WO2024053435A1 - Steel wire manufacturing method and steel cord manufacturing method - Google Patents
Steel wire manufacturing method and steel cord manufacturing method Download PDFInfo
- Publication number
- WO2024053435A1 WO2024053435A1 PCT/JP2023/030800 JP2023030800W WO2024053435A1 WO 2024053435 A1 WO2024053435 A1 WO 2024053435A1 JP 2023030800 W JP2023030800 W JP 2023030800W WO 2024053435 A1 WO2024053435 A1 WO 2024053435A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- steel
- rubber
- manufacturing
- steel wire
- steel cord
- Prior art date
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 170
- 239000010959 steel Substances 0.000 title claims abstract description 170
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 37
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 31
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 27
- 238000007747 plating Methods 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 229910001369 Brass Inorganic materials 0.000 claims abstract description 15
- 239000010951 brass Substances 0.000 claims abstract description 15
- 238000005491 wire drawing Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims description 33
- 238000004140 cleaning Methods 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- -1 alkaline earth metal salt Chemical class 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229940050410 gluconate Drugs 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 3
- 229910001510 metal chloride Inorganic materials 0.000 claims description 3
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 3
- 230000002093 peripheral effect Effects 0.000 claims 1
- 230000006866 deterioration Effects 0.000 abstract description 25
- 238000005406 washing Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004073 vulcanization Methods 0.000 description 9
- 150000001868 cobalt Chemical class 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- 239000002318 adhesion promoter Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
-
- 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
Definitions
- the present invention relates to a method of manufacturing a steel wire and a method of manufacturing a steel cord.
- the present invention also relates to a steel wire and a steel cord using the manufacturing method, a composite of the steel wire or steel cord and rubber, and a rubber product using the composite.
- a pneumatic radial tire which is a typical example of a rubber product
- its belt or carcass is made of multiple strands of brass-plated steel wire, or a steel cord made of a single steel wire coated with rubber.
- a rubber composite material made of rubber is applied, and reinforcement is mainly done with steel cords.
- the steel cord In order to utilize the steel cord as a reinforcing material for tires, it is necessary to reliably bond the steel cord to its coating rubber, and for this purpose, the circumferential surface of the wire that makes up the steel cord is plated with brass. There is.
- Patent Document 1 proposes cleaning the surface of a brass-plated steel wire with an aqueous solution containing cobalt salt, and coating the obtained steel wire or steel cord with cobalt-free rubber. .
- the present invention has been made in view of the above-mentioned problems, and provides a method for manufacturing a steel wire and a steel cord that have excellent initial adhesion to rubber and excellent deterioration resistance in a process with a small environmental impact.
- deterioration resistance means resistance to the above-mentioned rubber deterioration.
- Another object of the present invention is to provide a steel wire and a steel cord manufactured by the manufacturing method.
- the present invention provides the following [1] to [19].
- [1] A step of applying brass plating to the circumferential surface of the steel wire and then performing a wire drawing process, and a step of cleaning the surface of the steel wire after the wire drawing process with an aqueous solution containing an alkaline earth metal as a salt.
- a method of manufacturing steel wire including: [2] The method for producing a steel wire according to [1], wherein the alkaline earth metal is magnesium.
- the alkaline earth metal salt is selected from a metal chloride, a metal nitrate, a metal sulfate, a metal acetate, a metal citrate, a metal gluconate, and a metal acetylacetonate.
- a method for producing a steel cord comprising the step of twisting together a plurality of steel wires produced by the method for producing a steel wire according to any one of [1] to [3].
- [5] The method for manufacturing a steel cord according to [4], wherein the washing step is performed after the step of twisting the steel wires.
- [8] A steel wire manufactured by the manufacturing method according to any one of [1] to [3]. [9] The steel wire according to [8], wherein the concentration of alkaline earth metal on the surface is 0.5 mg/m 2 or more and 30 mg/m 2 or less. [10] A steel cord manufactured by the manufacturing method according to any one of [4] to [7]. [11] The steel cord according to claim 10, wherein the concentration of alkaline earth metal on the surface of the steel wire is 0.5 mg/m 2 or more and 30 mg/m 2 or less. [12] A rubber composite obtained by coating the steel wire according to [8] or [9] or the steel cord according to [10] or [11] with rubber. [13] The rubber composite according to [12], wherein the content of cobalt in the rubber is 0.01 parts by mass or less based on 100 parts by mass of the rubber component.
- the environmental load can be reduced by cleaning the surface of a brass-plated steel wire with an aqueous solution containing an alkaline earth metal as a salt. Furthermore, by the manufacturing method of the present invention, it is possible to obtain steel wires and steel cords that have excellent initial adhesion to rubber and also have excellent deterioration resistance.
- the method for manufacturing a steel wire of the present invention includes the steps of applying brass plating to the circumferential surface of the steel wire and then performing wire drawing, and the surface of the steel wire after the wire drawing includes an alkaline earth metal as a salt. A step of washing with an aqueous solution is included.
- the steel wire is subjected to brass plating and wire drawing using a known method.
- brass plating is applied to the circumferential surface of a steel wire with a diameter of about 5 mm.
- wire thinning (wire drawing) is performed using a lubricant.
- thinning is performed using a die placed in a liquid lubricant for about 20 passes.
- extreme pressure is generated between the cord and the die and the temperature is extremely high. Therefore, in order to ensure lubricity under extreme pressure and high temperature conditions, phosphoric acid-based lubrication is used. It is customary to use agents.
- This lubricant reacts with the wire surface during wire drawing to form a lubricating film layer, that is, a phosphoric acid compound layer.
- a lubricating film layer that is, a phosphoric acid compound layer.
- the copper in the brass plating diffuses to the rubber side, forms copper sulfide (CuxS), and inhibits the adhesion reaction in which adhesion occurs.
- the surface of a drawn steel wire is cleaned with an aqueous solution containing an alkaline earth metal as a salt.
- the alkaline earth metals refer to magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba).
- magnesium is preferred in view of its adhesion to rubber, deterioration resistance, and abundance of resources.
- alkaline earth metal salt one or more selected from metal chloride, metal nitrate, metal sulfate, metal acetate, metal citrate, metal gluconate, and metal acetylacetonate. It is preferable that In particular, from the viewpoint of workability, it is preferable to use acetic acid metal salts.
- the phosphoric acid compound layer and zinc oxide layer formed on the circumferential surface of the steel wire are removed. That is, by performing the above-described cleaning treatment, substances that inhibit the adhesion reaction with rubber are removed. Furthermore, alkaline earth metals remain on the surface of the steel wire after cleaning. As a result, a steel wire with excellent adhesion to rubber can be obtained. Therefore, even if the adhesion promoter (cobalt compound) on the rubber side is omitted, the wire and rubber can be reliably bonded. On the other hand, since the adhesion promoter on the rubber side can be omitted, it is also possible to improve the resistance (deterioration resistance) of the rubber to deterioration caused by heat, moisture, or oxygen.
- initial adhesion and deterioration resistance can be significantly improved compared to cleaning using an aqueous solution containing cobalt salt.
- cleaning with an aqueous solution containing a magnesium salt is highly effective in improving initial adhesion and deterioration resistance.
- the reason for this is not certain, but it is thought that the alkaline earth metals attached to the surface of the steel wire have some kind of effect on the crosslinking of the rubber component, such as accelerating the vulcanization rate, which is an unexpected effect. I can say that.
- the use of alkaline earth metal salts has the advantage of reducing environmental impact.
- the pH of the aqueous solution containing the alkaline earth metal as a salt is preferably about 5 to 8.
- the pH of the aqueous solution containing the alkaline earth metal as a salt is preferably about 5 to 8.
- the concentration of alkaline earth metal in the aqueous solution is preferably 0.01 mol/L or more, and 0.05 mol/L or more, considering the removal efficiency of the phosphoric acid compound layer and the zinc oxide layer and the adhesion promoting effect. It is more preferable that the amount is 0.1 mol/L or more, and even more preferably 0.1 mol/L or more. On the other hand, considering the amount of alkaline earth metal remaining on the steel wire surface and processing cost, it is preferably 1 mol/L or less, more preferably 0.5 mol/L or less, and 0.3 mol/L. It is more preferable that it is the following.
- the cleaning time and the temperature of the aqueous solution may be appropriately set depending on the concentration of the aqueous solution, processing cost, and the like.
- the cleaning time can be in the range of 5 to 100 seconds and the temperature can be in the range of 10 to 40°C.
- the cleaning method is not particularly limited, and immersion, spraying, etc. can be applied.
- the steel cord manufacturing method of the present invention includes the step of twisting together a plurality of steel wires manufactured by the above-described steel wire manufacturing method.
- twist structure There is no particular restriction on the twist structure, and twist structures such as single twist, double twist, layered twist, and composite twist of layered twist and multi-twist can be used.
- the steel cord may have a monofilament structure using a single steel wire, a structure in which multiple steel wires are bundled without twisting them together, or a structure in which multiple steel wires are arranged in parallel.
- the cross section can be not only a perfect circle but also an ellipse or a rectangle.
- the relationship between the twisting process and the cleaning process is not particularly limited. Specifically, the following process order can be mentioned. (1) After performing the step of twisting the steel wires, a step of cleaning is performed. (2) After performing the cleaning process, a process of twisting the steel wires is performed. (3) After performing the step of twisting the steel wires together, a step of cleaning is performed, and a step of further twisting the twisted steel wires is performed.
- the process sequence (1) is suitable for producing single-strand and layer-twist steel cords.
- the process order (2) is applicable to manufacturing steel cords of any twisted structure, but is particularly suitable for manufacturing double-twisted steel cords.
- the process order (3) is applicable to manufacturing steel cords of any twisted structure, but is particularly suitable for manufacturing layer-twisted and multi-twisted steel cords.
- the steel wire manufactured by the manufacturing method of the present invention has an oxide layer such as a zinc oxide layer or a phosphoric acid compound layer removed from the surface of the brass plating, and furthermore, an alkaline earth metal is present on the surface of the brass plating.
- the situation is such that As mentioned above, due to the removal of the oxide layer and the alkaline earth metal on the surface, the initial adhesion to rubber and the resistance to deterioration are excellent. Further, the steel cord manufactured using the steel wire manufactured by the manufacturing method of the present invention also has excellent initial adhesion to rubber and deterioration resistance.
- the concentration of alkaline earth metal on the surface of the steel wire manufactured by the manufacturing method of the present invention is preferably 0.5 mg/m 2 or more and 30 mg/m 2 or less.
- the concentration of alkaline earth metal on the surface of the steel wire is preferably 0.5 mg/m 2 or more and 30 mg/m 2 or less.
- the lower limit of the alkaline earth metal concentration is more preferably 1 mg/m 2 or more, and even more preferably 2 mg/m 2 or more.
- the lower limit of the alkaline earth metal concentration is more preferably 25 mg/m 2 or less, and even more preferably 20 mg/m 2 or less.
- the alkaline earth metal concentration in the present invention is a value measured by ICP analysis.
- the "surface of the steel wire" herein refers to the surface layer region up to a depth of 10 nm inside the filament in the radial direction.
- the steel wire and steel cord of the present invention can be applied to various rubber products as a composite with rubber.
- the rubber composite is made by coating a steel wire or steel cord obtained by the manufacturing method of the present invention with rubber.
- the coating rubber preferably does not substantially contain cobalt as an adhesion promoter.
