US20110241269A1 - Atmospheric plasma treatment of reinforcement cords and use in rubber articles - Google Patents

Atmospheric plasma treatment of reinforcement cords and use in rubber articles Download PDF

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Publication number
US20110241269A1
US20110241269A1 US12/910,919 US91091910A US2011241269A1 US 20110241269 A1 US20110241269 A1 US 20110241269A1 US 91091910 A US91091910 A US 91091910A US 2011241269 A1 US2011241269 A1 US 2011241269A1
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Prior art keywords
cord
treated
group
carrier gas
tire
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Abandoned
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US12/910,919
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English (en)
Inventor
Frederic Gerard Auguste Siffer
James Gregory Gillick
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Goodyear Tire and Rubber Co
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Goodyear Tire and Rubber Co
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Filing date
Publication date
Priority claimed from US12/752,171 external-priority patent/US8445074B2/en
Application filed by Goodyear Tire and Rubber Co filed Critical Goodyear Tire and Rubber Co
Priority to US12/910,919 priority Critical patent/US20110241269A1/en
Priority to EP11160064.9A priority patent/EP2371882B1/fr
Priority to BRPI1100838-5A2A priority patent/BRPI1100838A2/pt
Priority to KR1020110029896A priority patent/KR101800460B1/ko
Priority to JP2011081888A priority patent/JP5944107B2/ja
Priority to CN201110081903.3A priority patent/CN102212963B/zh
Publication of US20110241269A1 publication Critical patent/US20110241269A1/en
Priority to US14/074,097 priority patent/US9133360B2/en
Abandoned legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
    • 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
    • C09D119/00—Coating compositions based on rubbers, not provided for in groups C09D107/00 - C09D117/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/20—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wires
    • 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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/041—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with metal fibres
    • 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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • 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
    • C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/48—Tyre cords
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
    • D07B1/0606—Reinforcing cords for rubber or plastic articles
    • D07B1/0666—Reinforcing cords for rubber or plastic articles the wires being characterised by an anti-corrosive or adhesion promoting coating
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/16—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics
    • D07B1/162—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics characterised by a plastic or rubber enveloping sheathing
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B7/00—Details of, or auxiliary devices incorporated in, rope- or cable-making machines; Auxiliary apparatus associated with such machines
    • D07B7/02—Machine details; Auxiliary devices
    • D07B7/14—Machine details; Auxiliary devices for coating or wrapping ropes, cables, or component strands thereof
    • D07B7/145—Coating or filling-up interstices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2201/00—Polymeric substrate or laminate
    • B05D2201/02—Polymeric substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2256/00—Wires or fibres
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
    • D07B1/0606—Reinforcing cords for rubber or plastic articles
    • D07B1/0613—Reinforcing cords for rubber or plastic articles the reinforcing cords being characterised by the rope configuration
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1355—Elemental metal containing [e.g., substrate, foil, film, coating, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]

Definitions

  • Rubber is typically reinforced with various embodiments of textile, glass or steel fibers to provide basic strength, shape, stability, and resistance to bruises, fatigue, and heat. These fibers may be twisted into plies and cabled into cords. Rubber tires of various construction as well as various industrial products such as belts, hoses, seals, bumpers, mountings, and diaphragms can be prepared using such cords.
  • the present invention is directed to a method of treating a reinforcement cord, comprising the steps of
  • carrier gas 13 is fed from storage vessel 12 to atomizer 20 along with monomer 15 from storage vessel 14 , halogenated saturated hydrocarbon 17 from storage vessel 16 .
  • one or more curatives 19 may be added from storage vessel 18 .
  • Carrier gas 13 , monomer 15 , halogenated saturated hydrocarbon 17 and optional curative 19 are atomized in atomizer 20 to form atomized mixture 21 .
  • Atomized mixture 21 is sent to plasma generator 22 , where atmospheric plasma 24 is generated from atomized mixture 21 .
