JPH1193086A - Steel cord for tire - Google Patents
Steel cord for tireInfo
- Publication number
- JPH1193086A JPH1193086A JP9245729A JP24572997A JPH1193086A JP H1193086 A JPH1193086 A JP H1193086A JP 9245729 A JP9245729 A JP 9245729A JP 24572997 A JP24572997 A JP 24572997A JP H1193086 A JPH1193086 A JP H1193086A
- Authority
- JP
- Japan
- Prior art keywords
- steel cord
- coating layer
- content
- tire
- steel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B1/00—Constructional features of ropes or cables
- D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
- D07B1/0606—Reinforcing cords for rubber or plastic articles
- D07B1/0666—Reinforcing cords for rubber or plastic articles the wires being characterised by an anti-corrosive or adhesion promoting coating
-
- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2205/00—Rope or cable materials
- D07B2205/30—Inorganic materials
- D07B2205/3021—Metals
- D07B2205/3085—Alloys, i.e. non ferrous
- D07B2205/3089—Brass, i.e. copper (Cu) and zinc (Zn) alloys
Landscapes
- Tires In General (AREA)
- Ropes Or Cables (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は高温多湿環境下での
接着低下を改善した空気入りラジアルタイヤ等に使用す
るタイヤ用スチールコードに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a steel cord for a tire for use in a pneumatic radial tire or the like having improved adhesion under a high temperature and high humidity environment.
【０００２】[0002]
【従来の技術】空気入りタイヤ、特に空気入りラジアル
タイヤには、一般に走行中の形状を安定させるためにス
チールコードが補強材として使用されている。このスチ
ールコードはその表面にＣｕ−Ｚｎ合金である真ちゅう
がメッキされ、タイヤ加硫中に前記真ちゅうメッキ層と
ゴムと直接接着反応させて、スチールコードとゴム物質
との剥離を防止している。2. Description of the Related Art In a pneumatic tire, in particular, a pneumatic radial tire, a steel cord is generally used as a reinforcing material for stabilizing a running shape. The steel cord is plated with brass, which is a Cu-Zn alloy, and has a direct adhesive reaction between the brass plating layer and the rubber during vulcanization of the tire to prevent the steel cord from being separated from the rubber material.
【０００３】ところが従来のこの種スチールコードを使
用した空気入りタイヤでは、自己発熱のための温度上昇
によって、スチールコードの真ちゅうメッキ層の破壊に
よるゴム物質とスチールコードとの剥離が起り、更には
スチールコードとゴム物質との接着界面における真ちゅ
うメッキ中のＣｕの硫化物であるＣｕＳが多量に生成
し、タイヤの走行振動および衝撃等によってＣｕＳの破
壊による、メッキ層とゴム物質との接着破壊が起る等の
各種問題点がある。However, in a conventional pneumatic tire using a steel cord of this type, a rise in temperature due to self-heating causes the rubber material to separate from the steel cord due to the destruction of the brass plating layer of the steel cord, and further, the steel A large amount of CuS, which is a sulfide of Cu in the brass plating at the bonding interface between the cord and the rubber substance, is generated. Various problems.
【０００４】これらの問題点を解消するため、スチール
コードの表面のメッキ層を改変したものが提案されてい
るが、これはスチールコードとゴム物質の接着力は初期
では良好であるが、経年とともに低下する傾向があり、
特に高温多湿環境下では、接着力が低下する傾向が強
い。[0004] In order to solve these problems, there has been proposed a steel cord having a modified plating layer on the surface thereof. The adhesive strength between the steel cord and the rubber material is good at an early stage. Tend to decline,
Particularly in a high-temperature and high-humidity environment, the adhesive strength tends to decrease.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、前記スチー
ルコードの表面のメッキ層の改変による接着剥離の改良
技術から更に一歩を進め、特定の技術内容を採用するこ
とにより、特に高温多湿環境下において、経年後も引き
続き接着剥離を起こさない耐久性に優れたスチールコー
ドを提供することを目的とする。SUMMARY OF THE INVENTION The present invention goes one step further from the technology for improving the adhesion and peeling by modifying the plating layer on the surface of the steel cord, and adopts a specific technical content, particularly in a high-temperature and high-humidity environment. An object of the present invention is to provide a steel cord excellent in durability that does not cause adhesive peeling even after aging.
