WO2017065242A1 - スチールコードおよびその製造方法 - Google Patents
スチールコードおよびその製造方法 Download PDFInfo
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- WO2017065242A1 WO2017065242A1 PCT/JP2016/080448 JP2016080448W WO2017065242A1 WO 2017065242 A1 WO2017065242 A1 WO 2017065242A1 JP 2016080448 W JP2016080448 W JP 2016080448W WO 2017065242 A1 WO2017065242 A1 WO 2017065242A1
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- steel cord
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/623—Porosity of the layers
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- 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
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
- C21D8/065—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/525—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length for wire, for rods
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- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F17/00—Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25
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- 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- 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
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
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- 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
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- 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
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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
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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
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- 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
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- 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
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- 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
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- 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
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- 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)
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- 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)
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- 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
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- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2501/00—Application field
- D07B2501/20—Application field related to ropes or cables
- D07B2501/2046—Tire cords
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2505/00—Industrial
- D10B2505/12—Vehicles
Definitions
- the present invention relates to a steel cord and a manufacturing method thereof.
- Patent Document 1 proposes a technique for improving initial adhesiveness by including Co in the surface layer region of a steel cord.
- the present invention relates to a steel cord excellent in both initial adhesion and wet heat resistance and a method for producing the same.
- a steel wire and a plating layer comprising Cu, Zn and Co covering the steel wire, Cu and Zn are alloyed,
- a steel cord is provided in which a region covered with Co and a region not covered with Co are mixed on the outermost surface of the plating layer.
- a steel cord manufacturing method in which a region covered with Co and a region not covered with Co are mixed on the surface of the steel cord after the wire drawing step.
- a steel cord excellent in both initial adhesion and wet heat resistance and a method for producing the same.
- One embodiment of the steel cord according to the present invention is: (1) comprising a steel wire and a plating layer having Cu, Zn and Co covering the steel wire; Cu and Zn are alloyed, A region covered with Co and a region not covered with Co are mixed on the outermost surface of the plating layer.
- the ratio of the area of the region covered with Co and the area of the region not covered with Co may be 2:98 to 30:70.
- the Co content in the plating layer may be 2 to 8 wt%.
- Co may not exist between the outermost surface of the plating layer and the interface with the steel wire.
- At least a part of the region not covered with Co may be present in an island shape on the outermost surface of the plating layer in a plan view of the plating layer.
- Co may exist in a position away from the steel wire in a cross-sectional view of the steel cord.
- One embodiment of the tire according to the present invention is a tire including the steel cord of any one of (1) to (6) above.
- One embodiment of a method for manufacturing a steel cord according to the present invention includes: A method of manufacturing a steel cord provided with a plating layer having Cu, Co, Zn, A first plating step of plating the steel wire with the Cu; A second plating step of plating the Co and Zn on the Cu to obtain a plated wire; A wire drawing step of drawing the plated wire to obtain a steel cord; After the wire drawing step, a region covered with Co and a region not covered with Co are mixed on the surface of the steel cord.
- heat treatment may be performed at a temperature equal to or higher than the alloying temperature of Cu and Zn to expose part of the Co on the surface of the plating wire.
- the heat treatment may be performed at a temperature equal to or higher than a temperature at which Zn becomes a liquid phase.
- the Zn may be plated after the Co is plated.
- FIG. 1 is a cross-sectional view of a tire 1 including a steel cord 10 according to an embodiment of the present invention. As shown in FIG. 1, the tire 1 includes a tread portion 2, a sidewall portion 3, and a bead portion 4.
- the tread part 2 is a part in contact with the road surface.
- the bead portion 4 is provided on the inner diameter side from the tread portion 2.
- the bead part 4 is a part in contact with the rim of the wheel W of the vehicle.
- the sidewall portion 3 connects the tread portion 2 and the bead portion 4. When the tread portion 2 receives an impact from the road surface, the sidewall portion 3 is elastically deformed and absorbs the impact.
- the tire 1 includes an inner liner 5, a carcass 6, a belt 7, and a bead wire 8.
