WO2020226170A1 - ゴム補強用金属線及び、ゴム補強用金属線の製造方法 - Google Patents

ゴム補強用金属線及び、ゴム補強用金属線の製造方法 Download PDF

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Publication number
WO2020226170A1
WO2020226170A1 PCT/JP2020/018606 JP2020018606W WO2020226170A1 WO 2020226170 A1 WO2020226170 A1 WO 2020226170A1 JP 2020018606 W JP2020018606 W JP 2020018606W WO 2020226170 A1 WO2020226170 A1 WO 2020226170A1
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WO
WIPO (PCT)
Prior art keywords
rubber
cobalt
layer
metal wire
wire
Prior art date
Application number
PCT/JP2020/018606
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English (en)
French (fr)
Japanese (ja)
Inventor
稔 若宮
Original Assignee
トクセン工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by トクセン工業株式会社 filed Critical トクセン工業株式会社
Priority to CN202080034130.0A priority Critical patent/CN113795625B/zh
Publication of WO2020226170A1 publication Critical patent/WO2020226170A1/ja

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    • 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
    • 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
    • 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 metal wire for rubber reinforcement such as a steel cord used as a reinforcing material for rubber such as a tire, and a method for manufacturing the same.
  • the invention relating to the steel substrate existing between the two is known (see Patent Document 1).
  • the average thickness of the adhesive reaction layer is 50 nm in a moist heat deteriorated state after the rubber is calcified and bonded and held in an atmosphere of a temperature of 50 to 100 ° C. and a humidity of 60 to 100% for 1 hour to 20 days.
  • the fractal dimension of the interface between the adhesive reaction layer and the rubber is in the range of 1.001 to 1.300, and the brass plating layer is 0.1 to 5.0 weight with respect to 100 parts by weight of the plating. A portion of cobalt or 1.0 to 10.0 parts by weight of nickel is included.
  • the following invention is known regarding a rubber-steel cord composite composed of a rubber composition and a brass-plated steel filament or a steel cord formed by twisting them (see Patent Document 3). ..
  • the rubber composition comprises 100 parts by weight of the rubber component and 0.1 part by weight or less of the cobalt salt as the cobalt metal.
  • the brass-plated steel filament or the steel cord formed by twisting these is a filament radial direction from the peripheral surface of the steel filament having a copper concentration of 15 to 45 atomic% on the peripheral surface.
  • the surface region to a depth of 15 nm on the inside contains at least one of a cobalt (Co) atom and a nickel (Ni) atom.
  • Co salt oxidizes the vulcanized rubber and causes deterioration, which also causes a decrease in tire durability.
  • Co salt is expensive, and it is desired to reduce the amount of Co salt used.
  • An object of the present invention is to solve the above problems, and it is possible to improve the strength characteristics of the adhesive interface between the rubber reinforcing metal wire and the rubber, and to suppress the deterioration due to the oxidation of the rubber to improve the durability of the rubber. It is to provide technology that can be improved.
  • the present invention for solving the above problems is a metal wire for rubber reinforcement provided with a brass plating layer containing copper and zinc on the surface thereof. Cobalt is contained in the surface layer of the brass plating layer,
  • the rubber reinforcing metal wire is characterized in that the cobalt concentration on the surface of the brass plating layer is 3 atomic% or more and 7 atomic% or less.
  • cobalt is contained in the surface of the brass-plated layer provided on the surface of the rubber reinforcing metal wire at a concentration of 3 atomic% or more and 7 atomic% or less. According to this, when the rubber is reinforced with the metal wire, cobalt having an appropriate concentration can be present in the reaction layer formed between the rubber and the metal wire. As a result, it is not necessary to contain cobalt in the rubber before the reaction, and deterioration of the rubber due to the oxidation of cobalt can be suppressed.
  • the cobalt may be contained in a region having a depth of 9 nm or less from the surface of the brass plating layer. By doing so, cobalt can be concentrated near the surface of the brass plating layer, and when the rubber is reinforced by the metal wire, the cobalt is reliably supplied to the rubber during the vulcanization reaction between the rubber and the metal wire. be able to.
  • the copper concentration in the region from the surface of the brass plating layer to a depth of 9 nm may be 45 atomic% or more.
  • the cobalt present in the brass plating layer is the sulfur (S) in the rubber and the copper (S) in the brass plating layer in the reaction layer between the rubber and the metal wire when the rubber is reinforced by the metal wire. Since the reaction of Cu) is inhibited, if the copper concentration in the surface layer of the brass plating layer is too low, the reaction between the rubber and the metal wire becomes poor, and it becomes difficult to obtain sufficient initial adhesive strength.
  • the copper concentration in the region from the surface of the brass-plated layer of the metal wire to the depth of 9 nm is set to 45 atomic% or more. According to this, even if cobalt is contained in the surface layer of the brass plating layer, sulfur (S) in the rubber and copper (Cu) in the brass plating layer are separated in the reaction layer between the rubber and the metal wire. It can be sufficiently reacted and a sufficient initial adhesive strength can be obtained.
