Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
  • B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B38/00—Ancillary operations in connection with laminating processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
  • B62D—MOTOR VEHICLES; TRAILERS
  • B62D55/00—Endless track vehicles
  • B62D55/08—Endless track units; Parts thereof
  • B62D55/18—Tracks
  • B62D55/24—Tracks of continuously flexible type, e.g. rubber belts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65G—TRANSPORT OR STORAGE DEVICES, e.g. CONVEYORS FOR LOADING OR TIPPING, SHOP CONVEYOR SYSTEMS OR PNEUMATIC TUBE CONVEYORS
  • B65G15/00—Conveyors having endless load-conveying surfaces, i.e. belts and like continuous members, to which tractive effort is transmitted by means other than endless driving elements of similar configuration
  • B65G15/30—Belts or like endless load-carriers
  • B65G15/32—Belts or like endless load-carriers made of rubber or plastics
  • B65G15/34—Belts or like endless load-carriers made of rubber or plastics with reinforcing layers, e.g. of fabric
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
  • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
  • C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B38/00—Ancillary operations in connection with laminating processes
  • B32B2038/0052—Other operations not otherwise provided for
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
  • B60C2001/005—Compositions of the bead portions, e.g. clinch or chafer rubber or cushion rubber
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
  • B60C2001/0066—Compositions of the belt layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
  • B60C9/0007—Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal
  • B60C2009/0021—Coating rubbers for steel cords
• • 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
  • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
  • Y10T156/10—Methods of surface bonding and/or assembly therefor
• • 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
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31678—Of metal

Definitions

• the present invention relates to a rubber composition, a method for producing a rubber-metal composite, a rubber-metal composite, a tire, an industrial belt, and a rubber crawler.
• a rubber-metal composite in which a metal material is embedded in the rubber composition for the purpose of reinforcing the rubber and improving the strength and durability.
• the body is used.
• a metal body such as a steel cord plated with zinc or brass is coated with a rubber composition containing sulfur, and the rubber composition is added.
• So-called direct vulcanization bonding in which these are bonded together with vulcanization, is widely used.
• a steel cord with brass plating containing a specific amount of a metal such as phosphorus or zinc on the outermost surface is immersed in a solution containing a metal salt whose pH is usually in the range of 6.1 to 8.0.
• an object of the present invention is to provide a rubber composition having excellent initial adhesiveness and heat-resistant adhesiveness with a metal material. Another object of the present invention is to provide a method for producing a rubber-metal composite, from which a rubber-metal composite having excellent initial adhesion and heat-resistant adhesion between a metal material and a rubber composition can be obtained. . Furthermore, an object of the present invention is to provide a rubber-metal composite having excellent initial adhesion and heat-resistant adhesion between a metal material and a rubber composition. Still another object of the present invention is to provide a tire, an industrial belt, and a rubber crawler excellent in durability.
• the rubber composition of the present invention is characterized in that it contains 0.0025 to 0.05 parts by mass of a cobalt compound in terms of cobalt with respect to 100 parts by mass of the rubber component.
• the present invention it is possible to provide a rubber composition having excellent initial adhesiveness and heat-resistant adhesiveness with a metal material. According to the present invention, it is possible to provide a method for producing a rubber-metal composite, which can obtain a rubber-metal composite having excellent initial adhesion and heat-resistant adhesion between a metal material and a rubber composition. According to the present invention, it is possible to provide a rubber-metal composite having excellent initial adhesion and heat-resistant adhesion between a metal material and a rubber composition. ADVANTAGE OF THE INVENTION According to this invention, the tire excellent in durability, an industrial belt, and a rubber crawler can be provided.
• the rubber composition of the present invention is characterized by containing a cobalt compound in an amount of 0.0025 to 0.05 parts by mass with respect to 100 parts by mass of the rubber component in terms of cobalt.
• the rubber composition becomes a rubber material of the rubber-metal composite of the present invention.
• Examples of the cobalt compound used in the present invention include a cobalt salt of an organic acid, a cobalt metal complex, and the like, and a cobalt salt of an organic acid is preferable.
• Examples of organic acid cobalt salts include cobalt naphthenate, cobalt stearate, cobalt neodecanoate, cobalt rosinate, cobalt versatate, cobalt tall oil, cobalt oleate, cobalt linoleate, cobalt linolenate, cobalt palmitate Etc.