  • Tire cord 26 is unwound from spool 30 and conveyed through plasma generator 22 and atmospheric plasma 24 for deposition of a surface treatment by the plasma 24 .
  • Treated tire cord 28 exits plasma generator 22 and is wound onto spool 32 for storage.
  • the plasma generator may be any suitable plasma generation device as are known in the art to generate atmospheric pressure plasmas, such as atmospheric pressure plasma jet, atmospheric pressure microwave glow discharge, atmospheric pressure glow discharge, and atmospheric dielectric barrier discharge.
  • the plasma generator is of the dielectric barrier discharge type.
  • the dielectric barrier discharge apparatus generally includes two electrodes with a dielectric-insulating layer disposed between the electrodes and operate at about atmospheric pressures.
  • the dielectric barrier discharge apparatus does not provide one single plasma discharge, but instead provides a series of short-lived, self terminating arcs, which on a long time scale (greater than a microsecond), appears as a stable, continuous, and homogeneous plasma.
  • the dielectric layer serves to ensure termination of the arc. Further reference may be made to U.S. Pat. No. 6,664,737 for its teaching regarding the operation of a dielectric barrier discharge apparatus.
  • atmospheric pressure plasma it is meant that the pressure of the plasma is equal to or slightly above the ambient pressure of the surroundings.
  • the pressure of the plasma may be somewhat higher than ambient, such that the plasma pressure is sufficient to induce the desired flow rate through the atomizer and plasma generator.
  • the atomized mixture includes a carrier gas, at least one monomer, and a halogenated saturated hydrocarbon.
  • Suitable carrier gas includes any of the noble gases including helium, argon, xenon, and neon. Also suitable as carrier gas are oxygen, nitrogen, carbon dioxide, and air. In one embodiment, the carrier gas is argon.
  • Suitable monomers include any of the various monomers used to produce elastomers for use in tires. Such monomers include conjugated diolefin monomers and vinyl aromatic monomers.
  • the conjugated diolefin monomers generally contain from 4 to 12 carbon atoms. In particular 1,3-butadiene and isoprene may be used.
  • Some additional conjugated diolefin monomers that can be utilized include 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, 2-phenyl-1,3-butadiene, and the like, alone or in admixture.
  • short chain length oligomers of polybutadiene and polyisoprene are also suitable.
  • squalene is also suitable.
  • Vinyl aromatic monomers are another group of ethylenically unsaturated monomers which may be used. Such vinyl aromatic monomers typically contain from 8 to 20 carbon atoms. Usually, the vinyl aromatic monomer will contain from 8 to 14 carbon atoms. In one embodiment the vinyl aromatic monomer is styrene. Some examples of vinyl aromatic monomers that can be utilized include styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, ⁇ -methylstyrene, 4-phenylstyrene, 3-methylstyrene and the like.
  • the amount of monomer may be expressed as a percent of the total components in the atomized mixture excluding the carrier gas, i.e., on a carrier gas free basis. In one embodiment, the amount of monomer ranges from 10 to 50 percent by weight of the total components in the atomized mixture on a carrier gas free basis. In one embodiment, the amount of monomer ranges from 20 to 40 percent by weight of the total components in the atomized mixture on a carrier gas free basis.
  • Suitable halogenated saturated hydrocarbon includes for example dichloromethane (methylene chloride).
  • dichloromethane methylene chloride
  • Other examples include trichloromethane (chloroform), carbon tetrachloride, trichloroethane, chlorobutane, bromoethane, dibromomethane (methylene bromide), and tribromomethane (bromoform).
  • the amount of halogenated saturated hydrocarbon may be expressed as a percent of the total components in the atomized mixture with the exception of the carrier gas, i.e., on a carrier gas free basis. In one embodiment, the amount of halogenated saturated hydrocarbon ranges from 90 to 50 percent by weight of the total components in the atomized mixture on a carrier gas free basis. In one embodiment, the amount of halogenated saturated hydrocarbon ranges from 80 to 60 percent by weight of the total components in the atomized mixture on a carrier gas free basis.
