US20030178117A1 - Steel wire and steel cord for the reinforcing rubber article, and tire - Google Patents

Steel wire and steel cord for the reinforcing rubber article, and tire Download PDF

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Publication number
US20030178117A1
US20030178117A1 US10/258,123 US25812302A US2003178117A1 US 20030178117 A1 US20030178117 A1 US 20030178117A1 US 25812302 A US25812302 A US 25812302A US 2003178117 A1 US2003178117 A1 US 2003178117A1
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Prior art keywords
rubber
adhesion
wire
copper
atomic
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US10/258,123
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English (en)
Inventor
Ryuzo Oosawa
Tadashi Honna
Hisakatsu Hara
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Bridgestone Corp
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Bridgestone Corp
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Assigned to BRIDGESTONE CORPORATION reassignment BRIDGESTONE CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HARA, HISAKATSU, HONNA, TADASHI, OOSAWA, RYUZO
Publication of US20030178117A1 publication Critical patent/US20030178117A1/en
Priority to US11/053,867 priority Critical patent/US7162902B2/en
Abandoned 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
    • 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
    • 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
    • B60C9/02—Carcasses
    • 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
    • B60C9/18—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers
    • B60C9/20—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel
    • B60C9/2003—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel characterised by the materials of the belt cords
    • B60C9/2006—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel characterised by the materials of the belt cords consisting of steel cord plies only
    • 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
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2095—Auxiliary components, e.g. electric conductors or light guides
    • D07B2201/2097—Binding wires
    • 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
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12431—Foil or filament smaller than 6 mils
    • Y10T428/12438—Composite
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556—Organic component
    • Y10T428/12562—Elastomer
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12903—Cu-base component
    • Y10T428/12917—Next to Fe-base component
    • Y10T428/12924—Fe-base has 0.01-1.7% carbon [i.e., steel]
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2958—Metal or metal compound in coating

Definitions

  • This invention relates to a steel wire and a steel cord used as a reinforcing member for rubber articles such as a pneumatic tire, an industrial belt and the like, and more particularly to a steel wire and a steel cord having an excellent adhesion property to rubber.
  • the thus added adhesion promoter including sulfur is effective to promote the adhesion reaction, but causes the oozing of the adhesion promoter from the uncured rubber or so-called blooming of chemicals.
  • the operability in the plying of the uncured rubber sheet at, for example, a tire building step lowers and also the closing property or adhesion property between the uncured rubber sheet and rubber is obstructed and further a residue of the adhesion promoter in a cured rubber causes a cutting reaction of rubber molecule or a reversion, which result in the lowering of the tire durability.
  • adhesion promoters particularly adhesion promoters such as cobalt metal salt and the like are expensive
  • the decrease of the adhesion promoter in the coating rubber is effective to not only improve the performances of the tire but also reduce the compounding cost of rubber and is important from a viewpoint of source-saving.
  • the change in the kind of the adhesion promoter is only the application of a local optimization. Since the Co content is obliged to be basically the same, it is unavoidable to cause two-conflicting condition that when the initial adhesion property is improved, the adhesion durability lowers or the blooming property lowers.
  • the method of locating the adhesion promoter as a thin film between the coating rubber and the cord as disclosed in JP-A-10-324753 is possible to certainly remove the compounding of Co in the coating rubber.
  • a ratio of Co diffused in the coating rubber becomes inversely large before the adhesion reaction, so that it is required to arrange the thin film containing the adhesion promoter at a thickness of about several ten ⁇ m and hence it can not be said that the effect of decreasing Co is sufficient and a further improvement is desired.
  • the initial adhesion property is excellent as regards the adhesion property between the steel cord made of brass-plated filament(s) and the rubber coating it.
  • it is examined to control the brass plating properties on the surface of the filament, and there are reported various examination results on a plating composition, particularly a plating composition on an outermost surface, a plated thickness, an influence of an oxidation degree of copper and zinc and the like.
  • a plating composition particularly a plating composition on an outermost surface, a plated thickness, an influence of an oxidation degree of copper and zinc and the like.
