Example 6
The composition of Example 6 was prepared as described in
Example 1 except dimer acid diisocyanate, which is available under the trade
de~i~n~tion "DDI-1410" from Henkel Corporation of ~n~ke~, IL, was used in
30 place of the 70% isophorone diisocyanate trimer solution. The composition in the
vial was placed in a 60~C oven and monitored daily for formation of insoluble
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cyanuric acid. Even after 21 days, the solution rçm~ined colorless with no
appalen~ eci~ e formation.
Pl .,pa~ation and Stability of Co~ll?ar~ e Example A
The composition of Co.,.pa.dli~re Example A was pr~,pal~d as
described in Example I except an isophorone diisocyanate poly-tella-,ltL}.ylene
ether glycol prepolymer, which is available under the trade decignation "APC-
504" from Air Products and Chemicals Incorporated of Allentown, PA, was used
in place of the 70% isopho- unc diisocyanate trimer solution. The composition inthe vial was placed in a 60~C oven and monitored daily for formation of insoluble
cyanuric acid. After 6 days, the solution turned brown with the noticeable
formation of a plecipilate. This example demonstrates the instability of an active
hydrogen-cont~inin~ compound capable of reacting with the halogen donor
compound.
Pl ePa- ~lion and Stability of CGnllJal ~ re Example B
The composition of Co--.pa-ali~.re Example B was p~epaled as
described in Example 1 except 4,4'-diphenylmeth~ne diisocyanate, which is
available under the trade de~ign~tion "MONDUR M" from Bayer Corporation of
Pittsburgh, PA, was used in place of the 70% isophorone diisocyanate trimer
solution. The composition in the vial was placed in a 60~C oven and monitored
daily for formation of insoluble cyanuric acid. Atter 6 days, the solution turned
brown with the noticeable formation of a plecipi~ate. This example demonstrates
the instability of a composition pl ~pal cd from an aromatic isocyanate.
P~epalalion and Stability of Colll~)alali~e Example C
The composition of Co-npa- ~ re Example C was p~ epal ed as
described in F.Y~mple I except tris(para-isocyanatophenyl)thiophosph~t~, which is
available under the trade desi~n~tion "DESMODUR RFE" from Bayer
Corporation of Pittsburgh, PA, was used in place of the 70% isophorone
diisocyanate trimer solution. The composition in the vial was placed in a 60~C
, . . .... . .
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oven and monitored daily for formation of insoluble cyanuric acid. After 3 days,the solution turned yel1Ow. This example demonstrates the instability of a
composition p,.,pared from an aromatic isocyanate.
5 ~l ~pa. alion and Stability of Co...?a~ /e Example D
The composition of Col-,pa, ali~/e Example D was prepared as
described in Example 1 except a reaction product of a low molecular weight
polyol and toluene diisocyanate, which is available under the trade desi~r qtion"DESMODUR L-75N' from Bayer Corporation, was used in place of the 70%
10 isophorone diisocyanate trimer solution. The composition in the vial was placed
in a 60~C oven and monitored daily for formation of insoluble cyanuric acid.
After 3 days, the solution turned yellow. This example demonstrates the
instability of a composition prepared from an aromatic isocyanate.
15 P, epa. ation and Stability of Control I
The composition of Control I was a solution contqinin~ 2%
trichloroisocyanuric acid in ethyl acetate, prepared as described in Example 1 but
without the isocyanate. The composition in the vial was placed in a 60~C oven
and monitored daily for formation of insoluble cyanuric acid. Even after 21 days,
20 the solution le.nained clear with no apparent pre~;ip;late forrnation.
