JP3096159B2 - Steel wire for rubber article reinforcement with excellent rubber adhesion - Google Patents
Steel wire for rubber article reinforcement with excellent rubber adhesionInfo
- Publication number
- JP3096159B2 JP3096159B2 JP04194092A JP19409292A JP3096159B2 JP 3096159 B2 JP3096159 B2 JP 3096159B2 JP 04194092 A JP04194092 A JP 04194092A JP 19409292 A JP19409292 A JP 19409292A JP 3096159 B2 JP3096159 B2 JP 3096159B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- adhesion
- wire
- steel wire
- brass
- 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.)
- Expired - Lifetime
Links
- 229920001971 elastomer Polymers 0.000 title claims description 48
- 239000005060 rubber Substances 0.000 title claims description 48
- 229910000831 Steel Inorganic materials 0.000 title claims description 26
- 239000010959 steel Substances 0.000 title claims description 26
- 230000002787 reinforcement Effects 0.000 title 1
- 238000007747 plating Methods 0.000 claims description 26
- 229910001369 Brass Inorganic materials 0.000 claims description 22
- 239000010951 brass Substances 0.000 claims description 22
- 230000003746 surface roughness Effects 0.000 claims description 15
- 230000002093 peripheral effect Effects 0.000 claims description 9
- 230000003014 reinforcing effect Effects 0.000 claims description 6
- 238000009826 distribution Methods 0.000 description 11
- 230000032683 aging Effects 0.000 description 8
- 239000000314 lubricant Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003878 thermal aging Methods 0.000 description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241001422033 Thestylus Species 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 238000005491 wire drawing Methods 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- -1 fatty acid compound Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007586 pull-out test Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Ropes Or Cables (AREA)
- Tires In General (AREA)
- Reinforced Plastic Materials (AREA)
- Tyre Moulding (AREA)
Description
【０００１】[0001]
【産業上の利用分野】この発明は、タイヤや工業用ベル
ト等のゴム物品の補強に供する、ブラスめっきを施した
スチールワイヤに関し、特にゴムとの初期接着性、熱経
時接着性及び湿熱経時接着性の全てにわたる改善を達成
しようとするものである。ここで初期接着性は、ゴム物
品製造時における、スチールワイヤに接着したゴムの剥
離に対する強度及び剥離した際のゴム付着率に基き、ま
た熱経時接着性は、ゴム物品使用時における熱の影響、
例えばタイヤを高速又は長距離走行に供した際に発生す
る熱の影響を受けたのちのスチールワイヤに接着したゴ
ムの剥離に対する強度及び剥離した際のゴム付着率に基
き、さらに湿熱経時接着性は、例えば多湿雰囲気中での
保管や使用中に受けた傷からの水分侵入など、スチール
ワイヤとゴムとの界面が水分に晒された後のスチールワ
イヤに接着したゴムの剥離に対する強度及び剥離した際
のゴム付着率に基き、それぞれ評価できる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a brass-plated steel wire for reinforcing rubber articles such as tires and industrial belts, and more particularly to an initial adhesive property with rubber, an adhesive property with heat and an adhesive property with wet heat. It seeks to achieve improvements in all aspects of gender. Here, the initial adhesiveness is based on the strength of the rubber adhered to the steel wire against peeling and the rubber adhesion rate when peeled off during the production of the rubber article, and the thermal aging adhesiveness is the effect of heat when using the rubber article,
For example, based on the strength against peeling of the rubber bonded to the steel wire after being affected by the heat generated when the tire is subjected to high-speed or long-distance running and the rubber adhesion rate at the time of peeling, the wet-heat adhesive property over time is further For example, when the interface between the steel wire and the rubber is exposed to moisture, such as moisture penetration from scratches during storage or use in a humid atmosphere, and the strength against peeling of the rubber adhered to the steel wire and the peeling Can be evaluated on the basis of the rubber adhesion rate.
【０００２】[0002]
【従来の技術】この種ゴム物品の補強に使用されるスチ
ールワイヤ又はワイヤを撚り合わせたスチールコードに
おいては、補強効果を発揮させるためにゴムとの接着性
に優れることが要求される。ブラスめっき付のスチール
ワイヤやスチールコードでは、ブラスめっきのCu／Zn
比、ブラスめっきの厚さを適正化することにより接着性
を改善させる方法が広く知られている。またブラスめっ
き付スチールワイヤに隣接するゴム組成物に有機酸金属
塩を配合することによって接着性を改善できることも広
く知られている。2. Description of the Related Art Steel wires or steel cords obtained by twisting wires used for reinforcing rubber articles of this kind are required to have excellent adhesion to rubber in order to exert a reinforcing effect. For brass-plated steel wires and cords, brass-plated Cu / Zn
There is widely known a method of improving the adhesiveness by optimizing the ratio and the thickness of the brass plating. It is also widely known that the adhesion can be improved by adding an organic acid metal salt to the rubber composition adjacent to the brass-plated steel wire.