- substantially free means that the content of cobalt in the rubber is 0.01 parts by mass or less based on 100 parts by mass of the rubber component. Therefore, in the rubber composite of the present invention, cobalt is not used or the cobalt content is extremely reduced. More preferably, the content of cobalt in the rubber is 0 parts by mass based on 100 parts by mass of the rubber component.
- cobalt acts as an adhesion promoter, it also becomes a factor that inhibits the deterioration resistance of rubber.
- the steel wire and steel cord obtained by the manufacturing method of the present invention can ensure excellent initial adhesion even when using rubber that does not contain an adhesion promoter. Since the content of cobalt is reduced in either the steel wire or the steel cord or the rubber, the deterioration resistance is particularly excellent.
- the covering rubber is not particularly limited. Rubber that is commonly used in specific applications described below can be used. It is preferable to use a coating rubber containing sulfur as a vulcanizing agent in an amount of 1 to 10 parts by mass based on 100 parts by mass of the rubber component. By containing sulfur in the above range, it is possible to ensure the original adhesive strength of the bond due to vulcanization between sulfur and rubber, and it is also possible to suppress deterioration of heat aging resistance and heat-resistant adhesive properties among the rubber physical properties.
- the above-mentioned rubber composite can be used for tires (pneumatic tires), crawlers, hoses, seismic isolation rubber, etc. If the rubber composite is a pneumatic tire, the steel wire or steel cord obtained according to the invention is applied to the reinforcement of the carcass ply or belt ply.
- the tire structure itself is a general structure.
- sample The surface of a steel wire with a diameter of 1.7 mm was repeatedly plated with copper and then zinc in the order of 63.0% by mass of copper and 37.0% by mass of zinc, followed by thermal diffusion treatment at 550°C for 5 seconds. A copper-zinc binary plating was formed. Thereafter, the steel wire was subjected to wire drawing to obtain a steel wire with an average plating thickness of 0.25 ⁇ m and a diameter of 0.34 mm. A steel cord, which is a twisted cord having a 1+6 structure, was produced using each of the obtained steel wires. Thereafter, the steel cord was immersed in a 0.2 mol/L magnesium acetate aqueous solution for 10 seconds to perform a cleaning treatment.
- the magnesium concentration on the surface of the steel wire after the cleaning treatment was evaluated by the following steps. First, a steel wire was immersed in dilute hydrochloric acid to dissolve the surface of the steel wire. The magnesium concentration in the dilute sulfuric acid after the dissolution treatment was determined by ICP analysis (device: Agilent 5110). The magnesium concentration on the surface of the steel cord in Example 1 was calculated from the magnesium concentration determined by ICP analysis and the dimensions of the immersed steel wire, and was found to be 2.5 mg/m 2 .
- Comparative example 1 A steel cord, which is a twisted cord, was produced in the same process as in Example 1. Without washing the steel cords, 25 steel cords are arranged in parallel at intervals of 50 mm. A rubber composition having the composition shown in "Composition B" in Table 1 is coated on both the upper and lower sides of the steel cord. Thereafter, it was vulcanized at 145° C. for 10 minutes to obtain a sample of Comparative Example 1 (steel cord-rubber composite).
- Example 2 A steel cord, which is a twisted cord, was produced in the same process as in Example 1. Thereafter, the steel cord was immersed in a 0.2 mol/L cobalt acetate aqueous solution for 10 seconds to perform a cleaning treatment. After dipping, the liquid adhering to the surface of the steel cord was removed by air blowing, and the cord was dried at 50° C. for 30 seconds. 25 steel cords obtained through the above steps are arranged in parallel at intervals of 50 mm. A rubber composition having the composition shown in "Composition A" in Table 1 is coated on both the upper and lower sides of the steel cord. Thereafter, it was vulcanized at 145° C. for 10 minutes to obtain a sample of Comparative Example 2 (steel cord-rubber composite).
- Results Table 2 shows the evaluation results of initial adhesiveness and adhesiveness after deterioration.
- Example 1 and Comparative Example 2 have higher coverage rates than Comparative Example 1. From this, as a result of the removal of oxides on the surface of the steel cord by cleaning after brass plating, both the initial adhesion and the adhesion after deterioration are improved. Furthermore, Example 1 has a higher coverage rate than Comparative Example 2. From this, the initial adhesiveness and the adhesiveness after deterioration are improved. The fact that the coverage rates differ even though the rubber compositions were vulcanized under the same conditions is considered to be the result of accelerated vulcanization in the rubber of Example 1. That is, from the results in Table 2, it can be inferred that the magnesium adhering to the surface of the steel cord had some effect on the rubber component, promoting vulcanization.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Ropes Or Cables (AREA)
Abstract
Provided are a method for manufacturing a steel wire and a method for manufacturing a steel cord, in which initial adhesion to rubber and resistance to deterioration are excellent in steps that have low environmental impact. A steel wire and a steel cord manufactured according to these manufacturing methods are provided. The method for manufacturing a steel wire includes a step of applying brass plating to the circumferential surface of a steel wire, and then applying a wire drawing process, and a step of washing the surface of the steel wire after the wire drawing process with an aqueous solution containing an alkaline earth metal as a salt.
Description
本発明は、スチールワイヤの製造方法及びスチールコードの製造方法に関する。また本発明は、該製造方法を用いたスチールワイヤ及びスチールコード、及び、該スチールワイヤまたはスチールコードとゴムとの複合体、該複合体を用いたゴム製品に関する。
The present invention relates to a method of manufacturing a steel wire and a method of manufacturing a steel cord. The present invention also relates to a steel wire and a steel cord using the manufacturing method, a composite of the steel wire or steel cord and rubber, and a rubber product using the composite.
ゴム製品の典型例である空気入りラジアルタイヤでは、そのベルトやカーカスに、ブラスめっきが施されたスチールワイヤの複数本を撚り合わせて成る、又はスチールワイヤの単線から成る、スチールコードをゴムで被覆したゴム複合体を適用し、主にスチールコードによる補強をはかっている。そして、スチールコードをタイヤの補強材として活用するには、該スチールコードをその被覆ゴムと確実に接着する必要があり、そのためにスチールコードを構成するワイヤの周面にはブラスめっきが施されている。
In a pneumatic radial tire, which is a typical example of a rubber product, its belt or carcass is made of multiple strands of brass-plated steel wire, or a steel cord made of a single steel wire coated with rubber. A rubber composite material made of rubber is applied, and reinforcement is mainly done with steel cords. In order to utilize the steel cord as a reinforcing material for tires, it is necessary to reliably bond the steel cord to its coating rubber, and for this purpose, the circumferential surface of the wire that makes up the steel cord is plated with brass. There is.
ブラスめっきされたスチールコードを、硫黄を配合したゴム組成物に埋設し、加熱加硫時にゴムの加硫と同時に接着させる、いわゆる直接加硫接着が広く用いられている。これまで、この直接加硫接着におけるコードとゴムとの接着性を向上するために、様々な検討が行われている。
例えば、ゴムとの接着性を確保するために、ブラスにおける銅と亜鉛の割合やめっき厚を適正化すること等が検討され、これらに関する一定の知見が確立している。
このような知見に基づいて適正化されたブラスめっきを、スチールコードを構成するワイヤに施すことによって、ゴムとの接着性は改善される。 So-called direct vulcanization adhesion is widely used, in which a brass-plated steel cord is embedded in a rubber composition containing sulfur and bonded to it simultaneously with the vulcanization of the rubber during heat vulcanization. Up to now, various studies have been conducted to improve the adhesion between the cord and rubber in this direct vulcanization bonding.
For example, in order to ensure adhesion with rubber, optimizing the ratio of copper and zinc in brass and the plating thickness have been studied, and a certain amount of knowledge regarding these has been established.
By applying brass plating optimized based on such knowledge to the wires that make up the steel cord, the adhesion to rubber can be improved.
例えば、ゴムとの接着性を確保するために、ブラスにおける銅と亜鉛の割合やめっき厚を適正化すること等が検討され、これらに関する一定の知見が確立している。
このような知見に基づいて適正化されたブラスめっきを、スチールコードを構成するワイヤに施すことによって、ゴムとの接着性は改善される。 So-called direct vulcanization adhesion is widely used, in which a brass-plated steel cord is embedded in a rubber composition containing sulfur and bonded to it simultaneously with the vulcanization of the rubber during heat vulcanization. Up to now, various studies have been conducted to improve the adhesion between the cord and rubber in this direct vulcanization bonding.
For example, in order to ensure adhesion with rubber, optimizing the ratio of copper and zinc in brass and the plating thickness have been studied, and a certain amount of knowledge regarding these has been established.
By applying brass plating optimized based on such knowledge to the wires that make up the steel cord, the adhesion to rubber can be improved.
それでもなお、接着相手であるゴムに対して種々の条件が要求されている。例えば、タイヤを一定の時間内に加硫成形するには、コードとゴムとの接着速さやそれらの完全な結合により充分な接着力を確保することが求められる。すなわち、いわゆる初期接着性が要求される。初期接着性を確保するため、ゴム中に接着促進剤としてコバルト塩やニッケル塩を相当の割合で添加したり、硫黄を高い比率で配合したりすること等が行われている。
However, various conditions are still required for the rubber to be bonded. For example, in order to vulcanize and mold a tire within a certain amount of time, it is necessary to ensure sufficient adhesion force through the speed of adhesion between the cord and rubber and the complete bonding between them. That is, so-called initial adhesion is required. In order to ensure initial adhesion, a considerable proportion of cobalt salt or nickel salt is added to the rubber as an adhesion promoter, or a high proportion of sulfur is blended into the rubber.
しかしながら、ゴムにコバルト塩を配合した場合、コバルトを配合してないゴムと対比して、ゴム劣化や耐亀裂成長性といった物性面で課題が生じ得る。そこで、ゴムの組成調整ではなく、ゴムの接着相手であるワイヤについても種々の提案がなされている。
However, when cobalt salt is blended into rubber, problems may arise in terms of physical properties such as rubber deterioration and crack growth resistance compared to rubber that does not contain cobalt. Therefore, instead of adjusting the composition of the rubber, various proposals have been made regarding the wire to which the rubber is bonded.
特許文献１には、ブラスめっきを施したスチールワイヤの表面を、コバルト塩を含む水溶液で洗浄し、得られたスチールワイヤあるいはスチールコードを、コバルトを含まないゴムで被覆することが提案されている。
Patent Document 1 proposes cleaning the surface of a brass-plated steel wire with an aqueous solution containing cobalt salt, and coating the obtained steel wire or steel cord with cobalt-free rubber. .
特許文献１の方法では、コバルト塩の使用量を大幅に削減することができる。しかしながら、スチールコードの製造に依然としてコバルト塩が用いられることから、ゴムの劣化、すなわち、熱、湿気または酸素に起因したゴム劣化の促進が懸念されていた。また、近年では、リチウムイオン電池などのコバルト化合物を使用する製品の需要が高まっていることから、原料コバルトの調達が困難になる可能性がある。これらの理由から、コバルト塩を使用しないでスチールコードとゴムとの良好な接着性を確保する技術が求められていた。
With the method of Patent Document 1, the amount of cobalt salt used can be significantly reduced. However, since cobalt salts are still used in the production of steel cords, there have been concerns about rubber deterioration, that is, acceleration of rubber deterioration due to heat, moisture, or oxygen. Furthermore, in recent years, demand for products that use cobalt compounds, such as lithium ion batteries, has increased, so it may become difficult to procure raw material cobalt. For these reasons, there has been a need for a technology that ensures good adhesion between steel cord and rubber without using cobalt salts.
