Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
  • C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
  • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined

Definitions

• the present invention relates to a surface treatment 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.
• 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
• EPDM ethylene-propylene-diene terpolymer
• EPR ethylene-propylene rubber
• EPDM ethylene-propylene-diene terpolymer
• EPR ethylene-propylene rubber
• compositions of styrene-ethylene/butylene-styrene block copolymers and acrylic polymers in a solvent mixture for priming polymers of low surface energy are known.
• compositions improve the bonding of pressure sensitive and structural adhesives to polymers of low surface energy.
• rubbers e.g., copolymer of styrene and butadiene (SBR) used for shoe soling, and other solid high polymers
• adhesives e.g., solvent-based polyurethane and polychloroprenes
• chlorination of the surface with solutions of halogen donors such as trichloroisocyanuric acid and N,N- dichlorobenzene sulfonamide.
• halogen donors such as trichloroisocyanuric acid and N,N- dichlorobenzene sulfonamide.
• solutions containing only halogen donors are effective only on substrates containing a high level of ethylenic unsaturation.
• adhesive compositions such as polyurethane adhesives, containing a halogen donor, have limited stability.
• Primer compositions and adhesive compositions that display improved adhesion to organic 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 attached 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.
• the primed substrate if exposed to UV radiation, 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.
• compositions whether primer compositions or adhesive compositions, require mechanical roughening or abrasion of the surface of the substrate prior to or during application of the composition.
• 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 primer.
• primer compositions and application procedures which will effectively prime a variety of different substrates, especially elastomers, for bonding.
• primer compositions should possess a long shelf-life, and after application, be stable to UV radiation and high temperature and humidity.
• the present invention provides a primer composition comprising a halogen donor compound, an aliphatic isocyanate-containing compound, and an organic solvent.
• the primer composition comprises a solution of: a halogen donor compound selected from the group consisting of l,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, ⁇ -isocyanatopropyl trimethoxysilane, and oligomers and combinations thereof; and an organic solvent.
• the present invention also provides a method for adhering two substrates together and the article prepared 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 is preparable by combining components comprising a halogen donor compound, an aliphatic isocyanate-containing compound, and an organic solvent; applying an adhesive 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 forming a traction coating on an article comprising 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 combining components comprising a halogen donor compound, an aliphatic isocyanate-containing compound, and an organic solvent; and applying a traction coating comprising a plurality of hard, inorganic particles to the primed surface.
• the step of applying a traction coating comprises: 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- coated primed surface.
• the step of applying a traction coating comprises applying a sheet material having a plurality of hard, inorganic particles adhered thereto.
• an article comprising an organic polymeric substrate having at least one surface on which is coated a traction coating.
• the traction coating is preparable by: applying a primer composition to a surface of the organic polymeric substrate to provide a primed surface; wherein the primer composition is preparable by combining components comprising a halogen donor compound, an aliphatic isocyanate-containing compound, and an organic solvent; and applying a traction coating comprising a plurality of hard, inorganic particles to the primed surface.
• the article is preferably an article of footwear, such as a shoe having an elastomeric sole, particularly an athletic shoe, or a boot.
• 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 includes materials that are capable of retracting quickly to approximately their original length after being stretched to at least twice their original length, such as thermosetting polymers like natural and synthetic rubbers. This also includes materials such as uncrosslinked polyolefins that are thermoplastic, which may yield upon stretching.
• FIGS. 1 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. 3 A is a traction coating on the exposed surface of the sole of the boot of FIG. 3.
• the present invention provides primer compositions of a halogen donor compound and an aliphatic isocyanate-containing compound in an organic solvent.
• these components are substantially unreactive (i.e., 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 preferred compositions.
• the primer compositions are stable at elevated temperatures up to about 60°C for at least about 14 days, when stored in a moisture-free environment. More preferably, they are stable at room temperature (25-30°C) for at least about 1 month, and most preferably at room temperature for at least about 6 months, when stored in a moisture-free environment.
• stable refers to a composition that does not decompose, react, precipitate, or significantly discolor during the specified time when stored in a moisture-free environment. That is, the composition is substantially unchanged after a period of time when stored in a moisture-free environment.
