JP4036362B2 - Method and apparatus for manufacturing steel wire for reinforcing rubber articles - Google Patents

Description

＊めっき表面からワイヤ半径方向内側へ５ｎｍの深さまでの領域
【００３４】
【表２】

＊めっき表面からワイヤ半径方向内側へ５ｎｍの深さまでの領域
【００３５】
【発明の効果】
以上説明してきたように、本発明によれば、スチールコードの生産性を損なうことなくワイヤ表面のリンの量を抑制し、ゴムとスチールコードとの間の接着性を向上させることができる。この結果、高耐久性を有するゴム物品、例えば、高耐久性タイヤ等の製造が可能となる。また、ワイヤ表面のリンの量を抑制するためにダイスの材質を変更する方法では、各最終伸線機毎への新規ダイスの適用が必要となるが、本発明によれば、伸線後ボビンに巻き取るまでの間で数台分をまとめて処理でき、コスト面、管理面でも有利である。
【図面の簡単な説明】
【図１】 本発明の一実施の形態に係るスチールワイヤの製造装置を模式的に示す斜視図である。
【図２】 図１に示す矢視Ａ−Ａ線に沿う断面図である。
【図３】 密集体を形成するスチールワイヤ１本を取り出して示す説明図である。
【図４】 本発明の他の実施の形態に係るスチールワイヤの製造装置を模式的に示す工程図である。
【符号の説明】
１ 製造装置
２ 箱体
３ 任意に変形されたスチールワイヤ
４ 入口
５ 出口
６ 落とし蓋
１０ ブラスめっきが施されたスチールワイヤ
１１ 伸線機本体
１２ 巻き取りリール[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method of manufacturing a steel wire for reinforcing rubber articles used for reinforcing rubber articles such as tires and industrial belts, and a manufacturing apparatus used in the method, and more particularly, to a steel wire subjected to brass plating. The present invention relates to a method for manufacturing a steel wire for reinforcing rubber articles in which the amount of phosphorus on the wire surface is suppressed without impairing productivity and the adhesion to rubber is improved, and a manufacturing apparatus used in this method.
[0002]
[Prior art]
Conventionally, in rubber articles such as radial tire belts, carcass body plies, and various industrial belt members, steel wires coated with brass or a steel cord formed by twisting a plurality of these wires are covered with rubber. Reinforcing effects are obtained by using the above. Therefore, in this case, in order to fully obtain the reinforcing effect, it is necessary to sufficiently secure the adhesion between the steel cord and the rubber. From this point of view, the ratio of copper and zinc and the plating thickness in brass plating In order to optimize the thickness, etc., some knowledge has been established so far.
[0003]
Japanese Laid-Open Patent Publication No. 63-33135 proposes to reduce adhesive deterioration due to wet heat by containing 4 mg / m ² or more of phosphorus in a brass-plated steel wire. Yes.
[0004]
Furthermore, in international application WO097 / 23311, a steel wire obtained by continuously wet-welding a wire material subjected to brass plating through a group of dies dipped in a lubricant containing phosphate is spooled. Then, the spool is attached to the unwinding part of the twisting machine, and the area reduction rate is 5% or more 1 or 2 or more disposed between the unwinding part and the twisting part of the twisting machine. The diameter is reduced by drawing with a die, and the phosphorus compound in the coating formed on the surface of the brass plating of the steel wire is in the range of 0.2 to 0.9 mg / m ² with phosphorus, and zinc oxide is 20.0 to It is disclosed that within the range of 70.0 mg / m ² , the initial adhesiveness with rubber can be improved and the vulcanization time can be shortened.
[0005]
[Problems to be solved by the invention]
The present applicant controls the surface factor of the cord that governs the adhesion reaction between the steel cord subjected to the brass plating and the rubber by using an instrumental analysis method more than ever, and creates the surface in detail, As a result of examining the correspondence with adhesiveness, when the bulk composition of the brass plating is the same, the amount of phosphorus contained as an oxide in the surface layer region from the brass plating surface to a depth of 5 nm in the wire radial direction inside is determined. Obtaining knowledge that it is extremely effective to suppress the content to 1.5 atomic% or less, a patent application was filed first.
