WO1994019414A1

WO1994019414A1 - Slip resistant compositions and uses

Info

Publication number: WO1994019414A1
Application number: PCT/US1994/001701
Authority: WO
Inventors: Donald D. Stone
Original assignee: Stone Industries, Inc.
Priority date: 1993-02-23
Filing date: 1994-02-22
Publication date: 1994-09-01
Also published as: AU6242494A

Abstract

Surfaces with exceptional slip resistance are produced from compositions comprising mixtures of a polymer and a petroleum wax or synthetic wax or silicone, and optionally, independently, a tackifier agent, an ultraviolet light absorber or an antioxidant. Polymers may be thermoplastic, elastomeric or thermoset polymers, or polymers exhibiting combinations of such physical properties. Preferred compositions are composed of a vinyl acetate-ethylene heteropolymer, a polyurethane homopolymer or a natural or synthetic rubber, and a slip resistance effective amount of a petrolatum wax, and, optionally, with a polyisobutylene or polyalphaolefin tackifier. Such surfaces are particularly advantageous in applications in which the skin of the user is in contact with a water-wet surface, or in objects that are in contact with water such as tires, shoe soles, and sports equipment and tool handles, hoses and pipes, and the like.

Description

SLIP RESISTANT COMPOSITIONS AND USES

This is a continuation-in-part of patent application 08/021,131, filed February 23, 1993.

BACKGROUND OF THE INVENTION Field of the Invention The invention relates generally to compositions useful as slip resistant coatings in wet use environments, and particularly to copolymer compositions that are devoid of abrasive particulate matter and that produce coatings and surfaces and that exhibit improved slip resistance even when water-wet. Description of the Prior Art

It is often painfully apparent that water-wetted surfaces exhibit reduced friction. Water-wetted surfaces such as are found in or on surf boards, bath tubs, shower stalls, bathroom floors, boat decks, and the like are particularly slippery, often leading to personal injury. A great need, therefore, exists for surfaces and coatings that exhibit substantial traction or friction even when wetted by water. Prior art attempts to solve the aforementioned problems have included patterned or textured surfaces such as affixed appliques, mats, and the like. Unfortunately, these attempts to improve the wet frictional characteristics of bath tub and shower stall surfaces have been less than successful, in part due to the fact that many such products are movable and are thus not always in place when desired. Adhesively- mounted appliques and the like have also proven to be less than generally successful, in part due to the fact that the appliques cover only a limited portion of the wet, slippery surfaces and do not typically provide surfaces that increase in friction when wetted. Mats also create hygiene problems as the result of microbial growth beneath them. It is also known in the prior art to provide surface coatings whose anti-slip properties are created by particulate abrasives admixed with the coating materials. For example, U.S. 4,536,454 and 4,745,139 to Haasl and Haasl et al, respectively, disclose slip resistant compositions for surface coating applications in which the anti-slip characteristics are produced by particulate colloidal or powdered silicon dioxide or calcium carbonate along with glass microspheres; admixed polymeric material serves merely as an adhesive carrier. U.S. 5,110,657 discloses an anti-skid coating composition comprising a binder composition admixed with an aggregate having a particle size of 20-60 mesh, such as walnut shells, rubber chips and/or waste plastic. U.S. 4,931,330 discloses a prefabricated, self-adhesive, slip-resistant surface coating said to be suitable for bath tubs, comprising a rigid plastic sheet coated on one side with an adhesive layer for attachment to a surface and on the contralateral side with a polymer having embedded within it abrasive silica particles of 150-200 microns particle size. While such surfaces do indeed produce anti-slip characteristics, they do so by means of abrasive surfaces that are unsuitable for contact with the bare feet or other unprotected parts of the anatomy of the human user. Furthermore, these documents do not disclose increased friction when the coated surfaces are water-wetted.

JP52000825 describes gravure-printing-applied antislip coatings containing ethylene-vinylacetate copolymers, parrafin or microcrystalline wax, adhesive resins and butyl synthetic rubbers, which provides to plastic vessels or bags slippage resistance when stacked. This composition is not known to provide slip resistance when water wet. A great need exists, therefore, for slip resistant surface coatings that: (a) exhibit increased friction under water wet conditions; (b) have a smooth, non- abrasive surface; and, (c) are applicable to a wide variety of surfaces with which human skin comes in contact. The present invention meets these needs, and thus provides a substantial advance in the art.