本発明は、上記課題に鑑みなされたものであり、環境負荷が小さい工程にて、ゴムとの初期接着性及び耐劣化性に優れるスチールワイヤを製造する方法及びスチールコードを製造する方法を提供することを目的とする。ここで、耐劣化性とは、上記したゴム劣化に対する耐性を意味する。また、本発明は、当該製造方法により製造されたスチールワイヤ及びスチールコードを提供することを目的とする。
The present invention has been made in view of the above-mentioned problems, and provides a method for manufacturing a steel wire and a steel cord that have excellent initial adhesion to rubber and excellent deterioration resistance in a process with a small environmental impact. The purpose is to Here, deterioration resistance means resistance to the above-mentioned rubber deterioration. Another object of the present invention is to provide a steel wire and a steel cord manufactured by the manufacturing method.
上記課題を解決するために、本発明は、以下の［１］～［１９］を提供する。
［１］スチールワイヤの周面にブラスめっきを施し、次いで伸線加工を施す工程と、前記伸線加工後のスチールワイヤの表面を、アルカリ土類金属を塩として含む水溶液にて洗浄する工程と、を含む、スチールワイヤの製造方法。
［２］前記アルカリ土類金属がマグネシウムである、［１］に記載のスチールワイヤの製造方法。
［３］前記アルカリ土類金属の塩が、塩化金属塩、硝酸金属塩、硫酸金属塩、酢酸金属塩、クエン酸金属塩、グルコン酸金属塩、及び、アセチルアセトナト金属塩の中から選択される１種以上である、［１］または［２］に記載のスチールワイヤの製造方法。
［４］［１］～［３］のいずれかに記載のスチールワイヤの製造方法により製造されたスチールワイヤを、複数本撚り合わせる工程を含む、スチールコードの製造方法。
［５］前記スチールワイヤを撚り合わせる工程を行った後、前記洗浄する工程を行う、［４］に記載のスチールコードの製造方法。
［６］前記洗浄する工程を行った後、前記スチールワイヤを撚り合わせる工程を行う、［４］に記載のスチールコードの製造方法。
［７］前記複数のスチールワイヤを撚り合わせる工程の後に、前記洗浄する工程を行い、次いで、撚り合わせた前記スチールワイヤを更に撚り合わせる工程を含む、［４］に記載のスチールコードの製造方法。 In order to solve the above problems, the present invention provides the following [1] to [19].
[1] A step of applying brass plating to the circumferential surface of the steel wire and then performing a wire drawing process, and a step of cleaning the surface of the steel wire after the wire drawing process with an aqueous solution containing an alkaline earth metal as a salt. A method of manufacturing steel wire, including:
[2] The method for producing a steel wire according to [1], wherein the alkaline earth metal is magnesium.
[3] The alkaline earth metal salt is selected from a metal chloride, a metal nitrate, a metal sulfate, a metal acetate, a metal citrate, a metal gluconate, and a metal acetylacetonate. The method for producing a steel wire according to [1] or [2], which is one or more types of steel wires.
[4] A method for producing a steel cord, comprising the step of twisting together a plurality of steel wires produced by the method for producing a steel wire according to any one of [1] to [3].
[5] The method for manufacturing a steel cord according to [4], wherein the washing step is performed after the step of twisting the steel wires.
[6] The method for manufacturing a steel cord according to [4], wherein after performing the cleaning step, a step of twisting the steel wires is performed.
[7] The method for manufacturing a steel cord according to [4], which includes performing the washing step after the step of twisting the plurality of steel wires, and then further twisting the twisted steel wires.
［１］スチールワイヤの周面にブラスめっきを施し、次いで伸線加工を施す工程と、前記伸線加工後のスチールワイヤの表面を、アルカリ土類金属を塩として含む水溶液にて洗浄する工程と、を含む、スチールワイヤの製造方法。
［２］前記アルカリ土類金属がマグネシウムである、［１］に記載のスチールワイヤの製造方法。
［３］前記アルカリ土類金属の塩が、塩化金属塩、硝酸金属塩、硫酸金属塩、酢酸金属塩、クエン酸金属塩、グルコン酸金属塩、及び、アセチルアセトナト金属塩の中から選択される１種以上である、［１］または［２］に記載のスチールワイヤの製造方法。
［４］［１］～［３］のいずれかに記載のスチールワイヤの製造方法により製造されたスチールワイヤを、複数本撚り合わせる工程を含む、スチールコードの製造方法。
［５］前記スチールワイヤを撚り合わせる工程を行った後、前記洗浄する工程を行う、［４］に記載のスチールコードの製造方法。
［６］前記洗浄する工程を行った後、前記スチールワイヤを撚り合わせる工程を行う、［４］に記載のスチールコードの製造方法。
［７］前記複数のスチールワイヤを撚り合わせる工程の後に、前記洗浄する工程を行い、次いで、撚り合わせた前記スチールワイヤを更に撚り合わせる工程を含む、［４］に記載のスチールコードの製造方法。 In order to solve the above problems, the present invention provides the following [1] to [19].
[1] A step of applying brass plating to the circumferential surface of the steel wire and then performing a wire drawing process, and a step of cleaning the surface of the steel wire after the wire drawing process with an aqueous solution containing an alkaline earth metal as a salt. A method of manufacturing steel wire, including:
[2] The method for producing a steel wire according to [1], wherein the alkaline earth metal is magnesium.
[3] The alkaline earth metal salt is selected from a metal chloride, a metal nitrate, a metal sulfate, a metal acetate, a metal citrate, a metal gluconate, and a metal acetylacetonate. The method for producing a steel wire according to [1] or [2], which is one or more types of steel wires.
[4] A method for producing a steel cord, comprising the step of twisting together a plurality of steel wires produced by the method for producing a steel wire according to any one of [1] to [3].
[5] The method for manufacturing a steel cord according to [4], wherein the washing step is performed after the step of twisting the steel wires.
[6] The method for manufacturing a steel cord according to [4], wherein after performing the cleaning step, a step of twisting the steel wires is performed.
[7] The method for manufacturing a steel cord according to [4], which includes performing the washing step after the step of twisting the plurality of steel wires, and then further twisting the twisted steel wires.
［８］［１］～［３］のいずれかに記載の製造方法により製造されたスチールワイヤ。
［９］表面におけるアルカリ土類金属の濃度が、０．５ｍｇ／ｍ２以上３０ｍｇ／ｍ２以下である、［８］に記載のスチールワイヤ。
［１０］［４］～［７］のいずれかに記載の製造方法により製造されたスチールコード。［１１］前記スチールワイヤの表面におけるアルカリ土類金属の濃度が、０．５ｍｇ／ｍ２以上３０ｍｇ／ｍ２以下である、請求項１０に記載のスチールコード。
［１２］［８］もしくは［９］に記載のスチールワイヤ、または、［１０］もしくは［１１］に記載のスチールコードにゴムを被覆してなる、ゴム複合体。
［１３］前記ゴム中のコバルトの含有量がゴム成分１００質量部に対して０．０１質量部以下である、［１２］に記載のゴム複合体。 [8] A steel wire manufactured by the manufacturing method according to any one of [1] to [3].
[9] The steel wire according to [8], wherein the concentration of alkaline earth metal on the surface is 0.5 mg/m 2 or more and 30 mg/m 2 or less.
[10] A steel cord manufactured by the manufacturing method according to any one of [4] to [7]. [11] The steel cord according to claim 10, wherein the concentration of alkaline earth metal on the surface of the steel wire is 0.5 mg/m 2 or more and 30 mg/m 2 or less.
[12] A rubber composite obtained by coating the steel wire according to [8] or [9] or the steel cord according to [10] or [11] with rubber.
[13] The rubber composite according to [12], wherein the content of cobalt in the rubber is 0.01 parts by mass or less based on 100 parts by mass of the rubber component.
［９］表面におけるアルカリ土類金属の濃度が、０．５ｍｇ／ｍ２以上３０ｍｇ／ｍ２以下である、［８］に記載のスチールワイヤ。
［１０］［４］～［７］のいずれかに記載の製造方法により製造されたスチールコード。［１１］前記スチールワイヤの表面におけるアルカリ土類金属の濃度が、０．５ｍｇ／ｍ２以上３０ｍｇ／ｍ２以下である、請求項１０に記載のスチールコード。
［１２］［８］もしくは［９］に記載のスチールワイヤ、または、［１０］もしくは［１１］に記載のスチールコードにゴムを被覆してなる、ゴム複合体。
［１３］前記ゴム中のコバルトの含有量がゴム成分１００質量部に対して０．０１質量部以下である、［１２］に記載のゴム複合体。 [8] A steel wire manufactured by the manufacturing method according to any one of [1] to [3].
[9] The steel wire according to [8], wherein the concentration of alkaline earth metal on the surface is 0.5 mg/m 2 or more and 30 mg/m 2 or less.
[10] A steel cord manufactured by the manufacturing method according to any one of [4] to [7]. [11] The steel cord according to claim 10, wherein the concentration of alkaline earth metal on the surface of the steel wire is 0.5 mg/m 2 or more and 30 mg/m 2 or less.
[12] A rubber composite obtained by coating the steel wire according to [8] or [9] or the steel cord according to [10] or [11] with rubber.
[13] The rubber composite according to [12], wherein the content of cobalt in the rubber is 0.01 parts by mass or less based on 100 parts by mass of the rubber component.
［１４］［１２］に記載のゴム複合体を用いたタイヤ。
［１５］カーカスプライに前記ゴム複合体を用いた［１４］に記載のタイヤ。
［１６］ベルトに前記ゴム複合体を用いた［１４］に記載のタイヤ。
［１７］［１２］に記載のゴム複合体を用いたクローラ。
［１８］［１２］に記載のゴム複合体を用いたホース。
［１９］［１２］に記載のゴム複合体を用いた免震ゴム。 [14] A tire using the rubber composite according to [12].
[15] The tire according to [14], wherein the rubber composite is used in the carcass ply.
[16] The tire according to [14], wherein the rubber composite is used for the belt.
[17] A crawler using the rubber composite according to [12].
[18] A hose using the rubber composite described in [12].
[19] A seismic isolation rubber using the rubber composite according to [12].
［１５］カーカスプライに前記ゴム複合体を用いた［１４］に記載のタイヤ。
［１６］ベルトに前記ゴム複合体を用いた［１４］に記載のタイヤ。
［１７］［１２］に記載のゴム複合体を用いたクローラ。
［１８］［１２］に記載のゴム複合体を用いたホース。
［１９］［１２］に記載のゴム複合体を用いた免震ゴム。 [14] A tire using the rubber composite according to [12].
[15] The tire according to [14], wherein the rubber composite is used in the carcass ply.
[16] The tire according to [14], wherein the rubber composite is used for the belt.
[17] A crawler using the rubber composite according to [12].
[18] A hose using the rubber composite described in [12].
[19] A seismic isolation rubber using the rubber composite according to [12].