[0006]
As a method for suppressing the amount of phosphorus in the surface layer region, it has been confirmed that adjustments such as a wire drawing pass schedule, the shape and angle of the die entrance and approach, the material of the die, and the lubricant composition are effective. Yes.
[0007]
However, the above-described method for suppressing the amount of phosphorus in the surface area of the wire may impair the lubricity inherently required between the die and the wire to be drawn, resulting in wire breakage, frequent die change, and the like. There was a problem that the productivity of the steel wire was lowered.
[0008]
Further, when diamond is used as a material for the die, there is a problem that it is more expensive than a normal die and the manufacturing cost of the steel cord is increased.
[0009]
Accordingly, an object of the present invention is to provide a steel wire for reinforcing rubber articles that can suppress the amount of phosphorus in the surface region of the wire without impairing the productivity of the steel wire subjected to brass plating and can improve the adhesion to rubber. And a manufacturing apparatus used for the method.
[0010]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the method of manufacturing a steel wire for reinforcing rubber articles according to the present invention includes a step of drawing a steel wire subjected to brass plating in a final wet drawing process, and then arbitrarily deforming the steel wire. The following conditions, while the steel wire is dense
Passing length L (m): (0.0018 × S−0.23) × 0.9 <L <(0.0018 × S−0.23) × 1.1
(Where S is the wire drawing speed (m / min))
・ Dense pressure: 90 to 110 g / cm ² (8.82 to 10.78 kPa)
- optionally modified steel wire having a diameter: 0.1 mm or less, dense Density: Passing at 1.9 g / cm ³ or more, to suppress the amount of phosphorus in the steel wire surface area brass-plated It is characterized by this. Thereby, the amount of phosphorus on the wire surface can be suppressed to a desired amount without impairing the productivity of the steel cord, and the adhesion between the rubber and the steel cord can be improved.
[0011]
In the manufacturing method of the present invention, the steel wire to which the brass plating is applied can be suitably applied to a steel wire having a wire diameter of 0.15 to 0.40 mm. It is preferable that the curl diameter is about 5 mm.
[0012]
Also, the steel wire manufacturing apparatus for reinforcing rubber articles according to the present invention is a steel wire manufacturing apparatus for reinforcing rubber articles subjected to brass plating, which is long in the passing direction of the steel wire and has the steel wire inside. A box having an inlet and an outlet for passing through the steel, and a dense body of arbitrarily deformed steel wire that cuts phosphorus in a surface layer region of the steel wire in the box. It is a feature. This manufacturing apparatus can be suitably applied to the method of the present invention. In addition, in the conventional method of changing the material of the die in order to suppress the amount of phosphorus on the wire surface, it is necessary to apply a new die to each final wire drawing machine. It is possible to process several units at a time until it is rolled up, which is advantageous in terms of cost and management.
[0013]
In the manufacturing apparatus of the present invention, the length L (m) of the box in the steel wire passing direction is the following formula:
(0.0018 × S−0.23) × 0.9 <L <(0.0018 × S−0.23) × 1.1
(Wherein S is the wire drawing speed (m / min)) is preferably satisfied, and the upper surface of the box is appropriately formed of steel wire compacts inside the box. It is preferable to be in the form of a drop lid so that pressurization is possible.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be specifically described.
A steel wire manufacturing apparatus 1 for reinforcing rubber articles according to an embodiment of the present invention shown in FIG. 1 is a manufacturing apparatus for suppressing the amount of phosphorus in the surface layer region of a steel wire 10 subjected to brass plating. The present invention can be preferably applied to the method of the present invention. The manufacturing apparatus 1 includes a box 2 and a dense body of arbitrarily deformed steel wires 3 in the box 2. The box 2 is formed to be long in the passing direction of the steel wire, and the box 2 has an inlet 4 and an outlet 5 for allowing the steel wire 10 to pass therethrough. In the example shown in FIG. 1, the inlet 4 and the outlet 5 provided on both opposite side surfaces of the box body 2 are each one place, but a plurality of steel wires 10 can be passed at the same time so that a plurality of steel wires 10 can be passed simultaneously. The inlet 4 and the outlet 5 may be provided on both sides.