SUMMARY OF THE INVENTION The invention provides compositions comprising a mixture of a polymer with a slip-resistance-increasing effective amount of a petroleum or synthetic wax or a silicone and, optionally, independently, including a tackifier agent, an ultraviolet light absorber and an antioxidant, that unexpectedly produce surfaces and surface coatings exhibiting friction when water-wet equal to or greater than the same surfaces or surface coatings when dry or greater than a water-wet polymeric surface devoid of the petroleum or synthetic wax or silicone, while providing a smooth, slip-resistant surface in the absence of added abrasive fillers, aggregates or particulate matter of any kind.

Compositions of the invention may be used in alternate modes. They may be formulated in solution phase or emulsion phase in a solvent, the solution or emulsion applied to a surface, and the solvent removed, thereby providing an adherent slip-resistant surface.

In another aspect, the compositions may be converted by heat from a solid form to a fluid state in the absence of any solvent, applied to a surface, and allowed to cool whereby an adherent, slip-resistant coating is produced.

In yet another aspect, compositions of the invention may be used in compression injection or extrusion molding of a product so as to disperse the inventive composition throughout the product.

Accordingly, it is an object of the invention to describe such polymeric compositions that produce such smooth, slip-resistant, non-abrasive surfaces useful on or in products that are typically wetted by water when in use.

It is another object of the invention to provide articles coated with the inventive compositions, including a prefabricated film or sheet coated with the inventive composition on the top surface, the opposite surface of which being layered with an adhesive for affixing the coated film or sheet to a solid surface. It is yet another object to provide articles in which the inventive compositions are either applied to the surface of the article or incorporated into the materials of which the article is composed.

Further objects and advantages of the invention will become more readily apparent in light of the following detailed description of the preferred embodiments.

DESCRIPTION OF THE PREFERRED EMBODIMENTS It has been unexpectedly found that novel, completely smooth, non-slippery, slip-resistant surfaces, with friction when water-wet that is equal to or greater than that obtained when the same surface is dry, that achieve these properties without the need for abrasive fillers, particulates or aggregates, are produced by coating surfaces with, or incorporating into the materials of which a product is made, a composition comprising a mixture of a polymer, a slip resistance producing effective amount of a petroleum wax or synthetic wax or a silicone and, optionally, independently, also a tackifier, an ultraviolet light absorber and an antioxidant. The formulations of the invention not only produce coatings and surfaces whose friction when wet with water is equal to or greater than when the corresponding coating or surface is dry, but also produce coatings and surfaces whose friction when wet with water is greater than a water-wet coating or surface produced without a petroleum wax or synthetic wax or a silicone. These compositions may be solution-based, emulsion-based or molten.

By "effective amount" is meant a ratio of a petroleum or synthetic wax or silicone to a polymer that produces a slip-resistant coating or surface that exhibits friction when wet with water equal to or greater than when dry or greater than a wax-free or silicone-free coating or surface when water wet, and which does so without the presence of abrasive fillers, aggregates or similar particulate materials.

The cipolymers of tis invention include thermoplastic, thermoset and elastomeric copolymerss. By "thermoplastic" is meant capable of being repeatedly softened by heat and hardened by cooling. By

"thermoset" is meant a material that will undergo or has undergone a chemical reaction by the action of heat, catalysts, UV light, cross-linkers, chain extenders and the like, leading to a relatively inflexible and cross linked state. By "elastomeric" is meant a material that at room temperature is capable under low stress to at least twice its original length and snapping back to its original length upon release of the stress. Preferred solution-based formulations include as the thermoplastic copolymer vinyl acetate-ethylene ("VAE") heteropolymers, such as those are produced by Quantum Chemicals Corp., Rolling Meadow, IL, under the trademark VYNATHENE®. The VYNATHENE group of VAE heteropolymers constitute a series of heteropolymers containing 40-51 weight percent vinyl acetate. A highly preferred VAE heteropolymer is produced by Quantum Chemicals under the designation EY 904-00 although other VYNATHENE VAE heteropolymers (e.g.,

VYNATHENE EY 901-25, EY 902-30, EY 903 and EY 905) also find utility in the present compositions. Also suitable in the inventive compositions are ethylene- vinyl acetate ("EVA") heteropolymers produced by Quantum under the trademark ULTRATHENE® which are available in grades containing from 9 to 33 percent by weight incorporated vinyl acetate. The high vinyl acetate content EVA copolymer (over 30 percent) is preferred. Ethylene-ethylacrylate (15-30 weight percent acrylate) and ethylene-methacrylate (8-40 weight percent of the acrylate) heterocopoly ers are also useful in the inventive formulations.

