WO2024094639A1 - A bead wire, a bead bundle and a tire - Google Patents

A bead wire, a bead bundle and a tire Download PDF

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Publication number
WO2024094639A1
WO2024094639A1 PCT/EP2023/080267 EP2023080267W WO2024094639A1 WO 2024094639 A1 WO2024094639 A1 WO 2024094639A1 EP 2023080267 W EP2023080267 W EP 2023080267W WO 2024094639 A1 WO2024094639 A1 WO 2024094639A1
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WO
WIPO (PCT)
Prior art keywords
bead
thermoplastic resin
bead wire
wire
resin layer
Prior art date
Application number
PCT/EP2023/080267
Other languages
French (fr)
Inventor
Baoxing WANG
Jianhui GONG
Original Assignee
Nv Bekaert Sa
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.)
Filing date
Publication date
Application filed by Nv Bekaert Sa filed Critical Nv Bekaert Sa
Publication of WO2024094639A1 publication Critical patent/WO2024094639A1/en

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Classifications

    • 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
    • B60C15/00—Tyre beads, e.g. ply turn-up or overlap
    • B60C15/04—Bead cores
    • 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
    • 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
    • B60C15/00—Tyre beads, e.g. ply turn-up or overlap
    • B60C15/04—Bead cores
    • B60C2015/042—Bead cores characterised by the material of the core, e.g. alloy