- the inner liner 5 is made of rubber and seals the space between the tire 1 and the wheel W.
- the carcass 6 forms a skeleton of the tire 1.
- the carcass is composed of organic fibers such as polyester, nylon and rayon and rubber.
- the belt 7 tightens the carcass 6 to increase the rigidity of the tread portion 2.
- the belt 7 is composed of a steel cord 10 and rubber.
- the tire 1 has a four-layer belt 7.
- the bead wire 8 is provided in the bead portion 4.
- the bead wire 8 is formed by twisting steel wires and coating rubber.
- the bead wire 8 receives a tensile force acting on the carcass 6.
- the steel cord 10 of the present embodiment is a member that constitutes the belt 7.
- the steel cord 10 is required to have initial adhesiveness with rubber such as butadiene rubber and wet heat resistance.
- initial adhesiveness When rubber is topped on the steel cord 10 and cross-linked, the rubber adheres to the steel cord 10.
- the adhesion strength between the rubber and the steel cord 10 when the crosslinking reaction is performed is referred to as initial adhesiveness.
- the moisture that has entered the tire 1 acts on the steel cord 10 and the rubber and gradually decreases the adhesion strength between the steel cord 10 and the rubber.
- high temperature and high humidity may repeatedly act on the tire 1 to promote a decrease in the adhesive strength between the steel cord 10 and rubber.
- Such deterioration of adhesive strength increases with time, and is promoted in a hot and humid environment.
- This durability against a decrease in adhesion strength caused by repeatedly acting heat and moisture is called wet heat resistance.
- FIG. 6 is a cross-sectional view showing the steel cord 10 according to the present embodiment.
- the steel cord 10 according to the present embodiment includes a steel wire 20 and a plating layer 50 provided on the outer periphery of the steel wire 20.
- the plating layer 50 includes Cu, Co, and Zn. Cu and Zn are alloyed.
- a region 51 covered with Co and a region 52 not covered with Co are mixed.
- Co is present without being alloyed.
- “Co is not alloyed” means that at least the Co that is present on the outermost surface of the plating layer 50 is 95 wt% or more of the portion that is not alloyed.
- the part which is not alloyed is 99 wt% or more. Note that Co may be contained in a layer below the outermost surface of the plating layer 50.
- FIGS. 2 to 5 are views showing a manufacturing process of the steel cord 10 and showing a cross section.
- a steel wire 20 is prepared, and the first layer 30 is formed by plating Cu on the steel wire 20 (first plating step).
- Co and Zn are plated on the first layer 30 to form the second layer 40 to obtain a plated wire 60 (second plating step).
- Co is first plated on the first layer 30, and then Zn is plated.
- Zn is plated so as to enter the discretely formed Co gaps.
- Zn is preferably plated so that Zn forms a region in direct contact with Cu.
- FIGS. 3 to 6 in order to make Co easy to see, it is drawn in an amount larger than the actual amount.
- plating can be performed so that Co is unevenly distributed as shown in FIG.
- plating can be performed so that Co is unevenly distributed.
- plating can be performed so that Co is unevenly distributed by performing plating while generating bubbles in a plating tank or using a porous plating technique.
- the steel wire 20 or the steel wire plated with Cu may be subjected to a pretreatment such as pickling so that a portion where the seed is likely to be formed and a portion where the seed is difficult to be formed may be plated with Co.
- Co can be plated so that Co is unevenly distributed.
- the heat treatment temperature is set to a temperature equal to or higher than the alloying temperature of Cu and Zn.
- the heat treatment temperature is preferably 550 ° C. or higher and 650 ° C. or lower, which is higher than the melting point (419.5 ° C.) at which Zn becomes a liquid phase.
- the heat treatment time is preferably 3 seconds or more and 7 seconds or less.
- the steel cord 10 in which the area 51 covered with Co and the area 52 not covered with Co are mixed on the surface of the steel cord 10 is obtained.
- the area of Co exposed on the outermost surface can be increased when the wire drawing is performed.