  • proposals on the reduction of a phosphoric acid coating layer produced in the drawing to exist on the outermost surface and contributing to ensure the drawability.
  • the steel wire is required to take a work strengthening by repeatedly subjecting a wire rod of, for example, about 5 mm to a drawing, so that the change in the plating influencing upon the drawing is naturally restricted.
  • a surface brass-plated layer applied to the wire and conducting an adhesion to rubber is largely different from a matrix portion to be plated or the wire rod in the chemical composition.
  • the ratio of Cu and Zn contents is reverse, or the plated surface is frequently covered with a phosphoric acid coating or zinc oxide to suppress the activity of the plated layer itself.
  • the conventional adhesion promoter containing sulfur is effective for promoting the adhesion reaction, but does not contribute to control the adhesion when the rubber-cord composite in the tire or the like is exposed to water or oxygen (or active gas in air) under a heat environment and may promote the adhesion deterioration according to circumstances. Therefore, when the tire and the like are used under a thermally severe environment co-existing a relatively large amount of water and air, e.g.
  • JP-A-6-49783 proposes a technique focusing attention on the amount of phosphoric acid at the surface of the wire constituting the steel cord.
  • this publication discloses that as the amount of phosphoric acid remaining on the surface of the wire becomes large, the adhesion properties after the deterioration are excellent under a high-temperature and high-humidity environment but it is difficult to ensure the initial adhesion property, while as the remaining phosphoric acid becomes small, the initial adhesion property is improved but the adhesion properties after the deterioration become insufficient. For this end, it is generally recognized that it is difficult to simultaneously establish both the properties.
  • a first object of the invention to establish a way for giving an excellent adhesion property between a steel cord and a coating rubber in the brass plating applied to a wire constituting the steel cord even if an adhesion promoter usually added to a coating rubber composition for the steel cord is decreased or is not added.
  • a second object of the invention is to establish a way of strongly ensuring an adhesion property to rubber in the brass plating applied to the wire constituting the steel cord by removing limitations on an outermost plated surface, which have hitherto been limited in a production process of the steel cord.
  • the inventors have made various studies with respect to factors controlling an adhesion reaction between brass plating and rubber in order to achieve the first object, and found that when a phosphorus compound in a surface layer region of a brass plating is reduced as far as possible, an adhesion is completed in a very short time under a remarkably fast adhesion reaction inherent to the brass and that when the chemical composition of the brass plating is same, the adhesion property to rubber is substantially principally governed by the phosphorus compound in the plated surface layer.
  • the wire having the above reduced phosphorus compound in the plated surface layer region can ensure the adhesion in a short time even if a cobalt salt as an adhesion promoter in rubber to be adhered is reduced or is not added.
  • the phosphorus compound is a reaction product between the brass and an extreme-pressure additive component among liquid lubricants used in the drawing of the wire and has a function of reducing friction between a die and the wire to control a temperature rise on the surface of the wire, so that it is an essential component in the drawing of the wire, and it is not too much to say that it is substantially impossible to conduct the wire drawing without such a component. Therefore, the phosphorus compound is naturally included in the plated layer on the surface of the wire after the drawing. Particularly, it is unavoidable that the phosphorus compound is included in the plated layer of the mass-produced wire.
  • the inventors have made further examinations on the factors controlling the adhesion reaction between the brass plating and the rubber in order to achieve the second object, and found that when the chemical composition of the brass plating is same, the adhesion property to rubber is substantially principally governed by the presence or absence of a difference between copper content in the outermost surface of the plated layer and copper content in the plated layer itself.
  • the inventors have examined the adhesion property from various angles by strictly making up the plated surface layer with free use of a precise instrumental analysis, which is not used up to now, and a modifying way of a cord production process with respect to the factor controlling the adhesion reaction between the brass plating and the cord in order to achieve the third object, and elucidated that it is possible to simultaneously improve the initial adhesion property and the adhesion properties after the deterioration.
  • the invention is based on the above knowledge and a gist and construction thereof are the followings 1-8.