Definitions

  • the invention relates to a bead wire for the tire.
  • the invention also relates to a bead bundle or a tire comprising the bead wire.
  • Bead wire is a metal wire for making the bead bundle for reinforcing the bead of the tire.
  • the bead wire has a metal coating for the adhesion with the rubber compound of the tire after the vulcanization, such as the coating of brass, bronze or zinc.
  • the metal wire has a cross section of round shape or polygonal shape including flat, rectangular or square shape.
  • the bead wire has a resin layer upon the metal coating.
  • the bead wire has a thin raw rubber compound layer upon the resin coating, or the bead wire has a thin raw rubber compound layer directly upon the metal coating.
  • the thin raw rubber compound layer on the bead wire makes the adjacent bead wires tacking to each other for avoiding the filament sliding and thereby stabilizing the shape of the bead bundle.
  • WO201 4/102031 discloses a bead wire having a resin layer, the resin layer comprises a corrosion inhibiting reagent.
  • the corrosion inhibiting reagent is for improving the corrosion resistance of the bead wire.
  • LIS5176957 discloses a bead wire having a bronze coating and a rubber compound coating upon the bronze coating, the bronze coating has a specific weight ratio of Cu and Sn for improving the adhesion between the bead wire and the rubber compound coating after the vulcanization. “Adhesion” takes place between metal coating and vulcanized rubber compound which is already crosslinking reacted into three-dimensional network structures.
  • the thin raw rubber compound layer is applied by extrusion.
  • the thin raw rubber compound layer can’t be very well evenly applied on the resin layer, so that part of the surface of the bead wire are not covered with the raw rubber compound.
  • green tack is the tackiness performance between the bead wire and the raw rubber compound which is not yet crosslinking reacted.
  • the adjacent bead wires may be not able to stick to each other due to insufficient coverage of raw rubber compound on the bead wire, and the risk of filament sliding is increased, and this makes the trouble for the making of bead bundle.
  • the primary object of the invention is to solve the problem of the prior arts.
  • the first object of the invention is to provide a bead wire with good green tack performance with the raw rubber compound.
  • the second object of the invention is to provide a bead bundle comprising the bead wire.
  • the third object of the invention is to provide a tire comprising the bead wire.
  • a bead wire comprises a steel wire, a metal coating covering the steel wire and a thermoplastic resin layer covering the metal coating, wherein the thermoplastic resin layer contains sulphur.
  • the invention is beneficial for the next step process of the bead bundle manufacture, particular for the step of applying the raw rubber compound layer on the thermoplastic resin layer of the bead wire.
  • a raw rubber compound layer is applied on the bead wire by extrusion at a temperature of 65-95 °C, and then at least part or all of the thermoplastic resin of the thermoplastic resin layer is permeated into the boundary section of the raw rubber compound layer after extrusion, “boundary section” means the part of the raw rubber compound layer close to or even contacting with the metal coating.
  • boundary section means the part of the raw rubber compound layer close to or even contacting with the metal coating.
  • the sulphur dispersed in the boundary section of the raw rubber compound layer would react with the metal coating of the bead wire, and then metal sulfides are relatively uniformly generated in the boundary section of the raw rubber compound layer, and such metal sulfides have a dendrite structure which is beneficial to anchor and tack the raw rubber compound to the bead wire, as thus the raw rubber compound tacks more to the bead wire, and the coverage of the raw rubber compound on the surface of the bead wire is increased after extrusion, and the problem of the absence of the raw rubber compound on the bead wire is significantly reduced after extrusion and even after passing through a series of guiding pulleys. The green tack problem is reduced.
  • the bead wires stick better with each other.
  • the bead bundle made of the bead wire with a resin layer and a raw rubber compound layer will have an improved stability of the shape, and the risk of wire sliding within the bead bundle is reduced.
  • thermoplastic resin layer can be detected by X-Ray Photo Electron Spectroscopy method (XPS).
  • the content of the sulphur is more than 0% and less than 40% expressed as an atomic percent related to the total of oxygen, iron, sulphur, nitrogen and metal of the metal coating determined by XPS. More preferably, the content of the sulphur ranges between 5% and 25% expressed as an atomic percent related to the total of oxygen, iron, sulphur, nitrogen and metal of the metal coating determined by XPS.