本発明に依れば、ブラスめっきされたスチールワイヤの表面を、アルカリ土類金属を塩として含む水溶液にて洗浄することにより、環境負荷を低減することができる。更には、本発明の製造方法により、ゴムとの初期接着性に優れるとともに、耐劣化性にも優れるスチールワイヤ及びスチールコードを得ることができる。
According to the present invention, the environmental load can be reduced by cleaning the surface of a brass-plated steel wire with an aqueous solution containing an alkaline earth metal as a salt. Furthermore, by the manufacturing method of the present invention, it is possible to obtain steel wires and steel cords that have excellent initial adhesion to rubber and also have excellent deterioration resistance.
以下に、本発明をその実施形態に基づき詳細に例示説明する。なお、以下の説明において、数値範囲を示す「Ａ～Ｂ」の記載は、端点であるＡ及びＢを含む数値範囲を表し、「Ａ以上Ｂ以下」（Ａ＜Ｂの場合）、又は「Ａ以下Ｂ以上」（Ａ＞Ｂの場合）を表す。
また、質量部及び質量％は、それぞれ、重量部及び重量％と同義である。 EMBODIMENT OF THE INVENTION Below, this invention will be illustrated and explained in detail based on the embodiment. In addition, in the following explanation, the description "A to B" indicating a numerical range represents a numerical range that includes the endpoints A and B. "B or more" (in the case of A>B).
Furthermore, parts by mass and % by mass have the same meaning as parts by weight and % by weight, respectively.
また、質量部及び質量％は、それぞれ、重量部及び重量％と同義である。 EMBODIMENT OF THE INVENTION Below, this invention will be illustrated and explained in detail based on the embodiment. In addition, in the following explanation, the description "A to B" indicating a numerical range represents a numerical range that includes the endpoints A and B. "B or more" (in the case of A>B).
Furthermore, parts by mass and % by mass have the same meaning as parts by weight and % by weight, respectively.
［スチールワイヤの製造方法］
本発明のスチールワイヤの製造方法は、スチールワイヤの周面にブラスめっきを施し、次いで伸線加工を施す工程と、前記伸線加工後のスチールワイヤの表面を、アルカリ土類金属を塩として含む水溶液にて洗浄する工程と、を含む。 [Method for manufacturing steel wire]
The method for manufacturing a steel wire of the present invention includes the steps of applying brass plating to the circumferential surface of the steel wire and then performing wire drawing, and the surface of the steel wire after the wire drawing includes an alkaline earth metal as a salt. A step of washing with an aqueous solution is included.
本発明のスチールワイヤの製造方法は、スチールワイヤの周面にブラスめっきを施し、次いで伸線加工を施す工程と、前記伸線加工後のスチールワイヤの表面を、アルカリ土類金属を塩として含む水溶液にて洗浄する工程と、を含む。 [Method for manufacturing steel wire]
The method for manufacturing a steel wire of the present invention includes the steps of applying brass plating to the circumferential surface of the steel wire and then performing wire drawing, and the surface of the steel wire after the wire drawing includes an alkaline earth metal as a salt. A step of washing with an aqueous solution is included.
スチールワイヤには、公知の方法によりブラスめっき及び伸線加工が施される。例えば径が５ｍｍ程度のスチールワイヤの周面に、ブラスめっきが施される。その後、潤滑剤を使用しながら細線化（伸線加工）が行われる。中でも最終伸線工程では、液体潤滑剤中に配置した２０パス程度のダイスを用いて細線化が行われる。この最終伸線工程では、コードとダイスとの間に極圧が発生し、温度も非常に高くなることから、極圧かつ高温状態での潤滑性を確保するために、燐酸をベースとする潤滑剤を用いることが通例である。
この潤滑剤は、伸線加工中にワイヤ表面と反応して潤滑皮膜層、すなわち燐酸化合物層を生成する。これにより、極圧高温条件の下でのワイヤ表面への入力を緩和し、ワイヤの量産を実現している。従って、製造プロセス上、ワイヤのめっき中に燐酸が取り込まれることは避けられない。この燐酸化合物層がめっき表面にあると、ブラスめっき中の銅がゴム側に拡散し、硫化銅（ＣｕｘＳ）を形成して接着が行われる接着反応を阻害する。
また、銅と亜鉛との合金であるブラスめっきを施すと、経時的に表面が酸化されて酸化亜鉛層が生成し、この酸化亜鉛層もまた燐酸化合物層と同様に、接着反応を阻害することになる。 The steel wire is subjected to brass plating and wire drawing using a known method. For example, brass plating is applied to the circumferential surface of a steel wire with a diameter of about 5 mm. Thereafter, wire thinning (wire drawing) is performed using a lubricant. Among these, in the final wire drawing process, thinning is performed using a die placed in a liquid lubricant for about 20 passes. In this final wire drawing process, extreme pressure is generated between the cord and the die and the temperature is extremely high. Therefore, in order to ensure lubricity under extreme pressure and high temperature conditions, phosphoric acid-based lubrication is used. It is customary to use agents.
This lubricant reacts with the wire surface during wire drawing to form a lubricating film layer, that is, a phosphoric acid compound layer. This reduces the input force on the wire surface under extreme pressure and high temperature conditions, making it possible to mass-produce wire. Therefore, due to the manufacturing process, it is inevitable that phosphoric acid will be incorporated into the wire during plating. When this phosphoric acid compound layer exists on the plating surface, the copper in the brass plating diffuses to the rubber side, forms copper sulfide (CuxS), and inhibits the adhesion reaction in which adhesion occurs.
In addition, when brass plating, which is an alloy of copper and zinc, is applied, the surface is oxidized over time and a zinc oxide layer is formed, and this zinc oxide layer also inhibits the adhesion reaction in the same way as the phosphoric acid compound layer. become.
この潤滑剤は、伸線加工中にワイヤ表面と反応して潤滑皮膜層、すなわち燐酸化合物層を生成する。これにより、極圧高温条件の下でのワイヤ表面への入力を緩和し、ワイヤの量産を実現している。従って、製造プロセス上、ワイヤのめっき中に燐酸が取り込まれることは避けられない。この燐酸化合物層がめっき表面にあると、ブラスめっき中の銅がゴム側に拡散し、硫化銅（ＣｕｘＳ）を形成して接着が行われる接着反応を阻害する。
また、銅と亜鉛との合金であるブラスめっきを施すと、経時的に表面が酸化されて酸化亜鉛層が生成し、この酸化亜鉛層もまた燐酸化合物層と同様に、接着反応を阻害することになる。 The steel wire is subjected to brass plating and wire drawing using a known method. For example, brass plating is applied to the circumferential surface of a steel wire with a diameter of about 5 mm. Thereafter, wire thinning (wire drawing) is performed using a lubricant. Among these, in the final wire drawing process, thinning is performed using a die placed in a liquid lubricant for about 20 passes. In this final wire drawing process, extreme pressure is generated between the cord and the die and the temperature is extremely high. Therefore, in order to ensure lubricity under extreme pressure and high temperature conditions, phosphoric acid-based lubrication is used. It is customary to use agents.
This lubricant reacts with the wire surface during wire drawing to form a lubricating film layer, that is, a phosphoric acid compound layer. This reduces the input force on the wire surface under extreme pressure and high temperature conditions, making it possible to mass-produce wire. Therefore, due to the manufacturing process, it is inevitable that phosphoric acid will be incorporated into the wire during plating. When this phosphoric acid compound layer exists on the plating surface, the copper in the brass plating diffuses to the rubber side, forms copper sulfide (CuxS), and inhibits the adhesion reaction in which adhesion occurs.
In addition, when brass plating, which is an alloy of copper and zinc, is applied, the surface is oxidized over time and a zinc oxide layer is formed, and this zinc oxide layer also inhibits the adhesion reaction in the same way as the phosphoric acid compound layer. become.
そこで、ゴムとの接着を行う前に、めっきの表面から燐酸化合物層や酸化亜鉛層を除去することが、ゴムとの接着性（初期接着性）を改善するのに有効になる。そのためには、伸線後のスチールワイヤの表面に対して燐酸化合物層や酸化亜鉛層を除去する、洗浄処理を施すことが重要になる。
Therefore, it is effective to remove the phosphoric acid compound layer and zinc oxide layer from the plating surface before adhesion with rubber to improve the adhesion with rubber (initial adhesion). To this end, it is important to perform a cleaning treatment on the surface of the steel wire after wire drawing to remove the phosphoric acid compound layer and the zinc oxide layer.
本発明においては、伸線加工を施したスチールワイヤの表面を、アルカリ土類金属を塩として含む水溶液にて洗浄する。ここで、アルカリ土類金属とは、マグネシウム（Ｍｇ）、カルシウム（Ｃａ）、ストロンチウム（Ｓｒ）、バリウム（Ｂａ）を指す。この中でも、ゴムとの接着性及び耐劣化性や、資源の豊富さを考慮すると、マグネシウムが好ましい。
In the present invention, the surface of a drawn steel wire is cleaned with an aqueous solution containing an alkaline earth metal as a salt. Here, the alkaline earth metals refer to magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). Among these, magnesium is preferred in view of its adhesion to rubber, deterioration resistance, and abundance of resources.
アルカリ土類金属の塩としては、塩化金属塩、硝酸金属塩、硫酸金属塩、酢酸金属塩、クエン酸金属塩、グルコン酸金属塩、及び、アセチルアセトナト金属の中から選択される１種以上であることが好ましい。特に、作業性の観点から、酢酸金属塩を用いることが好ましい。
As the alkaline earth metal salt, one or more selected from metal chloride, metal nitrate, metal sulfate, metal acetate, metal citrate, metal gluconate, and metal acetylacetonate. It is preferable that In particular, from the viewpoint of workability, it is preferable to use acetic acid metal salts.
アルカリ土類金属を塩として含む水溶液にて洗浄することにより、スチールワイヤの周面に形成された燐酸化合物層や酸化亜鉛層が除去される。すなわち、上記した洗浄処理を行うことによって、ゴムとの接着反応阻害物が除去される。更に、洗浄後のスチールワイヤの表面にアルカリ土類金属が残留する。この結果、ゴムに対する接着性に優れるスチールワイヤを得ることができる。従って、ゴム側の接着プロモーター（コバルト化合物）を省略したとしても、ワイヤとゴムとの接着を確実にはかることができる。一方で、ゴム側の接着プロモーターを省略できるから、熱、湿気または酸素に起因した劣化に対するゴムの耐性（耐劣化性）を向上することも可能である。
By cleaning with an aqueous solution containing an alkaline earth metal as a salt, the phosphoric acid compound layer and zinc oxide layer formed on the circumferential surface of the steel wire are removed. That is, by performing the above-described cleaning treatment, substances that inhibit the adhesion reaction with rubber are removed. Furthermore, alkaline earth metals remain on the surface of the steel wire after cleaning. As a result, a steel wire with excellent adhesion to rubber can be obtained. Therefore, even if the adhesion promoter (cobalt compound) on the rubber side is omitted, the wire and rubber can be reliably bonded. On the other hand, since the adhesion promoter on the rubber side can be omitted, it is also possible to improve the resistance (deterioration resistance) of the rubber to deterioration caused by heat, moisture, or oxygen.