As noted above, slip-resistant compositions according to this invention can also be based on emulsion-based formulations. Multipolymer thermoplastic acrylic resin emulsions such as GELVA 2484 (Monsanto Co., St. Louis, MO 63167), acrylic emulsions such as VANACRYL 954 (Air Products & Chemicals, Inc., Allentown, PA 18195-1501), and thermoplastic elastomeric aliphatic polyurethane emulsions such as PERMUTHANE UE40-350 (Permuthane Coatings (ICI) , Peabody, MA 01961-3039) are suitable in producing slip-resistant compositions in conjunction with an effective amount of a petroleum or synthetic wax or silicone.

The polymer of the inventive compositions may also be natural or synthetic rubbers polymers such as synthetic polybutadiene and polyisoprene rubbers, and rubber and natural latexes, optionally along with accelerators, curing agents, fillers, retarders and other additives common to the art, depending on the type of processing. Petroleum or synthetic waxes or silicones, along with optional tackifiers, ultraviolet light absorbers and antioxidants, are added during compounding by conventional methods in order to produce the inventive slip resistant compositions surfaces.

The polymers of the inventive compositions are not limited to those listed herein, and are meant to include any thermoplastic, elastomeric or thermoset polymer to which slip resistance is imparted by the addition of effective amounts of a petroleum or synthetic wax or silicone.

As noted above, the inventive compositions include slip resistance effective amounts of a petroleum or synthetic wax or a silicone for imparting slip resistance to the polymer even when water-wet. Members of the petroleum wax subgenus include petrolatums, microcrystalline waxes, paraffin waxes, and hydrocarbon waxes. Synthetic waxes include materials such as polypropylene, polyethylene, polymethylene, chemically modified hydrocarbon, long chain fatty acid esters such as octyl isononate and acetyl palmitate, and long chain fatty acid amide waxes. Highly preferred are the petrolatums.

The presence of a petroleum or synthetic wax or silicone is additionally important, as these materials unexpectedly endow tackifier additives with slip resistance even when water-wet. Without the present wax or silicone additive, tackifiers produce traction only with dry surfaces; when water-wet, such formulations produce slippery surfaces with little or no slip resistance.

Suitable petrolatums may be obtained from the Sonneborn Division of the Witco Corp. (New York, NY) under the trademarks PROTOPET®, PERFECTA®, FONOLINE®, SUPERSNOW®, and SUPERSOFT®. In general, the Sonneborn petrolatums are homogeneous, semi-solid mixtures of oily and waxy hydrocarbons characterized by viscosity, sheer strength, chemical and biological inertness and apolar hydrophobic characteristics. The PROTOPET® Petrolatum U.S.P. series includes ALBA, White IS. White 2L, White 3C, and Yellow 2A; White IS is most preferred. FONOLINE® Petrolatums U.S.P. include white and yellow; white is preferred. SUPERSNOW® White Petrolatum U.S.P. and SUPERSOFT® White Petrolatum U.S.P. are also preferred. Petrolatum may also be obtained from Michelman, Inc., Cincinnati, OH 45236, PA. as No. ML-343-25.

Hydrocarbon paraffin waxes may be obtained from Witco under the trademark SUNOLITE® (preferably SUNOLITE 240 pastilles) and from Uniroyal Chemical Co. , Naugatuck, CT under the trademark SUNPROOF®. Hydrocarbon microcrystalline waxes may be obtained from Kloster Keunen, Inc. , Sayville, NY (the white material is preferred), as well as from Petrolite Corp., Tulsa, OK 74112 as Polymekon SPP-W. Carnauba waxes (e.g. ML- 209-25) , polyethylene and copolymer waxes (e.g. ME-687- 25 and EE-074-30) , microcrystalline waxes (e.g., ME-

015-46), and paraffin wax (e.g., ME-659-35) may also be obtained from Michelman, Inc.