【０００６】[0006]
【課題を解決するための手段】本発明は、上記課題を解
決するため、次の手段を採用した。即ちタイヤ用スチー
ルコードとして、スチールコードのゴム物質に接触する
スチールフィラメントは、含有率がＣｕ：６０〜６６
％，Ｚｎ：３４〜４０％の範囲内の平均合金比であるメ
ッキ真ちゅう被覆層を有し、かつこの真ちゅう被覆層の
厚さは０．２〜０．３μｍであるものにおいて、前記真
ちゅう被覆層の最外表面に占めるＣｕの含有率が２５〜
３５％であり、前記被覆層中に占めるＣｕ含有率はその
深さ方向に増大して表面より０．０２〜０．０４μｍの
ところでＣｕ：Ｚｎ＝５０：５０％の合金比とされ、か
つ、Ｃｕの反応性指標として硫化反応後の還元時間が２
０〜４０秒であるフィラメントでなるスチールコードを
構成した（請求項１）。更には該スチールコード表面に
有機酸コバルト配合ゴムのコーティング層を設けてなる
ものである（請求項２）。The present invention employs the following means in order to solve the above-mentioned problems. That is, as a steel cord for a tire, the content of the steel filament in contact with the rubber substance of the steel cord is Cu: 60 to 66.
%, Zn: a plated brass coating layer having an average alloy ratio in the range of 34 to 40%, and the thickness of the brass coating layer is 0.2 to 0.3 μm. Content of Cu in the outermost surface of
35%, the Cu content in the coating layer increases in the depth direction, and the alloy ratio is Cu: Zn = 50: 50% at 0.02 to 0.04 μm from the surface, and The reduction time after the sulfurization reaction is 2 as the Cu reactivity index.
A steel cord composed of a filament having a duration of 0 to 40 seconds was constituted (claim 1). Further, a coating layer of an organic acid cobalt compounded rubber is provided on the surface of the steel cord (claim 2).
【０００７】なお以上の含有率は何れも重量％である。
まずスチールコードを構成するスチールフィラメントに
被覆されたメッキ真ちゅう被覆層の組成（平均合金比）
はＣｕ：Ｚｎ＝７０：３０またはＣｕ：Ｚｎ＝６０〜７
０：４０〜３０の範囲のものであり、好ましくはＣｕ：
Ｚｎ＝６０〜６６：４０〜３４のものを使用し、かつこ
の真ちゅう被覆層の厚さは０．２〜０．３、好ましくは
０．２４〜０．２６μｍとされている。The above contents are all by weight.
First, the composition (average alloy ratio) of the plated brass coating layer coated on the steel filament constituting the steel cord
Is Cu: Zn = 70: 30 or Cu: Zn = 60 to 7
0: 40-30, preferably Cu:
Zn = 60 to 66:40 to 34 is used, and the thickness of the brass coating layer is 0.2 to 0.3, preferably 0.24 to 0.26 μm.
【０００８】次に本発明では前記スチールフィラメント
に被覆されたメッキ真ちゅう被覆層において、メッキ被
覆層の表面層において、最外表面から深さ方向にＣｕと
Ｚｎの含有率に変化を与えるもので、最外表面に占める
Ｃｕの含有量が２５〜３５％、より好ましくは２８〜３
３％であり、前記被覆層中に占めるＣｕ含有率はその深
さ方向に増大して表面より０．０２〜０．０４μｍのと
ころでＣｕ：Ｚｎ＝５０：５０％になるような合金比と
されている。即ち被覆層の表面から０．０２〜０．０４
μｍの深さまでは、ＣｕとＺｎの合金の百分率におい
て、最外表面のＣｕの含有量が２５〜３５％、好ましく
は２８〜３３％の範囲から、深さ方向に順次Ｃｕの含有
％を増大し、深さが０．０２〜０．０４μｍのところで
Ｃｕの含有量が５０％になるように構成したのであり、
このようなＣｕの含有量の変化はスチールフィラメント
素線に対するメッキの際に電流、電圧等の制御で行なう
が、その詳細は省略する。Next, in the present invention, in the plated brass coating layer coated on the steel filament, the content of Cu and Zn is changed in the depth direction from the outermost surface in the surface layer of the plating coating layer, Cu content in the outermost surface is 25 to 35%, more preferably 28 to 3%.
3%, and the Cu content in the coating layer increases in the depth direction and the alloy ratio is such that Cu: Zn = 50: 50% at 0.02 to 0.04 μm from the surface. ing. That is, 0.02 to 0.04 from the surface of the coating layer.
At a depth of μm, the content of Cu on the outermost surface is increased from 25 to 35%, preferably from 28 to 33%, in the depth direction in the percentage of the alloy of Cu and Zn. The Cu content was set to be 50% at a depth of 0.02 to 0.04 μm.