• a “moisture-free environment” is an environment from which substantially all atmospheric moisture has been removed. Typically, there is less than about 0.01% water in a “moisture-free environment,” 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 adhesion of an adhesive, an ink, or other coating. They also preferably 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 substrates having low surface energies, thereby rendering them adherent to an adhesive, an ink, or other coating. This allows for improved adhesion to other organic polymeric substrates or other nonpolymeric substrates, such as glass, metal, ceramic, and the like, using a variety of adhesives.
• organic polymeric substrate e.g., substrates made of organic high polymers, which can be synthetic or natural
• Such primers are typically effective on a wide variety of organic polymeric substrates having low surface energies, thereby rendering them adherent to an adhesive, an ink, or other coating. This allows for improved adhesion to other organic polymeric substrates
• primers are generally particularly effective on organic polymeric substrates containing some degree of ethylenic unsaturation.
• adhesion of adhesives, inks, coatings, and the like, to substrates, particularly elastomers containing ethylenic unsaturation such as polybutadiene, polychloroprene, polyisoprene, natural rubber, isobutene-isoprene copolymer, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymers, and the like, can be improved using primers according to the present invention.
• adhesion of such materials to substrates that contain low levels of, or no ethylenic unsaturation can also be improved by the primer compositions of the present invention.
• 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 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 requirement.
• 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 this is not a necessary requirement for the present invention.
• Classes of such compounds include, but are not limited to, N-monohalogenated aromatic sulfonamides, N,N-dihalogenated aromatic sulfonamides, wherein sulfonamide nitrogen is bonded to two atoms of chlorine, bromine, or iodine and the sulfonyl sulfur is bonded directly to the aromatic nucleus; 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 which also reside on the heterocyclic ring.
• Examples of such compounds include l,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 commercial sources. Chlorine donors such as trichloroisocyanuric acid (which is available, for example, under the trade designation "ACL 90 PLUS" from Occidental Chemical Corporation of Dallas, TX) are preferred since they are more economical and available than are bromine or iodine donors.
• Aliphatic isocyanate-containing compounds useful in making primers according to the present invention are those in which the isocyanate (-NCO) groups are directly attached to aliphatic carbons.
• the aliphatic isocyanate-containing compounds may include aromatic moieties.
• the aliphatic isocyanate-containing compounds do not contain any aromatic moieties.
• the aliphatic isocyanate-containing compounds may include unsaturation, although saturated materials are typically preferred.
• preferred aliphatic isocyanate-containing compounds are substantially nonreactive with the halogen donor compounds.
• the isocyanate-containing compound can be in the form of monomers, oligomers, or polymers, as long as there are available (i.e., unreacted) isocyanate groups.
• aliphatic isocyanate-containing compounds include monomers such as 1,6-hexamethylene diisocyanate, methylene bis(4- cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, isophorone diisocyanate, ⁇ -isocyanatopropyl trimethoxysilane, dimer acid diisocyanate, xylene diisocyanate, benzene-l,3-bis(l-isocyanato-l-methylethyl), and benzene- l,4-bis(l-isocyanato-l-methylethyl), oligomers of aliphatic isocyanate monomers, and polymers or prepolymers (i.e., reaction products) of aliphatic iso
• isophorone diisocyanate ⁇ -isocyanatopropyl trimethoxysilane, and oligomers and combinations thereof are preferred.
• Oligomers of aliphatic isocyanates such as the trimer of isophorone diisocyanate (which is available, for example, under the trade designation "VESTANAT Tl 890E” from Hulls America, Inc. of Piscataway, NJ), are particularly preferred because they are less volatile and therefore less toxic than monomeric isocyanates.
• reaction products of aliphatic isocyanates with active hydrogen-containing compounds are suitable if they contain unreacted isocyanate groups.
• Preferred such materials are substantially unreactive with the halogen donor compound and the organic solvent. Any of the above-listed aliphatic isocyanates can be used to make such materials.
• active hydrogen- containing compounds include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylol propane, pentaerythritol, and 1,4-cyclohexane dimethanol. Polyester and polycarbonate polyols are also useful.
• reaction products of aliphatic isocyanates with active hydrogen-containing compounds that contain ethylenic unsaturation or other functional groups that react with the halogen donor compounds may be useful, but are not preferred.
• prepolymers of polytetramethylene oxide polyether, polypropylene oxide polyether, or polyethylene oxide polyether polyols with an aliphatic isocyanate, such as isophorone diisocyanate are typically not preferred 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.