  • the cobalt concentration in the entire brass plating layer may be 0.1% by weight or less.
  • the cobalt concentration in the entire brass plating layer exceeds 0.1% by weight, the cobalt concentration in the reaction layer between the rubber and the metal wire may be too high, and the thickness of the reaction layer may become too thick. .. It is known to cause the destruction of the reaction layer.
  • the present invention it is possible to appropriately maintain the cobalt concentration in the reaction layer between the rubber and the metal wire, suppress the excessive expansion of the thickness of the reaction layer, and cause the reaction layer to be destroyed. It can be suppressed.
  • the cobalt atom may be contained by substitution plating on the surface layer of the brass plating layer. According to this, it is possible to control the concentration of cobalt atoms in the surface layer of the brass plating layer more precisely, and it is possible to more reliably improve the initial adhesion state between the rubber and the metal wire, and further. More reliably, the excessive expansion of the reaction layer due to cobalt can be suppressed.
  • the present invention has a plurality of stages of wire drawing steps for drawing a wire rod, and In the stranded wire process of twisting a plurality of wire rods drawn in the wire drawing process, Of the plurality of stages of wire drawing steps, a brass plating step of performing brass plating on the wire rod at least before the final wire drawing step, and A cobalt plating step in which cobalt is contained in the surface layer of the brass plating layer formed in the brass plating step by replacement plating, and Have,
  • the cobalt plating step may be a method for producing a metal wire for rubber reinforcement, which is carried out after all the wire drawing steps and the stranded wire steps.
  • the above means for solving the problems can be used in combination as much as possible.
  • the strength characteristics of the adhesive interface between the rubber reinforcing metal wire and the rubber can be improved, and the oxidative deterioration of the rubber can be suppressed to improve the durability of the rubber.
  • FIG. 1 shows an example of a cross-sectional view of the tire reinforcing steel cord 1 (hereinafter, also simply referred to as steel cord 1) in this embodiment.
  • the steel cord 1 as shown in FIG. 1 has a structure in which a plurality of filaments 2 are twisted together, and further, the plurality of steel cords 1 are covered with a rubber material in a state of being aligned in parallel at predetermined intervals. This reinforces the tires. Therefore, the indispensable conditions for the steel cord 1 are excellent mechanical strength and good chemical adhesion to the rubber material.
  • Brass plating is often formed on the surface of the filament 2 of the steel cord 1 in FIG. 1.
  • This brass plating is a binary alloy plating containing copper and zinc as main components.
  • the rubber material is reinforced by the steel cord 1
  • the plurality of steel cords 1 are aligned in parallel, and the front and back surfaces of the arranged steel cords 1 are covered with the rubber material and vulcanized and bonded. ..
  • This "vulcanization adhesion" is carried out by the heat of vulcanization when vulcanizing and molding an unvulcanized raw tire in a mold.
  • a diene rubber such as natural rubber, isoprene rubber, butadiene rubber, and styrene / butadiene rubber is suitable. This diene rubber is used alone or in a blend of two or more.
  • FIG. 2 is a diagram showing an adhesive state between the conventional steel cord 1 and rubber. More specifically, FIG. 2 shows the vicinity of the interface where the plating layer 10b is formed on the steel surface 10a of the surface layer portion 10 of the steel cord 1 and further adhered to the rubber 12.
  • FIG. 2A shows an unvulcanized state
  • FIG. 2B shows an initial bonding state after the vulcanization reaction
  • FIG. 2C shows a moist heat deterioration state after use.
  • the plating layer 10b is brass-plated (Cu—Zn), and in addition to sulfur (S), cobalt (Co) for improving adhesiveness is dispersed in the rubber 12.
  • the steel cord 1 is subjected to brass plating (Cu—Zn) and further formed with cobalt (Co) plating to form a brass plating (Cu—Zn) layer. It was decided that the surface layer of the above would contain cobalt and then be adhered to the rubber.
  • FIG. 3 shows the state of adhesion between the steel cord 1 and the rubber 32 in this embodiment. More specifically, FIG. 3 shows the vicinity of the interface where the plating layer 30b is formed on the steel surface 30a in the surface layer portion 30 of the steel cord 1 and further adhered to the rubber 32. Further, FIG. 3A shows an unvulcanized state, and FIG. 3B shows an initial state of the vulcanization reaction.
  • cobalt (Co) plating layer 31 is replaced on the surface of the brass plating (Cu—Zn) plating layer 30b in an unvulcanized state. It is formed so that the surface layer of the plating layer 30b contains cobalt.
  • FIG. 3B in the initial state after the vulcanization reaction, cobalt (Co) can be intensively dispersed in the rubber near the adhesion interface of the rubber 32 with the steel cord 1. it can.
  • the cobalt (Co) plating layer 31 is formed by replacement plating, and is concentrated in a region having a depth of 9 nm or less from the surface of the plating layer 30b having a total thickness of about 200 to 300 nm. It is contained.
