CA2266021A1

CA2266021A1 - Primer composition and bonding of organic polymeric substrates

Info

Publication number: CA2266021A1
Application number: CA002266021A
Authority: CA
Inventors: James D. Groves
Original assignee: Individual
Current assignee: 3M Co
Priority date: 1996-10-08
Filing date: 1997-02-13
Publication date: 1998-04-16
Also published as: EP0931116A1; WO1998015601A1; BR9712211A; JP2000514129A; KR20000048920A; AU2274097A; CN1232485A

Abstract

The present invention provides a primer composition comprising a halogen donor compound, an aliphatic isocyanate-containing compound, and an organic solvent.

Description

CA 02266021 lsss-03-o~

wo 98115601 PcTruss7to2379 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 CA 0226602l l999-03-0~

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 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., CA 02266021 1999-03-o~

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 CA 02266021 1999-03-o~

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 CA 02266021 1999-03-0~

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 CA 02266021 1999-03-o~

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, CA 0226602l l999-03-o~

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 CA 0226602l l999-03-o~

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, CA 02266021 1999-03-o~

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 .. ~ , . .. . . . . . .

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 ,~ ."~ . ~

CA 02266021 1999-03-0~

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 CA 02266021 1999-03-o~

WO 98tlS601 PCT/US97102379 ~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 CA 02266021 1999-03-0~

WO 98tl5601 PCT/US97/02379 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

, . . .... . .

CA 02266021 1999-03-0~

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 CA 02266021 1999-03-0~

WO 98/lS601 PCT/US97/02379 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.

.. . .... . . .. . .

CA 02266021 1999-03-o~

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 CA 02266021 1999-03-0~

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 CA 02266021 1999-03-0~

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 CA 02266021 1999-03-o~

WO 98/lS601 PCT/US97/02379 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 . .

CA 02266021 1999-03-0~

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 CA 02266021 1999-03-o~

WO 98/lS601 PCT/US97/02379 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.

.

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.

Claims

What Is Claimed Is:

1. A coatable primer composition comprising a halogen donor compound, an aliphatic isocyanate-containing compound, and an organic solvent coheren the composition is stable at 60°C for at least about 14 days when stored in a moisture-free environment.

2. The primer composition according to claim 1 wherein the aliphatic isocyanate-containing compound is substantially nonreactive with the halogen donor compound.

3. The primer composition according to claim 1 wherein the organic solvent is substantially nonreactive with the halogen donor compound and the aliphatic isocyanate-containing compound.

4. The primer composition according to claim 1 which comprise, by weight, at least about 75% of the organic solvent, about 0.5% to about 10% of the halogen donor compound, and about 1% to about 15% of the aliphatic isocyanate-containing compound, based on the total weight of the primer composition.

5. The primer composition according to claim 1 wherein the aliphatic isocyanate-containing compound is a saturated aliphatic isocyanate.

6. The primer composition according to claim 1 wherein the aliphatic isocyanate is selected from the group consisting of 1,6-hexamethylene diisocyanate, methylene bis(4-cyclohexyl isocyanate), trimethyl hexamethylene diisocyanate, isophorone diisocyanate, y-isocyanatopropyl trimethoxysilane, dimer acid isocyanate, xylene diisocyanate, benzene- 1,3-bis( 1-isocyanato- 1 -methylethyl), benzene- 1 ,4-bis( 1 -isocyanato- l -methylethyl), and oligomers and combinations thereof.

7. The primer composition according to claim 1 wherein the halogen donor compound is selected from the group consisting of a saturated N-halogenated heterocyclic amide, an N,N-dihalogenated aromatic sulfonamide, an N-monohalogenated aromatic sulfonamide, and combinations thereof.

8. The primer composition according to claim 1 wherein the organic solvent is selected from the group consisting of an aliphatic ester, an aliphatic hydrocarbon, and an halogenated aromatic or aliphatic hydrocarbon.