  • the atomized mixture may include at least one curative, such as sulfur donors and accelerators.
  • curatives may be absent from the material deposited on the tire cord from the atmospheric plasma.
  • curatives present in a rubber composition contacted with the tire cord may serve to cure the deposited material via migration of the curatives from the rubber composition to the material deposited on the cord prior to cure.
  • curatives may be present in an amount ranging from 0.5 to 2 percent by weight on a carrier gas free basis.
  • the tire cord is constructed of any of the various reinforcement materials commonly used in tires.
  • the tire cord includes steel and polymeric cords.
  • Polymeric cords may include any of the various textile cords as are known in the art, including but not limited to cords constructed from polyamide, polyester, polyketone, rayon, and polyaramid.
  • the tire cord is exposed to the atmospheric plasma for a time sufficient to deposit an adhesively effect amount of polymerized or partially polymerized monomer onto the cord surface.
  • adhesively effective amount it is meant that the treated cord will show increased adhesion to a cured rubber compound as measured by a standard adhesion test, such as ASTM Standard D2229-73.
  • the exposure time required will depend on the concentration of monomer in the atomized mixture, the flow rate of atomized mixture into the plasma generator, and the power input to the plasma generator. For a batch process wherein stationary cord is exposed to an atmospheric plasma, the cord is exposed for from 1 to 100 seconds.
  • the exposure time may be characterized by a residence time expressed as the cord path length (e.g., in centimeters) through the plasma generator divided by the cord transit rate (e.g., in cm/sec).
  • the residence time in such a continuous process would then range from 1 to 100 seconds.
  • the flow rate of atomized mixture into the plasma generator necessary to obtain an adhesively effective amount of polymerized or partially polymerized monomer onto the cord surface will depend on the desired face velocity in the plasma generator, i.e., the gas velocity (e.g., in cm/sec) passing perpendicular to a characteristic internal cross-sectional area of the plasma generator. Necessary flow rate may be determined by one skilled in the art without undue experimentation.
  • the atmospheric pressure plasma treated cord is generally used in a component of a pneumatic tire.
  • the treated cord is calendered or otherwise contacted with a rubber composition to form the tire component using procedures as are known in the art.
  • the tire component may be a belt, carcass, apex, bead, chipper, flipper, or any other component including a cord reinforcement as are known in the art.
  • the tire component is a steel belt wherein treated steel tire cords are calendared into a rubber composition.
  • the tire component is a tire carcass wherein polymeric tire cords are contacted with a plycoat rubber composition.
  • the rubber compositions used in tire components would be compounded by methods generally known in the rubber compounding art, such as mixing the various sulfur-vulcanizable constituent rubbers with various commonly used additive materials such as, for example, curing aids, such as sulfur, activators, retarders and accelerators, processing additives, such as oils, resins including tackifying resins, silicas, and plasticizers, fillers, pigments, fatty acid, zinc oxide, waxes, antioxidants and antiozonants, peptizing agents and reinforcing materials such as, for example, carbon black.
  • curing aids such as sulfur, activators, retarders and accelerators
  • processing additives such as oils, resins including tackifying resins, silicas, and plasticizers
  • fillers pigments, fatty acid, zinc oxide, waxes, antioxidants and antiozonants
  • peptizing agents and reinforcing materials such as, for example, carbon black.
  • the additives mentioned above are selected and commonly used in conventional amounts.
  • the rubber compound may contain various conventional rubber additives.
  • the addition of carbon black comprises about 10 to 200 parts by weight of diene rubber (phr). In another embodiment, from about 20 to about 100 phr of carbon black is used.
  • carbon blacks may be used. Included in the list of carbon blacks are those known under the ASTM designations N299, N315, N326, N330, M332, N339, N343, N347, N351, N358, N375, N539, N550 and N582.