  • FIG. 4 shows the state after FIG. 3 in the state of adhesion between the steel cord 1 and the rubber 32 in this embodiment.
  • FIG. 4A shows an early state after the brewing reaction
  • FIG. 4B shows a moist heat deterioration state after use.
  • the relationship between the copper (Cu) concentration and the zinc (Zn) concentration in the reaction layer consisting of the CuxS layer + ZnS component is such that copper (Cu) concentration> zinc ( A relationship of Zn) concentration was observed (in FIG. 2C, copper (Cu) concentration ⁇ zinc (Zn)).
  • the reaction layer composed of the ZnO layer and the CuxS layer can be sufficiently expanded, and the excessive diffusion of cobalt (Co) into the rubber 32 can be suppressed. Therefore, the adhesive strength of the rubber 32 to the steel cord 1 can be sufficiently maintained even in a moist heat deteriorated state after use. Further, since the rubber 32 does not contain cobalt (Co), it is possible to suppress deterioration and peeling of the rubber 32 due to oxidation of the cobalt (Co).
  • Steel cord 1 is coated with the rubber composition shown in Table 1, press vulcanized under the condition of 150 ° C. for 30 minutes, and then subjected to a wet heat deterioration test for 96 hours in saturated steam at a temperature of 105 ° C. and evaluated. A test piece was prepared.
  • the cobalt surface concentration (atomic%) on the cobalt-plated surface of the steel cord 1 is 0%, 3%, 7%, 11%, and 17%, respectively, the X of CuxS at the time of initial bonding and after moist heat deterioration .
  • the value of the Cu / Zn concentration ratio, and the value of the reaction layer thickness ( ⁇ m) were measured with an Auger analyzer (manufactured by PHI700 ULVAC-PHI, Inc.).
  • Auger analyzer manufactured by PHI700 ULVAC-PHI, Inc.
  • the value of the Cu / Zn concentration ratio after moist heat deterioration is good if it is 1 or more as described above.
  • Table 2 shows the actual measurement results of the above characteristic values. As shown in Table 2, when the cobalt surface concentration on the surface of the plating layer was 3% or more and 7% or less, good results were obtained both at the time of initial adhesion and after moist heat deterioration.
  • Table 3 shows the other characteristics of the sample having a cobalt concentration of 3% on the surface of the plating layer and the sample having a cobalt concentration of 7% in Table 2.
  • cobalt (Co) was contained in a region having a depth of 9 nm or less from the surface of the plating layer 30b by brass plating (Cu—Zn).
  • Cu—Zn brass plating
  • Cobalt (Co) can be concentrated near the surface of the plating layer 30b, and when the rubber 32 is reinforced by the steel cord 1, the rubber 32 is vulcanized during the vulcanization reaction between the rubber 32 and the steel cord 1.
  • Cobalt (Co) could be reliably supplied to and the adhesiveness could be improved.
  • the copper concentration in the region from the surface of the plating layer 30b to the depth of 9 nm is 45 atomic% or more, even if the surface layer of the plating layer 30b contains cobalt (Co).
  • the sulfur (S) in the rubber 32 and the copper (Cu) in the plating layer 30b can be sufficiently reacted to obtain sufficient initial adhesive strength. Was done.
  • the cobalt concentration in the entire plating layer 30b is 0.1% by weight or less, the cobalt (Co) concentration in the reaction layer between the rubber 32 and the steel cord 1 can be appropriately maintained. Excessive expansion of the thickness of the reaction layer could be suppressed, and the occurrence of reaction layer destruction could be suppressed.
  • FIG. 5 shows a flowchart of the manufacturing process of the steel cord 1 in this embodiment.
  • the wire rod which is the material of the filament 2 is washed with an acid. More specifically, by treating the surface of a wire rod formed through wire making, steel making, and rolling processes with an acid, "rust" and fine "scale” generated on the metal surface are removed.
  • the primary wire drawing and the primary burning wire are performed.
  • this primary wire drawing for example, a wire rod having a diameter of 5.5 mm is stretched at an initial stage to make it thinner and improve its strength. Further, the toughness is restored and the linearity and rollability are maintained by performing the burning wire on the primary drawn wire.
  • S103 secondary wire drawing and secondary burning wire are further performed to secure the necessary physical property values.
  • brass plating is performed. This brass plating is often formed by sequentially forming a copper plating layer and a zinc plating layer on the surface of a wire rod, and then alloying both metals by thermal diffusion. The ratio of brass-plated copper to zinc and the plating thickness are appropriately selected in order to maintain the basic adhesion between rubber and steel wire.
  • cobalt plating is performed after the tertiary wire drawing and stranded wire.
  • cobalt plating with poor ductility after the tertiary wire drawing and stranded wire, it is possible to suppress peeling and cracking of the cobalt plating and reduce the burden of adding or changing the manufacturing process.
  • the present invention has been applied to the reinforcement of tires in the above examples, the present invention can also be applied to the reinforcement of rubber other than tires.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Ropes Or Cables (AREA)
  • Tires In General (AREA)
PCT/JP2020/018606 2019-05-09 2020-05-08 ゴム補強用金属線及び、ゴム補強用金属線の製造方法 WO2020226170A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202080034130.0A CN113795625B (zh) 2019-05-09 2020-05-08 橡胶补强用金属线及橡胶补强用金属线的制造方法