本発明の製造方法では、コバルト塩を含む水溶液を用いて洗浄した場合と比較して、初期接着性及び耐劣化性を大幅に向上させることができる。特に、マグネシウム塩を含む水溶液を用いて洗浄することにより、初期接着性及び耐劣化性の向上効果が高い。この理由としては定かではないが、スチールワイヤの表面に付着したアルカリ土類金属が、加硫速度の促進など、ゴム成分の架橋に何らかの影響を与えることが考えられ、予期し得ない効果であると言える。
また、アルカリ土類金属の塩を用いることにより、環境負荷を小さくすることができるという利点がある。 In the manufacturing method of the present invention, initial adhesion and deterioration resistance can be significantly improved compared to cleaning using an aqueous solution containing cobalt salt. In particular, cleaning with an aqueous solution containing a magnesium salt is highly effective in improving initial adhesion and deterioration resistance. The reason for this is not certain, but it is thought that the alkaline earth metals attached to the surface of the steel wire have some kind of effect on the crosslinking of the rubber component, such as accelerating the vulcanization rate, which is an unexpected effect. I can say that.
Furthermore, the use of alkaline earth metal salts has the advantage of reducing environmental impact.
また、アルカリ土類金属の塩を用いることにより、環境負荷を小さくすることができるという利点がある。 In the manufacturing method of the present invention, initial adhesion and deterioration resistance can be significantly improved compared to cleaning using an aqueous solution containing cobalt salt. In particular, cleaning with an aqueous solution containing a magnesium salt is highly effective in improving initial adhesion and deterioration resistance. The reason for this is not certain, but it is thought that the alkaline earth metals attached to the surface of the steel wire have some kind of effect on the crosslinking of the rubber component, such as accelerating the vulcanization rate, which is an unexpected effect. I can say that.
Furthermore, the use of alkaline earth metal salts has the advantage of reducing environmental impact.
アルカリ土類金属を塩として含む水溶液のｐＨは、５～８程度とすることが好ましい。水溶液のｐＨを当該範囲とすることにより、ブラスめっきの変質等の影響を抑制し、ゴムとの良好な接着性を確保することができる。また、中性に近いｐＨであるため、環境に与える負荷を小さくすることができるとともに、製造時にオペレータへの暴露に対する安全性および試薬安全性を確保することもできる。
The pH of the aqueous solution containing the alkaline earth metal as a salt is preferably about 5 to 8. By setting the pH of the aqueous solution within this range, it is possible to suppress the effects of deterioration of the brass plating and ensure good adhesion with rubber. Further, since the pH is close to neutral, the load on the environment can be reduced, and safety against exposure to operators and reagent safety can be ensured during manufacturing.
水溶液中のアルカリ土類金属の濃度は、燐酸化合物層及び酸化亜鉛層の除去効率、及び、接着促進作用を考慮すると、０．０１ｍｏｌ／Ｌ以上であることが好ましく、０．０５ｍｏｌ／Ｌ以上であることがより好ましく、０．１ｍｏｌ／Ｌ以上であることが更に好ましい。一方、スチールワイヤ表面に残留するアルカリ土類金属量や、処理コストなどを考慮すると、１ｍｏｌ／Ｌ以下であることが好ましく、０．５ｍｏｌ／Ｌ以下であることがより好ましく、０．３ｍｏｌ／Ｌ以下であることが更に好ましい。
The concentration of alkaline earth metal in the aqueous solution is preferably 0.01 mol/L or more, and 0.05 mol/L or more, considering the removal efficiency of the phosphoric acid compound layer and the zinc oxide layer and the adhesion promoting effect. It is more preferable that the amount is 0.1 mol/L or more, and even more preferably 0.1 mol/L or more. On the other hand, considering the amount of alkaline earth metal remaining on the steel wire surface and processing cost, it is preferably 1 mol/L or less, more preferably 0.5 mol/L or less, and 0.3 mol/L. It is more preferable that it is the following.
洗浄条件は、水溶液の濃度、処理コストなどに応じて、洗浄時間及び水溶液の温度を適宜設定すればよい。例えば、洗浄時間は５～１００秒の範囲、温度は１０～４０℃の範囲とすることができる。
洗浄方法としては特に制限されず、浸漬、スプレー等による噴霧等を適用することができる。 As for the cleaning conditions, the cleaning time and the temperature of the aqueous solution may be appropriately set depending on the concentration of the aqueous solution, processing cost, and the like. For example, the cleaning time can be in the range of 5 to 100 seconds and the temperature can be in the range of 10 to 40°C.
The cleaning method is not particularly limited, and immersion, spraying, etc. can be applied.
洗浄方法としては特に制限されず、浸漬、スプレー等による噴霧等を適用することができる。 As for the cleaning conditions, the cleaning time and the temperature of the aqueous solution may be appropriately set depending on the concentration of the aqueous solution, processing cost, and the like. For example, the cleaning time can be in the range of 5 to 100 seconds and the temperature can be in the range of 10 to 40°C.
The cleaning method is not particularly limited, and immersion, spraying, etc. can be applied.
［スチールコードの製造方法］
スチールコードは、スチールワイヤを撚り合わせて製造される。すなわち、本発明のスチールコードの製造方法は、上記のスチールワイヤの製造方法により製造されたスチールワイヤを、複数本の前記スチールワイヤを撚り合わせる工程を含む。
撚り構造についても特に制限はなく、単撚り、複撚り、層撚り、層撚り及び複撚りの複合撚りなどの撚り構造などとすることができる。 [Manufacturing method of steel cord]
Steel cord is manufactured by twisting steel wires together. That is, the steel cord manufacturing method of the present invention includes the step of twisting together a plurality of steel wires manufactured by the above-described steel wire manufacturing method.
There is no particular restriction on the twist structure, and twist structures such as single twist, double twist, layered twist, and composite twist of layered twist and multi-twist can be used.
スチールコードは、スチールワイヤを撚り合わせて製造される。すなわち、本発明のスチールコードの製造方法は、上記のスチールワイヤの製造方法により製造されたスチールワイヤを、複数本の前記スチールワイヤを撚り合わせる工程を含む。
撚り構造についても特に制限はなく、単撚り、複撚り、層撚り、層撚り及び複撚りの複合撚りなどの撚り構造などとすることができる。 [Manufacturing method of steel cord]
Steel cord is manufactured by twisting steel wires together. That is, the steel cord manufacturing method of the present invention includes the step of twisting together a plurality of steel wires manufactured by the above-described steel wire manufacturing method.
There is no particular restriction on the twist structure, and twist structures such as single twist, double twist, layered twist, and composite twist of layered twist and multi-twist can be used.
また、スチールコードは、スチールワイヤを単独で用いたモノフィラメント構造としてもよく、複数のスチールワイヤを撚り合わせずに複数本束ねた構造も可能としてもよく、複数のスチールワイヤを並列に並べた構造としてもよい。モノフィラメント構造の場合、断面が真円形状のみでなく、楕円や長方形などの断面形状とすることもできる。
In addition, the steel cord may have a monofilament structure using a single steel wire, a structure in which multiple steel wires are bundled without twisting them together, or a structure in which multiple steel wires are arranged in parallel. Good too. In the case of a monofilament structure, the cross section can be not only a perfect circle but also an ellipse or a rectangle.
撚り合わせ工程と洗浄工程との関係は特に制限されない。具体的には、以下の工程順が挙げられる。
（１）スチールワイヤを撚り合わせる工程を行った後、洗浄する工程を行う。
（２）洗浄する工程を行った後、スチールワイヤを撚り合わせる工程を行う。
（３）スチールワイヤを撚り合わせる工程を行った後、洗浄する工程を行い、撚り合わせたスチールワイヤを更に撚り合わせる工程を行う。
（１）の工程順は、単撚り及び層撚りのスチールコードの製造に適する。（２）の工程順は、いずれの撚り構造のスチールコードの製造に適用可能であるが、特に複撚りのスチールコードの製造に好適である。（３）の工程順は、いずれの撚り構造のスチールコードの製造に適用可能であるが、特に層撚り及び複撚りのスチールコードの製造に好適である。 The relationship between the twisting process and the cleaning process is not particularly limited. Specifically, the following process order can be mentioned.
(1) After performing the step of twisting the steel wires, a step of cleaning is performed.
(2) After performing the cleaning process, a process of twisting the steel wires is performed.
(3) After performing the step of twisting the steel wires together, a step of cleaning is performed, and a step of further twisting the twisted steel wires is performed.
The process sequence (1) is suitable for producing single-strand and layer-twist steel cords. The process order (2) is applicable to manufacturing steel cords of any twisted structure, but is particularly suitable for manufacturing double-twisted steel cords. The process order (3) is applicable to manufacturing steel cords of any twisted structure, but is particularly suitable for manufacturing layer-twisted and multi-twisted steel cords.
（１）スチールワイヤを撚り合わせる工程を行った後、洗浄する工程を行う。
（２）洗浄する工程を行った後、スチールワイヤを撚り合わせる工程を行う。
（３）スチールワイヤを撚り合わせる工程を行った後、洗浄する工程を行い、撚り合わせたスチールワイヤを更に撚り合わせる工程を行う。
（１）の工程順は、単撚り及び層撚りのスチールコードの製造に適する。（２）の工程順は、いずれの撚り構造のスチールコードの製造に適用可能であるが、特に複撚りのスチールコードの製造に好適である。（３）の工程順は、いずれの撚り構造のスチールコードの製造に適用可能であるが、特に層撚り及び複撚りのスチールコードの製造に好適である。 The relationship between the twisting process and the cleaning process is not particularly limited. Specifically, the following process order can be mentioned.
(1) After performing the step of twisting the steel wires, a step of cleaning is performed.
(2) After performing the cleaning process, a process of twisting the steel wires is performed.
(3) After performing the step of twisting the steel wires together, a step of cleaning is performed, and a step of further twisting the twisted steel wires is performed.
The process sequence (1) is suitable for producing single-strand and layer-twist steel cords. The process order (2) is applicable to manufacturing steel cords of any twisted structure, but is particularly suitable for manufacturing double-twisted steel cords. The process order (3) is applicable to manufacturing steel cords of any twisted structure, but is particularly suitable for manufacturing layer-twisted and multi-twisted steel cords.
［スチールワイヤ及びスチールコード］
本発明の製造方法により製造されたスチールワイヤは、ブラスめっきの表面に酸化亜鉛層や燐酸化合物層などの酸化物層が除去されたものであり、更にブラスめっきの表面にアルカリ土類金属が存在する状態となっている。上述したように、酸化物層が除去されることと、表面のアルカリ土類金属とによって、ゴムとの初期密着性及び耐劣化性に優れる。また、本発明の製造方法により製造されたスチールワイヤを用いて製造されたスチールコードも、同様にゴムとの初期密着性及び耐劣化性に優れる。 [Steel wire and steel cord]
The steel wire manufactured by the manufacturing method of the present invention has an oxide layer such as a zinc oxide layer or a phosphoric acid compound layer removed from the surface of the brass plating, and furthermore, an alkaline earth metal is present on the surface of the brass plating. The situation is such that As mentioned above, due to the removal of the oxide layer and the alkaline earth metal on the surface, the initial adhesion to rubber and the resistance to deterioration are excellent. Further, the steel cord manufactured using the steel wire manufactured by the manufacturing method of the present invention also has excellent initial adhesion to rubber and deterioration resistance.