• organic solvents may also be used, including, for example, aliphatic esters, aliphatic hydrocarbons, and halogenated aromatic or aliphatic hydrocarbons.
• the organic solvent is an aliphatic solvent (e.g., aliphatic hydrocarbons, aliphatic esters, and halogenated aliphatic hydrocarbons). Examples include, but are not limited to, ethyl acetate, butyl acetate, trichloroethylene, cyclohexane, heptane, and benzotrifluoride. Mixtures of such solvents can be used.
• the solvent is substantially nonreactive with the halogen donor compounds and the aliphatic isocyanate-containing compounds.
• Solvents such as ketones are not preferred since they react with the halogen donor to form chlorinated by-products, thereby decreasing the shelf stability and efficacy of the primer solutions.
• a preferred 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 aforementioned components in amounts sufficient for providing improved adhesion of an ink, an adhesive, and/or other coating to high organic polymeric substrates.
• the halogen donor compound is present in an amount of about 0.5% to 10% by weight, and more preferably about 1.5% to about 5% by weight, based on the total weight of the primer composition.
• the aliphatic isocyanate-containing compound is present in an amount of about 1% to about 15% by weight, and more preferably about 1% to about 10% by weight, based on the total weight of the primer composition.
• the organic solvent is 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.
• additives include, 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.
• 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 necessary requirement. They may be applied to a substrate using a variety of techniques including dipping, spraying, brushing, rotogravure coating, as well as Meir rod and knife coating.
• the primer is typically dried before the adhesive, ink, or other coating material is applied.
• a particularly preferred method involves mechanically abrading the surface of the substrate, brushing on the primer, and allowing it to dry, prior to adhesive bonding.
• the adhesives, inks, and other coating materials that demonstrate improved adhesion to primed organic high polymers can be thermosetting, thermoplastic, and hybrid materials.
• hybrid refers to combinations of two or more different types of materials (e.g., adhesives) as well as two or more polymers suitable for forming adhesives, inks, and other coating materials.
• the material coated on the primed organic high polymers are adhesives.
• Thermosetting adhesives are generally formed by addition polymerization.
• thermosetting adhesives examples include polysulfides, silicones, polyesters, polyurethanes, epoxies, anaerobic and aerobic acrylics, radiation curable polymers and vulcanizing 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).
• Thermoplastic adhesives are soluble and fusible materials.
• 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.
• Thermoplastic adhesives may be in the form of emulsions, solutions, or solids.
• the adhesive may include components that react with the aliphatic isocyanate- containing compound.
• the adhesive may include components that react with the aliphatic isocyanate- containing compound.
• polyurethane-based adhesives and epoxy- based adhesives may react with the aliphatic isocyanate-containing compounds.
• a catalyst may be added to the adhesive, although this is not required.
• Such catalysts include dialkyltin dicarboxylates, mixtures of dialkyltin dicarboxylates and trialkyltin oxides, metal acetyl acetonates, metal carboxylates, mixtures of metal acetyl acetonates and tertiary amines, and the like.
• Primer compositions according to the present invention may be used in the manufacture of any of a wide variety of articles, such as footwear, particularly footwear with elastomeric components such as athletic shoes, as well as tennis rackets, and roofing membranes. They are also suitable for bonding two organic polymeric substrates together, or one such substrate to a variety of other substrates such as those containing metal, glass, ceramic, wood, and the like. Primer compositions according to the present invention are particularly useful in the manufacture of footwear with elastomeric soles, such as athletic shoes. Referring 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.
• the primer composition is applied by spraying, brushing, or wiping to the attachment side of a rubber sole 26.
• 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. If the 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 different adhesive and any solvent allowed to evaporate.
• the sole 26, and optional midsoles 24 and 25, and upper 22 are bonded in a conventional manner, typically with heat reactivation of the adhesive coatings.
• 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.
• 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 coating.
• an adhesive-coated sheet e.g., paper or polymeric sheet material
• the adhesive used in the preparation of a traction coating can be any of the adhesives described above or other binders typically used in the abrasives industry.
• a boot 30 is shown having a boot body 32 secured to a sole 34.
• the exposed surface 36 of the sole 34 is coated with a primer composition, a layer of adhesive, and a plurality of hard, inorganic particles to form a traction coating 36A and 36B ( Figure 3 A).