  • a steel wire for the reinforcement of rubber articles according to the item 1 wherein when a distribution of a ratio of atomicity of copper to total atomicity of copper, zinc, carbon and oxygen at a region from the surface of the brass plating up to a depth of 6 nm in the radial direction of the wire is approximated to quadratic function, a parameter in a variable term of second degree of the quadratic function is not more than ⁇ 0.2 (atomic %/(nm) 2 ).
  • a steel cord for the reinforcement of rubber articles characterized by twisting a plurality of wires described in any one of the items 1 to 7.
  • a tire comprising a carcass toroidally extending between a pair of bead portions as a skeleton and a belt disposed outside the carcass in a radial direction, characterized in that the steel wire described in any one of the items 1 to 7 or the steel cord described in the item 8 is used in either the carcass or the belt or both.
  • the steel wire is produced by subjecting a wire rod having, for example, a diameter of about 5 mm to a drawing.
  • a lubricant is naturally used.
  • the thinning of the wire is carried out at a final drawing step by using dies of about 20 pass placed in a liquid lubricant.
  • an extreme pressure is produced between the cord and the die and also a temperature becomes very high, so that it is u usual to use a phosphoric acid based lubricant for ensuring the lubricity at an extreme pressure and a high temperature state.
  • This lubricant reacts with the surface of the wire in the drawing to form a lubrication film layer, i.e. a phosphorus compound layer and mitigates an input under a condition of extreme pressure and high temperature to attain a mass production of the wire. In the production process, therefore, it is unavoidable to incorporate phosphoric acid in the plating of the wire.
  • the feature that the phosphorus compound does not remain in the surface layer region of the wire after the final drawing is essential in order to improve the adhesion property to rubber, which is elucidated to be not solved by controlling an amount of phosphoric acid or phosphorus in the whole of the plated layer, for example, an amount of phosphoric acid or phosphorus as measured by dissolving in a diluted hydrochloric acid in the conventional technique.
  • wires are prepared by variously changing a pass schedule, a die material, a chemical composition of a lubricant, maturing conditions, a liquid temperature and so on at the drawing step for obtaining the aforementioned wire and then evaluated with respect to the adhesion property to rubber, from which it is clear that the adhesion property to rubber differs in accordance with the wires.
  • the adhesion property to rubber is not comprehended by a copper or phosphorus content in the plated layer as the conventionally general indication as to the adhesion property to rubber.
  • the amount of phosphorus included as the oxide in the surface layer region can be measured according to an X-ray photoelectron spectroscopy. That is, atomicity of all elements and atomicity of phosphorus in the oxide are detected in a region of escape depth of photoelectron measured according to the X-ray photoelectron spectroscopy, and the atomicity of phosphorus in the oxide is represented by an index on the basis that the atomicity of all elements is 100 as an atomic % of phosphorus included in the oxide at the above region.
  • the surface layer region up to the depth of 5 nm can be recognized by a kinetic energy and an escape depth of an electron shown in a general literature on a solid photoelectron spectroscopy.
  • the copper content in the outermost plated surface participating the adhesion property to rubber is lower than that in the plated inside portion as previously mentioned.
  • a region having such a low copper content is measured, it is a region ranging from the plated surface up to a depth of 5-10 nm in the radial direction of the wire and being substantially the same region as mentioned on phosphorus. In such a region, it has been found that the copper content has a concentration gradient of gradually decreasing toward the surface.
  • the lowering of the copper content in the surface layer region of the plated layer is a factor degrading the adhesion property to rubber irrespectively of the same plating composition.
  • it is important that the ratio of copper to sum of copper and zinc in the surface layer region is not less than 50 atomic %.
  • the copper content in the plated layer is made uniform in the radial direction of the wire. That is, it is recommended that copper has no concentration gradient.
  • the inventors have made the following examinations on the adhesion property to rubber, particularly adhesion properties after the deterioration.
  • the adhesion properties after the degradation for example, the deterioration of the adhesion property when the rubber article is used under a high-temperature and high-humidity environment results from the facts that Cu x S participating the initial adhesion is decomposed by water and oxygen and that zinc in the plating reacts with water and oxygen to progress zinc-removal.