本発明の製造方法により製造されたスチールワイヤは、ブラスめっきの表面に酸化亜鉛層や燐酸化合物層などの酸化物層が除去されたものであり、更にブラスめっきの表面にアルカリ土類金属が存在する状態となっている。上述したように、酸化物層が除去されることと、表面のアルカリ土類金属とによって、ゴムとの初期密着性及び耐劣化性に優れる。また、本発明の製造方法により製造されたスチールワイヤを用いて製造されたスチールコードも、同様にゴムとの初期密着性及び耐劣化性に優れる。 [Steel wire and steel cord]
The steel wire manufactured by the manufacturing method of the present invention has an oxide layer such as a zinc oxide layer or a phosphoric acid compound layer removed from the surface of the brass plating, and furthermore, an alkaline earth metal is present on the surface of the brass plating. The situation is such that As mentioned above, due to the removal of the oxide layer and the alkaline earth metal on the surface, the initial adhesion to rubber and the resistance to deterioration are excellent. Further, the steel cord manufactured using the steel wire manufactured by the manufacturing method of the present invention also has excellent initial adhesion to rubber and deterioration resistance.
本発明の製造方法により製造されたスチールワイヤの表面におけるアルカリ土類金属の濃度が、０．５ｍｇ／ｍ２以上３０ｍｇ／ｍ２以下であることが好ましい。同様に、本発明の製造方法により製造されたスチールコードも、スチールワイヤの表面におけるアルカリ土類金属の濃度が、０．５ｍｇ／ｍ２以上３０ｍｇ／ｍ２以下であることが好ましい。アルカリ土類金属の濃度が上記範囲であることにより、ゴム成分との初期密着性及び耐劣化性の改善効果を十分に得ることができる。アルカリ土類金属の濃度の下限値は、１ｍｇ／ｍ２以上であることがより好ましく、２ｍｇ／ｍ２以上であることが更に好ましい。また、アルカリ土類金属の濃度の下限値は、２５ｍｇ／ｍ２以下であることがより好ましく、２０ｍｇ／ｍ２以下であることが更に好ましい。
本発明におけるアルカリ土類金属の濃度は、ＩＣＰ分析により測定される値である。また、ここでいう「スチールワイヤの表面」とは、フィラメント半径方向内側に１０ｎｍの深さまでの表層領域である。 The concentration of alkaline earth metal on the surface of the steel wire manufactured by the manufacturing method of the present invention is preferably 0.5 mg/m 2 or more and 30 mg/m 2 or less. Similarly, in the steel cord manufactured by the manufacturing method of the present invention, the concentration of alkaline earth metal on the surface of the steel wire is preferably 0.5 mg/m 2 or more and 30 mg/m 2 or less. When the concentration of the alkaline earth metal is within the above range, it is possible to sufficiently improve the initial adhesion with the rubber component and the deterioration resistance. The lower limit of the alkaline earth metal concentration is more preferably 1 mg/m 2 or more, and even more preferably 2 mg/m 2 or more. Further, the lower limit of the alkaline earth metal concentration is more preferably 25 mg/m 2 or less, and even more preferably 20 mg/m 2 or less.
The alkaline earth metal concentration in the present invention is a value measured by ICP analysis. Furthermore, the "surface of the steel wire" herein refers to the surface layer region up to a depth of 10 nm inside the filament in the radial direction.
本発明におけるアルカリ土類金属の濃度は、ＩＣＰ分析により測定される値である。また、ここでいう「スチールワイヤの表面」とは、フィラメント半径方向内側に１０ｎｍの深さまでの表層領域である。 The concentration of alkaline earth metal on the surface of the steel wire manufactured by the manufacturing method of the present invention is preferably 0.5 mg/m 2 or more and 30 mg/m 2 or less. Similarly, in the steel cord manufactured by the manufacturing method of the present invention, the concentration of alkaline earth metal on the surface of the steel wire is preferably 0.5 mg/m 2 or more and 30 mg/m 2 or less. When the concentration of the alkaline earth metal is within the above range, it is possible to sufficiently improve the initial adhesion with the rubber component and the deterioration resistance. The lower limit of the alkaline earth metal concentration is more preferably 1 mg/m 2 or more, and even more preferably 2 mg/m 2 or more. Further, the lower limit of the alkaline earth metal concentration is more preferably 25 mg/m 2 or less, and even more preferably 20 mg/m 2 or less.
The alkaline earth metal concentration in the present invention is a value measured by ICP analysis. Furthermore, the "surface of the steel wire" herein refers to the surface layer region up to a depth of 10 nm inside the filament in the radial direction.
［スチールワイヤ及びスチールコードの用途］
本発明のスチールワイヤ及びスチールコードは、ゴムとの複合体として種々のゴム製品に適用することができる。具体的に、ゴム複合体は、本発明の製造方法により得られるスチールワイヤ、または、スチールコードにゴムを被覆してなる。
ここで、被覆ゴムは、接着プロモーターとしてコバルトを実質的に含まないことが好ましい。「実質的に含まない」とは、ゴム中のコバルトの含有量がゴム成分１００質量部に対して０．０１質量部以下であることを意味する。従って、本発明のゴム複合体は、コバルトが使用されない、あるいは、コバルトの含有量が極めて低減されているものである。ゴム中のコバルトの含有量がゴム成分１００質量部に対して０質量部であることがより好ましい。 [Applications of steel wire and steel cord]
The steel wire and steel cord of the present invention can be applied to various rubber products as a composite with rubber. Specifically, the rubber composite is made by coating a steel wire or steel cord obtained by the manufacturing method of the present invention with rubber.
Here, the coating rubber preferably does not substantially contain cobalt as an adhesion promoter. "Substantially free" means that the content of cobalt in the rubber is 0.01 parts by mass or less based on 100 parts by mass of the rubber component. Therefore, in the rubber composite of the present invention, cobalt is not used or the cobalt content is extremely reduced. More preferably, the content of cobalt in the rubber is 0 parts by mass based on 100 parts by mass of the rubber component.
本発明のスチールワイヤ及びスチールコードは、ゴムとの複合体として種々のゴム製品に適用することができる。具体的に、ゴム複合体は、本発明の製造方法により得られるスチールワイヤ、または、スチールコードにゴムを被覆してなる。
ここで、被覆ゴムは、接着プロモーターとしてコバルトを実質的に含まないことが好ましい。「実質的に含まない」とは、ゴム中のコバルトの含有量がゴム成分１００質量部に対して０．０１質量部以下であることを意味する。従って、本発明のゴム複合体は、コバルトが使用されない、あるいは、コバルトの含有量が極めて低減されているものである。ゴム中のコバルトの含有量がゴム成分１００質量部に対して０質量部であることがより好ましい。 [Applications of steel wire and steel cord]
The steel wire and steel cord of the present invention can be applied to various rubber products as a composite with rubber. Specifically, the rubber composite is made by coating a steel wire or steel cord obtained by the manufacturing method of the present invention with rubber.
Here, the coating rubber preferably does not substantially contain cobalt as an adhesion promoter. "Substantially free" means that the content of cobalt in the rubber is 0.01 parts by mass or less based on 100 parts by mass of the rubber component. Therefore, in the rubber composite of the present invention, cobalt is not used or the cobalt content is extremely reduced. More preferably, the content of cobalt in the rubber is 0 parts by mass based on 100 parts by mass of the rubber component.
コバルトは、接着プロモーターとして働く一方、ゴムの耐劣化性を阻害する要因にもなる。本発明の製造方法により得られるスチールワイヤ及びスチールコードは、接着プロモーターを含まないゴムを用いても、優れた初期接着性を確保することができる。そして、スチールワイヤまたはスチールコード、及び、ゴムのいずれでも、コバルトの含有量が低減されているので、耐劣化性に特に優れるものとなる。
While cobalt acts as an adhesion promoter, it also becomes a factor that inhibits the deterioration resistance of rubber. The steel wire and steel cord obtained by the manufacturing method of the present invention can ensure excellent initial adhesion even when using rubber that does not contain an adhesion promoter. Since the content of cobalt is reduced in either the steel wire or the steel cord or the rubber, the deterioration resistance is particularly excellent.
被覆ゴムとしては特に限定されない。後述する具体的な用途において汎用されるゴムを使用することができる。なお、被覆ゴムには、加硫剤としての硫黄をゴム成分１００質量部に対して１～１０質量部で配合したものを用いることが好ましい。上記範囲で硫黄を含むことにより、硫黄とゴムとの加硫による接着本来の接着力を確保することができるとともに、ゴム物性の中でも耐熱老化性および耐熱接着特性の低下を抑制することができる。
The covering rubber is not particularly limited. Rubber that is commonly used in specific applications described below can be used. It is preferable to use a coating rubber containing sulfur as a vulcanizing agent in an amount of 1 to 10 parts by mass based on 100 parts by mass of the rubber component. By containing sulfur in the above range, it is possible to ensure the original adhesive strength of the bond due to vulcanization between sulfur and rubber, and it is also possible to suppress deterioration of heat aging resistance and heat-resistant adhesive properties among the rubber physical properties.
上述のゴム複合体は、タイヤ（空気入りタイヤ）、クローラ、ホース、免震ゴムなどに用いることができる。ゴム複合体が空気入りタイヤである場合、本発明により得られるスチールワイヤまたはスチールコードは、カーカスプライまたはベルトプライの補強材に適用される。タイヤ構造自体は一般的な構造とされる。
The above-mentioned rubber composite can be used for tires (pneumatic tires), crawlers, hoses, seismic isolation rubber, etc. If the rubber composite is a pneumatic tire, the steel wire or steel cord obtained according to the invention is applied to the reinforcement of the carcass ply or belt ply. The tire structure itself is a general structure.
以下、実施例を挙げて本発明をさらに詳しく説明するが、これらの実施例は、本発明の例示を目的とするものであり、本発明を何ら限定するものではない。
Hereinafter, the present invention will be explained in more detail with reference to Examples, but these Examples are intended to illustrate the present invention and are not intended to limit the present invention in any way.
１．サンプルの作製
［実施例１］
直径１．７ｍｍのスチールワイヤの表面に、銅６３．０質量％、亜鉛３７．０質量％となるように、銅、亜鉛の順にブラスめっきを繰り返し行い、その後、５５０℃で５秒間熱拡散処理を行い、銅－亜鉛二元系めっきを形成した。その後、スチールワイヤに伸線加工を施し、めっき平均厚み０．２５μｍ、直径０．３４ｍｍのスチールワイヤを得た。
得られた各スチールワイヤを用いて、１＋６構造の撚りコードであるスチールコードを作製した。
その後、スチールコードを０．２ｍｏｌ／Ｌの酢酸マグネシウム水溶液中に１０秒間浸漬させて洗浄処理を行った。浸漬後、スチールコード表面に付着した液をエアーブローで除去した。その後、５０℃で３０秒間乾燥させた。
洗浄処理後のスチールワイヤ表面のマグネシウム濃度を、以下の工程により評価した。まず、スチールワイヤを希塩酸に浸漬し、スチールワイヤの表面を溶解させた。溶解処理後の希硫酸中のマグネシウム濃度を、ＩＣＰ分析（装置：Agilent 5110）により定量した。ＩＣＰ分析によるマグネシウム濃度と、浸漬したスチールワイヤの寸法から、実施例１のスチールコード表面のマグネシウム濃度を算出したところ、２.５ｍｇ／ｍ２であった。 1. Preparation of sample [Example 1]
The surface of a steel wire with a diameter of 1.7 mm was repeatedly plated with copper and then zinc in the order of 63.0% by mass of copper and 37.0% by mass of zinc, followed by thermal diffusion treatment at 550°C for 5 seconds. A copper-zinc binary plating was formed. Thereafter, the steel wire was subjected to wire drawing to obtain a steel wire with an average plating thickness of 0.25 μm and a diameter of 0.34 mm.