• This traction coating can be on the entire exposed surface of the sole 34 or it can be on selected 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 3 A.
• Hard, inorganic particles typically have irregular surfaces and sufficient hardness to provide improved gripping characteristics as described in U.S. Patent No. 5,038,500 (Nicholson), the disclosure of which is incorporated herein by reference.
• the particles are made of an inorganic compound having 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 particles for use in the traction coating include fused aluminum oxide, heat treated aluminum oxide, white fused aluminum oxide, black silicon carbide, green silicon carbide, titanium diboride, silica, silicates, boron carbide, tungsten carbide, titanium carbide, silicon nitride, ceria, zirconia, titania, diamond, cubic boron nitride, garnet, fused alumina zirconia, sol gel derived alumina particles and the like. Examples of sol gel derived alumina particles can be found in U.S. Pat. Nos.
• the diamond and cubic boron nitride hard, inorganic particles may be monocrystalline or polycrystalline.
• the preferred inorganic particles are metal oxides (e.g. alumina), metal carbides (including silicon carbide), metal borides and metal nitrides. In one preferred mode, silicon carbide is preferred due to the spectral appearance of the 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 of the hard, inorganic particles can range from about 0.2 mm to about 5 mm, preferably 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 of the hard, inorganic particle is typically measured by the longest dimension of the hard, inorganic particle. It is generally preferred that the traction coating contain at least 50% by weight of the hard, inorganic particles that have a particle size greater than about 50 micrometers and more preferably greater than about 100 micrometers.
• the traction coated hard, inorganic particles having a particle size less than about 7500 micrometers, and more preferably less than about 6000 micrometers.
• 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 instances, 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 instances, it is preferred 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.
• diluent particles coated along side of the hard, inorganic particles.
• these diluent particles may accomplish one of the following goals: (1) reduce the cost of the traction coating; (2) reduce the weight of the traction coating; (3) improve traction; or (4) increase cushion.
• diluent particles examples include metal carbonates (such as calcium carbonate (chalk, calcite, marl, travertine, marble and limestone), calcium magnesium carbonate, sodium carbonate, magnesium carbonate), metal sulfates (such as calcium sulfate, barium sulfate, sodium sulfate, aluminum sodium sulfate, aluminum sulfate), gypsum, aluminum trihydrate, graphite, metal oxides (such as calcium oxide (lime)) and metal sulfites (such as calcium sulfite), metal particles (tin, lead, copper and the like) and the like.
• the diluent particles may have essentially the same particle size as the hard, inorganic particles or the two particle size distributions may be different.
• the traction coating may also contain a mixture of two or more different hard, inorganic particles.
• the traction coating may comprise a uniform mixture of hard, inorganic particles and diluent particles.
• 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 paniculate of a plurality of individual hard, 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 and the like.
• inorganic binders examples include vitreous binders, silicate binders, frit binders, metal binders and the like. Examples of how to make such agglomerates containing 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 (Holmes et al.). These agglomerates of containing hard, inorganic agglomerates should have a particle size less than about 5 mm, typically less than about 2.5 mm and preferably less than about 1.5 mm.
• Example 1 Preparation and Stability of Example 1 A solution comprising 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 designation "VESTANAT T1890E" from Huls America, Incorporated, Piscataway, NJ, was prepared as follows. A 20 ml amber colored glass vial was dried at 120°C for 30 minutes, capped, and cooled.
• isophorone diisocyanate trimer i.e., the trimer of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate
• Ethyl acetate was dried over molecular sieves (Type 4 A, Grade 514 available from W.R. Grace and Company, Davison Chemical Division, Baltimore, MD) to remove residual water.
• the cap from the vial was removed, 14.4 grams of the 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. After the addition of the isophorone diisocyanate trimer solution the vial was again capped.
• Example 1 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 1 remained colorless with no apparent precipitate formation.
• Example 2 The composition of Example 2 was prepared as described in Example 1 except meta-tetramethylxylene diisocyanate, which is available under the trade designation "M-TMXDI” 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 after 21 days, the solution remained colorless with no apparent precipitate formation.
• Example 3 Preparation 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 designation "VESTANAT IPDI" from H ⁇ ls 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 solution remained colorless with no apparent precipitate formation.
• Example 4 was prepared as described in
• Example 1 methylene bis(4-cyclohexyl isocyanate), which is available under the trade designation "DESMODUR W” 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 remained colorless with no apparent precipitate formation.
