US20240229351A1 - Cord-rubber composite body, rubber product and method for producing cord-rubber composite body - Google Patents

Cord-rubber composite body, rubber product and method for producing cord-rubber composite body Download PDF

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Publication number
US20240229351A1
US20240229351A1 US18/558,615 US202218558615A US2024229351A1 US 20240229351 A1 US20240229351 A1 US 20240229351A1 US 202218558615 A US202218558615 A US 202218558615A US 2024229351 A1 US2024229351 A1 US 2024229351A1
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United States
Prior art keywords
rubber
metal nanoparticle
cord
metal
steel
Prior art date
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Pending
Application number
US18/558,615
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English (en)
Inventor
Ryoko Kanda
Hideaki SAKAIDA
Kazuki Okuno
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Sumitomo Electric Industries Ltd
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Sumitomo Electric Industries Ltd
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Filing date
Publication date
Application filed by Sumitomo Electric Industries Ltd filed Critical Sumitomo Electric Industries Ltd
Assigned to SUMITOMO ELECTRIC INDUSTRIES, LTD. reassignment SUMITOMO ELECTRIC INDUSTRIES, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OKUNO, KAZUKI, KANDA, RYOKO, SAKAIDA, Hideaki
Publication of US20240229351A1 publication Critical patent/US20240229351A1/en
Pending legal-status Critical Current

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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
    • 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
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2001—Wires or filaments
    • D07B2201/201—Wires or filaments characterised by a coating
    • D07B2201/2011—Wires or filaments characterised by a coating comprising metals
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2205/00—Rope or cable materials
    • D07B2205/20—Organic high polymers
    • D07B2205/2075—Rubbers, i.e. elastomers
    • 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
    • D07B2205/3025—Steel
    • 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
    • D07B2205/3067—Copper (Cu)
    • 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
    • D07B2205/3071—Zinc (Zn)