  • the initial adhesion layer is uniform and dense and has a plating composition hardly progressing the zinc-removal. Concretely, it is effective to control the concentration distribution of copper from the surface of the plated layer in the depth direction thereof as mentioned later.
  • the concentration distribution of copper is controlled in a region from the plated surface up to a depth of 6 nm in the radial direction of the wire.
  • the reason why the range controlling the concentration distribution of copper is the region from the plated surface up to the depth of 6 nm is due to the fact that this region is a region capable of diffusing copper in the plating dominating the uniformity and denseness of the adhesion layer, i.e. Cu required for forming Cu x S.
  • a parameter in a variable term of second degree of the quadratic function is not more than ⁇ 0.2 (atomic %/(nm) 2 ).
  • FIG. 1 As an example of the distribution of the ratio of atomicity of copper to total atomicity of copper, zinc, carbon and oxygen in the radial direction of the wire is shown in FIG. 1, when a line segment L connecting measured values of copper concentration every depth of 1 nm in the region from the plated surface up to the depth of 6 nm in the radial direction of the wire is grasped as a quadratic function and represented by the following quadratic equation:
  • the concentration distribution of copper is controlled so that the parameter a in the variable term of second degree of the line segment L is not more than ⁇ 0.2 (atomic %/(nm) 2 ).
  • the concentration distribution of copper in the conventional plated layer linearly increases from the plated surface toward the inside thereof (parameter in the variable term of second degree is close to zero).
  • the concentration distribution shown in FIG. 1 shows results obtained by quantifying copper atoms every each depth while repeating an ion etching from the plated surface toward the inside thereof.
  • the average thickness of the plated layer is 0.13-0.35 ⁇ m.
  • the average thickness of the plated layer is less than 0.13 ⁇ m, a portion exposing an iron matrix increases to obstruct the initial adhesion property, while when it exceeds 0.35 ⁇ m, the adhesion reaction is excessively progressed by heat in the use of the rubber article and hence only a brittle adhesion is obtained.
  • the ratio of copper to sum of copper and zinc in the brass plated layer is 60-70% by weight and the ratio of copper to sum of copper and zinc in the surface layer region is 15-45 atomic %.
  • the ratio of copper to sum of copper and zinc in the plated layer as a whole is less than 60% by weight, the drawability is degraded and the productivity is obstructed by wire breaking and hence the mass production becomes difficult, and also it is difficult to control the copper content in the surface layer region as mentioned later to not less than 15 atomic %.
  • the diameter of the wire is advantageous to be not more than 0.40 mm. When it exceeds 0.40 mm, surface strain becomes large if the rubber article used is subjected to repetitive strain under a bending deformation and hence buckling is easily caused.
  • the above wire can form a steel cord suitable as a reinforcing member of a rubber article, particularly a carcass or a belt of a tire by twisting a plurality of such wires.
  • the adhesion rate to rubber becomes fast, and it is possible to largely shorten a curing time of the tire.
  • the wire is applied to a carcass of a tire for truck and bus, particularly a radial tire for truck and bus, the adhesion rate to rubber becomes fast in the bead portion, and it is possible to improve the bead portion durability in addition to the shortening of the curing time.
  • the phosphorus amount included in the oxide at the surface layer region can be controlled by conducting adjustments of pass schedule in the drawing, shape and angle of entrance or approach of the die, die material and composition of lubricant alone or in a proper combination thereof. Especially, it is very effective to conduct the drawing by using a die made of a material having an excellent self-lubricity and an excellent cutting property such as a sintered diamond die in a final pass or in last several passes including the final pass among the dies of about 20 passes at a final drawing step while using a lubricant containing an extreme-pressure additive in the usual manner at the final drawing step.
  • cords having a so-called multi-layer twisting structure or a strand twisting structure as shown, for example, in FIG. 2 are used as a cord ruling the reinforcement.
  • this type of the cord since a wrapping wire 2 is helically wound on a peripheral face of a bundle of many filaments 1 , even if a large bending input is applied to the tire during the running under loading, the loosening of the filaments is prevented by the action of the wrapping wire 2 and hence the cord has an excellent durability including a resistance to buckling fatigue.
