JP2009091691A - Steel wire for reinforcing rubber article, method for producing the same, steel cord, rubber composite material, and pneumatic tire - Google Patents

Steel wire for reinforcing rubber article, method for producing the same, steel cord, rubber composite material, and pneumatic tire Download PDF

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JP2009091691A
JP2009091691A JP2007263651A JP2007263651A JP2009091691A JP 2009091691 A JP2009091691 A JP 2009091691A JP 2007263651 A JP2007263651 A JP 2007263651A JP 2007263651 A JP2007263651 A JP 2007263651A JP 2009091691 A JP2009091691 A JP 2009091691A
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rubber
cobalt
steel wire
steel
wire
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JP5094319B2 (en
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Katsutaka Sato
克隆 佐藤
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Bridgestone Corp
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    • DTEXTILES; PAPER
    • D07ROPES; CABLES OTHER THAN ELECTRIC
    • D07BROPES OR CABLES IN GENERAL
    • D07B1/00Constructional features of ropes or cables
    • D07B1/06Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
    • D07B1/0606Reinforcing cords for rubber or plastic articles
    • D07B1/0666Reinforcing cords for rubber or plastic articles the wires being characterised by an anti-corrosive or adhesion promoting coating
    • DTEXTILES; PAPER
    • D07ROPES; CABLES OTHER THAN ELECTRIC
    • D07BROPES OR CABLES IN GENERAL
    • D07B2205/00Rope or cable materials
    • D07B2205/30Inorganic materials
    • D07B2205/3021Metals
    • D07B2205/3085Alloys, i.e. non ferrous
    • D07B2205/3089Brass, i.e. copper (Cu) and zinc (Zn) alloys

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  • Ropes Or Cables (AREA)
  • Tires In General (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To achieve improvement in adhesiveness of a wire to rubber in a manner having reduced environmental load to avoid the problems of rubber material. <P>SOLUTION: The steel wire plated with brass on the circumference of a wire and the concentration of transition metals excluding Zn and Cu on the surface of the brass plating is set to 0.01 mass% or more. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、空気入りタイヤや工業用ベルト等のゴム物品の補強材として用いられるスチールワイヤおよびスチールコード、特にゴムとの接着性に優れたスチールワイヤに関するものである。   The present invention relates to a steel wire and a steel cord used as a reinforcing material for rubber articles such as pneumatic tires and industrial belts, and more particularly to a steel wire excellent in adhesion to rubber.

ゴム物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 pneumatic radial tires, which are typical examples of rubber articles, steel cords made of twisted steel wires with brass plating on the belt or carcass or made of a single wire of steel wire are covered with rubber. The rubber composite is applied and is mainly reinforced with steel cord. In order to use the steel cord as a tire reinforcing material, it is necessary to securely bond the steel cord to the covering rubber. For this purpose, the peripheral surface of the wire constituting the steel cord is subjected to brass plating. Yes.

すなわち、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。
That is, so-called direct vulcanization adhesion is widely used, in which a brass-plated steel cord is embedded in a rubber composition containing sulfur and adhered at the same time as vulcanization of rubber during heat vulcanization. So far, various studies have been made to improve the adhesion between the cord and rubber in this direct vulcanization adhesion.
For example, in order to ensure adhesion to rubber, it has been studied to optimize the ratio of copper and zinc in brass and the plating thickness, and certain knowledge about these has been established.

か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が、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ため、ゴム中に接着促進剤としてCo塩やNi塩を相当の割合で添加したり、硫黄を高い比率で配合すること等が必要となる。   By applying brass plating optimized based on such knowledge to the wire constituting the steel cord, the adhesion to rubber is improved. Conditions are required. For example, in order to vulcanize and mold a tire within a certain period of time, it is required to secure a sufficient adhesive force by the speed of bonding between a cord and rubber or by their complete bonding. That is, since so-called initial adhesiveness is required, it is necessary to add a Co salt or Ni salt as an adhesion promoter in the rubber in a considerable proportion, or to blend sulfur in a high proportion.