• Example 5 The composition of Example 5 was prepared as described in
• Example 1 except an isophorone diisocyanate polyester prepolymer, which is available under the trade designation "ASN-540 M” from Air Products and 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.
• Example 6 The composition of Example 6 was prepared as described in
• Example 1 except dimer acid diisocyanate, which is available under the trade designation "DDI-1410" from Henkel Corporation of Kankakee, LL, 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 remained colorless with no apparent precipitate formation.
• Comparative Example A The composition of Comparative Example A was prepared as described in Example 1 except an isophorone diisocyanate poly-tetramethylene ether glycol prepolymer, which is available under the trade designation "APC- 504" from Air Products and 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. After 6 days, the solution turned brown with the noticeable formation of a precipitate. This example demonstrates the instability of an active hydrogen-containing compound capable of reacting with the halogen donor compound.
• Comparative Example B The composition of Comparative Example B was prepared as described in Example 1 except 4,4'-diphenylmethane diisocyanate, which is available under the trade designation "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. After 6 days, the solution turned brown with the noticeable formation of a precipitate. This example demonstrates the instability of a composition prepared from an aromatic isocyanate.
• Comparative Example C The composition of Comparative Example C was prepared as described in Example 1 except tris(para-isocyanatophenyl)thiophosphate, which is available under the trade designation "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 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.
• Comparative Example D The composition of Comparative 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 designation "DESMODUR L-75N" from Bayer Corporation, 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. After 3 days, the solution turned yellow. This example demonstrates the instability of a composition prepared from an aromatic isocyanate.
• Control I was a solution containing 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, the solution remained clear with no apparent precipitate formation.
• Compression molded polyethylene vinyl acetate (EVA) foam plaques 203 mm x 203 mm x 15 mm, density of 193.3 Kg/m 3 , which is available under the trade designation "ECLLPSE-5000" from Kim Incorporated, Kyeong Nam, Korea, were die-cut into test specimens, 75 mm x 125 mm x 15 mm.
• the test specimens were cleaned with a lintless tissue, which is available under the trade designation "KTMWIPE” from Kimberly-Clark Corporation, Roswell, GA, saturated in a solvent mixture of heptane:xylene in a weight ratio of 7.0:3.0, and allowed to dry for 15 minutes.
• the primer compositions of Example 1 and of Comparative Example B were brushed onto the surfaces of individual specimens 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 UV and condensation for a total of 140 hours.
• the specimens were removed and the chromaticity of each were measured in L*a*b* coordinates using a portable color analyzer for measuring reflected-light color, which is available under the trade designation "MINOLTA CHROMAMETER CR-221" 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 Table 1.
• Examples 7-12 were prepared as described for Examples 1-6, respectively, 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.
• Control II was prepared by combining 0.3 gram of trichloroisocyanuric acid and 14.7 grams of the solvent mixture described above in Examples 7-12 in a 30 ml dried amber glass vial.
• a 25% by weight solution of the reaction product of 1,6- hexanediol and isophorone diisocyanate was prepared by combining 21.0 grams of the 70% isophorone diisocyanate trimer described in Example 1, 6.0 grams of 1,6-hexanediol, and 81.0 grams of the 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 combining 0.3 gram of trichloroisocyanuric acid, 1.2 grams of the above reaction product, and 13.5 grams of the ethyl acetate/trichloroethylene solvent mixture in a 30 ml dried amber glass vial.
• 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 Specialties, Danbury, CT, and 0.5 gram of gamma- glycidyloxypropyl trimethoxysilane coupling agent, which is available under the trade designation "SILQUEST A-l 87” from OSI Specialties, Danbury, CT, and stored in a dry, amber, narrow-mouthed bottle.
• 3-isocyanopropyl trimethoxysilane coupling agent which is available under the trade designation "SILQUEST A- 1310” from OSI Specialties, Danbury, CT
• gamma- glycidyloxypropyl trimethoxysilane coupling agent which is available under the trade designation "SILQUEST A-l 87" from OSI Specialties, Danbury, CT, and stored in a
• Vulcanized EPDM rubber plaques 127 mm x 127 mm x 2.5 mm, which are available under the trade designation "SHORE A-68" from Shin Ho Incorporated, Pusan, Korea, were die-cut into 25.4 mm x 127 mm x 2.5 mm test specimens.