- the outermost brass of the plated wire 60 is shaved to expose Co by setting the wire drawing conditions as appropriate, and the outermost surface is made of Co. It is also possible to obtain the steel cord 10 in which the covered region 51 and the region 52 not covered with Co are mixed.
- the method of plating Cu, Co, and Zn in this order has been described, but the present invention is not limited to this.
- Zn and Co may be plated in this order.
- a plating solution containing both Zn and Co may be used to simultaneously plate Zn and Co.
- the area 51 covered with Co and the area 52 not covered with Co are mixed on the surface of the steel cord 10.
- the present inventor found that such a steel cord 10 is particularly excellent in initial adhesion and heat-and-moisture resistance by comparing the following examples and comparative examples. Since Co and Zn are mixed in an appropriate ratio at the interface between the rubber and the steel cord 10, it is presumed that both initial adhesiveness and heat-and-moisture resistance are compatible.
- the ratio of the area of the region 51 covered with Co to the area of the region 52 not covered with Co on the outermost surface of the plating layer 50 is 2:98 to 30:70. If the region 51 covered with Co is too small, the heat and moisture resistance cannot be improved. If the region 52 not covered with Co is too small, the initial adhesiveness cannot be improved.
- the ratio of the area of the region 51 covered with Co to the area of the region 52 not covered with Co is preferably 4:96 to 20:80. More preferably, the ratio of the area of the region 51 covered with Co and the area of the region 52 not covered with Co is 8:92 to 15:85.
- the Co content in the plating layer 50 is 2 to 8 wt%.
- gum and the plating layer 50 cannot be improved. If there is too much Co, it is difficult to form the region 52 not covered with Co, and therefore sufficient initial adhesion cannot be ensured.
- Co is not present between the outermost surface of the plating layer 50 and the interface with the steel wire 20 in at least a part of the region 52 not covered with Co. As shown in the region sandwiched between two two-dot chain lines in FIG. 6, from the region 52 not covered with Co in the outermost surface of the steel cord 10, toward the depth direction (radially inward), It is preferable that Co does not exist in the region up to the interface with the steel wire 20.
- Co is present at a position separated from the steel wire 20 in a cross-sectional view of the steel cord 10. Compared with the case where Co is buried in the plating layer 50, the moisture and heat resistance of the steel cord 10 can be effectively increased with a smaller amount of Co.
- At least a part of the region 51 covered with Co is preferably present in an island shape on the outermost surface of the plating layer 50 in a plan view of the plating layer 50. Since the area 51 not covered with Co surrounds the area 51 covered with island-like Co, both initial adhesion and wet heat resistance can be easily improved.
- the island shape here refers to a state in which the region 51 covered with Co has a certain area.
- the area 51 covered with Co may be circular, linear, rectangular, star-shaped, polygonal, elliptical, or the like.
- the area 51 covered with Co and the area 51 covered with other Co are separated by an area 52 not covered with Co.
- the area covered with Co and the area not covered with Co may be mixed on the surface of the steel cord at the time of wire drawing, or covered with Co before wire drawing. And a region not covered with Co may be mixed.
- FIG. 7 is a diagram showing Co on the outermost surface of the steel cord 10 according to the present embodiment, measured by an energy dispersive X-ray analyzer (EDX: Energy Dispersive X-ray Spectroscopy).
- EDX Energy Dispersive X-ray Spectroscopy
- FIG. 7 shows an analysis using an Oxford X-Max80 Premium with an acceleration voltage of 3 kV.
- FIG. 7 in the present embodiment, it was confirmed that the area 51 covered with Co and the area 52 not covered with Co were mixed on the surface of the steel cord 10.
- the area 51 covered with Co appears white, and the area 52 not covered with Co appears black.
- the present inventor made steel cords of Examples 1 to 4 and Comparative Examples 1 and 2 by changing the plating order and Co plating conditions, and performed wire drawing workability and initial adhesion to rubber. And wet heat resistance with rubber.