9. The primer composition according to claim 1 further comprising a silane coupling agent.

10. The primer composition according to claim 1 further comprising an epoxy resin.

11. The primer composition of claim 1 comprising a solution of: a halogen donor compound selected from the group consisting of 1,3-dichloro-5, 5-dimethylhydantoin, tetrachloroglycoluril, trichloroisocyanuric acid, and combinations thereof; an aliphatic isocyanate-containing compound selected from the group consisting of 1,6-hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), trimethyl hexamethylene diisocyanate, isophorone diisocyanate, y-isocyanatopropyl trimethoxysilane, and oligomers and combinations thereof; and an organic solvent.

12. A coatable composition preparable by combining components comprising a halogen donor compound, an aliphatic isocyanate-containing compound, and an organic solvent.

13 A method for adhering two substrates together, said method comprising the steps of:
(a) applying the primer composition of claim 12 to a surface of a first organic polymeric substrate to provide a primed surface;
(b) applying an adhesive to the primed surface or to a surface of a second substrate; and (c) positioning the surfaces of the first and second substrates together to form a bond.

14. The method according to claim 13 further comprising a step of applying the primer composition of claim 1 to the surface of the second organic polymeric substrate to provide a primed surface.

15. The method according to claim 13 wherein the first organic polymeric substrate is made of a material selected from the group consisting of ethylene propylene diene monomer, polyethylene, vinyl acetate foam, polyurethane rubber, synthetic leather, natural leather, plasticized polyvinyl chloride, polyamide, polyester, polybutadiene, polychloroprene, polyisoprene, natural rubber, isobutene-isoprene copolymer, styrene-butadiene copolymer, styrene-butadiene styrene block copolymers, butyl and bromobutyl rubber, polyethylene vinyl acetate foams, and polyurethane rubber, and foams.

16. The method according to claim 13 further comprising the step of roughening the surfaces before applying the primer composition thereto.

17. An article made according to the method of claim 13.

18. The article of claim 17 which is an article of footwear.

19. A method of forming a traction coating on an article comprising an organic polymeric substrate, the method comprising:
(a) applying the primer composition of claim 12 to a surface of the organic polymeric substrate to provide a primed surface; and (b) applying a traction coating comprising a plurality of hard, inorganic particles to the primed surface.

20. The method according to claim 19 wherein the step of applying a traction coating comprises:
(a) applying an adhesive to the primed surface to form an adhesive-coated primed surface; and (b) applying a plurality of hard, inorganic particles to the adhesive-coated primed surface.

21. The method according to claim 19 wherein the step of applying a traction coating comprises applying a sheet material having a plurality of hard,inorganic particles adhered thereto.

22. The method according to claim 19 wherein the article is an article of footwear.

23. The method according to claim 22 wherein the article of footwear is a shoe.

24. The method according to claim 23 wherein the organic polymeric substrate is an elastomeric sole on the shoe.

25. The method according to claim 24 wherein the shoe is an athletic shoe.

26. The method according to claim 20 wherein the article of footwear is a boot.

27. An article comprising an organic polymeric substrate having at least one surface on which is coated a traction coating the traction coating preparable by:
(a) applying the primer composition of claim 12 to a surface of the organic polymeric substrate to provide a primed surface; and (b) applying a traction coating comprising a plurality of hard, inorganic particles to the primed surface.

28. The article according to claim 27 wherein the step of applying a traction coating comprises:
(a) applying an adhesive to the primed surface to form an adhesive-coated primed surface; and (b) applying a plurality of hard, inorganic particles to the adhesive-coated primed surface.

29. The article according to claim 27 wherein the step of applying a traction coating comprises applying a sheet material having a plurality of hard,inorganic particles adhered thereto.

30. The article according to claim 27 which is an article of footwear.

31. The article according to claim 30 which is a shoe.

32. The article according to claim 31 wherein the organic polymeric substrate is an elastomeric sole on the shoe.

33. The article according to claim 32 which is an athletic shoe.

34. The article according to claim 30 which is a boot.

[35. A coatable primer composition comprising a halogen donor compound, an aliphatic isocyanate-containing compound, and an organic solvent, wherein the halogen donor compound, aliphatic isocyanate-containing compound, and organic solvent are substantially unreactive with each other.]

-31a-