Definitions

  • a cord-rubber composite of present disclosure includes one or more steel cords each including a steel wire, and rubber covering at least a part of a surface of each of the one or more steel cords.
  • the one or more steel cords each include the steel wire and a metal nanoparticle layer stacked on a surface of the steel wire, the metal nanoparticle layer contains a first metal nanoparticle and a second metal nanoparticle, the first metal nanoparticle contains copper, and the second metal nanoparticle contains one or two or more selected from zinc, cobalt, tin, iron, nickel, aluminum, and oxides thereof.
  • FIG. 1 is a schematic cross-sectional view of a cord-rubber composite according to one embodiment of the present disclosure.
  • the adhesion between the steel cord and the rubber is formed by the reaction between sulfur in the rubber and copper in the brass plating of the steel cord to form an adhesive layer.
  • the copper-sulfur layer which is the reaction layer, is a uniform film, if there is a defect, peeling is likely to occur at the surface from the fracture starting point, and there is a possibility that the adhesion is lowered.
  • Steel wire 2 is not limited to the specific wire, but is preferably a high carbon steel wire.
  • steel wire 2 a wire in which a plurality of element wires are twisted at a constant pitch or a wire in which a plurality of element wires are arranged in parallel without being twisted can be used.
  • a stranded element wire in which a plurality of element wires are twisted is used as steel wire 2
  • a single-stranded structure (1 ⁇ N) in which N element wires are stranded once is exemplified as the stranded structure of steel wire 2 .
  • the number N of filaments in the single-stranded structure can be set as appropriate.
  • Another stranded structure of steel wire 2 may be a layer-stranded structure (N+M) in which M sheaths are wound around N cores in a layered manner.
  • the metal nanoparticles contain first metal nanoparticles and second metal nanoparticles.
  • the first metal nanoparticle contains copper.
  • the second metal nanoparticle contains one or two or more selected from zinc, cobalt, tin, iron, nickel, aluminum, and oxides thereof.
  • the first metal nanoparticle and the second metal nanoparticle may be a single metal or may form an alloy. Since metal nanoparticle layer 3 contains the first metal nanoparticles and the second metal nanoparticles, the copper-sulfur layer of the first metal nanoparticles is not present in s planar shape but in a three dimensional shape between steel wire 2 and rubber 4 . As a result, the adhesion between rubber 4 and steel cord 10 can be further improved by the anchoring effect.
  • the metal nano-ink is coated on the steel wire.
  • the metal nano-ink includes, for example, a solvent, metal nanoparticles dispersed in the solvent, and a dispersant.
  • the metal nanoparticles contained in the metal nano-ink can be formed by a high-temperature treatment method, a liquid-phase reduction method, a gas-phase method, or the like.
  • the liquid-phase reduction method in which metal ions are reduced by a reducing agent in an aqueous solution to precipitate metal nanoparticles is preferably used.
  • Primary particle of the metal nanoparticle may has the range of the particle diameter of preferably more than 10 nm and less than 150 nm, more preferably more than 10 nm and less than 100 nm, and still more preferably 30 nm or more and less than 80 nm.
  • primary particle of the metal nanoparticle has the particle diameter of less than 10 nm, for example, the dispersibility and stability of the metal nanoparticle in the metal nano-ink may be deteriorated.
  • the particle diameter of the primary particle of the metal nanoparticle is more than 150 nm, the gaps between the metal nanoparticles become large, and thus a dense metal nanoparticle layer may not be formed.
  • the lower limit of the median diameter of the primary particle of the metal nanoparticle is preferably 30 nm, and more preferably 50 nm.
  • the upper limit of the median diameter of the primary particle of the metal nanoparticle is preferably 100 nm, and more preferably 80 nm.
  • the primary particle of the metal nanoparticle has the median diameter of less than 30 nm, for example, the dispersibility and stability of the metal nanoparticle in the metal nano-ink may be deteriorated.
  • the primary particle of the metal nanoparticle has the median diameter more than 100 nm, the void in the formed metal nanoparticle layer becomes large, and sufficient adhesion between the steel cord and the rubber may not be obtained.
  • the solvent of the metal nano-ink is not limited the specific solvent, but water is preferably used, and an organic solvent may be mixed with water.
  • the content ratio of water as a solvent in the metal nano-ink is preferably 20 parts by mass to 1900 parts by mass with respect to 100 parts by mass of the metal nanoparticles.
  • the content ratio of the water is less than 20 parts by mass, the concentration of the metal nanoparticles becomes too high, and there is a concern that uniform coating with the metal nano-ink cannot be performed.
  • the content ratio of the water is more than 1900 parts by mass, the ratio of the metal nanoparticles in the metal nano-ink decreases, and there is a concern that a good metal nanoparticle layer having a necessary thickness and density cannot be formed on the surface of the steel wire of the cord-rubber composite.
  • the metal nano-ink may further contain, for example, a dispersant.
  • a dispersant include polymer materials such as polyethylene glycol, polyvinyl alcohol, and polycarboxylic acid.
  • the method of coating the steel wire with the metal nano-ink is not limited to the specific method.
  • a conventionally known coating method such as a spin-coating method, a spray-coating method, a bar-coating method, a die-coating method, a slit-coating method, a roll-coating method or a dip-coating method can be used.
  • the metal nano-ink coating film on the steel wire is dried.
  • the metal nano-ink can be dried by cold air drying or natural drying. Therefore, heating is not required in the drying process.
  • the air velocity of the cold air is preferably set to such an extent that the coating film is not waved.
  • a specific wind velocity of the cold air on the coating film surface can be, for example, from 5 m/second to 10 m/second.
  • the steel wire after the drying process is drawn.
  • the steel cord can have a desired size and strength.
  • wire drawing can be performed without heating after coating ink.
  • the drawing conditions and the like are not particularly limited as long as the drawing process is performed according to a conventional method using a wire drawing machine which is usually used in the drawing process of steel wire.
  • the coating process and the drawing process can be performed at the same time by mixing metal nanoparticles in the lubricating liquid.
  • the rubber-covering process at least a part of the surface of the steel cord formed after the drawing process is covered with rubber.
  • the method of covering the steel cord with the rubber is not limited to the specific method, and a known method can be used. For example, it can be produced by arranging steel cords in parallel at regular intervals, embedding the steel cords in the rubber composition, and vulcanizing the rubber composition.
  • examples of the rubber composition include compositions containing a rubber component, a vulcanizing agent, a filler material, and other various additives.
  • FIG. 2 is a schematic and partial cross-sectional view of a rubber product according to one embodiment of the present disclosure.
  • a rubber product 50 shown in FIG. 2 includes cord-rubber composite 1 .
  • FIG. 2 shows a longitudinal cross-section of cord-rubber composite 1 embedded in a rubber base 8 of rubber product 50 .
  • a plurality of cord-rubber composites 1 are embedded in rubber base 8 to form a skeleton of a portion which is required to have durability such as repeated bending.
  • the steel cords of the present disclosure are embedded in a sheet-like unvulcanized rubber of the rubber composition to obtain a reinforced belt structure.
  • the rubber composition used in the rubber product for example, the same rubber composition as exemplified in the rubber can be used. Thereafter, the reinforced belt structure and the tire constituting member are bonded to each other and set in a vulcanizing machine, and a vulcanizing treatment is performed by applying pressing, heating and the like to obtain a tire as a rubber product. Accordingly, a tire having excellent durability can be manufactured.
  • cord-rubber composites of Test No. 1 and Test No. 2 including steel cords having a metal nanoparticle layer were prepared.
  • Copper plating and zinc plating were sequentially applied to surfaces of steel wires having diameters of q 1 mm and lengths of 150 mm, and a brass plating layer was stacked by performing thermal diffusion treatment at 600° ° C. for 10 seconds.
  • the mass ratio of zinc and copper was 1 : 3.
  • Wire drawing was performed in the same manner as in Test No. 1 except for the above, and 30 steel cords were produced. Thereafter, 30 steel cords were embedded in rubber and vulcanized at 165° C. for 18 minutes to prepare a cord-rubber composite of Test No. 2.
  • a uniform brass plating layer was confirmed at the interface between the steel wire and the rubber.
  • the average thickness of the brass plating layer was 0.25 ⁇ m.
  • the adhesion between the steel cord and the rubber was evaluated in four grades of A to D.
  • the evaluation criteria for the adhesiveness were as follows. When the evaluation of the adhesiveness is A to C, it is regarded as passing. The evaluation results are shown in Table 1.
  • the cord-rubber composite of Test No. 1 including the steel cord on which the metal nanoparticle layer containing the first metal nanoparticles and the second metal nanoparticles was stacked had excellent adhesion between the steel cord and the rubber.
  • the cord-rubber composite of Test No. 2 including the steel cord in which the brass plating layer was stacked by sequentially applying copper plating and zinc plating on the surface of the steel wire and performing the thermal diffusion treatment was inferior in adhesion to the cord-rubber composite of Test No. 1.
  • the cord-rubber composite has excellent adhesion between the rubber and the steel cord and does not require a thermal diffusion treatment such as a brass plating layer, so that carbon dioxide can be reduced during manufacturing.