- Example 1 A SWRS80A (80C material) piano wire was used as the steel wire.
- a steel wire having a diameter of 5.5 mm was subjected to a surface treatment for pickling. Next, this wire was subjected to rough wire drawing so as to have a diameter of 1.4 mm.
- Cu, Co, and Zn were plated in this order.
- Co plating conditions were set such that the current density was 7 dm 2 , the pH of the plating solution was 2.5, and the plating time (the time during which the steel wire was immersed in the plating solution) was 1.0 second. Further, the temperature in the furnace was set to 550 to 600 ° C., and heat treatment was performed for 5 seconds.
- Example 2 A steel cord according to Example 2 was manufactured by changing only Co plating conditions from Example 1.
- the Co plating conditions were set such that the current density was 28 dm 2 , the pH of the plating solution was 2.5, and the plating time was 1.0 second. Then, the Co plating amount of the steel cord according to Example 2 was larger than the plating amount of Example 1.
- Example 3 A steel cord according to Example 3 was manufactured by changing only the Co plating conditions from Example 1.
- the Co plating conditions were set such that the current density was 56 dm 2 , the pH of the plating solution was 2.5, and the plating time was 1.0 second. Then, the Co plating amount of the steel cord according to Example 3 was larger than the plating amount of Example 1. Moreover, the Co plating amount of the steel cord according to Example 3 was larger than the plating amount of Example 2.
- Example 4 In Example 4, after plating Cu, Co and Zn were simultaneously plated using a plating solution containing Co and Zn.
- the Co and Zn plating conditions were such that the current density was 33 dm 2 , the pH of the plating solution was 2.5, and the plating time was 4 seconds.
- the amount of Co plating on the obtained steel cord was larger than that in Example 1 and smaller than that in Example 3.
- the plated wire 60 obtained under the plating conditions of Examples 1 to 4 was subjected to finish drawing to obtain a filament of ⁇ 0.25 mm, and four filaments were twisted to obtain a steel cord.
- a region covered with Co and a region not covered with Co were mixed on the outermost surface.
- Comparative Example 1 In Comparative Example 1, after plating Cu, Co is plated so that Co covers the surface of Cu without any gap. Thereafter, Zn was plated on the Co surface covering the Cu surface without any gaps. Co plating conditions were set such that the current density was 70 dm 2 , the pH of the plating solution was 2.5, and the plating time was 1 second. The plated wire 60 thus obtained was subjected to finish wire drawing to obtain a steel cord. As a result, only the region 51 covered with Co was present on the outermost surface and not covered with Co. Region 52 did not exist.
- Comparative Example 2 is a steel cord in which only Zn is plated on Cu and Co is not plated. Naturally, only the region not covered with Co was present on the outermost surface of the steel cord.
- Example 1 had a high maximum linear velocity and was difficult to break. In the steel cord of Example 2, the maximum linear velocity was lower than that of Example 1, but no disconnection was observed.
- the steel cords of Examples 3 and 4 were inferior to Example 1 in terms of maximum line speed and difficulty in breaking, but were in an acceptable range.
- the steel cords of Examples 1 to 4 were excellent in moisture heat resistance of 6 points or more.
- Comparative Examples 1 and 2 were inferior in heat and humidity resistance of 3 points or less.
- the steel cords according to Examples 1 to 4 had both high initial adhesiveness and wet heat resistance. Further, the steel cords according to Examples 1 to 4 have high wire drawing workability. Compared to this, the steel cord according to Comparative Example 1 had low initial adhesiveness and wet heat resistance. Although the steel cord according to Comparative Example 2 had high initial adhesiveness, the heat and moisture resistance was low, and the initial adhesion and wet heat resistance were not compatible.
