WO1994019414A1 - Compositions resistant au glissement et leurs utilisations - Google Patents

Compositions resistant au glissement et leurs utilisations Download PDF

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Publication number
WO1994019414A1
WO1994019414A1 PCT/US1994/001701 US9401701W WO9419414A1 WO 1994019414 A1 WO1994019414 A1 WO 1994019414A1 US 9401701 W US9401701 W US 9401701W WO 9419414 A1 WO9419414 A1 WO 9419414A1
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WIPO (PCT)
Prior art keywords
composition
slip
polymer
ethylene
coating
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PCT/US1994/001701
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English (en)
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WO1994019414B1 (fr
Inventor
Donald D. Stone
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Stone Industries, Inc.
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Publication date
Application filed by Stone Industries, Inc. filed Critical Stone Industries, Inc.
Priority to AU62424/94A priority Critical patent/AU6242494A/en
Publication of WO1994019414A1 publication Critical patent/WO1994019414A1/fr
Publication of WO1994019414B1 publication Critical patent/WO1994019414B1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D121/00—Coating compositions based on unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
    • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09D131/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • C08L91/08—Mineral waxes

Definitions

  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • compositions 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.
  • an 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.
  • thermoplastic is meant capable of being repeatedly softened by heat and hardened by cooling.
  • 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.
  • 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®.
  • 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.
  • EVA ethylene- vinyl acetate
  • EVA copolymer 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.
  • 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.
  • 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.
  • 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.
  • a 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.
  • 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®.
  • 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.
  • 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 Klein 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-
  • paraffin wax e.g., ME-659-35
  • Michelman, Inc 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.
  • a VAE copolymer e.g., VYNATHENE® EY-904-00
  • a petrolatum e.g. PROTOPET® White IS
  • 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.
  • 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).
  • 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).
  • VISTANEX® LM Polyisobutylene Exxon Chemical Co., Houston, TX 77001
  • REGALREZ® Hercules, Inc., Wilmington, DE 19894
  • VAE Quantum Chemical's VYNATHENE®
  • petrolatum Witco 1 s PROTOPET White IS
  • a polyalphaolefin e.g., Rexene Products Co., Dallas, TX 75244, REXTAC® 2535
  • formulations of the invention can be compounded other than as specifically described hereinabove.
  • 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.
  • 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.
  • a surface such as a hand rail, pipe, boat deck or surf board
  • Formulations that include a tackifier such as
  • VISTANEX® in addition to copolymer and petroleum wax, are particularly useful for watercraft surfaces.
  • 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.
  • 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.
  • the effective drying temperatures range between about 70° and 90° F, most preferably between 75° and 85° F.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • melt temperatures are generally supplied in the polymer manufacturer's technical specifications.
  • 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®.
  • the molten composition may be applied as a smooth coating, a random pattern coating, or a dot matrix coating to increase traction.
  • 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.
  • inventive molten compositions in molded products examples 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 LM-MS-LC
  • a two-component polyurethane Conap, Inc., Olean, NY 14760, CONATHANE® TU-70
  • a petrolatum Witco 1 s PROTOPET® White IS
  • 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) .
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • UV ultraviolet
  • 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) .
  • 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.
  • ASTM test method for slip resistance other than a test for waxed or polished floors ASTM No. D-2047
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Des surfaces ayant une résistance exceptionnelle aux glissements sont obtenues à partir de compositions comprenant des mélanges d'un polymère et d'une cire de pétrole ou cire synthétique ou silicone, et éventuellement, indépendamment, d'un agent collant, d'un agent absorbant la lumière ultraviolette ou un antioxydant. Les polymères peuvent être des polymères thermoplastiques, élastomères ou thermodurcis, ou des polymères présentant des combinaisons de ces propriétés physiques. Les compositions préférées sont composées d'un hétéropolymère d'acétate de vinyle/ethylène, d'un homopolymère de polyuréthanne ou d'un caoutchouc naturel ou synthétique, et d'une quantité efficace résistant aux glissement d'une cire de pétrole, et éventuellement, d'un agent collant de polyisobutylène ou polyalphaoléfine. Ces surfaces sont notamment intéressantes dans des applications où la peau de l'utilisateur est en contact avec une surface mouillée par de l'eau, ou dans des objets qui sont en contact avec de l'eau tels que les pneux, les semelles de chaussures, et des articles de sport et des poignées d'outils, des flexibles et des conduites, et autres.
PCT/US1994/001701 1993-02-23 1994-02-22 Compositions resistant au glissement et leurs utilisations WO1994019414A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU62424/94A AU6242494A (en) 1993-02-23 1994-02-22 Slip resistant compositions and uses