A steel cord, which is a twisted cord having a 1+6 structure, was produced using each of the obtained steel wires.
Thereafter, the steel cord was immersed in a 0.2 mol/L magnesium acetate aqueous solution for 10 seconds to perform a cleaning treatment. After dipping, the liquid adhering to the surface of the steel cord was removed by air blowing. Thereafter, it was dried at 50° C. for 30 seconds.
The magnesium concentration on the surface of the steel wire after the cleaning treatment was evaluated by the following steps. First, a steel wire was immersed in dilute hydrochloric acid to dissolve the surface of the steel wire. The magnesium concentration in the dilute sulfuric acid after the dissolution treatment was determined by ICP analysis (device: Agilent 5110). The magnesium concentration on the surface of the steel cord in Example 1 was calculated from the magnesium concentration determined by ICP analysis and the dimensions of the immersed steel wire, and was found to be 2.5 mg/m 2 .
［実施例１］
直径１．７ｍｍのスチールワイヤの表面に、銅６３．０質量％、亜鉛３７．０質量％となるように、銅、亜鉛の順にブラスめっきを繰り返し行い、その後、５５０℃で５秒間熱拡散処理を行い、銅－亜鉛二元系めっきを形成した。その後、スチールワイヤに伸線加工を施し、めっき平均厚み０．２５μｍ、直径０．３４ｍｍのスチールワイヤを得た。
得られた各スチールワイヤを用いて、１＋６構造の撚りコードであるスチールコードを作製した。
その後、スチールコードを０．２ｍｏｌ／Ｌの酢酸マグネシウム水溶液中に１０秒間浸漬させて洗浄処理を行った。浸漬後、スチールコード表面に付着した液をエアーブローで除去した。その後、５０℃で３０秒間乾燥させた。
洗浄処理後のスチールワイヤ表面のマグネシウム濃度を、以下の工程により評価した。まず、スチールワイヤを希塩酸に浸漬し、スチールワイヤの表面を溶解させた。溶解処理後の希硫酸中のマグネシウム濃度を、ＩＣＰ分析（装置：Agilent 5110）により定量した。ＩＣＰ分析によるマグネシウム濃度と、浸漬したスチールワイヤの寸法から、実施例１のスチールコード表面のマグネシウム濃度を算出したところ、２.５ｍｇ／ｍ２であった。 1. Preparation of sample [Example 1]
The surface of a steel wire with a diameter of 1.7 mm was repeatedly plated with copper and then zinc in the order of 63.0% by mass of copper and 37.0% by mass of zinc, followed by thermal diffusion treatment at 550°C for 5 seconds. A copper-zinc binary plating was formed. Thereafter, the steel wire was subjected to wire drawing to obtain a steel wire with an average plating thickness of 0.25 μm and a diameter of 0.34 mm.
A steel cord, which is a twisted cord having a 1+6 structure, was produced using each of the obtained steel wires.
Thereafter, the steel cord was immersed in a 0.2 mol/L magnesium acetate aqueous solution for 10 seconds to perform a cleaning treatment. After dipping, the liquid adhering to the surface of the steel cord was removed by air blowing. Thereafter, it was dried at 50° C. for 30 seconds.
The magnesium concentration on the surface of the steel wire after the cleaning treatment was evaluated by the following steps. First, a steel wire was immersed in dilute hydrochloric acid to dissolve the surface of the steel wire. The magnesium concentration in the dilute sulfuric acid after the dissolution treatment was determined by ICP analysis (device: Agilent 5110). The magnesium concentration on the surface of the steel cord in Example 1 was calculated from the magnesium concentration determined by ICP analysis and the dimensions of the immersed steel wire, and was found to be 2.5 mg/m 2 .
上記工程により得られたスチールコード２５本を、５０ｍｍの間隔で平行に並べる。スチールコードの上下両側から、表１の「組成Ａ」に示す配合のゴム組成物をコーティングする。その後、１４５℃１０分の条件で加硫し、実施例１のサンプル（スチールコード－ゴム複合体）を得る。
25 steel cords obtained through the above steps are arranged in parallel at intervals of 50 mm. A rubber composition having the composition shown in "Composition A" in Table 1 is coated on both the upper and lower sides of the steel cord. Thereafter, vulcanization was performed at 145° C. for 10 minutes to obtain the sample of Example 1 (steel cord-rubber composite).
［比較例１］
実施例１と同じ工程で、撚りコードであるスチールコードを作製した。
このスチールコードを洗浄することなく、スチールコード２５本を、５０ｍｍの間隔で平行に並べる。スチールコードの上下両側から、表１の「組成Ｂ」に示す配合のゴム組成物をコーティングする。その後、１４５℃１０分の条件で加硫し、比較例１のサンプル（スチールコード－ゴム複合体）を得る。 [Comparative example 1]
A steel cord, which is a twisted cord, was produced in the same process as in Example 1.
Without washing the steel cords, 25 steel cords are arranged in parallel at intervals of 50 mm. A rubber composition having the composition shown in "Composition B" in Table 1 is coated on both the upper and lower sides of the steel cord. Thereafter, it was vulcanized at 145° C. for 10 minutes to obtain a sample of Comparative Example 1 (steel cord-rubber composite).
実施例１と同じ工程で、撚りコードであるスチールコードを作製した。
このスチールコードを洗浄することなく、スチールコード２５本を、５０ｍｍの間隔で平行に並べる。スチールコードの上下両側から、表１の「組成Ｂ」に示す配合のゴム組成物をコーティングする。その後、１４５℃１０分の条件で加硫し、比較例１のサンプル（スチールコード－ゴム複合体）を得る。 [Comparative example 1]
A steel cord, which is a twisted cord, was produced in the same process as in Example 1.
Without washing the steel cords, 25 steel cords are arranged in parallel at intervals of 50 mm. A rubber composition having the composition shown in "Composition B" in Table 1 is coated on both the upper and lower sides of the steel cord. Thereafter, it was vulcanized at 145° C. for 10 minutes to obtain a sample of Comparative Example 1 (steel cord-rubber composite).
［比較例２］
実施例１と同じ工程で、撚りコードであるスチールコードを作製した。その後、スチールコードを０．２ｍｏｌ／Ｌの酢酸コバルト水溶液中に１０秒間浸漬させて、洗浄処理を行った。浸漬後、スチールコード表面に付着した液をエアーブローで除去し、５０℃で３０秒間乾燥させた。
上記工程により得られたスチールコード２５本を、５０ｍｍの間隔で平行に並べる。スチールコードの上下両側から、表１の「組成Ａ」に示す配合のゴム組成物をコーティングする。その後、１４５℃１０分の条件で加硫し、比較例２のサンプル（スチールコード－ゴム複合体）を得る。 [Comparative example 2]
A steel cord, which is a twisted cord, was produced in the same process as in Example 1. Thereafter, the steel cord was immersed in a 0.2 mol/L cobalt acetate aqueous solution for 10 seconds to perform a cleaning treatment. After dipping, the liquid adhering to the surface of the steel cord was removed by air blowing, and the cord was dried at 50° C. for 30 seconds.
25 steel cords obtained through the above steps are arranged in parallel at intervals of 50 mm. A rubber composition having the composition shown in "Composition A" in Table 1 is coated on both the upper and lower sides of the steel cord. Thereafter, it was vulcanized at 145° C. for 10 minutes to obtain a sample of Comparative Example 2 (steel cord-rubber composite).
実施例１と同じ工程で、撚りコードであるスチールコードを作製した。その後、スチールコードを０．２ｍｏｌ／Ｌの酢酸コバルト水溶液中に１０秒間浸漬させて、洗浄処理を行った。浸漬後、スチールコード表面に付着した液をエアーブローで除去し、５０℃で３０秒間乾燥させた。
上記工程により得られたスチールコード２５本を、５０ｍｍの間隔で平行に並べる。スチールコードの上下両側から、表１の「組成Ａ」に示す配合のゴム組成物をコーティングする。その後、１４５℃１０分の条件で加硫し、比較例２のサンプル（スチールコード－ゴム複合体）を得る。 [Comparative example 2]
A steel cord, which is a twisted cord, was produced in the same process as in Example 1. Thereafter, the steel cord was immersed in a 0.2 mol/L cobalt acetate aqueous solution for 10 seconds to perform a cleaning treatment. After dipping, the liquid adhering to the surface of the steel cord was removed by air blowing, and the cord was dried at 50° C. for 30 seconds.
25 steel cords obtained through the above steps are arranged in parallel at intervals of 50 mm. A rubber composition having the composition shown in "Composition A" in Table 1 is coated on both the upper and lower sides of the steel cord. Thereafter, it was vulcanized at 145° C. for 10 minutes to obtain a sample of Comparative Example 2 (steel cord-rubber composite).
表１中の成分の詳細は以下のとおりである。
老化防止剤：Ｎ－フェニル－Ｎ’－（１，３－ジメチルブチル）－ｐ－フェニレンジアミン（大内新興化学工業（株）製、ノクラック６Ｃ）
コバルト脂肪酸塩：ネオデカン酸コバルトホウ素化合物
なお、表１に示す「その他薬品」とは、一般にスチールコード－ゴム複合体に用いられるゴム組成物中に含まれる成分であって、表１に標記した成分以外の成分を指す。表１では、その他成分の合計量を表記した。 Details of the components in Table 1 are as follows.
Antiaging agent: N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (manufactured by Ouchi Shinko Chemical Co., Ltd., Nocrac 6C)
Cobalt fatty acid salt: cobalt boron neodecanoate compound Note that "other chemicals" shown in Table 1 are the components generally contained in the rubber composition used for steel cord-rubber composites, and are the components listed in Table 1. Refers to ingredients other than In Table 1, the total amounts of other components are listed.
老化防止剤：Ｎ－フェニル－Ｎ’－（１，３－ジメチルブチル）－ｐ－フェニレンジアミン（大内新興化学工業（株）製、ノクラック６Ｃ）
コバルト脂肪酸塩：ネオデカン酸コバルトホウ素化合物
なお、表１に示す「その他薬品」とは、一般にスチールコード－ゴム複合体に用いられるゴム組成物中に含まれる成分であって、表１に標記した成分以外の成分を指す。表１では、その他成分の合計量を表記した。 Details of the components in Table 1 are as follows.
Antiaging agent: N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (manufactured by Ouchi Shinko Chemical Co., Ltd., Nocrac 6C)
Cobalt fatty acid salt: cobalt boron neodecanoate compound Note that "other chemicals" shown in Table 1 are the components generally contained in the rubber composition used for steel cord-rubber composites, and are the components listed in Table 1. Refers to ingredients other than In Table 1, the total amounts of other components are listed.
２．評価
［初期接着性試験］
常温（２５℃）で、実施例１及び比較例１～２のスチールコード－ゴム複合体からスチールコードを引き抜く。スチールコードに付着している加硫ゴムの被覆状態を目視で観察し、被覆率を０～１００％で決定する。 2. Evaluation [Initial adhesion test]
Steel cords are pulled out from the steel cord-rubber composites of Example 1 and Comparative Examples 1 and 2 at room temperature (25° C.). Visually observe the coating state of the vulcanized rubber attached to the steel cord, and determine the coverage rate from 0 to 100%.