しかしながら、ゴムにCo塩を配合した場合、Coを配合してないゴム対比、ゴム劣化や耐亀裂成長性といった物性に大きな問題がある。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 a Co salt is compounded with rubber, there are significant problems with physical properties such as rubber deterioration, rubber deterioration, and crack growth resistance, compared with rubber not containing Co. Therefore, various proposals have been made not for adjusting the composition of the rubber but for the wire that is the bonding partner of the rubber.

例えば、使用するスチールワイヤ及びスチールコードの表面を酸性あるいはアルカリ性水溶液で洗浄し、接着反応阻害物である燐化合物(スチールワイヤの製造時に使用される潤滑剤に由来する)を取り除くことによって、ゴムとの接着性を向上させる技術が知られている(特許文献1参照)。
しかしながら、用いる前処理溶液が酸性およびアルカリ性溶液であり、環境上好ましくない上、製造プロセスを考えた場合に安全性が問題になる場合がある。従って、より中性領域の溶液で処理できることが要求されるのである。
特開2001−234371号公報
For example, the surface of steel wires and steel cords to be used is washed with an acidic or alkaline aqueous solution, and the phosphorus compound (derived from the lubricant used in the manufacture of steel wires) is removed by removing the adhesion reaction inhibitor. There is known a technique for improving the adhesiveness of the film (see Patent Document 1).
However, the pretreatment solutions used are acidic and alkaline solutions, which are not environmentally preferable, and safety may be a problem when considering the manufacturing process. Therefore, it is required to be able to process with a solution in a more neutral region.
JP 2001-234371 A

また、スチールコードの製造時に使用する湿式潤滑剤中に、スチールコードとゴムの接着改良材として考えられる、レゾルシンを添加してスチールフィラメント表面にレゾルシンを付着させる方法が、特許文献2に開示されている。しかし、伸線時の発熱によりレゾルシンが変質してしまうため、スチールフィラメントとゴムとの接着耐久性を十分に向上させることは難しい。
特開2004−66298号公報
Further, Patent Document 2 discloses a method of adding resorcin to the surface of a steel filament by adding resorcin, which is considered as a steel cord / rubber adhesion improver, in a wet lubricant used in manufacturing a steel cord. Yes. However, since resorcin is altered by heat generation during wire drawing, it is difficult to sufficiently improve the durability of adhesion between the steel filament and the rubber.
JP 2004-66298 A

タイヤ等に用いられる直接加硫接着におけるゴム−コード間の接着を考えた場合、ゴムに接着プロモーターを配合することが一般的であるが、ゴム劣化や耐亀裂成長性といったゴム物性を阻害する問題がある。
そこで、本発明は、かようなゴム材料側の問題を回避するために、ワイヤのゴムに対する接着性の改善を、環境負荷の少ない手法にて達成することを目的とする。
When considering adhesion between rubber and cord in direct vulcanization adhesion used for tires, etc., it is common to add an adhesion promoter to the rubber, but this is a problem that inhibits rubber properties such as rubber deterioration and crack growth resistance There is.
Therefore, an object of the present invention is to achieve an improvement in adhesion of a wire to rubber by a method with a small environmental load in order to avoid such a problem on the rubber material side.