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Abstract
Description
本発明は、初期接着性と耐湿熱性がともに優れたスチールコードおよびその製造方法に関する。
鋼線と、前記鋼線を覆うCu、ZnおよびCoを有するめっき層とを備え、
前記Cuと前記Znは合金化されており、
前記めっき層の最表面に、Coで覆われた領域と、Coで覆われていない領域とが混在している、スチールコードが提供される。
Cu,Co,Znを有するめっき層を備えたスチールコードの製造方法であって、
鋼線に前記Cuをめっきする第一めっき工程と、
前記Cuの上に前記Coおよび前記Znをめっきしてめっき線を得る第二めっき工程と、
前記めっき線を伸線してスチールコードを得る伸線工程を有し、
前記伸線工程後において、前記スチールコードの表面に、Coで覆われた領域と、Coで覆われていない領域とが混在している、スチールコードの製造方法が提供される。
最初に本発明の実施形態の概要を説明する。
本発明にかかるスチールコードの一実施形態は、
(1)鋼線と、前記鋼線を覆うCu、ZnおよびCoを有するめっき層とを備え、
前記Cuと前記Znは合金化されており、
前記めっき層の最表面に、Coで覆われた領域と、Coで覆われていない領域とが混在している。
前記Coで覆われた領域の面積と、前記Coで覆われていない領域の面積との比が、2:98~30:70であってもよい。
前記めっき層におけるCoの含有量が2~8wt%であってもよい。
前記Coで覆われていない領域の少なくとも一部においては、前記めっき層の最表面から前記鋼線との界面までの間にCoが存在していなくてもよい。
前記Coで覆われていない領域の少なくとも一部は、前記めっき層の平面視において、前記めっき層の最表面に島状に存在していてもよい。
前記スチールコードの断面視で、Coは前記鋼線から離間した位置に存在していてもよい。
Cu,Co,Znを有するめっき層を備えたスチールコードの製造方法であって、
鋼線に前記Cuをめっきする第一めっき工程と、
前記Cuの上に前記Coおよび前記Znをめっきしてめっき線を得る第二めっき工程と、
前記めっき線を伸線してスチールコードを得る伸線工程を有し、
前記伸線工程後において、前記スチールコードの表面に、Coで覆われた領域と、Coで覆われていない領域とが混在している。
前記第二めっき工程で、前記Znが前記Cuと直接接触する領域を形成してもよい。
前記第二めっき工程の後に、前記Cuと前記Znとの合金化温度以上の温度で熱処理を行い、前記めっき線の表面に前記Coの一部を露出させてもよい。
前記熱処理は、Znが液相となる温度以上の温度で行ってもよい。
前記第二めっき工程において、前記Coをめっきした後に前記Znをめっきしてもよい。
以下、本発明に係るスチールコードおよびその製造方法の実施の形態の例を、図面を参照して説明する。なお、本発明はこれらの例示に限定されるものではなく、請求の範囲によって示され、請求の範囲と均等の意味および範囲内でのすべての変更が含まれることが意図される。
インナーライナー5は、ゴムで構成されており、タイヤ1とホイールWとの間の空間を密閉する。
カーカス6は、タイヤ1の骨格を形成している。カーカスは、ポリエステル、ナイロン、レーヨンなどの有機繊維とゴムとにより構成されている。
ベルト7は、カーカス6を締め付けて、トレッド部2の剛性を高めている。ベルト7は、スチールコード10とゴムとにより構成されている。図示の例では、タイヤ1は4層のベルト7を有している。
ビードワイヤ8は、ビード部4に設けられている。ビードワイヤ8は、スチールワイヤを撚り合わせてゴムを被覆したものである。ビードワイヤ8は、カーカス6に作用する引っ張り力を受け止める。
この繰り返し作用する熱と水分に起因する密着強度の低下に対する耐久性を耐湿熱性と呼んでいる。
めっき層50において、Coは合金化されておらずに存在している。ここで、「Coが合金化されていない」とは、少なくともめっき層50の最表面に存在するCoのうち、合金化されていない部分が95wt%以上であることを言う。また、合金化されていない部分が99wt%以上であることが好ましい。なお、めっき層50の最表面よりも下方の層中にCoが含まれていても良い。