Accele.a~ed A~in~ of Example 1 and ComparaLi~/e Example B
Co,..pression molded polyethylene vinyl acetate (EVA) foam
plaques, 203 mm x 203 mm x 15 mm, density of 193.3 K~/m3, which is available
25 under the trade ~lesignqtion "ECLIPSE-5000" from Kim Incorporated, Kyeong
Nam, Korea, were die-cut into test speçim~nS/ 75 mm x 125 mm x 15 mm. The
test specim~n~ were cleaned with a lintless tissue, which is available under thetrade designstion "KIMWIPE" from Kimberly-Clark Corporation, Roswell, GA,
saturated in a solvent mixture of hept~ne:xylene in a weight ratio of 7.0:3.0, and
30 allowed to dry for 15 minutes The primer compositions of Example 1 and of
CO~P~ ~ e F.Y~ 11rIe B were brushed onto the surfaces of individual specimens
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and allowed to dry for 24 hours. The samples were mounted into an accelerated
weathering tester, which is available from Q-Panel Company of Cleveland, OH,
set to alternatively cycle 4 hours for exposure to W and conden~tion for a totalof 140 hours. The ~pcç;...~ .e were removed and the chromaticity of each were
5 measured in L*a~b* coordinates using a portable color analyzer for measuring
reflected-light color, which is available under the trade designqtion "MINOLTA
CHROMAMETER CR-22 1 " from Minolta Camera Company of Osaka, Japan.
The L*a*b* results for a calibration white standard, the primer composition of
Example 1, and the primer composition of Comparative Example B are given in
10 Table l.
Table 1
Test Speci~ n L* a* b*
Calibration Standard White 93.3 0.2 -4.0
Example 1 93 .3 -0.6 -0.5
Co"lpal~ re Example B 87.5 -0.7 18.0
This demonstrates that the primer compositions of the prior art
(colllpalali~e F.Y~mple B conlA~ g an aromatic isocyanate) severely discolor
when exposed to ultraviolet light and accelerated weathering while the
compositions of the present invention do not display significant discoloration.
Examples 7-14 and Control n: Peel Stren~ths of Adhesive on EPDM
Rubber
Pl ~,pal ~lion of Examples 7-12
Examples 7-12 were p~epaled as described for Examples 1-6,
25 respecli~/ely~ in 30 ml dried amber glass vials except that the solvent used was a
~ mixture of dried ethyl acetate and trichloroethylene in a ratio of 3.5:6.5 by
weight.
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Pl epa,ation of Control II
Control II was prepated by CG...~ 0.3 gram of
trichloroisocyanuric acid and 14.7 grams ofthe solvent mixture desc,;bed above
in Examples 7-12 in a 30 ml dried amber glass vial.
Pl ~pa- ~lion of Example 13
A 25% by weight solution of the reaction product of 1,6-
htoY~ne~liol and isophorone diisocyanate was pr~pared by colllbilling 21.0 gramsof the 70% isophorone diisocyanate trimer described in Example 1, 6.0 grams of
1,6-hexanediol, and 81.0 grams ofthe ethyl acetate/trichloroethylene solvent
mixture described above in Examples 7-12 in a dried, 250 ml, narrow-mouthed
amber bottle, which was then capped. The mixture was heated at 70~C for 24
hours. A priming solution of 2% by weight of the above reaction product and
2% by weight of trichloroisocyanuric acid was prepared by colllbil ing 0.3 gram
oftrichloroisocyanuric acid, 1.2 grams ofthe above reaction product, and 13.5
grams of the ethyl acetate/trichloroethylene solvent mixture in a 30 ml dried
amber glass vial.
Plepa,~lion of Example 14
About 98 grams of the primer solution prepared in Example 7 was
modified by the addition of 1.7grams of 3-isocyanopropyl trimethoxysilane
coupling agent, which is available under the trade designation "SILQUEST A-
1310" from OSI Speci~lties, Danbury, CT, and 0.5 gram of gamma-
glycidyloxypropyl trimethoxysilane coupling agent, which is available under the
trade design~tion "SILQUEST A-187" from OSI Specialties, Danbury, CT, and
stored in a dry, amber, narrow-mouthed bottle.