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JP2019089370A JP6781800B1 (ja) 2019-05-09 2019-05-09 ゴム補強用金属線及び、ゴム補強用金属線の製造方法
JP2019-089370 2019-05-09

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WO2020226170A1 true WO2020226170A1 (ja) 2020-11-12

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JP (1) JP6781800B1 (zh)
CN (1) CN113795625B (zh)
TW (1) TWI735224B (zh)
WO (1) WO2020226170A1 (zh)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5756110A (en) * 1980-05-27 1982-04-03 Sodetal Metallic body coated with brass for reinforcing rubber product
JPS6431837A (en) * 1987-07-28 1989-02-02 Bridgestone Corp Composite of steel cord and rubber composition
JP2002205506A (ja) * 2000-11-09 2002-07-23 Bridgestone Corp タイヤ
WO2017065242A1 (ja) * 2015-10-16 2017-04-20 栃木住友電工株式会社 スチールコードおよびその製造方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1598388A (en) * 1978-05-26 1981-09-16 Bekaert Sa Nv Steel wire reinforcing elements
US6814116B2 (en) * 2000-11-09 2004-11-09 Bridgestone Corporation Tire with specified rubber-steel cord composite
JP4602314B2 (ja) * 2005-12-13 2010-12-22 住友ゴム工業株式会社 金属コード、ゴム・コード複合体、及びそれを用いた空気入りタイヤ
JP2010018784A (ja) * 2008-06-11 2010-01-28 Sumitomo Chemical Co Ltd スチールコード被覆用ゴム組成物
JP6246653B2 (ja) * 2014-04-30 2017-12-13 株式会社ブリヂストン ブラスめっき付きゴム物品補強用スチールワイヤ
JP6431837B2 (ja) 2015-12-22 2018-11-28 株式会社三共 遊技機

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5756110A (en) * 1980-05-27 1982-04-03 Sodetal Metallic body coated with brass for reinforcing rubber product
JPS6431837A (en) * 1987-07-28 1989-02-02 Bridgestone Corp Composite of steel cord and rubber composition
JP2002205506A (ja) * 2000-11-09 2002-07-23 Bridgestone Corp タイヤ
WO2017065242A1 (ja) * 2015-10-16 2017-04-20 栃木住友電工株式会社 スチールコードおよびその製造方法

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CN113795625B (zh) 2023-05-30
JP2020186476A (ja) 2020-11-19
CN113795625A (zh) 2021-12-14
TW202041714A (zh) 2020-11-16
TWI735224B (zh) 2021-08-01
JP6781800B1 (ja) 2020-11-04

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