まず、図2に示すように、鋼線20を用意し、鋼線20にCuをめっきして第一層30を形成する(第一めっき工程)。
なお、めっき線60の表面にCoが露出されていなくても、伸線加工の条件を適宜設定することにより、めっき線60の最表面の真鍮を削ってCoを露出させ、最表面にCoで覆われた領域51と、Coで覆われていない領域52とが混在したスチールコード10を得ることもできる。
鋼線としてSWRS80A(80C材)のピアノ線を用いた。φ5.5mmの鋼線に、酸洗いの表面処理を施した。次に、この鋼線に、φ1.4mmとなるように粗伸線加工を施した。次に、Cu,Co,Znをこの順にめっきをした。このときのCoのめっき条件は、電流密度を7dm2、めっき液のpHを2.5、めっき時間(鋼線がめっき液中に浸かっている時間)を1.0秒に設定した。さらに、炉内の温度を550~600℃に設定し、5秒間、熱処理を施した。
実施例1とはCoのめっき条件のみを変更して、実施例2に係るスチールコードを作製した。実施例2において、Coのめっき条件は、電流密度を28dm2、めっき液のpHを2.5、めっき時間を1.0秒に設定した。すると、実施例2にかかるスチールコードのCoめっき量は、実施例1のめっき量よりも多くなった。
実施例1とはCoのめっき条件のみを変更して、実施例3に係るスチールコードを作製した。実施例3において、Coのめっき条件は、電流密度を56dm2、めっき液のpHを2.5、めっき時間を1.0秒に設定した。すると、実施例3にかかるスチールコードのCoめっき量は、実施例1のめっき量よりも多くなった。また、実施例3にかかるスチールコードのCoめっき量は、実施例2のめっき量よりも多くなった。
実施例4は、Cuをめっきした後に,CoとZnを含むめっき液を用いて、CoとZnを同時にめっきした。CoとZnのめっきの条件は、電流密度を33dm2、めっき液のpHを2.5、めっき時間を4秒に設定した。
得られたスチールコードのCoのめっき量は、実施例1よりも多く、実施例3よりも少なかった。
比較例1は、Cuをめっきした後にCoを、CoがCuの表面を隙間なく覆うようにめっきしたものである。その後、Cuの表面を隙間なく覆っているCoの表面にZnをめっきした。Coのめっき条件は、電流密度を70dm2、めっき液のpHを2.5、めっき時間を1秒に設定した。
このようにして得られためっき線60に仕上げ伸線加工を施して、スチールコードを得たところ、その最表面には、Coで覆われた領域51のみが存在し、Coで覆われていない領域52が存在していなかった。
比較例2は、Cuの上にZnのみをめっきし、Coをめっきしなかったスチールコードである。当然のことながら、スチールコードの最表面には、Coで覆われていない領域のみが存在していた。
上述のようにして作製した実施例1~4および比較例1,2に係るスチールコードについて、伸線加工性、ゴムとの初期接着性、ゴムとの耐湿熱性について評価した。
上述のようにして得られるスチールコードの仕上げ伸線加工において、安定して伸線加工できる線速(最大線速)と、断線の程度とを考慮して、伸線加工のしやすさを評価した。
Aは、最大線速が大きく、かつ、断線しにくかったものを示す。
Cは、最大線速が小さく、かつ、断線しやすかったものを示す。
Bは、断線しにくかったが最大線速が小さい、または、最大線速が大きいが断線しやすかったものを示す。
実施例1のスチールコードは、最大線速が大きく、かつ、断線しにくかった。
実施例2のスチールコードは、最大線速が実施例1よりも低かったものの、断線は観測されなかった。
実施例3,4のスチールコードは、最大線速および断線のしにくさにおいて、実施例1よりも劣ったが、許容できる範囲であった。
初期接着性として、ゴムでスチールコードをはさみ、加硫処理後にゴムを剥離した。このときにスチールコードの表面に付着したゴムの状態を10点満点評価で目視で評点付けをした。