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US18/558,615 2021-06-30 2022-06-13 Cord-rubber composite body, rubber product and method for producing cord-rubber composite body Pending US20240229351A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2021109610 2021-06-30
JP2021-109610 2021-06-30
PCT/JP2022/023658 WO2023276641A1 (ja) 2021-06-30 2022-06-13 コード－ゴム複合体、ゴム製品及びコード－ゴム複合体の製造方法

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US20240229351A1 true US20240229351A1 (en) 2024-07-11

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US18/558,615 Pending US20240229351A1 (en) 2021-06-30 2022-06-13 Cord-rubber composite body, rubber product and method for producing cord-rubber composite body

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US (1) US20240229351A1 (enrdf_load_stackoverflow)
JP (1) JPWO2023276641A1 (enrdf_load_stackoverflow)
CN (1) CN117222791A (enrdf_load_stackoverflow)
DE (1) DE112022003318T5 (enrdf_load_stackoverflow)
WO (1) WO2023276641A1 (enrdf_load_stackoverflow)

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1762629A (zh) * 2004-10-20 2006-04-26 弘德钢丝绳株式会社 用于金属丝放电加工的焊条钢丝及其制造方法
CN101316960B (zh) * 2005-12-01 2011-12-07 住友橡胶工业株式会社 金属帘线、橡胶帘线的复合物及使用该复合物的充气轮胎
US8202626B2 (en) * 2006-03-08 2012-06-19 Kabushiki Kaisha Bridgestone Brass-plated steel wire for reinforcing rubber articles and method for manufacturing the same
JP5628814B2 (ja) * 2009-09-09 2014-11-19 株式会社ブリヂストン ブラスめっき付きスチールコード及びスチールコード−ゴム複合体並びにこれらを用いたタイヤ
PL2812480T3 (pl) * 2012-02-06 2018-02-28 Bekaert Sa Nv Podłużny element stalowy zawierający powłokę z trójskładnikowego lub czteroskładnikowego stopu mosiężnego i odpowiedni sposób
CN102605308A (zh) * 2012-04-19 2012-07-25 南京工程学院 钢帘线直接热镀铜锌合金环保生产工艺及装置
FR2999975B1 (fr) * 2012-12-20 2015-02-27 Michelin & Cie Renfort metallique pret a l'emploi dont la surface est pourvue de nanoparticules de sulfure metallique
JP6408281B2 (ja) * 2014-07-31 2018-10-17 株式会社ブリヂストン ゴム物品補強用スチールワイヤの製造方法
JP6835104B2 (ja) * 2017-01-26 2021-02-24 日本製鉄株式会社 めっき鋼線、スチールコード及びゴム−めっき鋼線複合体
US11905654B2 (en) * 2019-01-31 2024-02-20 Nv Bekaert Sa Steel cord with a brass coating enriched with iron particles
JP7375565B2 (ja) 2020-01-15 2023-11-08 株式会社ジェイテクト ステアリング装置
CN111979568B (zh) * 2020-07-09 2022-08-12 江苏兴达钢帘线股份有限公司 一种一步法电镀黄铜钢丝镀后处理方法

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WO2023276641A1 (ja) 2023-01-05
DE112022003318T5 (de) 2024-05-23
JPWO2023276641A1 (enrdf_load_stackoverflow) 2023-01-05
CN117222791A (zh) 2023-12-12

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