  • the wrapping wire 2 Since the wrapping wire 2 is helically wound on the peripheral face of the filament bundle 3 as shown in FIG. 3, the wrapping wire 2 is easily moved in an axial direction, for example, during the running of the tire under loading, and hence the wrapping wire 2 is relatively shifted to a coating rubber 4 accompanied with the running for a long time to cause a fear that an adhesion failure 5 is produced therebetween as shown in FIG. 3( a ).
  • the adhesion failure 5 proceeds from FIG. 3( b ) to FIG. 3( c ) and finally the wrapping wire is broken by rubbing with the coating rubber and further the filaments themselves in the cord are fretted and abraded with each other to bring about the lowering of the cord tenacity.
  • This problem can be solved by omitting the wrapping wire.
  • it is actually difficult to omit the wrapping wire in order to satisfy various conditions required for the tire such as control of cord buckling under the running under loading and so on when the tire is used under a heavy load.
  • the ratio of copper to sum of copper and zinc in the surface layer region is 50-80 atomic %, and that when the distribution of a ratio of number of copper atoms to total number of copper, zinc, carbon and oxygen atoms in the radial direction of the wire is approximated to quadratic function, the parameter in a variable term of second degree of the quadratic function is not more than ⁇ 0.2 (atomic %/(nm) 2 ) as being expected for the improvement of the adhesion properties after the deterioration.
  • FIG. 1 is a graph showing a concentration distribution of copper in a depth direction of a plated layer
  • FIG. 2 is a diagrammatically section view illustrating a cord structure
  • FIG. 3 is a schematic view illustrating an adhesion failure between a wrapping wire and a coating rubber and its progress
  • FIG. 4 is a graph showing a Cu concentration distribution in a depth direction of a plated layer.
  • the steel cords shown in Table 1-1 are mainly used as a belt cord in passenger car tires, tires for small-size truck and the like, while the steel cords shown in Table 1-2 are mainly used as a belt cord and a carcass ply cord in tires for truck and bus.
  • the quantitative determination of phosphorus in the surface layer region of the plated layer is conducted by an X-ray photoelectron spectroscopy, in which atomicities of C, Cu, Zn, O, P and N existing in the plated surface layer region of the wire are measured at an analyzing area of 20-30 ⁇ m ⁇ not affected by curvature of the wire to determine a ratio of atomicity of P when total atomicity of C, Cu, Zn, O, P and N is 100.
  • the atomicity of each of the atoms is determined by using count number of photoelectron of each of C:C 1S , O:O 1S , P:P 2P , Cu:Cu 2P3/2 , Zn:Zn 2P3/2 and N:N 1S and correcting with the respective sensitivity coefficient.
  • the detected atomicity of phosphorus [P] can be determined by the following equation:
  • [P] F P (sensitivity coefficient of P 2P ) ⁇ (count of P 2P photoelectron per constant time)
  • the detected atomicity with respect to the other atoms is determined in the same manner as mentioned above, from which results a relative atomic % of phosphorus can be determined by the following equation:
  • Comparative Example 1-1 in Table 1-5 shows a result of an adhesion peeling test between a steel cord of 1 ⁇ 3 ⁇ 0.30 (mm) using the conventional wire and a coating rubber usually used
  • Comparative Example 1-2 shows a result of an adhesion peeling test between a steel cord of 1 ⁇ 5 ⁇ 0.225 (mm) using the conventional wire and a coating rubber usually used.
  • Invention Example 1-1 is an example wherein P in the plated surface layer region of the final wire is reduced to 1.50 atomic % by properly changing a drawing lubrication condition and using a sintered diamond die as a die in a suitable latter stage in the final drawing under the same heat treatment as in Comparative Example 1-1.
  • Invention Example 1-2 is an example wherein P in the plated surface layer region of the final wire is reduced to 1.00 atomic %.