初期接着性は、比較例2が10点であり、最も優れていた。実施例1~4も7点以上であり、優れていた。その中でも、実施例1,2は9点以上であり、特に優れていた。これに対して、比較例1は2点であり、初期接着性が良くなかった。比較例1においては、スチールコードの表面にCoが多く露出されていた結果、ゴムとの初期接着性が高まらなかったものと考えられる。
耐湿熱性は、以下のように評価した。上述のようにして得られた実施例1~4および比較例1,2に係るスチールコードに、ゴムをトッピングし、温度150℃、圧力50kg/cm2で20分間の加硫処理を施し、更に温度80℃湿度95%の高温多湿状態で5日間保管した。その後、ゴムをスチールコードから剥離して、スチールコードの外周面に付着しているゴムの状態から密着性を10段階評価した。
初期接着性と耐湿熱性の両方が所定のレベル以上であったものをOK、初期接着性と耐湿熱性の少なくとも一方が所定のレベルを下回っていたものをNGとした。実施例1~4に係るスチールコードは初期接着性と耐湿熱性の両方が所定のレベル以上でありOKであった。比較例1,2に係るスチールコードは初期接着性と耐湿熱性の少なくとも一方が所定のレベルを下回っておりNGであった。
これに比べて、比較例1に係るスチールコードは、初期接着性および耐湿熱性が低かった。比較例2に係るスチールコードは、初期接着性は高いものの、耐湿熱性が低く、初期接着性と耐湿熱性が両立できなかった。
2 トレッド部
3 サイドウォール部
4 ビード部
5 インナーライナー
6 カーカス
7 ベルト
8 ビードワイヤ
10 スチールコード
20 鋼線
30 第一層
40 第二層
50 めっき層
51 Coで覆われている領域
52 Coで覆われていない領域
60 めっき線
Claims (12)
- 鋼線と、前記鋼線を覆うCu、ZnおよびCoを有するめっき層とを備え、
前記Cuと前記Znは合金化されており、
前記めっき層の最表面に、Coで覆われた領域と、Coで覆われていない領域とが混在している、スチールコード。 - 前記Coで覆われた領域の面積と、前記Coで覆われていない領域の面積との比が、2:98~30:70である、請求項1に記載のスチールコード。
- 前記めっき層におけるCoの含有量が2~8wt%である、請求項1または2に記載のスチールコード。
- 前記Coで覆われていない領域の少なくとも一部においては、前記めっき層の最表面から前記鋼線との界面までの間にCoが存在していない、請求項1から3のいずれか一項に記載のスチールコード。
- 前記Coで覆われていない領域の少なくとも一部は、前記めっき層の平面視において、前記めっき層の最表面に島状に存在している、請求項1から4のいずれか一項に記載のスチールコード。
- 前記スチールコードの断面視で、Coは前記鋼線から離間した位置に存在している、請求項1から5のいずれか一項に記載のスチールコード。
- 請求項1から6のいずれか一項に記載のスチールコードを含むタイヤ。
- Cu,Co,Znを有するめっき層を備えたスチールコードの製造方法であって、
鋼線に前記Cuをめっきする第一めっき工程と、
前記Cuの上に前記Coおよび前記Znをめっきしてめっき線を得る第二めっき工程と、
前記めっき線を伸線してスチールコードを得る伸線工程を有し、
前記伸線工程後において、前記スチールコードの表面に、Coで覆われた領域と、Coで覆われていない領域とが混在している、スチールコードの製造方法。 - 前記第二めっき工程で、前記Znが前記Cuと直接接触する領域を形成する、請求項8にスチールコードの製造方法。
- 前記第二めっき工程の後に、前記Cuと前記Znとの合金化温度以上の温度で熱処理を行い、前記めっき線の表面に前記Coの一部を露出させる、請求項8または9に記載のスチールコードの製造方法。
- 前記熱処理は、Znが液相となる温度以上の温度で行う、請求項10に記載のスチールコードの製造方法。
- 前記第二めっき工程において,前記Coをめっきした後に前記Znをめっきする、請求項8から11のいずれか一項に記載のスチールコードの製造方法。
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