【０００３】ゴム物品、中でも空気入りタイヤは使用条
件が苛酷であるため、製品仕上がり時のゴム接着性が良
好であることは勿論、その後の使用時における温度上昇
や水分浸透によるゴム接着性の低下を極力回避すること
が望まれる。更に製品の使用期間が長いため、ゴム接着
部の耐老化性も優れていなければならない。またタイヤ
に用いる場合はゴムシート材の形で保管するが、この保
管期間中にゴムシート材が吸湿することはよくあること
から、このような吸湿した材料においても良好なゴム接
着性を与える必要がある。[0003] Since rubber articles, especially pneumatic tires, are used under severe conditions, the rubber adhesion at the time of finished products is of course good, and the rubber adhesion at the time of subsequent use decreases due to temperature rise and moisture penetration. It is desired to avoid as much as possible. Further, since the product is used for a long period of time, the aging resistance of the rubber bonded portion must be excellent. When used for tires, the rubber sheet is stored in the form of a rubber sheet material. During this storage period, the rubber sheet material often absorbs moisture. There is.
【０００４】上記の問題に対して、特開昭53−106853号
公報では熱拡散法によってブラスめっき付ワイヤを製造
する際に、熱拡散後のめっき表面に生成した酸化物を溶
解除去することにより、吸湿ゴムとの初期接着性及び熱
経時接着性を改善する方法が提案されているが、湿熱経
時接着性に問題が残る。また特開昭63−33135 号公報で
はブラスめっきしたゴム補強用ワイヤのブラスめっき
に、燐酸塩をＰ（リンを表す元素記号、以下同じ）とし
て４mg/m2 以上含有させることにより、熱および湿熱経
時接着性を改善することが提案されているが、熱に対す
る経時接着性は不十分で初期接着性にも問題が残る。[0004] In order to solve the above problem, Japanese Patent Application Laid-Open No. 53-106853 discloses a method of dissolving and removing oxides generated on a plated surface after thermal diffusion when manufacturing a wire with brass plating by a thermal diffusion method. Although there has been proposed a method for improving the initial adhesiveness with heat absorbing rubber and the adhesiveness with time with heat, there is a problem in the adhesiveness with time with wet heat. JP-A-63-33135 discloses that the brass plating of a brass-plated rubber reinforcing wire contains 4 mg / m 2 or more of phosphate as P (element symbol for phosphorus, the same applies hereinafter) , thereby obtaining heat and wet heat. Although it has been proposed to improve the aging adhesion, the aging adhesion to heat is insufficient and the initial adhesion remains problematic.
【０００５】[0005]
【発明が解決しようとする課題】上記のようにスチール
ワイヤにはあらゆる条件下で良好なゴム接着性が要求さ
れるが、タイヤの高寿命化と高速走行使用に伴って、と
りわけ熱経時接着性及び湿熱経時接着性の更なる改善が
のぞまれている。そこでこの発明は、熱及び湿熱下での
接着低下を回避し、さらに初期接着性にも優れたスチー
ルワイヤを提供しようとするものである。As described above, steel wires are required to have good rubber adhesion under all conditions. Further, further improvement in wet heat and heat aging adhesion is desired. Accordingly, an object of the present invention is to provide a steel wire that avoids a decrease in adhesion under heat and wet heat, and that also has excellent initial adhesion.
【０００６】[0006]
【課題を解決するための手段】この発明は、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
っきの表面に付着量：1.0mg/m2〜3.0mg/m2のＰを有し、
またブラスめっき層との境界をなすワイヤ周面の表面粗
さが、ワイヤの直径ｄ（mm）に関し、（0.019＋0.159
ｄ）μｍRa以下であることを特徴とする、ゴム接着性に
優れるゴム物品補強用スチールワイヤである。SUMMARY OF THE INVENTION This invention provides a steel wire subjected to brass plating on the peripheral surface, the amount adhering to the surface of the brass-plated: the P of 1.0mg / m 2 ~3.0mg / m 2 Have
In addition, the surface roughness of the peripheral surface of the wire forming the boundary with the brass plating layer is (0.019 + 0.159 ) with respect to the wire diameter d (mm).
d) A steel wire for reinforcing rubber articles having excellent rubber adhesion, characterized in that it is not more than μmRa.