  • the sulphur could be soluble sulphur or insoluble sulphur.
  • the sulphur is soluble sulphur.
  • the thermoplastic resin for the thermoplastic resin layer has a softening point of 70-125°C.
  • the thermoplastic resin for the thermoplastic resin layer has a softening point of 70-115°C. More preferably, the thermoplastic resin for the thermoplastic resin layer has a softening point of 70-95 °C.
  • Softening point is a property of resin, and it is the temperature at which the resin begins to soften. “Softening point” is a property different from “glass transition temperature” which is a property of a polymer, while “glass transition temperature” is the temperature at which the glass state transitions to a highly elastic state.
  • the thermoplastic resin could be any of the existing thermoplastic resin for bead wire.
  • the thermoplastic resin could be hydrocarbon resin or phenolic resin, including coumarone resin, petroleum resin, terpene resin, bitumen and rosin, their salt, ester, and other derivative and modification.
  • the thermoplastic resin is coumarone resin or petroleum resin.
  • the thermoplastic resin according to the present invention has a molecular weight of no more than 2000.
  • the thermoplastic resin generally doesn’t have double bonds, so that it can’t generate crosslinking with sulphur even when the temperature is high to 125°C or even higher. Therefore, the thermoplastic resin layer containing sulphur is a mixture, this means that there is no chemical reaction between the sulphur and the thermoplastic resin.
  • the metal coating could be any of the existing metal coating for bead wire.
  • the metal coating is zinc, zinc alloy, copper or copper alloy coating.
  • the copper alloy coating can be brass or bronze coating.
  • the ternary or quaternary metal alloy coating is also available.
  • the bead wire further has a rubber compound layer upon the thermoplastic resin layer.
  • the rubber compound layer is a raw rubber compound layer.
  • a bead bundle comprises a bead ring comprising at least one invention bead wire
  • the invention bead wire comprises a steel wire, a metal coating covering the steel wire and a thermoplastic resin layer covering the metal coating, wherein the thermoplastic resin layer contains sulphur.
  • the bead wire is subjected to an application of a raw rubber compound layer upon the thermoplastic resin layer, so that the bead wire in the bead bundle has a raw rubber compound layer as an outer layer.
  • the bead ring could be any of existing type of bead ring, that the bead ring has a cross section showing round, square, rectangular, quadrilateral or hexagon.
  • the rubber compound layer is a raw rubber compound layer which is not vulcanized yet, that “raw rubber compound layer” means that the rubber compound layer is unvulcanized, and this means there is no crosslinking generated in the raw rubber compound layer.
  • the raw rubber compound layer could be any of existing raw rubber compound layer applied on the bead wire.
  • the bead bundle optionally has one or more layers applied upon the bead ring for fixing and stabilizing the shape of the bead ring, i.e., a rubber layer, a fabric cover and/or a polymer layer.
  • a tire comprises a pair of the invention bead bundle or comprises a pair of bead bundle comprising at least one the invention bead wire.
  • Figure 1 describes the cross-section of the bead wire.
  • Figure 2 describes the POF test result.
  • the bead wire is made starting from a steel wire.
  • the steel wire is any of existing steel wire for bead wire. And then the steel wire is coated with any of existing metal coating such as bronze, brass or zinc coating.
  • Thermoplastic resin is prepared, such as coumarone resin or petroleum resin, with a softening point of 70-95 °C.
  • the thermoplastic resin is dissolved in the existing known organic solvent to prepare a thermoplastic resin solution, and the organic solvent could be acetone, gasoline, ethyl acetate or the mixture thereof.
  • the sulphur i.e., soluble sulphur or insoluble sulphur, is added into the thermoplastic resin solution. Make sure that the sulphur is relatively evenly distributed in the thermoplastic resin solution.
  • thermoplastic resin solution is applied on the steel wire by extrusion.
  • the steel wire is dried to evaporate the organic solvent. As thus the invention bead wire is finished.
  • the bead wire is then applied with a raw rubber compound layer by extrusion for the manufacturing of the bead bundle.
  • the raw rubber compound layer is for promoting the adjacent bead wires tacking or sticking to each other for avoiding the wire sliding and thereby stabilizing the shape of the bead bundle.
  • the invention increases the coverage of the raw rubber compound layer on the surface of the resin layer of the bead wire after extrusion. The more the coverage of the raw rubber compound layer, the better tacky or sticky performance the bead wire.