[0015]
Further, the box body 2 has its upper surface dropped as shown in FIG. 2 in the cross-sectional view in the direction of the arrow in FIG. 1 so that the dense body of steel wires 3 filled therein can be easily pressurized. It is preferable to form by. A desired pressure can be applied to the dense body of steel wires 3 by appropriately pressurizing the dense body of steel wires 3 from above the drop lid 6.
[0016]
In the box 2, as shown in FIG. 1, a dense body is formed in a state where the steel wires 3 are arbitrarily deformed, but the wire diameter of the steel wires 3 is 0.1 mm or less, Preferably it is 0.05-0.08 mm. When this wire diameter exceeds 0.1 mm, sufficient contact cannot be obtained with the wire 10 subjected to brass plating, and the cutting effect of phosphorus in the surface layer region becomes insufficient. Similarly, in order to obtain a sufficient phosphorus cutting effect, it is preferable that the arbitrarily deformed steel wire 3 has a curl diameter of about 5 mm as shown in FIG.
[0017]
In the method for manufacturing a steel wire for reinforcing rubber articles according to the present invention, the steel wire 10 subjected to brass plating is passed through the manufacturing apparatus 1 after being drawn in the final wet drawing process under the following conditions. Thus, a desired amount of phosphorus in the surface layer region of the steel wire 10 to which the brass plating is applied is cut.
[0018]
That is, the length L (m) in the steel wire passing direction of the box 2 in which the dense body of the steel wires 3 is stored is represented by the following formula:
(0.0018 × S−0.23) × 0.9 <L <(0.0018 × S−0.23) × 1.1
(Wherein S is the wire drawing speed (m / min)). This relationship is
L ≦ (0.0018 × S−0.23) × 0.9
In the case of the relationship represented by the formula, a sufficient phosphorus cutting effect cannot be obtained, while the following formula L ≧ (0.0018 × S−0.23) × 1.1
When the relationship is represented by the above, even the surface brass plating is cut, and conversely, the adhesiveness with the rubber is lowered.
[0019]
Moreover, the pressure from the drop lid 6 is adjusted so that the dense pressure of the steel wires 3 is 90 to 110 g / cm ² (8.82 to 10.78 kPa). If this pressure is less than 90 g / cm ² (8.82 kPa), a sufficient phosphorus cutting effect cannot be obtained, while if it exceeds 110 g / cm ² (10.78 kPa), up to the surface brass plating is cut, On the contrary, the adhesiveness with the rubber is lowered.
[0020]
Furthermore, the density of the box body 2 in the steel wire 3 is 1.9 g / cm ³ or more, preferably 2.1~3.0g / cm ^3. When this density is less than 1.9 g / cm ³ , sufficient contact cannot be obtained with the brass plating wire from which phosphorus is cut, and the cutting effect of phosphorus becomes insufficient.
[0021]
As another embodiment of the present invention, as shown in FIG. 4, a plurality of brass-plated steel wires 10 drawn in a final wet wire drawing step by a plurality of wire drawing machine bodies 11 (seven in the illustrated example) are used. You may let it pass through one box 2. After passing through the box 2, it is wound around the take-up reel 12. In addition, processes other than the multistage wet drawing in the manufacturing method of the steel wire of this invention, for example, the first dry drawing, a patenting process, a brass plating process, etc. can be performed in accordance with a conventional method.
[0022]
In the present invention, the content of phosphorus contained as an oxide in the wire surface layer region from the surface of the peripheral surface brass plating layer to a depth of 5 nm inward in the wire radial direction is favorably suppressed to 1.5 atomic% or less. be able to. If the phosphorus content exceeds 1.5 atomic%, the adhesion speed with the rubber becomes slower accordingly, and it becomes difficult to ensure the desired rubber adhesion. By making the amount of phosphorus 1.5 atomic% or less, rubber adhesion can be stably obtained.
[0023]
The average thickness of the brass plating layer is preferably 0.13 to 0.30 μm. When the average thickness of the brass plating layer is less than 0.13 μm, the portion where the iron base is exposed increases and the initial adhesiveness is inhibited. On the other hand, when the average thickness exceeds 0.30 μm, the adhesive reaction is excessively caused by heat during use of the rubber article. Progresses and only fragile adhesion can be obtained.