  • a rubber adhesion ratio of 100% is not ensured unless a curing time at 160° is 18 minutes in Comparative Example 1-1 and about 13 minutes in Comparative Example 1-2.
  • the rubber adhesion ratio of 100% is attained by curing at 160° C. for 9 minutes in Invention Example 1-1, while the rubber adhesion ratio of 100% is ensured even for about 5 minutes, which does not completely cure the rubber, in Invention Example 1-2.
  • the rubber adhesion ratio of 100% is obtained at 160° C. for 5 minutes in Invention Examples 1-3 and 1-4 because it is possible to more easily reduce P in the surface layer region though it is guessed that the diameter of the wire is thin and the tensile strength is low.
  • the amount of the adhesion promoter usually added is used in the rubber composition, if P amount in the surface layer region of the plated wire is not more than 1.5 atomic %, the adhesion rate can significantly be improved and it is possible to extensively improve the productivity such as shortening of curing time in the tire or the like.
  • Table 1-2 shows a case that a cord of a layer construction is mainly used in a large-size tire
  • Invention Examples 1-5 and 1-6 are cases of cords particularly suitable for the belt that the diameter is as thick as 0.34 mm and the tensile strength is higher.
  • the Invention Examples 1-5 and 1-6 are compared with Comparative Example 1-3 conducting the same production process up to the drawing, the Invention Examples 1-5 and 1-6 attain the significant improvement of the adhesion rate as shown in Table 1-6 because the reduction of P amount in the plated surface layer region is successful.
  • Invention Examples 1-7 and 1-8 are cases of cords suitable for carcass ply that the diameter is as thin as 0.21 mm and the tensile strength is a highest class.
  • the Invention Examples 1-7 and 1-8 attain the significant improvement of the adhesion rate because the reduction of P amount in the plated surface layer region is successful. That is, as the P amount in the plated surface layer region is reduced to not more than a half of a usual level (not more than 1.00 atomic %), the rubber adhesion ratio of 100% can be ensured at 145° C. in about 7.5 minutes.
  • the curing time becomes naturally long and is frequently restricted to the adhesion rate of rubber. Therefore, the significant improvement of the adhesion rate is immediately made possible to bring about the increase of the production number of tires. Furthermore, the shortening of the curing time is related to the control of degrading the properties of the over-cured material and can contribute to improve the tire performances.
  • Comparative Example 1-5 shown in Table 1-7 shows a result of an adhesion peeling test between a steel cord of 1 ⁇ 5 ⁇ 0.225 (mm) using the conventional filaments and rubber obtained by removing the adhesion promoter from the usually used coating rubber.
  • Invention Examples 1-9, 1-10 and 1-11 are cases of reducing P amount in the surface layer region of the final plated wire to 1.2-0.8 atomic % by properly changing a drawing lubrication condition and using a sintered diamond die as a die in a suitable latter stage in the final drawing under the same heat treatment as in Comparative Example 1-5.
  • the rubber adhesion ratio of 100% can not be ensured even in the curing of 160° C. for 15 minutes.
  • the adhesion property to rubber can be improved to a level exceeding the adhesion property to rubber containing the adhesion promoter shown in Comparative Example 1-2 by reducing the P amount in the plated surface layer region in the order of Invention Examples 1-9, 1-10 and 1-11.
  • Comparative Example 1-6 shown in Table 1-8 shows a result of an adhesion peeling test between a steel cord of (3+8) ⁇ 0.21 (mm) using the conventional filaments and rubber obtained by removing the adhesion promoter from the usually used coating rubber.
  • Invention Examples 1-12, 1-13 and 1-14 are cases of reducing P amount in the surface layer region of the final plated wire to 1.31-0.75 atomic % by properly changing a drawing lubrication condition and using a sintered diamond die as a die in a suitable latter stage in the final drawing under the same heat treatment as in Comparative Example 1-6.
  • the rubber adhesion ratio of 100% can not be ensured even in the curing of 145° C.
  • the adhesion property to rubber can be improved to a level exceeding the adhesion property to rubber containing the adhesion promoter shown in Comparative Example 1-4 by reducing the P amount in the plated surface layer region in the order of Invention Examples 1-12, 1-13 and 1-14.