  • a Pull-Out-Force (POF) test is done to know the green tack performance of the invention bead wire.
  • the POF test is according to ASTM D2229, one difference is that the raw rubber compound block specimen with the bead wires is not vulcanized, instead, the raw rubber compound block specimen is heated to 80 °C for 15min for simulating the green tack mode, while the rest is the same.
  • the invention bead wire is the bronze coated steel bead wire with coumarone resin layer with a softening point of about 85-90 °C, the coumarone resin layer has 10% sulphur (expressed as an atomic percent related to the total of oxygen, iron, sulphur, nitrogen, copper and tin determined by XPS).
  • Figure 1 shows the cross section of invention bead wire 100, the bead wire has a steel wire 105, a bronze coating 110 and a coumarone resin layer 120, the coumarone resin layer 120 contains the sulphur which is not shown.
  • Reference 1 is the bronze coated steel bead wire without resin layer
  • Reference 2 is the bronze coated steel bead wire with coumarone resin layer with a softening point of about 85-90 °C and without sulphur in the coumarone resin layer.
  • the POF test is done with the invention bead wire, Reference 1 and Reference 2.
  • the graph in figure 2 shows the test result. It is obvious that the invention bead wire has better green tack performance than Reference 1 and Reference 2, that the measured POF value of invention bead wire is much higher than the measured POF values of Reference 1 and Reference 2.
  • the softening point of the thermoplastic resin is measured according to China Standard GB/T 12007.6 -1989 “Epoxide resins-Determination of softening point-ring and ball method”.
  • XPS analysis can easily identify various elements including oxygen, sulphur, copper, zinc, tin, iron and nitrogen.
  • the atom of oxygen, iron, sulphur, nitrogen and metal of the metal coating such as copper and zinc of the brass coating, copper and tin of the bronze coating or zinc for zinc coating from the outmost surface of the thermoplastic resin layer till the sputtering time of 120s is measured.
  • the equipment can be K-Alpha X- Ray Photoelectron Spectrometer system obtainable from Thermo Fisher Scientific. From the kinetic energy distribution of the emitted electrons, information of the atoms probed is obtained in terms of element number (energy position of peak) and number of atoms present (height of the peak).
  • the elements to be retained is predetermined depending on the type of the metal coating, and the counts on the predetermined elements are retained.
  • the sputtering time is 120s with a beam spot size of 300pm
  • the sputter depth is relating to the sputtering time: ⁇ 1 .0 A/sec (for ct-Fe.).
  • the atomic percent of sulphur related to the total of oxygen, iron, sulphur, nitrogen and metal of the metal coating at sputtering time of Os, 6s, 12s, 30s, 60s, 90s and 120s is calculated and recorded.
  • the values of the atomic percent of sulphur at sputtering time of 0s and 6s are excluded to avoid surface S contamination.
  • the values of the atomic percent of sulphur at sputtering time of 12s, 30s, 60s, 90s and 120s are selected, and the average of these selected five values is calculated as the sulphur content of the thermoplastic resin layer of the bead wire, expressed in an atomic percent related to the total of oxygen, iron, sulphur, nitrogen and metal of the metal coating.
  • the bead wire has a raw rubber compound layer upon the thermoplastic resin layer, the raw rubber compound layer shall be removed before the XPS analysis.
  • a second embodiment is the bead wire with a bronze coating and a petroleum resin layer upon the bronze coating, the petroleum resin layer containing 16% sulphur (expressed as an atomic percent related to the total of oxygen, iron, sulphur, nitrogen, copper and tin determined by XPS), the petroleum resin has a softening point of 70-95 °C.
  • a third embodiment is the bead wire with a zinc coating and a coumarone resin layer upon the zinc coating, the coumarone resin layer has 11 % sulphur (expressed as an atomic percent related to the total of oxygen, iron, sulphur, nitrogen and zinc determined by XPS), the coumarone resin has a softening point of 70-95 °C.
  • a fourth embodiment is the bead bundle, the bead bundle is a cable bead, that all the steel wires of the cable bead have a bronze coating and a coumarone resin layer upon the bronze coating, the coumarone resin layer contains 25% sulphur (expressed as an atomic percent related to the total of oxygen, iron, sulphur, nitrogen, copper and tin determined by XPS), the steel wires have a raw rubber compound layer upon the coumarone resin layer.
  • a fifth embodiment is a tire, the tire has a pair of bead bundle of the fourth embodiment.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Ropes Or Cables (AREA)
  • Tires In General (AREA)