• cobalt salts of organic acids having 16 to 18 carbon atoms such as cobalt stearate, cobalt oleate, cobalt linoleate, cobalt linolenate, cobalt palmitate, etc. More preferred.
• the cobalt salt of the organic acid may be a complex salt in which part of the organic acid is replaced with boric acid.
• the cobalt metal complex include cobalt acetylacetonate.
• the said cobalt compound may be used individually by 1 type, and may be used in combination of 2 or more type.
• the rubber composition of the present invention contains the cobalt compound in an amount of 0.0025 to 0.05 parts by mass in terms of cobalt with respect to 100 parts by mass of a rubber component described later, and other process conditions (for example, a surface treatment process described later) Depending on the pH of the buffer solution, etc., it is preferably contained in an amount of 0.0025 to 0.025 parts by mass from the viewpoint of initial adhesiveness and heat-resistant adhesiveness.
• cobalt conversion means the mass of the cobalt atom contained in a cobalt compound.
• the cobalt content is less than 0.0025 parts by mass, sufficient initial adhesiveness and heat resistant adhesiveness cannot be obtained, and if it exceeds 0.05 parts by mass, the initial adhesiveness is affected by the organic component contained in the cobalt compound. It is inferior in heat-resistant adhesion, and the durability of the rubber itself against heat, moisture and oxidation deteriorates.
• the rubber component used in the rubber composition of the present invention is not particularly limited.
• natural rubber polybutadiene rubber, polyisoprene rubber, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, ethylene-propylene copolymer
• examples thereof include coalesced rubber, ethylene-propylene-diene terpolymer rubber, butyl rubber, halogenated butyl rubber, alkylated chlorosulfonated polyethylene rubber, isobutylene-isoprene copolymer rubber, and polychloroprene rubber.
• the said rubber component may be used individually by 1 type, and may be used in combination of 2 or more types.
• components generally employed in the rubber industry may be appropriately blended as long as the object of the present invention is not impaired.
• examples of other components include vulcanizing agents such as sulfur, fillers such as silica and carbon black, oils such as process oils, vulcanization accelerators, anti-aging agents, softeners, zinc oxide, and stearic acid. Can be mentioned.
• the rubber composition of the present invention can be produced by kneading these components by a conventional method, followed by heating and extrusion.
• the method for producing a rubber-metal composite of the present invention includes a surface treatment step for bringing a metal material into contact with a buffer solution, an adhesion step for bonding the metal material after the surface treatment step and the rubber composition, including.
• the surface treatment step in the present invention refers to a step of bringing a metal material into contact with a buffer solution.
• the mechanism for improving the adhesion between the rubber composition and the metal material is not limited by a specific theory, but is estimated as follows.
• the metal materials described below may have lubricant and rust preventives attached to their surfaces for the convenience of handling and to protect the metals from corrosion.
• oxides of metals such as copper and zinc contained in the plating layer are adhered. It is considered that the coating made of these deposits hinders the adhesion between the metal material and the rubber composition. Therefore, the adhesion between the metal material and the rubber composition is improved by removing at least a part of the coating film present on the surface of the metal material.
• the surface of the metal material is pretreated with a buffer solution, whereby at least a part of the coating film present on the surface of the metal material is removed, and the surface of the metal material Is moderately activated to a state suitable for adhesion to the rubber composition (that is, the state where the outermost surface composition of the metal material is optimized), so that the initial adhesion between the metal material and the rubber is improved.
• a state suitable for adhesion to the rubber composition that is, the state where the outermost surface composition of the metal material is optimized
• the metal material used in the method for producing a rubber-metal composite of the present invention is not particularly limited.
• iron, steel (stainless steel), lead, aluminum, copper, brass, bronze, monel metal alloy, nickel examples thereof include a linear shape made of a metal such as zinc, a plate shape, and a chain shape.
• the metal material may have a plating layer on the surface.
• the plating layer is not particularly limited, but examples include a zinc plating layer, a copper plating layer, a brass plating layer, etc., among these, from the viewpoint of the initial adhesiveness with the rubber composition, heat resistant adhesiveness, A brass plating layer is preferred.
• the brass plating layer usually has a copper / zinc ratio of 60:40 to 70:30 on a mass basis.
• the metal material is a metal material of the rubber-metal composite of the present invention.