  • processing aids may be present and can include, for example, aromatic, naphthenic, and/or paraffinic processing oils.
  • Silica if used, may be used in an amount of about 5 to about 100 phr, often with a silica coupling agent.
  • Representative silicas may be, for example, hydrated amorphous silicas.
  • Typical amounts of antioxidants comprise about 1 to about 5 phr.
  • Representative antioxidants may be, for example, diphenyl-p-phenylenediamine, polymerized 1,2-dihydro-2,2,4-trimethylquinoline and others, such as, for example, those disclosed in the Vanderbilt Rubber Handbook (1990), Pages 343 through 362.
  • Typical amounts of antiozonants comprise about 1 to about 5 phr.
  • Representative antiozonants may be, for example, those disclosed in the Vanderbilt Rubber Handbook (1990), Pages 363 through 367.
  • Typical amounts of fatty acids, if used, which can include stearic acid comprise about 0.5 to about 3 phr.
  • Typical amounts of zinc oxide comprise about 2 to about 10 phr.
  • Typical amounts of waxes comprise about 1 to about 5 phr. Often microcrystalline waxes are used.
  • Typical amounts of peptizers comprise about 0.1 to about 1 phr. Typical peptizers may be, for example, pentachlorothiophenol and dibenzamidodiphenyl disulfide.
  • the vulcanization is conducted in the presence of a sulfur vulcanizing agent.
  • suitable sulfur vulcanizing agents include elemental sulfur (free sulfur) or sulfur donating vulcanizing agents, for example, an amine disulfide, polymeric polysulfide or sulfur olefin adducts.
  • the sulfur vulcanizing agent is elemental sulfur.
  • sulfur vulcanizing agents are used in an amount ranging from about 0.5 to about 8 phr. In another embodiment about 3 to about 5 phr of sulfur vulcanizing agents are used.
  • Accelerators are used to control the time and/or temperature required for vulcanization and to improve the properties of the vulcanizate.
  • a single accelerator system may be used, i.e., primary accelerator.
  • a primary accelerator is used in amounts ranging from about 0.5 to about 2.5 phr.
  • combinations of two or more accelerators may be used, including a primary accelerator which is generally used in the larger amount (0.5 to 2.0 phr), and a secondary accelerator which is generally used in smaller amounts (0.05 to 0.50 phr) in order to activate and to improve the properties of the vulcanizate.
  • Combinations of these accelerators have been known to produce a synergistic effect of the final properties and are somewhat better than those produced by use of either accelerator alone.
  • delayed action accelerators may be used which are not affected by normal processing temperatures but produce satisfactory cures at ordinary vulcanization temperatures.
  • Suitable types of accelerators that may be used in the present invention are amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates and xanthates.
  • the primary accelerator is a sulfenamide.
  • the secondary accelerator may be a guanidine, dithiocarbamate or thiuram compound.
  • the rubber compound may contain any of the cobalt materials known in the art to further promote the adhesion of rubber to metal in the case of the use of steel tire cords.
  • One advantage of the present invention is the reduction and possible elimination of cobalt compounds. However, it may be desirable to have some amounts that are present.
  • suitable cobalt materials which may be employed include cobalt salts of fatty acids such as stearic, palmitic, oleic, linoleic and the like; cobalt salts of aliphatic or alicyclic carboxylic acids having from 6 to 30 carbon atoms, such as cobalt neodecanoate; cobalt chloride, cobalt naphthenate; cobalt carboxylate and an organo-cobalt-boron complex commercially available under the designation Manobond C from Wyrough and Loser, Inc, Trenton, N.J. Manobond C is believed to have the structure:
  • R 8 is an alkyl group having from 9 to 12 carbon atoms.
  • Amounts of cobalt compound which may be employed depend upon the specific nature of the cobalt material selected, particularly the amount of cobalt metal present in the compound.