発明者らは、スチールワイヤの製造時に使用される潤滑剤に由来する燐化合物や、ブラスめっき後に該めっき層表面に生成するZnOなどの、ワイヤ側に存在するゴムとの接着反応阻害物を取り除く前処理について鋭意検討したところ、このスチールワイヤの前処理技術の改良により、接着プロモーターをゴムに添加しなくても、従来以上のゴム−コード間の接着性を確保できることを見出した。さらに、前処理技術を工夫することによって、接着プロモーターとしての機能をワイヤ表面に付与できることも知見し、本発明を完成するに到った。   Inventors remove adhesion reaction inhibitors with rubber existing on the wire side, such as phosphorus compounds derived from lubricants used in the production of steel wires and ZnO formed on the surface of the plating layer after brass plating. As a result of intensive studies on pretreatment, it has been found that, by improving this steel wire pretreatment technique, the rubber-cord adhesion more than the conventional one can be secured without adding an adhesion promoter to the rubber. Furthermore, by devising the pretreatment technique, it has been found that a function as an adhesion promoter can be imparted to the wire surface, and the present invention has been completed.

本発明の要旨は、次のとおりである。
(1)ワイヤの周面にブラスめっきを施したスチールワイヤであって、該ブラスめっきの表面における、ZnおよびCuを除く遷移金属の濃度が0.01mass%以上であることを特徴とするゴム物品補強用スチールワイヤ。
The gist of the present invention is as follows.
(1) Reinforcement of rubber articles, characterized in that the steel wire is brass-plated on the peripheral surface of the wire, and the concentration of transition metals excluding Zn and Cu on the surface of the brass plating is 0.01 mass% or more. Steel wire for

(2)前記(1)において、該ブラスめっきの表面における燐濃度が2.5mass%以下および亜鉛濃度が15mass%以下であることを特徴とするゴム物品補強用スチールワイヤ。 (2) The steel wire for reinforcing rubber articles according to (1), wherein the phosphorus concentration on the surface of the brass plating is 2.5 mass% or less and the zinc concentration is 15 mass% or less.

(3)前記(1)または(2)に記載のスチールワイヤの複数本を撚り合せてなるゴム物品補強用スチールコード。 (3) A steel cord for reinforcing rubber articles formed by twisting a plurality of steel wires according to (1) or (2).

(4)前記(1)または(2)に記載のスチールワイヤ或いは前記(3)に記載のスチールコードにゴムを被覆してなるゴム物品。 (4) A rubber article obtained by coating the steel wire according to (1) or (2) or the steel cord according to (3) with rubber.

(5)前記(4)において、前記被覆ゴムは、ゴム成分100質量部に対して硫黄を1〜10質量部で配合してなるゴム物品。 (5) In the above (4), the coated rubber is a rubber article obtained by blending 1 to 10 parts by mass of sulfur with respect to 100 parts by mass of the rubber component.

(6)前記(4)または(5)において、前記被覆ゴムは、コバルトを含まないゴム物品。 (6) In the above (4) or (5), the coated rubber is a rubber article not containing cobalt.

(7)前記(4)、(5)または(6)に記載のゴム物品を補強材に適用した空気入りタイヤ。 (7) A pneumatic tire in which the rubber article according to (4), (5) or (6) is applied as a reinforcing material.

(8)前記(7)において、前記補強材がカーカスプライまたはベルトプライである空気入りタイヤ。 (8) The pneumatic tire according to (7), wherein the reinforcing material is a carcass ply or a belt ply.

(9)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したのち、該スチールワイヤの表面を、遷移金属を塩として含む水溶液にて洗浄することを特徴とするゴム物品補強用スチールワイヤの製造方法。 (9) The steel wire is subjected to brass plating and then subjected to wire drawing, and then the surface of the steel wire is washed with an aqueous solution containing a transition metal as a salt. Steel wire manufacturing method.

(10)前記(9)において、前記遷移金属がコバルトであるゴム物品補強用スチールワイヤの製造方法。 (10) A method for producing a steel wire for reinforcing rubber articles, wherein, in (9), the transition metal is cobalt.

(11)前記(10)において、前記コバルトの塩が、塩化コバルト、硝酸コバルト、硫酸コバルト、酢酸コバルト、クエン酸コバルト、グルコン酸コバルトまたはアセチルアセトナトコバルトであるゴム物品補強用スチールワイヤの製造方法。 (11) A method for producing a steel wire for reinforcing rubber articles, wherein, in (10), the salt of cobalt is cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt citrate, cobalt gluconate or acetylacetonato cobalt .