Such a change in the Cu content is performed by controlling current, voltage, and the like when plating the steel filament strand, but details thereof are omitted.
【０００９】ここで被覆層の最外表面に占めるＣｕの含
有量（以下「表面銅比」という）を２５〜３５％にする
ことにより、適量のＺｎＳを生成させ、過剰なＣｕＳの
生成を抑制する。この際、表面銅比が２５％より少ない
場合はＣｕＳ量が少なく十分な接着層を形成することが
できず、またＺｎが酸化されやすくＺｎＯ層ができてし
まう。一方、３５％を超える場合、過剰なＣｕＳが生成
され、初期接着力が低くなるばかりでなく、ＺｎＳが十
分に生成されない為、表面に残った未反応のＺｎが水分
等の影響でＺｎ（ＯＨ）2 となりやすく接着劣化を引き
起こす。[0009] Here, by setting the content of Cu in the outermost surface of the coating layer (hereinafter referred to as “surface copper ratio”) to 25 to 35%, an appropriate amount of ZnS is generated and the generation of excessive CuS is suppressed. I do. At this time, if the surface copper ratio is less than 25%, the amount of CuS is small and a sufficient adhesive layer cannot be formed, and Zn is easily oxidized, resulting in a ZnO layer. On the other hand, if it exceeds 35%, not only excessive CuS is generated and the initial adhesive strength is lowered, but also ZnS is not sufficiently generated. ) 2 easily causes adhesive deterioration.
【００１０】次に、本発明では真ちゅうメッキ被覆層の
表面より深さが０．０２〜０．０４μｍのところで、Ｃ
ｕの含有量が５０％（Ｚｎ５０％）にすることにより、
水分等でＺｎ（ＯＨ）2 に変化しやすい未反応のＺｎが
残るのを防ぐ。ここで前記深さが０．０２μｍより浅い
ところでＣｕの含有量が５０％になるということは、Ｃ
ｕの増加比率が大きいということで、内部のＣｕがＳと
優先的に反応しやすく、従って表面銅比が３５％を超え
る場合と同様な結果となる。一方、深さが０．０４μｍ
より深いところでＣｕの含有量が５０％になる場合、表
面近くのＺｎ比率が高いということで、未反応のＺｎが
残ってしまい、水分等の影響でＺｎ（ＯＨ）2 となりや
すく、そのため接着劣化を引き起こす。Next, in the present invention, when the depth is 0.02 to 0.04 μm below the surface of the brass plating coating layer, C
By setting the content of u to 50% (Zn 50%),
This prevents unreacted Zn, which easily changes to Zn (OH) 2 due to moisture or the like, from remaining. Here, the fact that the Cu content becomes 50% at a depth of less than 0.02 μm means that C
Since the increase ratio of u is large, Cu inside reacts preferentially with S, so that the same result as when the surface copper ratio exceeds 35% is obtained. On the other hand, the depth is 0.04 μm
When the Cu content becomes 50% at a deeper position, unreacted Zn remains because the Zn ratio near the surface is high, and Zn (OH) 2 is likely to be formed due to the influence of moisture and the like. cause.
【００１１】さらに、Ｃｕの反応性指標として硫化反応
後の還元時間を２０〜４０秒にすることにより、適量な
ＣｕＳを生成させることができる。前記ＣｕＳはスチー
ルコードのメッキ被覆層とゴム物質との間の接着層であ
り、これが多くても少なくても、前記Ｚｎ（ＯＨ）2 が
水分等の影響で生成されていると結合力が弱いため接着
層が破壊されやすい。Further, by setting the reduction time after the sulfurization reaction as a Cu reactivity index to 20 to 40 seconds, an appropriate amount of CuS can be generated. The CuS is an adhesion layer between the plating coating layer of the steel cord and the rubber substance. If the amount of CuS is large or small, the bonding force is weak when the Zn (OH) 2 is generated due to the influence of moisture or the like. Therefore, the adhesive layer is easily broken.
【００１２】従って本発明では前記の如くＣｕの反応性
指標として硫化反応後の還元時間を２０〜４０秒に特定
したのであり、この理由は２０秒より短かいとＣｕＳ量
が少ないということであり、４０秒を超えるとＣｕＳ量
が多いということであり、結局のところ２０〜４０秒が
初期接着が良好で高温多湿環境下での接着低下が少ない
範囲であることを知見した。Therefore, in the present invention, the reduction time after the sulfurization reaction is specified as the reactivity index of Cu to 20 to 40 seconds as described above. The reason is that if the time is shorter than 20 seconds, the CuS amount is small. , More than 40 seconds, it means that the amount of CuS is large, and after all, it was found that 20 to 40 seconds was within the range where the initial adhesion was good and the adhesion decrease under a high temperature and high humidity environment was small.