Examples 7-13 and Control II Peel Strengths
Vulcanized EPDM rubber plaques, 127 mm x 127 mm x 2.5 mm,
which are available under the trade desi~n~tion "SHORE A-68" from Shin Ho
Incorporated, Pusan, Korea, were die-cut into 25.4 mm x 127 mm x 2.5 mm test
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spec;.... nc The surface of each test ~pecil,.en was lightly abraded with grade P-
220, fabric-backed abrasive material, which is available under the trade
desi~ation "3M-ITE P-220" from the 3M Company, St. Paul, MN, and cleaned
of debris with corllpl~,ssed air. For each of FY~mrles 7-13 and Control II, the
plh2~-ng solution was brushed onto the abraded surface oftwo test specim~n~ and
allowed to dry for 30 mim~t~ A 20% by weight solution of polycaprolactone
polyurethane adhesive, which is available under the trade decign~tion
"DESMOCOLL 530" from Bayer Corporation, Pittsburgh, in methyl ethyl ketone
was brushed onto the primed surface of each test srec~ n except for a region
about 25 mm from one edge ofthe specimen, and allowed to dry for 30 minutes
The primed and adhesive coated speçimenS were placed in an 80~C oven for 5
minute~S.
For each of Ex~llp!es 7-13 and Control II, the adhesive-coated
surfaces of two spe~i~nçn~ having the same primer were bonded together under
about 10 Kpa pressure to form a peel sample and allowed to stand for 7 days at
room telllpel~ re and humidity. Each of the peel samples was mounted in an
Instron tensile tester, which is available from Instron Corporation, Canton, MA,to deterrnine the 180~ peel ofthe two speç;~e~c adhered together. The 180~ peel
adhesion was measured at a jaw speed of 12.7 cm per minute. The average of
three 180~ peel values for Control II and Ex~lllples 7-13 reported in N/100 mm
were 158, at least 386 (sample elongated to maximum jaw sepalalion)~ 298, 298,
316, 351, 316, 333, ~ ,e.lhfely. These results demonstrate that the primer
solutions of this invention improves the adhesion of polyurethane adhesives to
EPDM rubber over that of just a halogen donor compound.
Peel Sl-el1~ll.s With Humidity Aging of E~ las 7 and 14
The primer solution of Example 14, and for coulpalison, the
primer solution of FY~mrle 7 and Control II were brushed onto abraded EPDM
rubber test spec;~-ens, adhesively bonded together with the polyurelhane
adhesive, and tested as desclilJed above. The average ofthree 180~ peel values
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for Control II and Ex~..rles 7 and 14 reported in N/100 mm were 175, 368, and
386, le~pec~ ely.
The primer solution of Example 14, and for cor.lpal ison, the
primer solution of Example 7 and Control II were brushed onto abraded EPDM
rubber test s~)ec.;.. n.~ and adhesively bonded together with the polyurethaneadhesive as descl ibed above. The bonded spe~imer~ were then allowed to stand
for 7 days at room telllp~. al~re and humidity, and then they were exposed to
70~C and 100% relative humidity for 7 days. Peel values were then determined 7
days after te....~ ;on of the test. The 180~ peel adhesion was measured as
10 described above. The average of three 180~ peel values for Control II and
Examples 7 and 14 reported in N/100 mm were 123, 351, and 579 (sample
elongated to maximum jaw separation), respectively.
These results demonstrate that EPDM rubber primed with
- compositions of this invention and adhesively bonded result in improved peel
15 values even after humidity aging, when compared to the use of a halogen donorcompound alone. In addition, coupling agents that do not co-l.pror. ise solutionstability can be utilized to further improve peel values, particularly a~er humidity
~ aging.