Abstract

The invention provides a bead wire, the bead wire comprises a steel wire, a metal coating covering the steel wire and a thermoplastic resin layer covering the metal coating, wherein the thermoplastic resin layer contains sulphur. The invention improves the green tack problem of the bead wire during the manufacturing of the bead bundle for tire. The invention also provides a bead bundle and a tire.

Description

Title A bead wire, a bead bundle and a tire
Description
Technical Field
[1] The invention relates to a bead wire for the tire. The invention also relates to a bead bundle or a tire comprising the bead wire.
Background Art
[2] Bead wire is a metal wire for making the bead bundle for reinforcing the bead of the tire. Normally the bead wire has a metal coating for the adhesion with the rubber compound of the tire after the vulcanization, such as the coating of brass, bronze or zinc. The metal wire has a cross section of round shape or polygonal shape including flat, rectangular or square shape. Sometimes the bead wire has a resin layer upon the metal coating. In some cases, the bead wire has a thin raw rubber compound layer upon the resin coating, or the bead wire has a thin raw rubber compound layer directly upon the metal coating. During the manufacturing of the bead bundle, the thin raw rubber compound layer on the bead wire makes the adjacent bead wires tacking to each other for avoiding the filament sliding and thereby stabilizing the shape of the bead bundle.
[3] WO201 4/102031 discloses a bead wire having a resin layer, the resin layer comprises a corrosion inhibiting reagent. The corrosion inhibiting reagent is for improving the corrosion resistance of the bead wire.
[4] LIS5176957 discloses a bead wire having a bronze coating and a rubber compound coating upon the bronze coating, the bronze coating has a specific weight ratio of Cu and Sn for improving the adhesion between the bead wire and the rubber compound coating after the vulcanization. “Adhesion” takes place between metal coating and vulcanized rubber compound which is already crosslinking reacted into three-dimensional network structures.
[5] The thin raw rubber compound layer is applied by extrusion. However, during the manufacturing of the bead bundle, it is found that the thin raw rubber compound layer can’t be very well evenly applied on the resin layer, so that part of the surface of the bead wire are not covered with the raw rubber compound. This is so-called “green tack” problem, “green tack” is the tackiness performance between the bead wire and the raw rubber compound which is not yet crosslinking reacted. As a result, the adjacent bead wires may be not able to stick to each other due to insufficient coverage of raw rubber compound on the bead wire, and the risk of filament sliding is increased, and this makes the trouble for the making of bead bundle.
Disclosure of Invention
[6] The primary object of the invention is to solve the problem of the prior arts.
[7] The first object of the invention is to provide a bead wire with good green tack performance with the raw rubber compound.
[8] The second object of the invention is to provide a bead bundle comprising the bead wire.
[9] The third object of the invention is to provide a tire comprising the bead wire.
[10] According to a first object of the invention a bead wire is provided, the bead wire comprises a steel wire, a metal coating covering the steel wire and a thermoplastic resin layer covering the metal coating, wherein the thermoplastic resin layer contains sulphur.
[11 ] The invention is beneficial for the next step process of the bead bundle manufacture, particular for the step of applying the raw rubber compound layer on the thermoplastic resin layer of the bead wire. A raw rubber compound layer is applied on the bead wire by extrusion at a temperature of 65-95 °C, and then at least part or all of the thermoplastic resin of the thermoplastic resin layer is permeated into the boundary section of the raw rubber compound layer after extrusion, “boundary section” means the part of the raw rubber compound layer close to or even contacting with the metal coating. With the adding of sulphur into the thermoplastic resin layer, the sulphur is relatively uniformly dispersed in the boundary section of the raw rubber compound layer with the permeation of the thermoplastic resin to the raw rubber compound layer. The sulphur dispersed in the boundary section of the raw rubber compound layer would react with the metal coating of the bead wire, and then metal sulfides are relatively uniformly generated in the boundary section of the raw rubber compound layer, and such metal sulfides have a dendrite structure which is beneficial to anchor and tack the raw rubber compound to the bead wire, as thus the raw rubber compound tacks more to the bead wire, and the coverage of the raw rubber compound on the surface of the bead wire is increased after extrusion, and the problem of the absence of the raw rubber compound on the bead wire is significantly reduced after extrusion and even after passing through a series of guiding pulleys. The green tack problem is reduced. The bead wires stick better with each other. As a result, the bead bundle made of the bead wire with a resin layer and a raw rubber compound layer will have an improved stability of the shape, and the risk of wire sliding within the bead bundle is reduced.