Silicones for use in the inventive formulations are obtainable, for example, from GE Silicones, Waterford, NY. These include linear or highly branched chains of polyalkylsiloxanes such as polydimethylsiloxane and polymethyloctadecylsiloxane.

All ratios and amounts given herein are by weight, unless otherwise noted. In a preferred solution-based composition, a VAE copolymer (e.g., VYNATHENE® EY-904-00) was mixed with a petrolatum (e.g. PROTOPET® White IS) in a weight ratio of copolymer to petrolatum of about 1-10:1, preferably from about 3-8:1. In another embodiment, 2 parts of VAE copolymer were dissolved in 8 parts of toluene solvent. A second solution was formed from this first solution by mixing 3 parts of the first solution with approximately 0.2 parts of the petrolatum, to produce a formulation in which the copolymer:petrolatum weight ratio is about 3.

Among the emulsion-based formulations, mixtures of GELVA® 2484 with POLYMEKON® SPP-W (1.0:0.3), VANACRYL® 954 with Michelman Petrolatum ML-343-25 (1.5:0.8), PERMUTHANE® UE 40-350 with Michelman Petrolatum

(1.5:0.8), and PERMUTHANE® with Michelman Paraffin (1.5:0.9) all produced slip-resistant coatings according to this invention.

The properties of adhesiveness, tensile strength and resistance to permeation by water of the above- described formulations may be improved by the addition of a small amount of a permanent tackifier agent, such as polyisobutylene (VISTANEX® LM Polyisobutylene, Exxon Chemical Co., Houston, TX 77001) or a hydrocarbon resin (REGALREZ®, Hercules, Inc., Wilmington, DE 19894). As noted above, such tackifiers, when mixed with the above-described copolymers in the absence of a wax or a silicone according to the invention, will produce a coating that is slip resistant only when dry; in the presence of water, slip resistance is lost. However, when such a tackifier is used together with the above- described wax or a silicone according to the invention, the combination unexpectedly produces an increased wet friction, anti-slip surface. In a preferred formulation with a tackifier, 2 parts of VYNATHENE® EY 905-00 (Quantum Corp.) were dissolved in 8 parts of toluene. Six parts of this solution were mixed with 1 part of PROTOPET IS (WITCO) and 0.5 parts of VISTANEX® LM-MS-LC (Exxon Corp.). In another highly preferred formulation with a tackifier, 1.0 parts VAE (e.g., Quantum Chemical's VYNATHENE®), 0.2 parts petrolatum (Witco¹s PROTOPET White IS) and 0.2 parts of a polyalphaolefin (e.g., Rexene Products Co., Dallas, TX 75244, REXTAC® 2535) were dissolved in 4.0 parts of toluene for spray applications, and the same formulation without solvent was used in molten state embodiments for injection molding applications.

It should be understood that formulations of the invention can be compounded other than as specifically described hereinabove. When using polymers with a petroleum or synthetic wax or a silicone, the important factor is the selection of the effective amount of the wax or silicone to be mixed with the polymer so that formulations are produced that create coatings and surfaces that exhibit friction properties when wet that are equal to or greater than that obtained in the dry state. It would not require undue experimentation by those skilled in this art to devise appropriate ratios, given the guidance provided herein.

The compositions of the invention described above may be used directly to coat a surface, such as a hand rail, pipe, boat deck or surf board by application of the compositions, by coating methods well known in this art. Formulations that include a tackifier such as

VISTANEX®, in addition to copolymer and petroleum wax, are particularly useful for watercraft surfaces.