【０００７】[0007]
【作用】まずスチールワイヤに施すブラスめっきのCu／
Zn比は、Cu量の大きい方が初期接着性に対しては有利で
あるが、湿熱接着性に対しては不利となる。従ってブラ
スめっきは、Cu : 60 〜70wt% 及びZn :35〜40wt% を含
有する成分組成が有利に適合する。なお湿熱接着性はブ
ラスめっきの反応性が低い方が良好となる傾向にあり、
従ってブラスめっき表面に酸化物が存在しても差し支え
ない。[Function] First, brass plating Cu applied to steel wire
As for the Zn ratio, a larger amount of Cu is advantageous for the initial adhesiveness, but disadvantageous for the wet heat adhesiveness. Therefore, for brass plating, a component composition containing Cu: 60-70 wt% and Zn: 35-40 wt% is advantageously adapted. The wet heat adhesion tends to be better when the reactivity of brass plating is lower,
Therefore, an oxide may be present on the surface of the brass plating.
【０００８】さて、この発明では上記ブラスめっきの表
面にＰを、好ましくは30〜60Åの厚みで、付着させるこ
とが肝要である。すなわちブラスめっき表面にＰを付着
させることによって、ゴム接着性、特に湿熱経時接着性
を改善することができ、これには１mg/m2 以上の付着量
が必要である。一方、Ｐの付着量が多過ぎると初期接着
性が悪化するので、3.0mg/m2以下とする必要がある。こ
こで、Ｐの付着によって湿熱経時接着性が改善されるの
は、Ｐの付着した皮膜がめっき層の腐食環境に対する防
護壁となり、めっき層の腐食に伴う接着低下を抑制でき
るからである。In the present invention, it is important that P is adhered to the surface of the brass plating, preferably in a thickness of 30 to 60 °. That is, by attaching P to the surface of the brass plating, it is possible to improve the rubber adhesiveness, particularly the adhesiveness over time with wet heat, and this requires an adhesion amount of 1 mg / m 2 or more. On the other hand, if the amount of P attached is too large, the initial adhesion deteriorates, so it is necessary to be 3.0 mg / m 2 or less. Here, the reason why the adhesion with wet heat and heat is improved by the adhesion of P is that the film to which P is attached acts as a protective wall against the corrosive environment of the plating layer, and a decrease in adhesion due to the corrosion of the plating layer can be suppressed.
【０００９】また発明者らは、ブラスめっき表面のＰ付
着量を制御することで湿熱経時接着性のほかのゴム接着
性、つまり熱経時及び初期の各接着性は改善することが
できないことから、さらにこれらのゴム接着性をも改善
する手法について検討したところ、ブラスめっき層との
境界をなすワイヤ周面の表面粗さ（表面凹凸状態）の制
御が有効であることを新たに知見した。In addition, the inventors cannot control the rubber adhesion other than the wet heat aging adhesion, that is, the heat aging and initial adhesion, by controlling the amount of P attached to the surface of the brass plating. Furthermore, when the method of improving the rubber adhesiveness was examined, it was newly found that the control of the surface roughness (surface irregularity state) of the wire peripheral surface forming a boundary with the brass plating layer was effective.
【００１０】すなわち図１及び２に、スチールワイヤの
ブラスめっき表面に付着したＰの分布状態をＡＥＳ（Au
ger Electoron Spectroscopy）及びＳＥＭ（Scanning E
lectoron Microscope ）で観察した結果を示すように、
Ｐの分布状態とスチールワイヤ表面の凹凸との間に相関
が認められる。図１に示すワイヤ１の表面は、微小の凹
凸が規則正しく並んでおり、ブラスめっき２の表面に付
着したＰは凸部に対応して偏析している。これは図２の
表面の粗い凹凸が不規則に並ぶワイヤ１に施した、めっ
き２の表面においても同様である。従って、ブラスめっ
き表面のワイヤ周方向及び軸方向における、Ｐの分布
は、ワイヤ表面の凹凸が規則的（図１）であると同様に
規則的に分散し、一方ワイヤ表面の凹凸が不規則（図
２）であると同様に不規則な分散となる。That is, FIGS. 1 and 2 show the distribution of P adhered to the brass-plated surface of a steel wire by AES (Au).