  • the amount of the cobalt material may range from about 0.2 to 5 phr. In another embodiment, the amount of cobalt compound may range from about 0.5 to 3 phr. In one embodiment, the amount of cobalt material present in the stock composition is sufficient to provide from about 0.01 percent to about 0.50 percent by weight of cobalt metal based upon total weight of the rubber stock composition. In another embodiment, the amount of cobalt material present in the stock composition is sufficient to provide from about 0.03 percent to about 0.2 percent by weight of cobalt metal based on total weight of wire coat composition.
  • the atmospheric pressure plasma treated cord may be further treated with one or more of RFL (resorcinol-formaldehyde-latex), isocyanate or epoxide type dips.
  • RFL resorcinol-formaldehyde-latex
  • isocyanate epoxide type dips.
  • the tire containing the tire component can be built, shaped, molded and cured by various methods which will be readily apparent to those having skill in such art.
  • the prepared tire of this invention is conventionally shaped and cured by methods known to those having skill in such art.
  • reinforcement cords which includes tire cords, as treated by the methods described herein
  • Any rubber or elastomer article of manufacture reinforced with reinforcement cords can utilize cords as treated by the methods described herein.
  • applications of the treated reinforcement cords using the plasma methods described herein include reinforced hoses, transmission belts, drive belts, air springs, conveyor belts, drive tracks, and the like.
  • the methods as described herein as suitable for treatment of tire cords are equally applicable to the treatment of any reinforcement cord as used in reinforced rubber or elastomer articles of manufacture.
  • Such reinforcement cords may be in the form of individual cords or as a fabric.
  • a laboratory dielectric barrier discharge apparatus was constructed consisting of a quartz tube with aluminum tape electrodes wrapped at a spaced interval on the exterior of the tube, with a first electrode connected to a high voltage power supply and a second electrode grounded.
  • Argon gas at atmospheric pressure was atomized with mixture of 20 weight percent squalene, 5 weight percent sulfur and 75 weight percent dichloromethane and was passed through the interior of the quartz tube (all amounts given on a carrier gas free basis).
  • a steel tire cord of 3+5 ⁇ 7 ⁇ 0.15 galvanized construction was extended through the interior of the quartz tube and held stationary. Application of high voltage to the first electrode ignited a plasma in the quartz tube.
  • XPS and nano-SIMS analysis of the coatings showed that the coatings with high levels of adhesion showed a homogeneous, essentially defect-free coating with uniform distributions of sulfur, chlorine, and unsaturated (olefinic) carbon.
  • the coatings were also notable in that there was not a high level of oxygen and nitrogen incorporation as is typically seen in atmospheric plasma polymers.
  • Table 2 shows the atomic concentrations obtained by XPS analysis of the major elements composing the plasma coating for five different samples for which the process conditions are described in Table 3.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Toxicology (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Ropes Or Cables (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Tires In General (AREA)
  • Tyre Moulding (AREA)
  • Plasma Technology (AREA)
US12/910,919 2010-04-01 2010-10-25 Atmospheric plasma treatment of reinforcement cords and use in rubber articles Abandoned US20110241269A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US12/910,919 US20110241269A1 (en) 2010-04-01 2010-10-25 Atmospheric plasma treatment of reinforcement cords and use in rubber articles