20 E~lamples 15-17: Alternative Halo~en Donor Compounds, Adhesives, and
Substrates
Pl e?a. aliOn and Peel Strength of Example 15
A solution comprising 2% 1,3-dichloro-5,5-di...cll,ylhydantoin, a
halogen donor which is available from Aldrich Chemical Company Incorporated,
25 Milwaukee, WI, and 2% isophorone diisocyanate trimer (i.e., trimer of 3-
isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate), which is available as
70% isophorone diisocyanate trimer in butyl acetate under the trade des ign~tion"VESTANAT T1890E" from Huls America, Incorporated, Piscal~way, NJ, was
prepa.ed as follows. A 30 ml amber colored glass vial was dried at 120~C for 30
30 mimltes7 capped, and cooled. Ethyl acetate was dried over molecular sieves
(Type 4A, Grade 514 available from W.R. Grace and Company, Davison
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Chemical Division, PaltinlQre, MD) to remove residual water. A solvent mixture
of dried ethyl acetate and trichloroethylene in a ratio of 3.5 :6.5 by weight was
prepaled. The cap from the vial was removed, 14.3 grams ofthe ethyl
acetate/trichloroethylene solvent mixture were added to the vial, followed by the
additions of 0.3 gram of 1,3-dichloro-5,5-dimethylhydantoin and 0.4 gram ofthe
70% isophorolle diisocyanate trimer solution.
Test ~peç;...rn.s of abraded EPDM rubber were primed with this
primer solution and Control II solution, adhesively bonded together, and the 180~
peel strenBths detellnil1ed as described above for Exanlplçs 7-13. The average of
three peel values of Examples 15 and Control II in N/100 mm were 360 and 132,
respectively. This example demonstrates that other halogen donor compounds
are effective in priming solutions of this invention.
Example 16: Peel Stren~ths Usin~ Various Substrates
Plaques, 127 mm x 127 mm x 3.1 mm of a typical, vulc~ni~ed
SBR rubber of the following formulation were prepared by Rubber Industries,
Incorporated, Shakopee, MN: 65.0 parts SBR 1502, 35.0 parts per hundred
rubber (phr) SBR 1904, 25.0 phr silica, 23.0 phr carbon black (N-330), 1.8 phr
sulfur, 3.0 phr cun-arone-indene resin (85~C), 3.8 phr zinc oxide, 0.8 phr stearic
acid, 1.1 phr N-cyclohexyl-2-benzothiazolesulfenamide, and 0.8 phr phenolic
~ntioxirl~nt. Die cut test specimens of 25.4 mm x 127 mm x 3.1 mm were
plepdled from the plaques.
Colllples~ion molded polyethylene vinyl acetate (EVA) foam
plaques, 203 mm x 203 mm x 15 mm, density of 193.3 Kg/m3, which is available
under the trade de~:e~ ;on "Eclipse-5000" from Kim Incorporated, Kyeong
Nam, Korea, were die-cut into test sperim~n~ 25.4 mm x 127 mm x 15 mm.
The test spec: ..çn.c were cleaned with a lintless tissue, which is
available under the trade desi~n~tion "KIMWIPE" from Kimberly-Clark
Col ~oralion~ Roswell, GA, saturated in a solvent mixture of heptane:xylene in aweight ratio of 7.0:3.0, and allowed to dry for 15 minutes The primer
compositions of Examples 7 and Control II were brushed onto the speçimçn.~ (but
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were not abraded) and bonded with polyurethane adhesive to prepare test
salllplcs of EVA/EVA, EVA/SBR and SBRISBR in a manner described in
Exan~ s 7-13. The 1~0~ peel strengths were determined as described above for
Examples 7-13. The average ofthree peel values ofthe primer of Control II in
N/100 mm for EVA/EVA, EVA/SBR, and SBR/SBR were 509, 526, and 1754
(sample failure), respectively. The average of three peel values of the primer of
Example 7 in NtlO0 mm for EVA/EVA, EVA/SBR, and SBR/SBR were 710
(sample failure), 1017 (sample failure), and 1754 (sample failure), respectively.