It is necessary to use an appropriate temperature when drying coatings composed of the inventive compositions in solution or emulsion forms in order to produce effective coatings. Drying at temperatures below or above the effective temperature range will produce coatings with reduced slip resistance. In particular, excessive drying temperature may produce, with certain formulations, an "oily" surface with less than optimum slip resistance. By "appropriate temperature" is meant a composition drying temperature that produces a smooth, non-slippery, slip-resistant surface coating that exhibits friction when wet with water that is equal to or greater than the corresponding dry surface coating. For example, for the VAE-petrolatum solution-based compositions described above, the effective drying temperatures range between about 70° and 90° F, most preferably between 75° and 85° F. It would not require undue experimentation to determine the optimum drying temperature for different polymer/wax or silicone mixtures given the guidance herein. In one embodiment, the inventive compositions may be disposed as a coating on the upper surface of a sheet or pliable plastic film, such as a vinyl film, by conventional coating methods. In a preferred embodiment, the VYNATHENE-PROTOPET-VISTANEX formulation described above was applied in solvent as an about 15 mils (before drying) coating with a conventional coater to one surface of a Flexcon (Spencer, MA) CONFORMCAL® V-400F S.C., T/C 160, 4 mil film which comes already coated on the opposite surface with a pressure- sensitive adhesive for application of the coated sheet or film to a surface; the formulation was dried at about 80° F to achieve the desired coating. The surface to which the inventive composition is applied may be primed so as to improve adherence of the coating to the sheet or film; materials comprising such primers are conventional in the art. Other sheets or films are also within the scope of this invention. The present compositions can be used to coat at other thicknesses; however, a typical wet coating of 15 mils thickness produced an approximately 5 mils thick dried film which had an appropriately useful lifetime when in use.

The films or sheets thus produced require very little thickness and no surface texture to produce excellent slip resistance properties when wet with water. In other words, the present compositions provide a coating having a desirably very low profile due to the thinness of the coating. Coatings produced according to the invention can be readily cleaned with standard household cleaners without appreciable diminution of high slip-resistance properties. Unexpectedly, the traction properties of the coating so produced are increased by running warm water over the inventive surfaces such as when bathing or showering. Water-based inks can be used to imprint a design upon the aforementioned film or sheet prior to coating according to the present invention such that any eventual wearing of the coating exposes the ink design that will then be dissolved through continuing use in water. Disappearance of the design indicates that the film bearing the present coating should be replaced due to wear of the coating formulation.

As noted above, slip resistant compositions according to the invention need not be formulated in a solvent for application to surfaces. The components of the composition may be mixed in a dry state by conventional methods and heated to a molten, easily flowing state, and the molten composition either applied to the desired surface or incorporated into products by conventional molding and extrusion equipment and methods such as described in Baird et al.. Industrial Plastics. Goodheart-Willcox Publishers, South Holland, IL, 1986, pp. 1-276. Applications from the molten state have certain advantages, including avoidance of hazardous solvents, rapid solidification (a matter of several minutes) , tight bonding to a wide variety of surfaces, and requiring only a relatively small energy consumption for applications (see, Nelson, Adhesives Aσe_P page 6, May 31, 1993).

The temperature necessary to produce a particular molten composition will vary with the nature and proportion of the components of the mixture, and it would not require undue experimentation to determine particular melt temperatures. Melt temperatures are generally supplied in the polymer manufacturer's technical specifications. For example, the ring and ball softening points for Quantum Chemical's VAE EY 900 series heteropolymers described above range between 230° and 310°F, as determined by ASTM test method E28. Petrolatums melt at between about 120° and 140°F, and paraffin waxes at about 150°F (ASTM test method D127) .

Molten compositions are, as noted above, 100% solids. The process is begun by heating a mixture of solids at temperatures well above the melting points of the components, typically 250° to 350°F. As molten compositions melt require heating to elevated temperatures for use, concessions must be made in equipment design to assure temperature control and rapid application. Equipment suitable for applying the inventive molten compositions are conventional in the field, such as equipment sold by Spraymation, Inc., Ft. Lauderdale, FL 33309 under the name THERMOPULSE®, and by ITW Dynatec, Hendersonville, TN 37075 under the names Mercer NO-CHAR®, MELTIMATE®, and TEKNACOAT®. By the use of appropriate spray heads available with this equipment, the molten composition may be applied as a smooth coating, a random pattern coating, or a dot matrix coating to increase traction. Examples of surface applications using the molten composition of the invention include bathtubs, shower stalls, rubber boat hulls (such as in ZODIAK or AVON rubber boats) , surfboard foam traction pads (such as those made by Astradeck, Inc.), inflatable or thermoformed children's swimming pools, water craft decks, swimming pool decks, restaurant floors, and, as will be detailed below, on disposable sanitary shoe covers. Examples of the use of the inventive molten compositions in molded products include shoe soles, tires, nonskid mats and pads, tool handles, and various rubber products (see, e.g., Kirk- Othmer, Encyclopedia of Chemical Technology, 3d ed, 1982, John Wiley, NY, v. 20, pp 365-468). Use of the slip-resistant compositions of the invention provides to these otherwise conventional products the highly advantageous properties of slip resistance even in the presence of a wet environment.