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US2113193A 1993-02-23 1993-02-23
US08/021,131 1993-02-23
US14518993A 1993-11-03 1993-11-03
US08/145,189 1993-11-03

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WO1994019414A1 true WO1994019414A1 (fr) 1994-09-01
WO1994019414B1 WO1994019414B1 (fr) 1994-10-13

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* Cited by examiner, † Cited by third party
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US5773091A (en) * 1996-07-11 1998-06-30 Brandeis University Anti-graffiti coatings and method of graffiti removal
WO2003055661A1 (fr) * 2001-12-24 2003-07-10 Hee-Dae Park Composition utilisee pour la production de semelle sans utilisation d'agent de liberation, semelle ainsi fabriquee, et procede de production correspondant
US6833171B2 (en) 2002-04-03 2004-12-21 Kimberly-Clark Worldwide, Inc. Low tack slip-resistant shoe cover
GB2403395A (en) * 2003-07-03 2005-01-05 Roger Parsons Golf glove
CN102295882A (zh) * 2010-06-25 2011-12-28 米申产品控股有限公司 用于增强附着摩擦力的运动鞋鞋底涂层
US20170065030A1 (en) * 2010-07-13 2017-03-09 Mission Product Holding, Inc. Device attachable to item of clothing for dispensing material for enhancing gripping properties of shoe sole
US10016783B2 (en) * 2012-12-20 2018-07-10 Joseph Mosher Hawkins, JR. Process for making pad for localized increase of friction

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JPS52825A (en) * 1975-06-24 1977-01-06 Toyo Ink Mfg Co Ltd Slip-proof hot-metal coating composition
US4053676A (en) * 1975-07-18 1977-10-11 Litton Industries, Inc. Handle grip material
JPS5377274A (en) * 1976-12-18 1978-07-08 Yoshihiro Tada Processing of water absorbing polymer
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5773091A (en) * 1996-07-11 1998-06-30 Brandeis University Anti-graffiti coatings and method of graffiti removal
WO2003055661A1 (fr) * 2001-12-24 2003-07-10 Hee-Dae Park Composition utilisee pour la production de semelle sans utilisation d'agent de liberation, semelle ainsi fabriquee, et procede de production correspondant
US6833171B2 (en) 2002-04-03 2004-12-21 Kimberly-Clark Worldwide, Inc. Low tack slip-resistant shoe cover
GB2403395A (en) * 2003-07-03 2005-01-05 Roger Parsons Golf glove
CN102295882A (zh) * 2010-06-25 2011-12-28 米申产品控股有限公司 用于增强附着摩擦力的运动鞋鞋底涂层
US20110314706A1 (en) * 2010-06-25 2011-12-29 Mark French Athletic shoe sole coating for traction enhancement
WO2011163336A2 (fr) * 2010-06-25 2011-12-29 Mission Product Holdings, Inc Revêtement de semelle de chaussure athlétique pour amélioration de traction
WO2011163336A3 (fr) * 2010-06-25 2012-04-19 Mission Product Holdings, Inc Revêtement de semelle de chaussure athlétique pour amélioration de traction
CN102295882B (zh) * 2010-06-25 2016-08-17 米申产品控股有限公司 用于增强附着摩擦力的运动鞋鞋底涂层
TWI552692B (zh) * 2010-06-25 2016-10-11 米遜產品控股公司 用於增強抓地力之運動鞋鞋底塗層及其製備方法
US9578923B2 (en) * 2010-06-25 2017-02-28 Mission Product Holdings, Inc. Athletic shoe sole coating for traction enhancement
US20170065030A1 (en) * 2010-07-13 2017-03-09 Mission Product Holding, Inc. Device attachable to item of clothing for dispensing material for enhancing gripping properties of shoe sole
US10016783B2 (en) * 2012-12-20 2018-07-10 Joseph Mosher Hawkins, JR. Process for making pad for localized increase of friction

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