【００１３】かくして、得られたスチールフィラメント
で構成されたスチールコードの表面に有機酸コバルト配
合ゴムを通常の手段でコーティングすることによりＺｎ
Ｓの生成を促進し、接着層形成を安定化するという効果
を奏する。Thus, the surface of the steel cord composed of the obtained steel filament is coated with a rubber compounded with an organic acid cobalt by a usual means to obtain Zn.
This has the effect of promoting the generation of S and stabilizing the formation of the adhesive layer.
【００１４】[0014]
【発明の実施の形態】以下、本発明の実施例を比較例と
共に表に示す。Hereinafter, examples of the present invention will be shown in a table together with comparative examples.
【００１５】[0015]
【表１】 [Table 1]
【００１６】タイヤサイズ：ＴＬ２０５／６０Ｒ１５
スチールブレーカー補強層２枚使用した 初期接着力 ：新品タイヤのスチールコード層間剥離テ
スト（幅２５ｍｍ）を実施し、接着力を測定した 湿熱後接着力：７０°Ｃ〜９５％相対湿度雰囲気下で１
０日間放置した後、上記方法で接着力を測定した 還元時間 ：酸化ガスを発生するゴムとスチールコー
ドを加熱して酸化／硫化させる。このスチールコードに
電流を流してＣｕＯが還元される時間を測定し、Ｃｕの
反応性を評価する。Tire size: TL205 / 60R15
Initial adhesive strength using two steel breaker reinforcement layers: A new steel tire was subjected to a steel cord delamination test (25 mm width) to measure the adhesive strength. Adhesive strength after wet heat: 1 at 70 ° C. to 95% relative humidity atmosphere
After standing for 0 days, the adhesive strength was measured by the above method. Reduction time: The rubber and steel cord which generate an oxidizing gas were heated and oxidized / sulfided. A current is passed through the steel cord to measure the time during which CuO is reduced, and the reactivity of Cu is evaluated.
【００１７】[0017]
【評価】上記表によれば、本発明実施例１，２，３は初
期接着力、湿熱接着力のいずれにも優れるのに対し、比
較例１，２は何れも劣っており、また、比較例３，４は
初期接着力は実施例とほぼ同等であるが、湿熱接着力が
非常に劣っていることがわかる。[Evaluation] According to the above table, Examples 1, 2, and 3 of the present invention are excellent in both initial adhesive strength and wet heat adhesive strength, while Comparative Examples 1 and 2 are inferior in both. Examples 3 and 4 show that the initial adhesive strength is almost the same as that of the example, but the wet heat adhesive strength is very poor.
【００１８】[0018]
【発明の効果】本発明のタイヤ用スチールコードは、高
温多湿環境下において経年後も引続き接着剥離を起こさ
ない耐久性に優れたもので、特に空気入りラジアルタイ
ヤに用いて有効である。The steel cord for a tire according to the present invention is excellent in durability that does not cause adhesive peeling even after many years in a high-temperature and high-humidity environment, and is particularly effective for a pneumatic radial tire.
【手続補正書】[Procedure amendment]
【提出日】平成９年９月２２日[Submission date] September 22, 1997
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１５[Correction target item name] 0015
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１５】[0015]
【表１】 [Table 1]
Claims (2)
チールフィラメントは、含有率がＣｕ：６０〜６６％，
Ｚｎ：３４〜４０％の範囲内の平均合金比であるメッキ
真ちゅう被覆層を有し、かつこの真ちゅう被覆層の厚さ
は０．２〜０．３μｍであるものにおいて、 前記真ちゅう被覆層の最外表面に占めるＣｕの含有率が
２５〜３５％であり、前記被覆層中に占めるＣｕ含有率
はその深さ方向に増大して表面より０．０２〜０．０４
μｍのところでＣｕ：Ｚｎ＝５０：５０の合金比とさ
れ、かつ、Ｃｕの反応性指標として硫化反応後の還元時
間が２０〜４０秒であるフィラメントでなるスチールコ
ードを構成し、該スチールコード表面にコバルト配合ゴ
ムのコーティング層を設けてなることを特徴とするタイ
ヤ用スチールコード。The steel filament in contact with the rubber material of the steel cord has a Cu content of 60 to 66%,
Zn: a plated brass coating layer having an average alloy ratio in the range of 34 to 40%, and the thickness of the brass coating layer is 0.2 to 0.3 μm. The content of Cu in the outer surface is 25 to 35%, and the content of Cu in the coating layer increases in the depth direction to 0.02 to 0.04 from the surface.