This example demonstrates that a primer solution of this invention substantiallyimproves the peel values of a wide variety of adhesively bonded subsl~ates
compared to the control solution containing only a halogen donor compound and
solvent.
Example 17: Peel Strengths Usin~ Various Adhesives
Test ~)eci.. ens of SBR were prepared and cleaned as described in
Example 16. The primer of Example 1 was brushed on each and allowed to dry
for 30 minlltec A thin layer of a premixed, two-part polyurethane adhesive,
which is available under the trade design~tion "SCOTCH-WELD 3549 B/A"
from the 3M Company, was applied to the primed sides of two specimens as
previously described. The adhesive coated sides of the specimens were bonded
together using hand pressure from a light rubber-covered roller. In a similar
manner, primed test specimens were bonded with a two-part epoxy adhesive,
which is available under the trade dçcign~tion "SCOTCH-WELD 2216 B/A"
from the 3M Company.
A solvent-based neoplene contact adhesive, which is available
under the trade designation "FASTBOND 5" from the 3M Company was applied
to the primed sides of two specimens, al~owed to dry until tack-free, then bonded
together using hand pressure from a light rubber-covered roller.
A 50% polymer solids polyurethane dispersion in water, which is
available under the trade dç~ien~tion "DISPERCOLL U-54" from Bayer Corp.,
Pittsburgh, PA, was applied to the primed sides of two specimens and allowed to
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dry for 40 minlltes The spec.,nells were heated at 80~C for 5 minl~tes and
bonded together under 10 KPa pressure.
All bonded specimPn~ were allowed to condition for 7 days prior
to determining 180~ peel values. The average of three peel values of the primer
of Example 1 in N/100 mm for the 2-part polyurethane, the 2-part epoxy, the
neoprene contact adhesive, and the polyurethane dispersion were 1491, 1754
(sample elongated to m~Yimllm jaw separation), 351, and 965, respectively. This
example illustrates that adhesives other than solvent-based polyureth~ne~, result
in high peel values to substrates primed with a composition of this invention.
Example 18: P, ~pa, ~lion of Traction Enhanced Shoe Sole
A vulc~ni7ed rubber shoe sole made from a blend of natural
rubber, styrene-butadiene rubber, and inorganic fillers was obtained from
LaCrosse Footwear Inc., LaCrosse, WI (LaCrosse Number 200 black rubber
compound). The sole was abraded using a wire brush and rinsed with ethanol to
remove debris. The shoe sole was primed with one coat of the primer solution
detailed in Example 14 at a coating weight of 5 milligrams/square centimeter.
The sole was allowed to dry for 30 minutes. A urethane adhesive made from
86.7 parts of a toluene diisocyanate polyether prepolymer, which is available
under the trade design~tion "ADIPRENE L- 167" from Uniroyal Adhesives and
Sealants Co., Mishawaka, IN, and 13.3 parts of a catalyst, which is available
under the trade designation "ETHACURE 300" from Ethyl Corp., Baton Rouge,
LA, was brushed on the primed shoe sole in the areas where traction needed to beenhqrlced (as shown in Figure 3A) at a coating weight of 40 milligrams/square
centilnp~t~r. Silicon carbide mineral (ANSI grade 20 abrasive grit, typically about
980 micrometers in particle size) was drop coated on the surface and the excess
removed by gravity. The coating weight of the mineral was appru~in,alely 200
milligrams/square ce~ ler The traction coating was allowed to cure for 24
hours. This process yielded an excellent traction surface suitable for ruWer soled
shoes or boots on icy, oily, or greasy surfaces with eYcellen~ durability. Without
the primer, no adhesion between the urethane adhesive and the rubber occurred.
.
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Various modifications and alterations of this invention will become
appa~e.lL to those skilled in the art without depa.ling from the scope and spirit of
this invention, and it should be understood that this invention is not to be unduly
limited to the illustrative embotlim~nts set forth herein.
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