Elastomeric linear thermoplastic polyurethanes are currently widely used in producing non-leather shoe soles. These plastics, which generally are produced from difunctional monomers by the reaction of a diisocyanate with a polyol, have good impact strength, good physical properties and excellent processability, but slip-resistance is limited. I have discovered that the slip-resistance of such polyurethane shoe soles may be improved by incorporating an effective amount of a petroleum of synthetic wax or a silicone with polyurethane(s) prior or during the molding process. In one embodiment, 8.0 parts of VISTANEX (Exxon's polyisobutylene no. LM-MS-LC) was heated to 130°C for 15-20 minutes, mixed rapidly with the polyol component of 84 parts of a two-component polyurethane (Conap, Inc., Olean, NY 14760, CONATHANE® TU-70) and 8.0 parts of a petrolatum (Witco¹s PROTOPET® White IS); the mixture was then added to the isocyanate component of the polyurethane, and the final mixture poured into a mold. The working life of the mixture at room temperature is about 5-45 minutes, depending upon the proportions of the components (Conap brochure ES-170, 4/92) . These improved shoe soles displayed increased slip resistance when water wet.

Sanitary disposable shoe covers are important in hospital operating rooms for maintaining hygienic conditions. Modern operating rooms generally have smooth surfaces, substantially free of seams, cracks or crevices in which contaminating substances could accumulate. However, currently available disposable shoe covers are made of non-woven fabrics, such as polypropylene sheeting. The combination of smooth floors that are generally wet during use and conventional plastic shoe covers with no slip resistance produces hazardous conditions for operating room personnel. Efforts to solve these problems with disposable shoe covers are described in U.S. patent nos. 4,616,429, 4,918,839 and 4,140,418. In one such effort, a rubber strip is glued to the bottom of the shoe cover, but this method complicates the manufacturing procedure, increases cost to the point of noncompetitiveness, and produces uncomfortably stiff and heavy shoe soles. In another of these methods, the shoe cover is made of a non-woven fabric coated with a non-skid coating such as DuPont's TYVEK®, but this material is expensive and, because of stiffness, uncomfortable to the user. U.S. patent no. 4,598,485 describes a shoe cover made of a non-woven fabric having disposed on the bottom surface and through a bottom seam of the shoe cover a rib formed of rubber or rubber latex which is said to provide slip resistance, but this product has the disadvantages of complicated and expensive manufacturing procedures and, because of the bottom seam, a potential for a break in sanitary conditions.

I have overcome these problems and have conceived of an inexpensive, comfortable, easy to manufacture, slip-resistant disposable shoe cover. During manufacturing of what will become the sole of the final assembled product, a slip resistant composition of the present invention in a molten form is applied to what will become, after assembly, the undersurface of the sole. In one embodiment, the composition is applied to the non-woven fabric before or after die cutting shoe cover blanks from the fabric. The molten composition may be applied as a smooth band, a patterned band or a dot matrix band. Conventional non-woven fabrics may be used in the invention, including spunbonded webs of polyolefins and the like sold under the tradename EVOLUTION® and laminates of such materials such as are described in U.S. patent no. 4,041,203, RAYON®, TERELON® and other petrochemical fabrics. A preferable material is a polypropylene fabric marketed by Kimberly-Clark Co. and others under the mark POLYSPUNBOUND®. Elastic means for conforming the shoe cover to the foot are adhesively attached to the blank, and the blank is manufactured into a shoe cover by conventional means such as described in U.S. patent no. 4,918,839 and GB patent no. 2,124,472. The compositions of the invention may also be used in extrusion molding for the production of, e.g., thick commercial non-skid pads or mats.