  • the rubber adhesion ratio of approximately 100% with respect to rubber containing no cobalt can be ensured even in the curing of 145° C. for 10 minutes, so that it is possible to shorten the curing time but also remove various harmful effects of the adhesion promoter.
  • the amount of phosphorus in the surface layer region of the plated layer is quantified in the same manner as in Example 1. Also, the concentration of copper is possible to be quantified in the same manner as mentioned above.
  • Table 3-3 shows adhesion performances in case of adding an amount of cobalt metal salt usually used in the coating rubber
  • Table 3-4 shows adhesion performances to the coating rubber in case of adding no cobalt salt.
  • the steel cords shown in Tables 3-1 and 3-2 are mainly used as a belt cord in passenger car tires, tires for small-size truck and the like, while are easily affected by an active component from exterior in use.
  • the amount of phosphorus in the surface layer region of the plated layer is quantified in the same manner as in Example 1. Moreover, when the surface of the wire before the analysis is covered with an oil or the like or contaminated with an organic substance, it is washed with a proper solvent and further subjected to a slight argon ion etching to an extent not modifying the surface, if necessary.
  • the excellent adhesion property to the coating rubber containing the reduced adhesion promoter or containing no adhesion promoter is ensured by controlling the amount of phosphorus included as an oxide in the surface layer region of the brass plating applied to the wire constituting the steel cord, so that the reduction or omission of the adhesion promoter in the coating rubber material can be realized without sacrificing the performances of the cord-rubber composite.
  • the adhesion properties after the deterioration can be ensured in addition to the initial adhesion property by regulating the concentration distribution of copper in the plating depth direction.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Ropes Or Cables (AREA)
  • Tires In General (AREA)
  • Reinforced Plastic Materials (AREA)
US10/258,123 2001-02-21 2002-02-21 Steel wire and steel cord for the reinforcing rubber article, and tire Abandoned US20030178117A1 (en)

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JP2001-44,438 2001-02-21
JP2001044438 2001-02-21
JP2001356341 2001-11-21
JP2001-356,341 2001-11-21
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JP2001-360,826 2001-11-27

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US8859653B2 (en) 2009-07-01 2014-10-14 Bridgestone Corporation Rubber-steel cord composite
US9004128B2 (en) 2009-01-19 2015-04-14 Bridgestone Corporation Steel cord for reinforcing rubber article and pneumatic tire
US20150174960A1 (en) * 2012-09-04 2015-06-25 Continental Reifen Deutschland Gmbh Pneumatic vehicle tire, preferably pneumatic commercial vehicle tire
EP3138956A1 (fr) * 2014-04-30 2017-03-08 Bridgestone Corporation Câble d'acier pour renforcement de composant en caoutchouc avec placage en laiton
WO2020156967A1 (fr) * 2019-01-31 2020-08-06 Nv Bekaert Sa Câblé métallique doté d'un dépôt de laiton enrichi en particules de fer

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JP4497788B2 (ja) * 2002-04-09 2010-07-07 株式会社ブリヂストン ゴム物品補強用スチールワイヤおよびゴム物品補強用スチールコードとタイヤ