本発明によれば、ブラスめっきを施したスチールワイヤあるいはスチールコードを、遷移金属を塩として含む水溶液にて洗浄する前処理を行うことによって、環境負荷が少なく、製造プロセス上安全にゴムとの初期接着性に優れたブラスめっき付スチールワイヤおよびスチールコードを提供することができる。   According to the present invention, the steel wire or steel cord subjected to brass plating is pretreated by washing with an aqueous solution containing a transition metal as a salt. A steel wire and a steel cord with brass plating excellent in adhesiveness can be provided.

また、本発明のスチールワイヤあるいはスチールコードを用いることによって、接着プロモーターを除去したゴムに対しても初期接着性を十分にはかることができるため、ゴムから接着プロモーターを除去することによる、耐劣化性及び耐亀裂成長性の向上を享受することが可能となる。   In addition, by using the steel wire or steel cord of the present invention, the initial adhesion can be sufficiently applied to the rubber from which the adhesion promoter has been removed. And it becomes possible to enjoy the improvement of crack growth resistance.

さて、ゴム物品の補強に供するスチールワイヤは、例えば径が5mm程度のブラスめっきを施した線材に伸線加工を施して製造されるのが、一般的である。この製造プロセスにおいては、当然潤滑剤を使用することになるが、中でも最終伸線工程は、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を行っている。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。   Now, a steel wire used to reinforce a rubber article is generally manufactured by, for example, drawing a wire material subjected to brass plating having a diameter of about 5 mm. In this manufacturing process, a lubricant is naturally used, but in particular, in the final wire drawing step, thinning is performed using a die having about 20 passes disposed in the liquid lubricant. In this final wire drawing process, an extreme pressure is generated between the cord and the die, and the temperature becomes very high. Therefore, a lubricant based on phosphoric acid is used to ensure lubricity at extreme pressure and high temperature. It is customary to use

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し、極圧高温条件の下での入力を緩和し、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ものである。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 CuxSを形成して接着が行われる接着反応を阻害する。   This lubricant reacts with the wire surface during wire drawing to form a lubricant film layer, that is, a phosphoric acid compound layer, and relaxes input under extreme pressure and high temperature conditions, realizing mass production of wires. Therefore, in the manufacturing process, it is inevitable that phosphoric acid is taken in during the plating of the wire. If this phosphoric acid compound layer is present on the plating surface, copper in the brass plating diffuses to the rubber side and forms CuxS, thereby inhibiting the adhesion reaction in which adhesion is performed.

また、CuとZn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ZnOが生成し、このZnO層もまた燐酸化合物層と同様に、前記接着反応を阻害することになる。   In addition, when brass plating, which is an alloy of Cu and Zn, is applied, the surface is oxidized over time to produce ZnO, which, like the phosphate compound layer, also inhibits the adhesion reaction. .

従って、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ZnO層を除去することが、ゴムとの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ZnO層を除去する、洗浄処理を施すことが重要になるが、酸性あるいはアルカリ性水溶液での洗浄が問題になるのは、上述のとおりである。   Therefore, removing the phosphate compound layer and the ZnO layer from the plating surface before bonding with the rubber is effective for improving the adhesion with the rubber. For that purpose, it is important to remove the phosphate compound layer and ZnO layer on the surface of the steel wire after drawing, but it is important to perform a cleaning treatment, but cleaning with an acidic or alkaline aqueous solution becomes a problem. As described above.