Resistance of the inventive compositions to the destructive effects of ultraviolet ("UV") rays found in sunlight may be improved by the incorporation into the formulation of a small amount (e.g., 0.1 parts by weight) of a UV light absorber, such as 2-(3' ,5'-di-t- butyl-2'-hexaphenyl)-5-chloro-benzotriazole (TINUVIN® 327, Ciba-Geigy Corp., Hawthorne, NY 10532) or bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (TINUVIN® 770, Ciba-Geigy).

Resistance of the inventive compositions to air oxidation may be improved by the addition to the mixture of a small amount (e.g., 0.1 parts by weight) of an anti-oxidant such as tetrakis (methylene (3,5-di- t-butyl-4-hydroxyhydrocinnamate) ) (IRGONOX® 1010, Ciba- Geigy) .

Slip resistance of the thus-produced coatings and surfaces may be tested using an instrument such as the Brungraber Slip Tester Model Mark II ( Dr. Robert J. Brungraber, Lewisburg, PA 17837) . This instrument measures simultaneously both the normal force and lateral force (the one tending to cause people to slip) , and is therefore suited to the measurement of surfaces that are wet with water or other liquids. There currently is no ASTM test method for slip resistance other than a test for waxed or polished floors (ASTM No. D-2047) ; this test method is, however, inappropriate for the present compositions.

The present compositions may also be used to provide slip resistant gloves for applications where improved gripping security is important, as in medical gloves, leather sports gloves or work gloves. Alternate processes may be used to produce such gloves in accordance with the invention. In one embodiment, leather is immersed in a solution-based formulation made according to the invention for a brief period, e.g., 1-2 minutes, air-dried, preferably at room temperature, then used for the manufacture of the gloves. Even where an optional tackifier has been used with a copoly er-petrolatum mixture, it is not necessary to coat that surface of the impregnated leather that will be in contact with the glove user's skin with a detackifier, as is required in U.S. patent nos. 4,598,429 and 4,689,832. This is so because, as noted above, petrolatum unexpectedly improves the properties of tackifiers. In another embodiment, a composition according to the invention is applied to one (outer) surface of glove leather as a thin film of a molten composition described above. The depth of penetration of the leather is controlled by controlling the amount of heat and of viscosity by means well known in this art. A primer may be applied to the glove prior to application of the composition, although the adhesive characteristics of VAE copolymers with a petroleum or synthetic silicone wax, taken together with the increased adhesiveness of molten compositions, may make a primer unnecessary. Penetration of the molten composition may be adjusted so that it does not penetrate to what will become the inner surface of the leather, thereby also avoiding the need for detackification essential to U.S. patent nos. 4,598,429 and 4,689,832.

Although the present compositions and coatings and surfaces produced therefrom have been described above as being useful in particular applications, it is within the scope of this invention to use the inventive formulations to coat, or be incorporated into, any article of commerce that requires slip-resistance when handled by the user.

In the light of the foregoing, the invention is seen to be useful in a variety of applications and according to a variety of formulations, the invention thus being limited only by the recitations of the appended claims.

Claims

CLAIMS What is claimed is:

1. A composition for imparting slip resistance to a coating or surface in the absence of added fillers, aggregates or particulate matter of any kind, said composition comprising a mixture of: a thermoplastic, elastomeric or thermoset polymer, or a polymer exhibiting a combination of such physical properties; and, a slip-resistant effective amount of a petroleum wax or synthetic wax or a silicone; and, optionally, independently, an effective amount of a tackifier agent, an ultraviolet light absorber or an antioxidant, wherein said composition of claim 1 which, when formed into a surface coating and dried or incorporated into the materials of which a solid product is composed, produces a surface coating or surface that exhibits the same or an increased friction when said coated surface or surface is wet with water as compared to said coated surface when not wet or as compared to a water-wet similarly coated surface not containing said composition.

2. A composition of claim 1 wherein said polymer is a solution-based heteropolymer.

3. A composition of claim 2, wherein said heteropolymer is selected from the group consisting of vinyl acetate-ethylene, ethylene-vinyl acetate, ethylene-ethacrylate, and ethylene-methacrylate copolymers.

