Classifications

• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D7/00—Electroplating characterised by the article coated
  • C25D7/06—Wires; Strips; Foils
  • C25D7/0607—Wires
• • 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
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D3/00—Electroplating: Baths therefor
  • C25D3/02—Electroplating: Baths therefor from solutions
  • C25D3/56—Electroplating: Baths therefor from solutions of alloys
  • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
• • 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
• • 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
  • B60C2009/0014—Surface treatments of steel cords
• • D—TEXTILES; PAPER
  • D07—ROPES; CABLES OTHER THAN ELECTRIC
  • D07B—ROPES OR CABLES IN GENERAL
  • D07B2205/00—Rope or cable materials
  • D07B2205/30—Inorganic materials
  • D07B2205/3021—Metals
  • D07B2205/3085—Alloys, i.e. non ferrous
  • D07B2205/3089—Brass, i.e. copper (Cu) and zinc (Zn) alloys

Definitions

• the present invention relates to a rubber reinforcing metal wire for reinforcing a rubber composition, a method for producing the same, and a tire using the rubber reinforcing metal wire.
• rubber reinforcing metal wires such as steel cords to reinforce rubber compositions such as tires, timing belts and hoses.
• This type of rubber reinforcing metal wire is provided with a coating layer that covers the metal wire in order to provide adhesion to the rubber composition to be reinforced.
• the rubber reinforcing metal wire is subjected to wire drawing, it is common to form a brass plating layer as a coating layer in order to provide lubricity to the drawing die.
• Patent Document 1 performs brass plating containing 15 to 45 atm% of Cu in order to achieve both the adhesion between the rubber composition and the workability of the metal wire for rubber reinforcement.
• 0.5 to 5.0 atm% of at least one of Co and Ni is contained in the surface layer from the surface of the brass plating to a depth of 15 nm inside the metal wire in the radial direction.
• the present inventors have found that the metal wire described in Patent Document 1 still has room for improvement.
• attention is not paid to the amount of Cu in the surface layer, but the ratio of Cu, Co, Zn in the surface layer including the amount of Cu in the surface layer is the adhesive strength between the rubber composition and the rubber composition.
• the workability In particular, in the metal wire for rubber reinforcement described in Patent Document 1, there is a possibility that the Cu concentration in the surface layer may be low, and cracks are generated on the surface of the coating layer during the wire drawing process due to the low Cu content. It was considered that the yield of manufacturing metal wires for rubber reinforcement might be poor because it would cause a decrease in wire workability.
• an object of the present invention is to provide a rubber reinforcing metal wire excellent in wire drawing workability and adhesive strength and a method for producing the same.
• the present invention provides the following.
• the composition of the surface layer from the surface of the coating layer to a depth of 15 nm in the radial direction inside is Cu: 60 at% or more and less than 69 at%, Co: 0.5 at% or more and 5.0 at% or less Metal wire for reinforcement.
• the rubber according to (1) or (2), wherein the composition of the entire coating layer is Cu: 60 at% or more and 75 at% or less, Co: 1.0 at% or more and 7.0 at% or less.
• Metal wire for reinforcement is
• the rubber reinforcing metal wire according to any one of (1) to (3); A tire having a rubber layer covering the metal wire for rubber reinforcement.
• a coating layer containing Cu at 60 at% to 75 at% is formed on the core wire, In the core wire, the composition of the surface layer from the surface of the coating layer to the depth of 15 nm in the radial direction is Cu: 60 at% or more and less than 69 at%, Co: 0.5 at% or more and 5.0 at% or less.
• a method for producing a metal wire for rubber reinforcement comprising performing a heat treatment for 5 seconds or more at a temperature of 500 ° C or higher and 650 ° C or lower.
• the metal wire for reinforcing rubber according to the present invention has sufficient wire drawing workability because the surface layer of the coating layer which is liable to crack during wire drawing contains Cu having a ductility of 60 at% to 69 at%. In addition, since the surface layer of the coating layer serving as an interface with the rubber composition contains 0.5 to 5.0 at% of Co that improves adhesion to the rubber composition, the adhesion to the rubber composition is also excellent.
• the rubber reinforcing metal wire in the present invention is used to reinforce rubber products such as tires and hoses.
• a tire can be formed by covering a stranded wire cord formed by twisting a plurality of rubber reinforcing metal wires together with rubber.
• This metal wire for reinforcing rubber is composed of a core wire made of steel wire or the like and a coating layer covering the core wire.
• a metal wire having a diameter of 0.1 mm to 0.7 mm can be preferably used.
• the coating layer is provided to protect the metal core wire from the outside, and to improve the drawability of the rubber reinforcing metal wire and the adhesion to the rubber composition.
• the coating layer is formed of brass having high ductility and excellent workability.
• a coating layer is formed including Co.