そこで、環境負荷の小さい洗浄処理について鋭意究明したところ、遷移金属を塩として含む水溶液による表面処理が極めて有効であることを見出した。すなわち、ブラスめっきを施したスチールワイヤまたは該ワイヤを撚り合わせたコードに対して、遷移金属を塩として含む水溶液による洗浄を行うと、上述したゴムとの接着反応を阻害する燐酸化合物層やZnO層を溶解することができる。   Therefore, as a result of diligent research on cleaning treatment with a small environmental load, it was found that surface treatment with an aqueous solution containing a transition metal as a salt is extremely effective. That is, when a steel wire subjected to brass plating or a cord obtained by twisting the wire is washed with an aqueous solution containing a transition metal as a salt, a phosphate compound layer or a ZnO layer that inhibits the adhesion reaction with the rubber described above Can be dissolved.

ここで、遷移金属とは、周期律表の第4周期のスカンジウム(Sc)から亜鉛(Zn)まで、第5周期のイットリウム(Y)からカドミウム(Cd)まで、第6周期のルテチウム(Lu)から水銀(Hg)までの金属元素を指す。
この遷移金属としてはコバルトが典型例であり、該コバルトを塩として含む水溶液としては、塩化コバルト、硝酸コバルト、硫酸コバルト、酢酸コバルト、クエン酸コバルト、グルコン酸コバルトおよびアセチルアセトナトコバルト等が挙げられる。その他、遷移金属を塩として含む水溶液として代表的なものは、FeおよびAgを含む硝酸、硫酸または酢酸塩を用いることもできる。
Here, the transition metals are scandium (Sc) to zinc (Zn) in the fourth period of the periodic table, yttrium (Y) to cadmium (Cd) in the fifth period, and lutetium (Lu) in the sixth period. Refers to metal elements from mercury to mercury (Hg).
Cobalt is a typical example of the transition metal, and examples of the aqueous solution containing cobalt as a salt include cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt citrate, cobalt gluconate, and acetylacetonato cobalt. . In addition, as a typical aqueous solution containing a transition metal as a salt, nitric acid, sulfuric acid or acetate containing Fe and Ag can be used.

その際、当該水溶液のpHは5〜8程度とすることが好ましい。なぜなら、水溶液のpHがこの範囲を外れると、めっきに悪影響を及ぼし、ゴムとの接着性が低下するからである。また、pHを5〜8程度の中性領域にすれば、環境に与える負荷が少なくなる上、製造時における使用者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。   At that time, the pH of the aqueous solution is preferably about 5 to 8. This is because if the pH of the aqueous solution is out of this range, the plating is adversely affected and the adhesion to rubber is reduced. In addition, when the pH is in a neutral range of about 5 to 8, the load on the environment is reduced, and safety against exposure to the user during production and reagent safety can be ensured.

なお、洗浄条件は、水溶液の濃度に応じて洗浄時間を適宜設定すればよく、例えば酢酸コバルト含有水溶液の場合は、10g/lの濃度で洗浄時間は30〜60秒が好ましい条件となる。   The cleaning condition may be set as appropriate depending on the concentration of the aqueous solution. For example, in the case of a cobalt acetate-containing aqueous solution, the cleaning time is preferably 30 to 60 seconds at a concentration of 10 g / l.