[12] The sulphur in the thermoplastic resin layer can be detected by X-Ray Photo Electron Spectroscopy method (XPS).
[13] The content of the sulphur is more than 0% and less than 40% expressed as an atomic percent related to the total of oxygen, iron, sulphur, nitrogen and metal of the metal coating determined by XPS. More preferably, the content of the sulphur ranges between 5% and 25% expressed as an atomic percent related to the total of oxygen, iron, sulphur, nitrogen and metal of the metal coating determined by XPS.
[14] The sulphur could be soluble sulphur or insoluble sulphur. Preferably the sulphur is soluble sulphur.
[15] According to the invention, the thermoplastic resin for the thermoplastic resin layer has a softening point of 70-125°C. Preferably, the thermoplastic resin for the thermoplastic resin layer has a softening point of 70-115°C. More preferably, the thermoplastic resin for the thermoplastic resin layer has a softening point of 70-95 °C. “Softening point” is a property of resin, and it is the temperature at which the resin begins to soften. “Softening point” is a property different from “glass transition temperature” which is a property of a polymer, while “glass transition temperature” is the temperature at which the glass state transitions to a highly elastic state.
[16] The thermoplastic resin could be any of the existing thermoplastic resin for bead wire. The thermoplastic resin could be hydrocarbon resin or phenolic resin, including coumarone resin, petroleum resin, terpene resin, bitumen and rosin, their salt, ester, and other derivative and modification. Preferably, the thermoplastic resin is coumarone resin or petroleum resin. The thermoplastic resin according to the present invention has a molecular weight of no more than 2000. The thermoplastic resin generally doesn’t have double bonds, so that it can’t generate crosslinking with sulphur even when the temperature is high to 125°C or even higher. Therefore, the thermoplastic resin layer containing sulphur is a mixture, this means that there is no chemical reaction between the sulphur and the thermoplastic resin.
[17] According to the invention, the metal coating could be any of the existing metal coating for bead wire. Preferably the metal coating is zinc, zinc alloy, copper or copper alloy coating. The copper alloy coating can be brass or bronze coating. The ternary or quaternary metal alloy coating is also available.
[18] The bead wire further has a rubber compound layer upon the thermoplastic resin layer. Here the rubber compound layer is a raw rubber compound layer.
[19] According to a second object of the invention a bead bundle is provided, the bead bundle comprises a bead ring comprising at least one invention bead wire, the invention bead wire comprises a steel wire, a metal coating covering the steel wire and a thermoplastic resin layer covering the metal coating, wherein the thermoplastic resin layer contains sulphur.
[20] Preferably, the bead wire is subjected to an application of a raw rubber compound layer upon the thermoplastic resin layer, so that the bead wire in the bead bundle has a raw rubber compound layer as an outer layer.
[21 ] The bead ring could be any of existing type of bead ring, that the bead ring has a cross section showing round, square, rectangular, quadrilateral or hexagon.
[22] The rubber compound layer is a raw rubber compound layer which is not vulcanized yet, that “raw rubber compound layer” means that the rubber compound layer is unvulcanized, and this means there is no crosslinking generated in the raw rubber compound layer. The raw rubber compound layer could be any of existing raw rubber compound layer applied on the bead wire. [23] The bead bundle optionally has one or more layers applied upon the bead ring for fixing and stabilizing the shape of the bead ring, i.e., a rubber layer, a fabric cover and/or a polymer layer.
[24] According to a third object of the invention a tire is provided, the tire comprises a pair of the invention bead bundle or comprises a pair of bead bundle comprising at least one the invention bead wire.
[25] Due to the vulcanization of the tire, the raw rubber compound layer of the bead wire in the tire becomes the vulcanized rubber compound layer.
Brief Description of Figures in the Drawings
[26] Figure 1 describes the cross-section of the bead wire.
[27] Figure 2 describes the POF test result.
Mode(s) for Carrying Out the Invention
[28] The bead wire is made starting from a steel wire. The steel wire is any of existing steel wire for bead wire. And then the steel wire is coated with any of existing metal coating such as bronze, brass or zinc coating.
[29] Thermoplastic resin is prepared, such as coumarone resin or petroleum resin, with a softening point of 70-95 °C. The thermoplastic resin is dissolved in the existing known organic solvent to prepare a thermoplastic resin solution, and the organic solvent could be acetone, gasoline, ethyl acetate or the mixture thereof. And then the sulphur, i.e., soluble sulphur or insoluble sulphur, is added into the thermoplastic resin solution. Make sure that the sulphur is relatively evenly distributed in the thermoplastic resin solution.
[30] And then the thermoplastic resin solution is applied on the steel wire by extrusion. The steel wire is dried to evaporate the organic solvent. As thus the invention bead wire is finished.