• the thickness of the coating layer is preferably 0.1 ⁇ m or more and 0.5 ⁇ m or less.
• the coating layer is preferably brass containing 60 at% or more and 75 at 5 or less of Cu.
• the present inventors adhered when the Co component in the region having a depth of 15 nm in the radial direction from the surface of the coating layer was increased. It was confirmed that the performance was improved. Therefore, a region from the surface of the coating layer to a depth of 15 nm was defined as the surface layer, and it was studied to adjust the ratio of Cu and Co in the surface layer. In other words, pay attention only to the surface layer, not the entire coating layer of the metal wire for reinforcing rubber, and if the surface layer Cu is prone to crack during wire drawing, the workability is improved and it is also an interface with the rubber composition. It has been found that if the Co in the surface layer is increased, the drawability and adhesion of the metal wire for rubber reinforcement can be improved.
• the composition of the surface layer of the coating layer is Cu: 60 at% or more and less than 69 at%, Co: 0.5 or more and 5.0 at% or less, the wire drawing workability is excellent and the adhesion to the rubber composition is achieved. It has been found that a metal wire for rubber reinforcement excellent in properties can be obtained.
• the obtained rubber reinforcing metal wire is heat-treated for 5 to 25 seconds in a thermostatic bath at 500 ° C. to 650 ° C., and sufficiently alloyed, so that the final coating layer surface is exposed in the radial direction.
• Cu, Co, and Zn are diffused in the coating layer so that the composition of the surface layer up to a depth of 15 nm is Cu: 60 to 69 at%, Co: 0.5 to 5.0 at%, and the balance is Zn and impurities. .
• the temperature and time of the heat treatment if the temperature is lower than 500 ° C., it takes time for alloying, and there is a variation in the movement of Cu to the surface layer. The wire drawability is greatly reduced.
• the heat treatment temperature is higher than 650 ° C., the movement of Cu to the surface layer becomes too large, the Cu concentration of the surface layer becomes too high, and the adhesiveness over time may be lowered. Further, the surface Zn layer is melted or denatured to increase the surface layer impurities, thereby reducing the adhesiveness. Further, the surface layer portion of the metal core wire is denatured and the strength level is lowered, so that it is difficult to finally secure the necessary strength of the steel wire. In order to ensure such a problem, there is an appropriate heat treatment time according to the temperature, and this test is also conducted based on this.
• Examples 1 to 27 and Comparative Examples 1 to 13 having a wire diameter of 0.90 mm were prepared and evaluated for wire drawing workability and adhesiveness.
• the wire drawing workability was evaluated by a wire drawing test.
• a rubber reinforcing metal wire that could be drawn to 0.23 mm was evaluated as ⁇
• a rubber reinforcing metal wire that was broken and could not be drawn to 0.23 mm was evaluated as ⁇ .
• adhesiveness was evaluated as follows. In other words, as described above, four metal wires drawn to 0.23 mm are prepared, and the four metal wires are twisted together to create a metal reinforcing wire for rubber reinforcement. It is sandwiched between rubber, vulcanized for 20 minutes at a temperature of about 150 ° C. and a pressure of 50 kg / cm 2 , and further stored at a high temperature and high humidity of 80 ° C. and 95% humidity for 5 days. Then, rubber
• gum was peeled from the metal strand for rubber reinforcement, and the adhesiveness of rubber was evaluated 10 steps from the state of the rubber adhering to the metal strand for rubber reinforcement. In this embodiment, a steel wire having a score of 7 or more was evaluated as a steel wire excellent in adhesiveness.
• the steel wire of Examples 1 to 8 in which the ratio of Cu in the surface layer of the coating layer is 60 at% or more and less than 69 at% has good results of the core wire test, and the adhesiveness is also good. A good score of 7 and 8 was obtained.
• Comparative Examples 1 to 5 in which the ratio of Cu in the surface layer of the coating layer is less than 60 at% the amount of Cu is too small and the wire drawing workability is inferior.
• No. 6 it was confirmed that the amount of Cu was too large and the adhesiveness over time was inferior.
• the composition of the entire coating layer is Cu: 60 at% or more and 75 at% or less, Co: 1.0 at% or more and less than 7.0 at% It was confirmed that a steel wire having good drawing workability and adhesiveness could be obtained.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Mechanical Engineering (AREA)
• Ropes Or Cables (AREA)
• Electroplating Methods And Accessories (AREA)
• Tires In General (AREA)

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Publications (1)

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Cited By (1)

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Citations (9)

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• 2011
  • 2011-09-06 JP JP2011193887A patent/JP6137587B2/ja active Active
• 2012
  • 2012-09-06 KR KR1020147008833A patent/KR20140073518A/ko not_active Ceased
  • 2012-09-06 WO PCT/JP2012/072785 patent/WO2013035805A1/ja active Application Filing
  • 2012-09-06 CN CN201280043391.4A patent/CN103814159B/zh active Active
  • 2012-09-06 IN IN2314CHN2014 patent/IN2014CN02314A/en unknown

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