[0024]
In the present invention, the ratio of copper to the total amount of copper and zinc in the entire brass plating layer is 60 to 70% by weight, and the ratio of copper to the total amount of copper and zinc in the wire surface layer region is 15 to 45%. It is preferably atomic%. When the ratio of copper to the total amount of copper and zinc in the entire brass plating layer is less than 60% by weight, the wire drawing property deteriorates, the productivity is hindered by disconnection, and mass production becomes difficult. On the other hand, when it exceeds 70% by weight, the moisture-resistant adhesive property of heat resistance is lowered, and it becomes impossible to maintain sufficient durability against the environment where the rubber article, particularly the tire is exposed. Further, when the ratio of copper to the total amount of copper and zinc in the wire surface layer region is less than 15 atomic%, even if the amount of phosphorus in the wire surface region is limited to the above 1.5 atomic percent or less, rubber As a result, it becomes difficult to ensure better rubber adhesion. On the other hand, when it exceeds 45 atomic%, the heat resistant adhesiveness and moisture resistant adhesiveness are disadvantageously lowered.
[0025]
In the present invention, the wire diameter of the steel wire 3 after being drawn in the final wet drawing step is preferably 0.15 to 0.40 mm, and a good phosphorus cutting effect is obtained at such a wire diameter. It is done. On the other hand, when the diameter exceeds 0.40 mm, the used rubber article is subjected to repeated strain under bending deformation, the surface strain becomes large, and buckling is likely to occur.
[0026]
As the steel wire to be subjected to wire drawing, it is preferable to use a high carbon steel wire having a carbon content of 0.60 to 0.95% by weight, while suppressing the decarburization of the steel wire surface layer, It is preferable to perform heat treatment so as to form a uniform pearlite composition with a small amount of pro-eutectoid ferrite or bainite.
[0027]
The steel wire produced according to the present invention may be used as a single wire, or may be used as a steel cord for reinforcing rubber articles having a desired twisted structure by twisting together according to a conventional method using a twisting machine. When using a steel cord in which a plurality of such steel wires are twisted together, it is suitable as a reinforcing material for rubber articles, particularly tire carcass and belts.
[0028]
【Example】
Hereinafter, the present invention will be described based on examples, conventional examples, and comparative examples.
Conventional example A high carbon steel wire rod having a diameter of about 5.5 mm containing about 0.80% by weight of carbon is subjected to dry drawing until the diameter is about 1.72 mm, and then subjected to a patenting treatment. Then, a brass plating having a composition of 63% by weight of copper and 37% by weight of zinc was applied in an adhesion amount shown in Table 1 below, and then fully immersed in an aqueous lubricant containing zinc phosphate. Drawing was performed using a plurality of dies up to a diameter of 0.30 mm with a wire machine.
[0029]
The amount of phosphorus contained as an oxide in the surface layer region of the wire was measured according to X-ray photoelectron spectroscopy. In the escape depth region of the photoelectron measured according to the X-ray photoelectron spectroscopy, the number of atoms of all elements and the number of phosphorus atoms in the oxide are detected. The number of phosphorus atoms expressed as an index was defined as the atomic% of phosphorus contained in the oxide in the region.
[0030]
In addition, the wire obtained by the predetermined method is twisted to form a steel cord of 1 × 3 × 0.30 mm, and the following initial rubber adhesiveness in accordance with the rubber adhesion test method defined in JIS G3510 (1992) Tests and post-degradation adhesion tests were performed. The rubber compound used in this adhesion test was composed of 50 parts by weight of carbon black (HFC), 5 parts by weight of zinc white, 2 parts by weight of cobalt naphthenate (10% content), and 100% by weight of natural rubber. The agent (DZ) was 0.5 parts by weight and sulfur was 5 parts by weight.
[0031]
The initial adhesion test was evaluated by performing a peel test at room temperature after pressure-vulcanizing the rubber-coated cord at 160 ° C. for 5 minutes, 9 minutes, 13 minutes, and 18 minutes, respectively. In addition, the post-degradation adhesion test was evaluated by performing a peel test at room temperature after the rubber-coated cord was pressure vulcanized at 160 ° C. for 18 minutes and then deteriorated for 2 days, 4 days, and 6 days, respectively. Degradation was performed by forcibly penetrating moisture and oxygen into the rubber in an environment in which 0.02 MPa of oxygen was filled in a pressure kettle having a temperature of 60 ° C. and a humidity of 90%. The evaluated rubber adhesion rate is 100% when the cord surface is completely covered by observing the surface of the steel cord after peeling the cord from the rubber, and when the rubber is not completely covered. Was evaluated as 0%. The obtained results are shown in Tables 1 and 2 below.