WO2006062015A1 (fr) * 2004-12-08 2006-06-15 Bridgestone Corporation Pneumatique
JP2007009343A (ja) * 2005-06-28 2007-01-18 Bridgestone Corp ゴム物品補強用スチールワイヤおよびスチールコード
EP1975309B1 (fr) * 2005-12-13 2012-01-11 Sumitomo Rubber Industries, Ltd. Objet composite a base de caoutchouc/fil cable et pneu ainsi obtenu
JP5078055B2 (ja) * 2006-01-20 2012-11-21 株式会社ブリヂストン ゴム−スチールコード複合体
JP5094319B2 (ja) * 2007-10-09 2012-12-12 株式会社ブリヂストン ゴム物品補強用スチールワイヤ及びその製造方法、スチールコード、ゴム複合体並びに空気入りタイヤ
JP5415703B2 (ja) * 2008-03-10 2014-02-12 株式会社ブリヂストン スチールコード−ゴム複合体
JP5452875B2 (ja) * 2008-03-10 2014-03-26 株式会社ブリヂストン スチールコード−ゴム複合体
CN101979762B (zh) * 2010-11-25 2012-12-26 崔娟 磷化涂层钢丝绳
RS58183B1 (sr) * 2012-02-06 2019-03-29 Bekaert Sa Nv Izduženi čelični element koji sadrži oblogu od trostruke ili četvorostruke legure mesinga i odgovarajući postupak
EP2812480B1 (fr) 2012-02-06 2017-08-30 NV Bekaert SA Élément d'acier allongé enrobé d'un alliage de laiton ternaire ou quaternaire et procédé correspondant
JP6537966B2 (ja) 2012-07-24 2019-07-03 ナムローゼ・フェンノートシャップ・ベーカート・ソシエテ・アノニムＮ Ｖ Ｂｅｋａｅｒｔ Ｓｏｃｉｅｔｅ Ａｎｏｎｙｍｅ 選択的に真鍮が被覆されたフィラメントを有するゴム補強用鋼コード
FR2995249B1 (fr) * 2012-09-07 2016-04-01 Michelin & Cie Fil d'acier a haute trefilabilite comprenant un taux de carbone en masse compris entre 0,5 % et 0,6 % bornes incluses
US20160122944A1 (en) * 2013-05-30 2016-05-05 Bridgestone Corporation Steel cord-rubber composite
CN103785704B (zh) * 2014-01-23 2016-01-20 江苏兴达钢帘线股份有限公司 抗扭转分层且疲劳性能优异的特高强度钢丝的制备方法
HUE053878T2 (hu) * 2017-06-22 2021-07-28 Bekaert Sa Nv Acélmagvas huzal fémötvözet bevonattal
CN109576692A (zh) * 2017-09-28 2019-04-05 王群龙 一种橡胶轮胎内使用的铁丝磷化防锈工艺

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Publication number Priority date Publication date Assignee Title
US9004128B2 (en) 2009-01-19 2015-04-14 Bridgestone Corporation Steel cord for reinforcing rubber article and pneumatic tire
US8859653B2 (en) 2009-07-01 2014-10-14 Bridgestone Corporation Rubber-steel cord composite
US20150174960A1 (en) * 2012-09-04 2015-06-25 Continental Reifen Deutschland Gmbh Pneumatic vehicle tire, preferably pneumatic commercial vehicle tire
US9902203B2 (en) * 2012-09-04 2018-02-27 Continental Reifen Deutschland Gmbh Pneumatic vehicle tire, preferably pneumatic commercial vehicle tire
EP3138956A1 (fr) * 2014-04-30 2017-03-08 Bridgestone Corporation Câble d'acier pour renforcement de composant en caoutchouc avec placage en laiton
EP3138956A4 (fr) * 2014-04-30 2017-05-17 Bridgestone Corporation Câble d'acier pour renforcement de composant en caoutchouc avec placage en laiton
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WO2020156967A1 (fr) * 2019-01-31 2020-08-06 Nv Bekaert Sa Câblé métallique doté d'un dépôt de laiton enrichi en particules de fer
CN113383116A (zh) * 2019-01-31 2021-09-10 贝卡尔特公司 具有富含铁颗粒的黄铜涂层的钢丝帘线
US11905654B2 (en) 2019-01-31 2024-02-20 Nv Bekaert Sa Steel cord with a brass coating enriched with iron particles

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EP1365064B1 (fr) 2016-06-15
WO2002066732A1 (fr) 2002-08-29
US20050147818A1 (en) 2005-07-07
AU2002233673B2 (en) 2004-08-12
EP1365064A1 (fr) 2003-11-26
JP3971998B2 (ja) 2007-09-05
JPWO2002066732A1 (ja) 2004-06-24
CN1238594C (zh) 2006-01-25
CN1457378A (zh) 2003-11-19
EP1365064A4 (fr) 2004-09-22
US7162902B2 (en) 2007-01-16

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