[31] The bead wire is then applied with a raw rubber compound layer by extrusion for the manufacturing of the bead bundle. The raw rubber compound layer is for promoting the adjacent bead wires tacking or sticking to each other for avoiding the wire sliding and thereby stabilizing the shape of the bead bundle.
[32] The invention increases the coverage of the raw rubber compound layer on the surface of the resin layer of the bead wire after extrusion. The more the coverage of the raw rubber compound layer, the better tacky or sticky performance the bead wire.
[33] A Pull-Out-Force (POF) test is done to know the green tack performance of the invention bead wire. The POF test is according to ASTM D2229, one difference is that the raw rubber compound block specimen with the bead wires is not vulcanized, instead, the raw rubber compound block specimen is heated to 80 °C for 15min for simulating the green tack mode, while the rest is the same. The invention bead wire is the bronze coated steel bead wire with coumarone resin layer with a softening point of about 85-90 °C, the coumarone resin layer has 10% sulphur (expressed as an atomic percent related to the total of oxygen, iron, sulphur, nitrogen, copper and tin determined by XPS). Figure 1 shows the cross section of invention bead wire 100, the bead wire has a steel wire 105, a bronze coating 110 and a coumarone resin layer 120, the coumarone resin layer 120 contains the sulphur which is not shown. Reference 1 is the bronze coated steel bead wire without resin layer, and Reference 2 is the bronze coated steel bead wire with coumarone resin layer with a softening point of about 85-90 °C and without sulphur in the coumarone resin layer. The POF test is done with the invention bead wire, Reference 1 and Reference 2. The graph in figure 2 shows the test result. It is obvious that the invention bead wire has better green tack performance than Reference 1 and Reference 2, that the measured POF value of invention bead wire is much higher than the measured POF values of Reference 1 and Reference 2.
[34] According to the invention, the softening point of the thermoplastic resin is measured according to China Standard GB/T 12007.6 -1989 “Epoxide resins-Determination of softening point-ring and ball method”.
[35] XPS analysis can easily identify various elements including oxygen, sulphur, copper, zinc, tin, iron and nitrogen. The atom of oxygen, iron, sulphur, nitrogen and metal of the metal coating such as copper and zinc of the brass coating, copper and tin of the bronze coating or zinc for zinc coating from the outmost surface of the thermoplastic resin layer till the sputtering time of 120s is measured. The equipment can be K-Alpha X- Ray Photoelectron Spectrometer system obtainable from Thermo Fisher Scientific. From the kinetic energy distribution of the emitted electrons, information of the atoms probed is obtained in terms of element number (energy position of peak) and number of atoms present (height of the peak). The elements to be retained is predetermined depending on the type of the metal coating, and the counts on the predetermined elements are retained. The sputtering time is 120s with a beam spot size of 300pm, the sputter depth is relating to the sputtering time: ± 1 .0 A/sec (for ct-Fe.).
The atomic percent of sulphur related to the total of oxygen, iron, sulphur, nitrogen and metal of the metal coating at sputtering time of Os, 6s, 12s, 30s, 60s, 90s and 120s is calculated and recorded. The values of the atomic percent of sulphur at sputtering time of 0s and 6s are excluded to avoid surface S contamination. The values of the atomic percent of sulphur at sputtering time of 12s, 30s, 60s, 90s and 120s are selected, and the average of these selected five values is calculated as the sulphur content of the thermoplastic resin layer of the bead wire, expressed in an atomic percent related to the total of oxygen, iron, sulphur, nitrogen and metal of the metal coating. In case the bead wire has a raw rubber compound layer upon the thermoplastic resin layer, the raw rubber compound layer shall be removed before the XPS analysis.
[36] A second embodiment is the bead wire with a bronze coating and a petroleum resin layer upon the bronze coating, the petroleum resin layer containing 16% sulphur (expressed as an atomic percent related to the total of oxygen, iron, sulphur, nitrogen, copper and tin determined by XPS), the petroleum resin has a softening point of 70-95 °C.
[37] A third embodiment is the bead wire with a zinc coating and a coumarone resin layer upon the zinc coating, the coumarone resin layer has 11 % sulphur (expressed as an atomic percent related to the total of oxygen, iron, sulphur, nitrogen and zinc determined by XPS), the coumarone resin has a softening point of 70-95 °C.
[38] A fourth embodiment is the bead bundle, the bead bundle is a cable bead, that all the steel wires of the cable bead have a bronze coating and a coumarone resin layer upon the bronze coating, the coumarone resin layer contains 25% sulphur (expressed as an atomic percent related to the total of oxygen, iron, sulphur, nitrogen, copper and tin determined by XPS), the steel wires have a raw rubber compound layer upon the coumarone resin layer.
[39] A fifth embodiment is a tire, the tire has a pair of bead bundle of the fourth embodiment.