• the metal steel wire is steel, that is, a linear metal containing iron as a main component (the mass of iron exceeds 50% by mass with respect to the total mass of the metal steel wire).
• the metal may include a metal other than iron described above.
• the metal steel wire preferably has a wire diameter of 0.1 mm to 5.5 mm, more preferably 0.15 mm to 5.26 mm, from the viewpoints of workability and durability.
• the wire diameter of the metal steel wire refers to the longest length between two points on the outer periphery in a cross-sectional shape perpendicular to the axis of the metal steel wire.
• the cross-sectional shape perpendicular to the axis of the metal steel wire is not particularly limited, and may be elliptical, rectangular, triangular, polygonal or the like, but is generally circular.
• the cross-sectional shape of the metal steel wire is preferably circular and the wire diameter is preferably 0.1 mm to 0.5 mm.
• the cross-sectional shape is preferably circular, and the wire diameter is preferably 1 mm to 1.5 mm.
• the metal steel wire may have a plating layer on the surface.
• the thickness of the plating layer is not particularly limited. For example, in the case of a brass plating layer, it is generally 100 to 300 nm.
• a buffer solution is used in the surface treatment step.
• the buffer solution refers to a solution having a buffering action.
• the buffering action refers to an action of maintaining a substantially constant hydrogen ion concentration despite the addition or removal of a certain amount of acid or base.
• an acid solution or an aqueous metal salt solution is used in the above surface treatment step, when a rubber-metal composite is continuously produced, or after immersing the metal material in the treatment solution, it is washed with water, and the treatment solution is again treated.
• the pH of the treatment liquid may fluctuate greatly due to elution of metal from the surface of the metal material or mixing of water.
• the buffer solution since the buffer solution is used in the surface treatment step, it is advantageous that the pH of the buffer solution does not easily fluctuate.
• the buffer used in the present invention preferably has a pH in the range of 5.0 to 7.2, more preferably 5.2 to 7.0, and more preferably 5.4 to 6.8. Is more preferable, and 6.0 to 6.8 is particularly preferable. Since the pH of the buffer solution is 5.0 or more, the acid does not excessively corrode the metal material, and by being 7.2 or less, the coating existing on the surface of the metal material can be easily removed. Become. In addition, when the pH of the buffer solution is 5.0 to 7.2, it is possible to maintain good durability of the metal material of the obtained rubber-metal composite, and it is possible to maintain initial adhesiveness and heat-resistant adhesiveness. Can be further improved. In addition, when the pH of the buffer solution is 6.0 to 6.8, the storage stability (adhesiveness after treatment is left) is also good.
• the buffer solution contains at least one acid.
• the acid contained in the buffer solution is not particularly limited, but is preferably a weak acid and has an acid dissociation constant (pKa) of 4 to 8 from the viewpoint of adhesion between the rubber composition and the metal material and durability of the metal material. Certain acids are preferred. Since the buffer solution contains at least one acid selected from acids having an acid dissociation constant pKa of 4 to 8, good durability of the metal material can be maintained, and the rubber composition and the metal material can be maintained. The initial adhesiveness and heat resistant adhesiveness can be further improved.
• the weak acid include acetic acid, phosphoric acid, phthalic acid, succinic acid, citric acid, and carbonic acid. Among these, acetic acid and phosphoric acid are more preferable. These acids may be used alone or in combination of two or more.
• the metal component contained in the buffer is preferably sodium or potassium.
• the buffer solution substantially contains other metals, particularly transition metals, from the viewpoint of the ease of pH adjustment of the buffer solution or the ease of drainage treatment of the buffer solution after use. Preferably not.
• “substantially free” means that the transition metal concentration in the buffer is less than 0.01 mol / l.
• the transition metal concentration in the buffer is preferably 0.005 mol / l or less, particularly preferably 0 mol / l.
• the transition metal is from the fourth period scandium (Sc) to zinc (Zn), the fifth period yttrium (Y) to cadmium (Cd), the sixth period lutetium (Lu). It refers to metal elements up to mercury (Hg), including cobalt.
• Examples of the buffer include, for example, acetic acid-sodium acetate buffer, sodium dihydrogen phosphate-disodium hydrogen phosphate buffer, potassium hydrogen phthalate-sodium hydroxide buffer, sodium citrate-sodium hydroxide buffer, Examples include succinic acid-sodium tetraborate buffer.