4. A composition of claim 1 wherein said polymer is an emulsion-based heteropolymer or a homopolymer.

5. A composition of claim 4, wherein said heteropolymer is a styrene acrylate copolymer.

6. A composition of claim 4, wherein said homopolymer is a multipolymer acrylic resin or a polyurethane.

7. A composition of claim 1, wherein said polymer is a molten heteropolymer or molten homopolymer

8. A composition of claim 7, wherein said molten heteropolymer is selected from the group consisting of a vinyl acetate-ethylene, ethylene-vinyl acetate, ethylene ethacrylate, and ethylene methacryate.

9. A composition of claim 7 wherein said molten homopolymer is a multipolymer acrylic resin or a polyurethane.

10. A composition of claim 1, wherein said polymer is a natural or synthetic rubber.

11. A composition of claim 10, wherein said synthetic rubber is a polybutadiene or polyisoprene rubber.

12. A composition of claim 13, wherein said natural rubber is derived from natural latex.

13. A composition of claim 1 wherein said petroleum wax is selected from the group consisting of petrolatums, paraffin waxes, microcrystalline waxes, and hydrocarbon waxes.

14. A composition of claim 1, wherein said synthetic wax is selected from the group consisting of polyethylene, polymethylene, polypropylene, modified hydrocarbon, long chain fatty acid ester, and long chain fatty amide.

15. A composition of claim 1, wherein said optional tackifier is a polyisobutylene, hydrocarbon resin, or polyalphaolefin.

16. A composition of claim 1, wherein said ultraviolet light absorber is a benzotriazole or piperidyl sebacate.

17. A composition of claim 1, wherein said antioxidant is a hydroxyhydrocinnamate.

18. A composition of claim 1, wherein the weight ratio of said polymer to said petroleum or synthetic wax or silicone to said tackifier agent is about 2- 10:1:0.5-1.

19. A composition of claim 1, wherein said polymer is a vinyl acetate-ethylene copolymer, said petroleum wax is a petrolatum, and said optional tackifier is a polyisobutylene.

20. A composition of claim 19 wherein the weight ratio of copolymer to petrolatum to polyisobutylene is about 1-10:1:0.5-1.

21. A composition of claim 1, wherein said polymer is a polyurethane, said petroleum wax is a petrolatum, and said optional tackifier is polyisobutylene.

22. A composition of claim 21 wherein the ratio of polyurethane to petrolatum to polyisobutylene is about 10-12: 1: 1.

23. A solid surface having disposed thereon a coating comprising a composition of claim 1.

24. A solid surface of claim 23 wherein said coating comprises a prefabricated sheet or film consisting essentially of a top surface and a bottom surface, having disposed on said top surface a layer of said slip-resistant composition, and having disposed on said bottom surface an adhesive layer enabling said sheet or film to be attached to any desired location on a receiving solid surface.

25. A solid surface of claim 23, wherein said solid surface is selected from the group consisting of a surfboard, bath tub, shower stall, watercraft deck, pipe, hose, tool handle, sport equipment handle, mat and pad.

26. A solid surface of claim 23, wherein said coating comprises said composition applied directly to said solid surface.

27. A solid surface of claim 26, wherein said solid surface is selected from the group consisting of a surfboard, surfboard traction pad, rubber boat hull, pool decks, bath tub, shower stall, watercraft deck, pipe, hose, tool handle, sport equipment handle, mat and pad.

28. In a solid product requiring slip resistance properties, the improvement comprising the incorporation into the materials of which such products are made a slip-resistance-effective amount of a composition of claim 1.

29. A solid product of claim 28, wherein said solid product is selected from the group consisting of shoe soles, tires, hoses, tool handles, sport equipment handle grips, mats and pads.

30. In a leather glove product requiring slip resistance properties, the improvement comprising leather impregnated with an effective amount of a composition of claim 1.

31. In an golf club grip or tennis racket handle wrapping requiring slip resistance, the improvement comprising said grip or wrapping coated with or incorporating an effective amount of the composition of claim 1.

32. In a disposable shoe cover composed of a polymeric non-woven material, the improvement comprising disposing on the bottom sole of said shoe cover a layer comprising a slip-resistant effective amount of the composition of claim 1.