上記した遷移金属を塩として含む水溶液による洗浄処理を経たスチールワイヤは、そのブラスめっきの表面にZnO層や燐酸化合物層などの酸化物層がなく、さらには前記遷移金属がコバルトである水溶液を用いた場合は、めっき表面に0.01mass%以上のコバルトが存在する状態となる。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ないことに加え、接着プロモーターとして機能するコバルトを有するめっき表面が得られる結果、ワイヤのゴムに対する接着性は大幅に改善されるのである。従って、ゴム側の接着プロモーター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、ゴムの耐劣化性及び耐亀裂成長性を向上することも可能である。
一方、めっき表面に20mass%を超えるCoが存在すると、接着プロモーターとして機能するよりも、むしろゴムとの接着阻害要因として働いてしまうことから、Coの濃度は20mass%を上限とする。
Steel wire that has undergone a cleaning treatment with an aqueous solution containing a transition metal as a salt as described above does not have an oxide layer such as a ZnO layer or a phosphate compound layer on the surface of the brass plating, and further uses an aqueous solution in which the transition metal is cobalt. If it is, 0.01 mass% or more of cobalt is present on the plating surface. That is, by performing the above-described washing treatment, in addition to the absence of an inhibitor of adhesion reaction with rubber, a plating surface having cobalt functioning as an adhesion promoter is obtained, and as a result, the adhesion of wire to rubber is greatly improved. It is. Therefore, even if the adhesion promoter on the rubber side is omitted, the adhesion between the wire and the rubber can be ensured. On the other hand, since the adhesion promoter on the rubber side can be omitted, it is also possible to improve the deterioration resistance and crack growth resistance of the rubber.
On the other hand, if Co exceeding 20 mass% is present on the plating surface, it functions as an adhesion inhibiting factor with rubber rather than functioning as an adhesion promoter, so the upper limit of Co concentration is 20 mass%.

なお、ここでいうめっき表面とは、フィラメント半径方向内側に10mmの深さまでの表層領域である   In addition, the plating surface here is the surface layer region up to a depth of 10 mm inside the filament radial direction.

また、ブラスめっきについて、その表面における燐濃度が2.5mass%以下および亜鉛濃度が15mass%以下であることが好ましい。なぜなら、めっき表面における燐濃度が2.5mass%を超えると、接着阻害効果が大きくなり、ゴム中からCo塩を除去すると十分な接着性能が得られない、おそれがある。
同様に、亜鉛濃度が15mass%を超えると、接着阻害効果が大きくなり、ゴム中からCo塩を除去すると十分な接着性能が得られない、おそれがある。
Moreover, about brass plating, it is preferable that the phosphorus density | concentration in the surface is 2.5 mass% or less, and zinc concentration is 15 mass% or less. This is because if the phosphorus concentration on the plating surface exceeds 2.5 mass%, the adhesion inhibiting effect is increased, and if the Co salt is removed from the rubber, sufficient adhesion performance may not be obtained.
Similarly, if the zinc concentration exceeds 15 mass%, the adhesion inhibiting effect is increased, and if the Co salt is removed from the rubber, sufficient adhesion performance may not be obtained.

前記洗浄処理を経たスチールワイヤ或いはスチールコードはゴムを被覆して、例えば空気入りタイヤや工業用ベルトなどのゴム物品とするが、その際、被覆ゴムには、ゴム成分100質量部に対して硫黄を1〜10質量部で配合したものを用いるとよい。なぜなら、硫黄が1質量部未満では、硫黄とゴムとの加硫接着本来の接着力を確保することが難しくなり、一方10質量部を超えると、ゴム物性の耐熱老化性および耐熱接着特性の低下を招き、好ましくない。   The steel wire or steel cord subjected to the washing treatment is coated with rubber to form a rubber article such as a pneumatic tire or an industrial belt. In this case, the coated rubber contains sulfur with respect to 100 parts by mass of the rubber component. It is good to use what mix | blended 1-10 mass parts. This is because, if sulfur is less than 1 part by mass, it becomes difficult to secure the original adhesive strength of vulcanized adhesion between sulfur and rubber, whereas if it exceeds 10 parts by mass, the heat aging resistance of rubber properties and the heat-resistant adhesive properties deteriorate. This is not preferable.

さらに、被覆ゴムは、コバルトを含まないことが好ましい。すなわち、コバルトは接着プロモーターとして働く一方、ゴムの熱、湿気または酸素に起因した劣化に対する耐性及び耐亀裂成長性を阻害する要因にもなるため、本発明のワイヤが接着相手であるならば、コバルトは含まないことが好ましい。   Furthermore, it is preferable that the coating rubber does not contain cobalt. That is, while cobalt acts as an adhesion promoter, it also becomes a factor that inhibits the resistance to degradation caused by heat, moisture or oxygen of rubber, and crack growth resistance, so if the wire of the present invention is a bonding partner, Is preferably not included.