A steel cord consisting of filaments having an alloy ratio of Cu: Zn = 50: 50 at μm and having a reduction time of 20 to 40 seconds after a sulfidation reaction as a Cu reactivity index is formed. A steel cord for a tire, characterized in that a coating layer of a cobalt compound rubber is provided on the tire.
コバルト配合ゴムのコーティング層を設けてなることを
特徴とするタイヤ用スチールコード。2. A steel cord for a tire, wherein a coating layer of a rubber compounded with an organic acid cobalt is provided on the surface of the steel cord according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24572997A JP4073526B2 (en) | 1997-09-10 | 1997-09-10 | Steel cord for tire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24572997A JP4073526B2 (en) | 1997-09-10 | 1997-09-10 | Steel cord for tire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1193086A true JPH1193086A (en) | 1999-04-06 |
| JP4073526B2 JP4073526B2 (en) | 2008-04-09 |
Family
ID=17137944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24572997A Expired - Fee Related JP4073526B2 (en) | 1997-09-10 | 1997-09-10 | Steel cord for tire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4073526B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100318045B1 (en) * | 1999-04-06 | 2001-12-22 | 서곤 | Process for preparing copper-film-plated cord for vehicle tire |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5330505A (en) * | 1976-08-31 | 1978-03-22 | Toyo Tire & Rubber Co Ltd | Tire for bad road |
| JPS559880A (en) * | 1978-07-07 | 1980-01-24 | Toyo Tire & Rubber Co Ltd | Rubber compound containing steel cord |
| JPS5655250A (en) * | 1979-10-12 | 1981-05-15 | Sumitomo Rubber Ind | Steel corddrubber composite material |
| JPS5686639A (en) * | 1979-11-23 | 1981-07-14 | Sodetal | Manufacture of wire for strengthening rubber article and device used for said method |
| JPS5756110A (en) * | 1980-05-27 | 1982-04-03 | Sodetal | Metallic body coated with brass for reinforcing rubber product |
| JPS63190157A (en) * | 1986-10-31 | 1988-08-05 | エヌ・ヴイ・ベカルト・エス・エイ | Steel base material having brass coating layer for adhering rubber and its production |
| JPH02256503A (en) * | 1988-12-28 | 1990-10-17 | Bridgestone Corp | Bead wire/rubber compound |
| JPH08253004A (en) * | 1994-12-14 | 1996-10-01 | Bridgestone Corp | Highly endurable pneumatic steel radial tire |
| JPH08260368A (en) * | 1994-12-14 | 1996-10-08 | Bridgestone Corp | Brass-plated steel wire for reinforcing rubber article |
-
1997
- 1997-09-10 JP JP24572997A patent/JP4073526B2/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5330505A (en) * | 1976-08-31 | 1978-03-22 | Toyo Tire & Rubber Co Ltd | Tire for bad road |
| JPS559880A (en) * | 1978-07-07 | 1980-01-24 | Toyo Tire & Rubber Co Ltd | Rubber compound containing steel cord |
| JPS5655250A (en) * | 1979-10-12 | 1981-05-15 | Sumitomo Rubber Ind | Steel corddrubber composite material |
| JPS5686639A (en) * | 1979-11-23 | 1981-07-14 | Sodetal | Manufacture of wire for strengthening rubber article and device used for said method |
| JPS5756110A (en) * | 1980-05-27 | 1982-04-03 | Sodetal | Metallic body coated with brass for reinforcing rubber product |
| JPS63190157A (en) * | 1986-10-31 | 1988-08-05 | エヌ・ヴイ・ベカルト・エス・エイ | Steel base material having brass coating layer for adhering rubber and its production |
| JPH02256503A (en) * | 1988-12-28 | 1990-10-17 | Bridgestone Corp | Bead wire/rubber compound |
| JPH08253004A (en) * | 1994-12-14 | 1996-10-01 | Bridgestone Corp | Highly endurable pneumatic steel radial tire |
| JPH08260368A (en) * | 1994-12-14 | 1996-10-08 | Bridgestone Corp | Brass-plated steel wire for reinforcing rubber article |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100318045B1 (en) * | 1999-04-06 | 2001-12-22 | 서곤 | Process for preparing copper-film-plated cord for vehicle tire |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4073526B2 (en) | 2008-04-09 |
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