[0032]
Examples and Comparative Examples 1-6
Each steel wire was obtained by the same method as in the above-described conventional example except that the plating adhesion amount was changed as shown in Tables 1 and 2 below. The obtained steel wire was passed through the production apparatus 1 shown in FIG. 1 under the conditions shown in Table 1 and Table 2 below, and a steel cord was produced in the same manner as in the conventional example. The amounts of phosphorus in the surface layer region of these cords and the results of the initial adhesion test and the post-degradation adhesion test are shown in Table 2 and Table 3 below, respectively.
[0033]
[Table 1]

* Area from the plating surface to the depth of 5 nm inward in the wire radial direction [0034]
[Table 2]

* Area from the plating surface to the depth of 5 nm inward in the wire radial direction [0035]
【The invention's effect】
As described above, according to the present invention, the amount of phosphorus on the wire surface can be suppressed without impairing the productivity of the steel cord, and the adhesion between the rubber and the steel cord can be improved. As a result, it becomes possible to produce a highly durable rubber article, for example, a highly durable tire. In addition, in the method of changing the material of the die in order to suppress the amount of phosphorus on the wire surface, it is necessary to apply a new die to each final wire drawing machine. It is possible to process several units at a time until it is rolled up, which is advantageous in terms of cost and management.
[Brief description of the drawings]
FIG. 1 is a perspective view schematically showing a steel wire manufacturing apparatus according to an embodiment of the present invention.
FIG. 2 is a cross-sectional view taken along the line AA shown in FIG.
FIG. 3 is an explanatory view showing one steel wire forming a dense body.
FIG. 4 is a process diagram schematically showing a steel wire manufacturing apparatus according to another embodiment of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Production apparatus 2 Box 3 Steel wire 4 arbitrarily deformed 4 Inlet 5 Outlet 6 Dropping lid 10 Steel wire 11 plated with brass 11 Wire drawing machine body 12 Winding reel

Claims (6)

After drawing the steel wire subjected to brass plating in the final wet drawing step, the steel wire is subjected to the following conditions while the arbitrarily deformed steel wire is closely packed:
Passing length L (m): (0.0018 × S−0.23) × 0.9 <L <(0.0018 × S−0.23) × 1.1
(Where S is the wire drawing speed (m / min))
・ Dense pressure: 90 to 110 g / cm ² (8.82 to 10.78 kPa)
- optionally modified steel wire having a diameter: 0.1 mm or less, dense Density: Passing at 1.9 g / cm ³ or more, to suppress the amount of phosphorus in the steel wire surface area brass-plated A method for producing a steel wire for reinforcing rubber articles.   The manufacturing method according to claim 1, wherein a wire diameter of the steel wire to which the brass plating is applied is 0.15 to 0.40 mm.   The manufacturing method according to claim 1 or 2, wherein the arbitrarily deformed steel wire is curled with a curl diameter of about 5 mm.   In an apparatus for manufacturing a steel wire for reinforcing rubber articles subjected to brass plating, a box body that is long in the passing direction of the steel wire and has an inlet and an outlet for allowing the steel wire to pass therethrough, An apparatus for producing a steel wire for reinforcing rubber articles, comprising: a densely-assembled steel wire deformed by cutting phosphorus in a surface layer region of the steel wire in a box. The steel wire passing direction length L (m) of the box is the following formula:
(0.0018 × S−0.23) × 0.9 <L <(0.0018 × S−0.23) × 1.1
The manufacturing apparatus of Claim 4 which satisfies the relationship represented by (In formula, S is a wire drawing speed (m / min)).   6. The manufacturing apparatus according to claim 4 or 5, wherein the upper surface of the box is in the form of a drop lid so that a dense body of steel wires inside the box can be appropriately pressurized.

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