前記ゴム物品が空気入りタイヤである場合、タイヤ構造自体は一般的な構造でよく、カーカスプライまたはベルトプライの補強材として本発明のワイヤまたはコードを適用する。   When the rubber article is a pneumatic tire, the tire structure itself may be a general structure, and the wire or cord of the present invention is applied as a reinforcing material for a carcass ply or a belt ply.

以下に、本発明を更に具体的に説明するが、本発明は以下の実施例に何ら限定されるものではない。
(発明例)
Cu:63mass%およびZu:37mass%組成のブラスめっき(厚さ:0.25μm)を施したスチールフィラメントを撚り合わせて、1×5構造のコードを作製し、次いで、このコードを表1に示す洗浄液を用いて洗浄し、50℃で1分間乾燥させた。この洗浄処理を終了したスチールコードのワイヤめっき表面の組成をX線光電子分光(X-ray photoelectron Spectroscopy:XPS)にて調査した結果を表1に示す。
かくして洗浄処理を終了したスチールコードを用い、表2に示す配合のゴムを用いて、以下の方法で初期接着性及び湿熱接着性を評価した。
Hereinafter, the present invention will be described more specifically, but the present invention is not limited to the following examples.
(Invention example)
A steel filament coated with brass plating (thickness: 0.25 μm) with a composition of Cu: 63 mass% and Zu: 37 mass% is twisted to produce a cord of 1 × 5 structure. And then dried at 50 ° C. for 1 minute. Table 1 shows the results obtained by examining the composition of the wire plating surface of the steel cord after the cleaning treatment by X-ray photoelectron spectroscopy (XPS).
Using the steel cord thus finished, the initial adhesion and wet heat adhesion were evaluated by the following methods using the rubbers shown in Table 2.

(比較例1、2)
前記と同様のブラスめっきを施したのち洗浄処理を行わないスチールコードを用い、表2に示すゴム配合を用いて、以下の方法で初期接着性及び湿熱接着性を測定して、接着性を評価した。その結果を、表1に併記する。
(Comparative Examples 1 and 2)
Using steel cord not subjected to cleaning treatment after brass plating similar to the above, using the rubber composition shown in Table 2, the initial adhesion and wet heat adhesion were measured by the following methods to evaluate the adhesion. did. The results are also shown in Table 1.

接着性試験
前記スチールコードを平行に並べ、このスチールコードを上下両側から各ゴム組成物でコーティングして、これを表1に記載の条件で加硫し、サンプルを作製した。各サンプルの下記の各接着性について、ASTM D−2229に準拠して、各サンプルからスチールコードを引き抜き、ゴムの被覆状態を目視で観察し、0〜100%で表示し、各接着性の指標とした。
Adhesion test The steel cords were arranged in parallel, and the steel cords were coated with each rubber composition from the upper and lower sides, and vulcanized under the conditions shown in Table 1 to prepare samples. For each of the following adhesive properties of each sample, in accordance with ASTM D-2229, pull out the steel cord from each sample, visually observe the rubber coating state, display 0-100%, each adhesive index It was.

また、ゴムの耐劣化性については、未加硫ゴムを160℃で20分加硫後に、100℃で2日間、次いで70℃、湿度100%で4日間の湿熱条件下で老化させた後に、 JIS K6251に準拠して引張試験を行うことによって、EbおよびTbを測定し、タフネスTF(=Eb×Tb)を求めた。   Regarding the deterioration resistance of rubber, after vulcanizing unvulcanized rubber at 160 ° C for 20 minutes, after aging under wet heat conditions at 100 ° C for 2 days and then at 70 ° C and 100% humidity for 4 days, By performing a tensile test according to JIS K6251, Eb and Tb were measured, and toughness TF (= Eb × Tb) was obtained.