• acetic acid-sodium acetate buffer solution, sodium dihydrogen phosphate-disodium hydrogen phosphate A buffer is preferred.
• the above buffer solution may be prepared by adding an inorganic salt, alcohol, or the like, if necessary, within a range that does not impair the object of the present invention.
• examples of the method of bringing the metal material into contact with the buffer solution include a method of spraying a buffer solution on the metal material and a method of immersing the metal material in the buffer solution.
• the time during which the metal material is in contact with the buffer solution (hereinafter referred to as the surface treatment time) may be appropriately changed depending on the pH of the buffer solution, and is usually in the range of 0.5 to 20 seconds, preferably The range is from 1 second to 15 seconds.
• the surface treatment time When the pH of the buffer solution is low, the surface treatment time can be short.
• the pH of the buffer solution is high, the surface treatment time can be increased.
• the surface treatment time can be easily adjusted, that is, the degree of surface treatment of the metal material can be finely adjusted.
• the temperature of the buffer solution is preferably 10 ° C. to 40 ° C., more preferably 15 ° C. to 30 ° C.
• the adhesion step in the present invention refers to a step of bonding the metal material after the surface treatment step and the rubber composition.
• Examples of a method for bonding the metal material after the surface treatment step and the rubber composition include a method of vulcanizing and bonding the metal material and the rubber composition under pressure and heating.
• Vulcanization conditions are not particularly limited, but the pressure is preferably 2 MPa to 15 MPa, more preferably 2 MPa to 5 MPa, and the temperature is preferably 120 to 200 ° C, more preferably 130 to 170 ° C.
• the vulcanization time is not particularly limited, but is preferably 3 minutes to 60 hours.
• the method for producing a rubber-metal composite of the present invention may include a washing step of washing the metal material brought into contact with the buffer solution with water after the surface treatment step and before the bonding step. By having this step, the buffer solution adhering to the metal material can be washed away, and corrosion of the metal material, particularly the plating layer, can be further prevented.
• the water used in the washing step may be ion exchange water or tap water, but is preferably ion exchange water.
• the rubber-metal composite of the present invention is produced by the above production method, and is excellent in initial adhesion and heat-resistant adhesion between the rubber composition and the metal material.
• the ply to which the rubber-metal composite is applied is preferably used as a tire carcass ply and a belt ply, and the rubber-metal composite is preferably used for a tire bead and the like.
• the rubber-metal composite is suitably used for industrial belts such as conveyor belts and rubber crawlers.
• Rubber composition 100 parts by weight of natural rubber, 60 parts by weight of HAF carbon, 8 parts by weight of zinc, 2 parts by weight of anti-aging agent (Ouchi Shinsei Chemical Co., Ltd. Nocrack 6C), vulcanization accelerator (Ouchi Shinsei Chemical Industry Co., Ltd.) Noxeller DZ) Cobalt stearate was added to 1 part by mass and 5 parts by mass of sulfur to a cobalt equivalent amount shown in Table 1, kneaded by a conventional method, heated and extruded, and Examples 1 to 14 and Comparative Examples The rubber composition used for 1 and 2 was obtained.
• sodium dihydrogen phosphate (special grade reagent) was dissolved in ion-exchanged water at a concentration of 0.2 mol / l. These liquids were mixed at a ratio of 1: 1 to prepare a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer having a pH of 6.6. At that time, the buffer solution was prepared so that other ions were not substantially mixed.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• General Chemical & Material Sciences (AREA)
• Combustion & Propulsion (AREA)
• Transportation (AREA)
• Tires In General (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
• Tyre Moulding (AREA)
• Laminated Bodies (AREA)

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• 2012
  • 2012-03-23 JP JP2012067858A patent/JP5887171B2/ja active Active
• 2013
  • 2013-03-22 WO PCT/JP2013/001969 patent/WO2013140820A1/ja not_active Ceased
  • 2013-03-22 EP EP13764809.3A patent/EP2829571B1/en active Active
  • 2013-03-22 RU RU2014142692/11A patent/RU2595732C2/ru active
  • 2013-03-22 IN IN7906DEN2014 patent/IN2014DN07906A/en unknown
  • 2013-03-22 US US14/386,420 patent/US9708464B2/en active Active
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