EP11160064.9A EP2371882B1 (fr) 2010-04-01 2011-03-28 Traitement au plasma atmosphérique de câble à pneu
BRPI1100838-5A2A BRPI1100838A2 (pt) 2010-04-01 2011-03-30 Tratamento de plasma atmosférico de cabos de reforço e uso em artigos de borracha
KR1020110029896A KR101800460B1 (ko) 2010-04-01 2011-03-31 보강 코드의 대기압 플라즈마 처리 및 고무 제품에서의 용도
JP2011081888A JP5944107B2 (ja) 2010-04-01 2011-04-01 強化コードの大気圧プラズマ処理及びゴム製品における使用
CN201110081903.3A CN102212963B (zh) 2010-04-01 2011-04-01 增强帘子线的大气压等离子体处理和在橡胶制品中的应用
US14/074,097 US9133360B2 (en) 2010-04-01 2013-11-07 Atmospheric plasma treatment of reinforcement cords and use in rubber articles

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US9433971B2 (en) 2012-10-04 2016-09-06 The Goodyear Tire & Rubber Company Atmospheric plasma treatment of reinforcement cords and use in rubber articles
US9441325B2 (en) 2012-10-04 2016-09-13 The Goodyear Tire & Rubber Company Atmospheric plasma treatment of reinforcement cords and use in rubber articles
US20180223953A1 (en) * 2015-09-29 2018-08-09 Mitsuboshi Belting Ltd. V-Ribbed Belt and Method for Producing Same
US11802353B2 (en) 2019-11-21 2023-10-31 The Goodyear Tire & Rubber Company Tire textile cord

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EP3336141B1 (fr) * 2016-12-19 2019-08-14 The Goodyear Tire & Rubber Company Traitement au plasma atmosphérique de cordons de renfort et utilisation dans des articles en caoutchouc
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CN108050207A (zh) * 2017-12-06 2018-05-18 无锡市贝尔特胶带有限公司 一种增强型v带
JP7045181B2 (ja) * 2017-12-25 2022-03-31 株式会社ブリヂストン 金属コード－ゴム複合体、タイヤ用ベルト、タイヤ用カーカス及びタイヤ
EP3848191A1 (fr) 2020-01-07 2021-07-14 Glanzstoff Industries A.G. Matériau de renfort et produit élastomère renforcé avec celui-ci
EP3865292B1 (fr) 2020-02-12 2023-06-07 The Goodyear Tire & Rubber Company Dispositif de revêtement de cordon de plasma
FR3122657A1 (fr) 2021-05-10 2022-11-11 Compagnie Generale Des Etablissements Michelin Composite à base d’une composition de caoutchouc et d’un élément de renfort métallique traité en milieu supercritique
FR3122658A1 (fr) 2021-05-10 2022-11-11 Compagnie Generale Des Etablissements Michelin Composite à base d’une composition de caoutchouc et d’un élément de renfort métallique traité au plasma

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US20150152590A1 (en) * 2012-06-24 2015-06-04 The Gates Corporation Carbon Cord For Reinforced Rubber Products and the Products
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US9433971B2 (en) 2012-10-04 2016-09-06 The Goodyear Tire & Rubber Company Atmospheric plasma treatment of reinforcement cords and use in rubber articles
US9441325B2 (en) 2012-10-04 2016-09-13 The Goodyear Tire & Rubber Company Atmospheric plasma treatment of reinforcement cords and use in rubber articles
US20160176232A1 (en) * 2014-12-19 2016-06-23 The Goodyear Tire & Rubber Company Tire with thermoplastic innerliner
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US20180223953A1 (en) * 2015-09-29 2018-08-09 Mitsuboshi Belting Ltd. V-Ribbed Belt and Method for Producing Same
US10760646B2 (en) * 2015-09-29 2020-09-01 Mitsuboshi Belting Ltd. V-ribbed belt and method for producing same
US11802353B2 (en) 2019-11-21 2023-10-31 The Goodyear Tire & Rubber Company Tire textile cord

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US20140072741A1 (en) 2014-03-13
CN102212963B (zh) 2014-07-23
JP2011214214A (ja) 2011-10-27
JP5944107B2 (ja) 2016-07-05
US9133360B2 (en) 2015-09-15
KR20110110731A (ko) 2011-10-07
EP2371882A1 (fr) 2011-10-05
BRPI1100838A2 (pt) 2014-01-07
KR101800460B1 (ko) 2017-11-22
CN102212963A (zh) 2011-10-12

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