• the surface of each test specimen was lightly abraded with grade P- 220, fabric-backed abrasive material, which is available under the trade designation "3M-ITE P-220" from the 3M Company, St. Paul, MN, and cleaned of debris with compressed air.
• the priming solution was brushed onto the abraded surface of two test specimens and allowed to dry for 30 minutes.
• a 20% by weight solution of polycaprolactone polyurethane adhesive which is available under the trade designation "DESMOCOLL 530" from Bayer Corporation, Pittsburgh, in methyl ethyl ketone was brushed onto the primed surface of each test specimen, except for a region about 25 mm from one edge of the specimen, and allowed to dry for 30 minutes.
• the primed and adhesive coated specimens were placed in an 80°C oven for 5 minutes.
• Example 14 The primer solution of Example 14, and for comparison, the primer solution of Example 7 and Control II were brushed onto abraded EPDM rubber test specimens, adhesively bonded together with the polyurethane adhesive, and tested as described above.
• the primer solution of Example 14, and for comparison, the primer solution of Example 7 and Control II were brushed onto abraded EPDM rubber test specimens and adhesively bonded together with the polyurethane adhesive as described above.
• the bonded specimens were then allowed to stand for 7 days at room temperature 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 termination of the test.
• the 180° peel adhesion was measured as 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.
• Ethyl acetate was dried over molecular sieves (Type 4 A, Grade 514 available from W.R. Grace and Company, Davison Chemical Division, Baltimore, 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 prepared.
• the cap from the vial was removed, 14.3 grams of the ethyl acetate/trichloroethylene solvent mixture were added to the vial, followed by the additions of 0.3 gram of l,3-dichloro-5,5-dimethylhydantoin and 0.4 gram of the 70% isophorone diisocyanate trimer solution.
• Example 16 Peel Strengths Using Various Substrates Plaques, 127 mm x 127 mm x 3.1 mm of a typical, vulcanized
• 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 cumarone-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 antioxidant. Die cut test specimens of 25.4 mm x 127 mm x 3.1 mm were prepared from the plaques.
• Compression molded polyethylene vinyl acetate (EVA) foam plaques 203 mm x 203 mm x 15 mm, density of 193.3 Kg/m 3 , which is available under the trade designation "Eclipse-5000" from Kim Incorporated, Kyeong Nam, Korea, were die-cut into test specimens, 25.4 mm x 127 mm x 15 mm.
• EVA Compression molded polyethylene vinyl acetate
• test specimens were cleaned with a lintless tissue, which is available under the trade designation "KIMWTPE” from Kimberly-Clark Corporation, Roswell, GA, saturated in a solvent mixture of heptane:xylene in a weight 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 specimens (but were not abraded) and bonded with polyurethane adhesive to prepare test samples of EVA/EVA, EVA/SBR and SBR/SBR in a manner described in Examples 7-13.
• the 180° peel strengths were determined as described above for Examples 7-13.
• the average of three peel values of the 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 N/100 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 substantially improves the peel values of a wide variety of adhesively bonded substrates compared to the control solution containing only a halogen donor compound and solvent.
• Example 17 Peel Strengths Using Various Adhesives Test specimens 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 minutes. A thin layer of a premixed, two-part polyurethane adhesive, which is available under the trade designation "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 designation "SCOTCH-WELD 2216 B/A" from the 3M Company.
• a solvent-based neoprene contact adhesive which is available under the trade designation "FASTBOND 5" from the 3M Company was applied to the primed sides of two specimens, allowed 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 designation "DISPERCOLL U-54" from Bayer Corp., Pittsburgh, PA, was applied to the primed sides of two specimens and allowed to dry for 40 minutes. The specimens were heated at 80°C for 5 minutes and bonded together under 10 KPa pressure.
• a vulcanized 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.
• ADLPRENE L-167 from Uniroyal Adhesives and Sealants Co., Mishawaka, IN
• ETHACURE 300 from Ethyl Corp., Baton Rouge, LA
• the coating weight of the mineral was approximately 200 milligrams/square centimeter
• the traction coating was allowed to cure for 24 hours. This process yielded an excellent traction surface suitable for rubber soled shoes or boots on icy, oily, or greasy surfaces with excellent durability. Without the primer, no adhesion between the urethane adhesive and the rubber occurred.

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• 1997
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