耐亀裂成長性評価は、上島製疲労試験機を用い、定応力疲労試験を行い、破断するまでの回数を測定した。   For evaluation of crack growth resistance, a constant stress fatigue test was performed using a Uejima fatigue tester, and the number of times until fracture occurred was measured.

Figure 2009091691
Figure 2009091691

Figure 2009091691
Figure 2009091691

表1から明らかなように、本発明に従って洗浄処理を施したワイヤを用いることによって、ゴムとの接着性を格段に高めることができる。   As is apparent from Table 1, the use of a wire that has been subjected to a cleaning treatment according to the present invention can significantly improve the adhesion to rubber.

Claims (11)

ワイヤの周面にブラスめっきを施したスチールワイヤであって、該ブラスめっきの表面における、ZnおよびCuを除く遷移金属の濃度が0.01mass%以上であることを特徴とするゴム物品補強用スチールワイヤ。   A steel wire for reinforcing rubber articles, wherein the peripheral surface of the wire is subjected to brass plating, and the concentration of transition metal excluding Zn and Cu on the surface of the brass plating is 0.01 mass% or more. . 請求項1において、該ブラスめっきの表面における燐濃度が2.5mass%以下および亜鉛濃度が15mass%以下であることを特徴とするゴム物品補強用スチールワイヤ。   The steel wire for reinforcing rubber articles according to claim 1, wherein a phosphorus concentration on the surface of the brass plating is 2.5 mass% or less and a zinc concentration is 15 mass% or less. 請求項1または2に記載のスチールワイヤの複数本を撚り合せてなるゴム物品補強用スチールコード。   A steel cord for reinforcing rubber articles formed by twisting a plurality of steel wires according to claim 1 or 2. 請求項1または2に記載のスチールワイヤ或いは請求項3に記載のスチールコードにゴムを被覆してなるゴム物品。   A rubber article obtained by coating the steel wire according to claim 1 or 2 or the steel cord according to claim 3 with rubber. 請求項4において、前記被覆ゴムは、ゴム成分100質量部に対して硫黄を1〜10質量部で配合してなるゴム物品。   5. The rubber article according to claim 4, wherein the covering rubber is compounded with 1 to 10 parts by mass of sulfur with respect to 100 parts by mass of the rubber component. 請求項4または5において、前記被覆ゴムは、コバルトを含まないゴム物品。   6. The rubber article according to claim 4, wherein the coated rubber does not contain cobalt. 請求項4、5または6に記載のゴム物品を補強材に適用した空気入りタイヤ。   A pneumatic tire in which the rubber article according to claim 4 is applied to a reinforcing material. 請求項7において、前記補強材がカーカスプライまたはベルトプライである空気入りタイヤ。   The pneumatic tire according to claim 7, wherein the reinforcing material is a carcass ply or a belt ply. 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したのち、該スチールワイヤの表面を、遷移金属を塩として含む水溶液にて洗浄することを特徴とするゴム物品補強用スチールワイヤの製造方法。   A steel wire for reinforcing rubber articles, characterized in that after the steel wire is subjected to brass plating and then subjected to wire drawing, the surface of the steel wire is washed with an aqueous solution containing a transition metal as a salt. Production method. 請求項9において、前記遷移金属がコバルトであるゴム物品補強用スチールワイヤの製造方法。   The method for manufacturing a steel wire for reinforcing rubber articles according to claim 9, wherein the transition metal is cobalt. 請求項10において、前記コバルトの塩が、塩化コバルト、硝酸コバルト、硫酸コバルト、酢酸コバルト、クエン酸コバルト、グルコン酸コバルトまたはアセチルアセトナトコバルトであるゴム物品補強用スチールワイヤの製造方法。   The method for producing a steel wire for reinforcing rubber articles according to claim 10, wherein the cobalt salt is cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt citrate, cobalt gluconate or acetylacetonato cobalt.
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