［初期接着性試験］
常温（２５℃）で、実施例１及び比較例１～２のスチールコード－ゴム複合体からスチールコードを引き抜く。スチールコードに付着している加硫ゴムの被覆状態を目視で観察し、被覆率を０～１００％で決定する。 2. Evaluation [Initial adhesion test]
Steel cords are pulled out from the steel cord-rubber composites of Example 1 and Comparative Examples 1 and 2 at room temperature (25° C.). Visually observe the coating state of the vulcanized rubber attached to the steel cord, and determine the coverage rate from 0 to 100%.
［劣化後の接着性試験（耐劣化性評価）］
実施例１及び比較例１～２のスチールコード－ゴム複合体を１４５℃４０分の条件で加硫し、劣化させる。その後、常温（２５℃）でスチールコード－ゴム複合体からスチールコードを引き抜く。スチールコードに付着している加硫ゴムの被覆状態を目視で観察し、被覆率を０～１００％で決定する。 [Adhesion test after deterioration (deterioration resistance evaluation)]
The steel cord-rubber composites of Example 1 and Comparative Examples 1 and 2 were vulcanized at 145° C. for 40 minutes and allowed to deteriorate. Thereafter, the steel cord is pulled out from the steel cord-rubber composite at room temperature (25° C.). Visually observe the coating state of the vulcanized rubber attached to the steel cord, and determine the coverage rate from 0 to 100%.
実施例１及び比較例１～２のスチールコード－ゴム複合体を１４５℃４０分の条件で加硫し、劣化させる。その後、常温（２５℃）でスチールコード－ゴム複合体からスチールコードを引き抜く。スチールコードに付着している加硫ゴムの被覆状態を目視で観察し、被覆率を０～１００％で決定する。 [Adhesion test after deterioration (deterioration resistance evaluation)]
The steel cord-rubber composites of Example 1 and Comparative Examples 1 and 2 were vulcanized at 145° C. for 40 minutes and allowed to deteriorate. Thereafter, the steel cord is pulled out from the steel cord-rubber composite at room temperature (25° C.). Visually observe the coating state of the vulcanized rubber attached to the steel cord, and determine the coverage rate from 0 to 100%.
３．結果
初期接着性及び劣化後の接着性の評価結果を、表２に示す。 3. Results Table 2 shows the evaluation results of initial adhesiveness and adhesiveness after deterioration.
初期接着性及び劣化後の接着性の評価結果を、表２に示す。 3. Results Table 2 shows the evaluation results of initial adhesiveness and adhesiveness after deterioration.
実施例１及び比較例２は、比較例１と対比して被覆率が高い。このことから、ブラスめっき後の洗浄によってスチールコード表面の酸化物が除去された結果、初期接着性及び劣化後の接着性のいずれもが改善している。
また、実施例１は、比較例２と対比して被覆率が高い。このことから、初期接着性及び劣化後の接着性が向上している。同じゴム組成物を同じ条件で加硫したゴムであるにもかかわらず、被覆率が異なるということは、実施例１のゴムは加硫が促進された結果であることが考えられる。すなわち、表２の結果から、スチールコードの表面に付着したマグネシウムが、ゴム成分に何らかの影響を及ぼし、加硫が促進されたと推測することができる。 Example 1 and Comparative Example 2 have higher coverage rates than Comparative Example 1. From this, as a result of the removal of oxides on the surface of the steel cord by cleaning after brass plating, both the initial adhesion and the adhesion after deterioration are improved.
Furthermore, Example 1 has a higher coverage rate than Comparative Example 2. From this, the initial adhesiveness and the adhesiveness after deterioration are improved. The fact that the coverage rates differ even though the rubber compositions were vulcanized under the same conditions is considered to be the result of accelerated vulcanization in the rubber of Example 1. That is, from the results in Table 2, it can be inferred that the magnesium adhering to the surface of the steel cord had some effect on the rubber component, promoting vulcanization.
また、実施例１は、比較例２と対比して被覆率が高い。このことから、初期接着性及び劣化後の接着性が向上している。同じゴム組成物を同じ条件で加硫したゴムであるにもかかわらず、被覆率が異なるということは、実施例１のゴムは加硫が促進された結果であることが考えられる。すなわち、表２の結果から、スチールコードの表面に付着したマグネシウムが、ゴム成分に何らかの影響を及ぼし、加硫が促進されたと推測することができる。 Example 1 and Comparative Example 2 have higher coverage rates than Comparative Example 1. From this, as a result of the removal of oxides on the surface of the steel cord by cleaning after brass plating, both the initial adhesion and the adhesion after deterioration are improved.
Furthermore, Example 1 has a higher coverage rate than Comparative Example 2. From this, the initial adhesiveness and the adhesiveness after deterioration are improved. The fact that the coverage rates differ even though the rubber compositions were vulcanized under the same conditions is considered to be the result of accelerated vulcanization in the rubber of Example 1. That is, from the results in Table 2, it can be inferred that the magnesium adhering to the surface of the steel cord had some effect on the rubber component, promoting vulcanization.
Claims (20)
- スチールワイヤの周面にブラスめっきを施し、次いで伸線加工を施す工程と、前記伸線加工後のスチールワイヤの表面を、アルカリ土類金属を塩として含む水溶液にて洗浄する工程と、を含む、スチールワイヤの製造方法。 The method includes the steps of applying brass plating to the peripheral surface of the steel wire and then performing wire drawing, and cleaning the surface of the steel wire after the wire drawing with an aqueous solution containing an alkaline earth metal as a salt. , a method of manufacturing steel wire.
- 前記アルカリ土類金属がマグネシウムである、請求項１に記載のスチールワイヤの製造方法。 The method for manufacturing a steel wire according to claim 1, wherein the alkaline earth metal is magnesium.
- 前記アルカリ土類金属の塩が、塩化金属塩、硝酸金属塩、硫酸金属塩、酢酸金属塩、クエン酸金属塩、グルコン酸金属塩、及び、アセチルアセトナト金属塩の中から選択される１種以上である、請求項１または請求項２に記載のスチールワイヤの製造方法。 The alkaline earth metal salt is one selected from metal chloride, metal nitrate, metal sulfate, metal acetate, metal citrate, metal gluconate, and metal acetylacetonate. The method for manufacturing a steel wire according to claim 1 or 2, which is the above.
- 請求項１または請求項２に記載のスチールワイヤの製造方法により製造されたスチールワイヤを、複数本撚り合わせる工程を含む、スチールコードの製造方法。 A method for manufacturing a steel cord, comprising the step of twisting together a plurality of steel wires manufactured by the method for manufacturing a steel wire according to claim 1 or 2.
- 前記スチールワイヤを撚り合わせる工程を行った後、前記洗浄する工程を行う、請求項４に記載のスチールコードの製造方法。 The method for manufacturing a steel cord according to claim 4, wherein the cleaning step is performed after the step of twisting the steel wires.
- 前記洗浄する工程を行った後、前記スチールワイヤを撚り合わせる工程を行う、請求項４に記載のスチールコードの製造方法。 The method for manufacturing a steel cord according to claim 4, wherein after performing the cleaning step, a step of twisting the steel wires is performed.
- 前記複数のスチールワイヤを撚り合わせる工程の後に、前記洗浄する工程を行い、次いで、撚り合わせた前記スチールワイヤを更に撚り合わせる工程を含む、請求項４に記載のスチールコードの製造方法。 The method for manufacturing a steel cord according to claim 4, further comprising performing the cleaning step after the step of twisting the plurality of steel wires, and then further twisting the twisted steel wires.
- 請求項１または請求項２に記載の製造方法により製造されたスチールワイヤ。 A steel wire manufactured by the manufacturing method according to claim 1 or 2.
- 表面におけるアルカリ土類金属の濃度が、０．５ｍｇ／ｍ２以上３０ｍｇ／ｍ２以下である、請求項８に記載のスチールワイヤ。 The steel wire according to claim 8, wherein the concentration of alkaline earth metal on the surface is 0.5 mg/m 2 or more and 30 mg/m 2 or less.
- 請求項４に記載の製造方法により製造されたスチールコード。 A steel cord manufactured by the manufacturing method according to claim 4.
- 前記スチールワイヤの表面におけるアルカリ土類金属の濃度が、０．５ｍｇ／ｍ２以上３０ｍｇ／ｍ２以下である、請求項１０に記載のスチールコード。 The steel cord according to claim 10, wherein the concentration of alkaline earth metal on the surface of the steel wire is 0.5 mg/m 2 or more and 30 mg/m 2 or less.
- 請求項８に記載のスチールワイヤにゴムを被覆してなる、ゴム複合体。 A rubber composite formed by coating the steel wire according to claim 8 with rubber.
- 請求項１０に記載のスチールコードにゴムを被覆してなる、ゴム複合体。 A rubber composite formed by coating the steel cord according to claim 10 with rubber.
- 前記ゴム中のコバルトの含有量がゴム成分１００質量部に対して０．０１質量部以下である、請求項１３に記載のゴム複合体。 The rubber composite according to claim 13, wherein the content of cobalt in the rubber is 0.01 parts by mass or less based on 100 parts by mass of the rubber component.
- 請求項１３に記載のゴム複合体を用いたタイヤ。 A tire using the rubber composite according to claim 13.
- カーカスプライに前記ゴム複合体を用いた請求項１５に記載のタイヤ。 The tire according to claim 15, wherein the rubber composite is used for the carcass ply.
- ベルトに前記ゴム複合体を用いた請求項１５に記載のタイヤ。 The tire according to claim 15, wherein the rubber composite is used for the belt.
- 請求項１３に記載のゴム複合体を用いたクローラ。 A crawler using the rubber composite according to claim 13.
- 請求項１３に記載のゴム複合体を用いたホース。 A hose using the rubber composite according to claim 13.
- 請求項１３に記載のゴム複合体を用いた免震ゴム。 Seismic isolation rubber using the rubber composite according to claim 13.
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| JP2022142105 | 2022-09-07 | ||
| JP2022-142105 | 2022-09-07 |
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| WO2024053435A1 true WO2024053435A1 (en) | 2024-03-14 |
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| Application Number | Title | Priority Date | Filing Date |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53106853A (en) * | 1977-02-28 | 1978-09-18 | Yokohama Rubber Co Ltd | Wire for reinforcing rubber wares |
| US4333785A (en) * | 1980-05-15 | 1982-06-08 | The General Tire & Rubber Company | Adhesion of brass to rubber |
| JP2011179152A (en) * | 2010-03-03 | 2011-09-15 | Bridgestone Corp | Method for producing rubber-reinforcing wire, rubber-reinforcing wire and rubber-reinforcing wire-rubber composite material using the same |
-
2023
- 2023-08-25 WO PCT/JP2023/030800 patent/WO2024053435A1/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53106853A (en) * | 1977-02-28 | 1978-09-18 | Yokohama Rubber Co Ltd | Wire for reinforcing rubber wares |
| US4333785A (en) * | 1980-05-15 | 1982-06-08 | The General Tire & Rubber Company | Adhesion of brass to rubber |
| JP2011179152A (en) * | 2010-03-03 | 2011-09-15 | Bridgestone Corp | Method for producing rubber-reinforcing wire, rubber-reinforcing wire and rubber-reinforcing wire-rubber composite material using the same |
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