Claims

Claims
1 . A bead wire, said bead wire comprising a steel wire, a metal coating covering said steel wire and a thermoplastic resin layer covering said metal coating, characterized in that said thermoplastic resin layer contains sulphur.
2. A bead wire as claimed in claim 1 , characterized in that said sulphur content is more than 0% and less than 40% expressed as an atomic percent related to the total of oxygen, iron, sulphur, nitrogen and metal of the metal coating determined by X-Ray Photo Electron Spectroscopy method.
3. A bead wire as claimed in claim 2, characterized in that said sulphur content ranges between 5% and 25% expressed as an atomic percent related to the total of oxygen, iron, sulphur, nitrogen and metal of the metal coating determined by X-Ray Photo Electron Spectroscopy method.
4. A bead wire as claimed in any one of claims 1 to 3, characterized in that the thermoplastic resin for said thermoplastic resin layer has a softening point of 70-125 °C.
5. A bead wire as claimed in claim 4, characterized in that the thermoplastic resin for said thermoplastic resin layer has a softening point of 70-115°C.
6. A bead wire as claimed in claim 5, characterized in that the thermoplastic resin for said thermoplastic resin layer has a softening point of 70-95 °C.
7. A bead wire as claimed in any one of claims 1 to 6, characterized in that the thermoplastic resin for said thermoplastic resin layer is coumarone resin or petroleum resin.
8. A bead wire as claimed in any one of claims 1 to 7, characterized in that the thermoplastic resin for said thermoplastic resin layer has a molecular weight of no more than 2000.
9. A bead wire as claimed in any one of claims 1 to 8, characterized in that said metal coating is a zinc, zinc alloy, copper or copper alloy coating.
10. A bead wire as claimed in claim 9, characterized in that said copper alloy coating is a brass or a bronze coating.
11 . A bead wire as claimed in any one of claims 1 to 10, characterized in that said thermoplastic resin layer containing the sulphur is a mixture. A bead bundle, comprising a bead ring, said bead ring comprising at least one bead wire as claimed in any one of claims 1 to 10, said bead wire is applied with a raw rubber compound layer upon said thermoplastic resin layer. A tire, comprising a pair of bead bundle, each of said a pair of bead bundle comprises at least one bead wire as claimed in any one of claims 1 to 10 or is the bead bundle as claimed in claim 11 or 12.
PCT/EP2023/080267 2022-11-04 2023-10-30 A bead wire, a bead bundle and a tire WO2024094639A1 (en)

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CNPCT/CN2022/129998 2022-11-04

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5176957A (en) 1989-12-05 1993-01-05 Sumitomo Rubber Industries, Ltd. Bead wire for tire, rubber-coated bead wire for tire and tire using the same
JP2004300608A (en) * 2003-03-31 2004-10-28 Bridgestone Corp Steel cord, bead wire and tire
WO2014102031A1 (en) 2012-12-26 2014-07-03 Nv Bekaert Sa Corrosion inhibiting reagent and resin coated bead wire
US20150030851A1 (en) * 2012-02-08 2015-01-29 Compagnie Generale Des Etablissements Michelin Composite reinforcer sheathed with a rubber self-adhesive polymer layer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5176957A (en) 1989-12-05 1993-01-05 Sumitomo Rubber Industries, Ltd. Bead wire for tire, rubber-coated bead wire for tire and tire using the same
JP2004300608A (en) * 2003-03-31 2004-10-28 Bridgestone Corp Steel cord, bead wire and tire
US20150030851A1 (en) * 2012-02-08 2015-01-29 Compagnie Generale Des Etablissements Michelin Composite reinforcer sheathed with a rubber self-adhesive polymer layer
WO2014102031A1 (en) 2012-12-26 2014-07-03 Nv Bekaert Sa Corrosion inhibiting reagent and resin coated bead wire
US20150368478A1 (en) * 2012-12-26 2015-12-24 Nv Bekaert Sa Corrosion inhibiting reagent and resin coated bead wire

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