ger Electoron Spectroscopy) and SEM (Scanning E)
lectoron Microscope)
A correlation is observed between the distribution state of P and the unevenness of the steel wire surface. On the surface of the wire 1 shown in FIG. 1, fine irregularities are regularly arranged, and P adhered to the surface of the brass plating 2 is segregated corresponding to the projection. The same applies to the surface of the plating 2 applied to the wire 1 in FIG. Therefore, the distribution of P in the circumferential and axial directions of the wire on the brass-plated surface is regularly distributed in the same manner as when the unevenness on the wire surface is regular (FIG. 1), while the unevenness on the wire surface is irregular ( As in FIG. 2), the distribution becomes irregular.
【００１１】以上の観察結果から、ワイヤ表面の凹凸が
Ｐの分布に影響を与えることがわかり、ワイヤ周面の表
面粗さを制御し表面の凹凸をより規則正しくすること、
すなわち表面粗さを小さくすることによって、Ｐの分布
状態を細かくかつ均一に分散することができ、全てのゴ
ム接着性を一様に向上することができる。ところで、ワ
イヤ周面の表面粗さを制御するに当たっては、ワイヤの
表面が平面でなく曲面であるところから、その周面の曲
率によって適合する表面粗さの範囲が変化する可能性が
ある。そこで、種々の線径のワイヤを用いて、その周面
の表面粗さを変化したときの、ゴム接着性について調査
した。その結果を図３に示すように、ワイヤ周面の表面
粗さが、その線径ｄに関し、（0.019 ＋0.159 ｄ）μｍ
Ra以下の範囲にあれば、優れたゴム接着性が得られるこ
とがわかる。すなわち、表面粗さが（0.019 ＋0.159
ｄ）μｍRaをこえると、Ｐの分布は不均一となり熱およ
び湿熱経時接着性が不良となるため、表面粗さを（0.01
9 ＋0.159 ｄ）μｍRa以下とする。From the above observation results, it was found that the irregularities on the wire surface affect the distribution of P, and that the surface roughness of the peripheral surface of the wire was controlled to make the irregularities on the surface more regular.
That is, by reducing the surface roughness, the distribution state of P can be finely and uniformly dispersed, and all the rubber adhesiveness can be uniformly improved. In controlling the surface roughness of the peripheral surface of the wire, since the surface of the wire is not a flat surface but a curved surface, the range of the suitable surface roughness may change depending on the curvature of the peripheral surface. Then, the rubber adhesion was investigated when the surface roughness of the peripheral surface was changed using wires of various wire diameters. As shown in FIG. 3, the results show that the surface roughness of the wire peripheral surface is (0.019 + 0.159 d) μm with respect to the wire diameter d.
It can be seen that excellent rubber adhesiveness can be obtained if it is in the range of Ra or less. That is, the surface roughness is (0.019 + 0.159)
d) If it exceeds μmRa, the distribution of P becomes non-uniform and the heat and wet heat aging adhesion becomes poor.
9 +0.159 d) It shall be not more than μmRa.
【００１２】ここで、Ｐの分布を均一化すると熱および
湿熱経時接着性が向上するのは、熱又は腐食反応による
生成物を一様に分散させ得るからである。すなわち、こ
の生成物は接着部を破壊する因子であり、Ｐの分布を均
一化して接着破壊箇所を分散させることによって、接着
部の破壊応力を低減できる。The reason why the uniformity of the distribution of P improves the adhesive property over time in heat and wet heat is that the product of the heat or corrosion reaction can be uniformly dispersed. In other words, this product is a factor that destroys the bonded portion, and the distribution of P is made uniform to disperse the bonded portion, whereby the breaking stress of the bonded portion can be reduced.
【００１３】なお、ブラスめっきへのＰの付着は、例え
ばめっき後の伸線工程における、Ｐを含む湿式潤滑剤の
供給によって行う。すなわち湿式潤滑剤のpH及び脂肪酸
化合物濃度を調整することによって、潤滑剤中の燐酸亜
鉛濃度を0.5 〜1.8g/lとした潤滑剤を供給しながら伸線
を行う。The P is attached to the brass plating by, for example, supplying a wet lubricant containing P in a wire drawing process after the plating. That is, by adjusting the pH and the fatty acid compound concentration of the wet lubricant, wire drawing is performed while supplying a lubricant having a zinc phosphate concentration of 0.5 to 1.8 g / l in the lubricant.
【００１４】[0014]
【実施例】1.24mmφの鋼線材を複数本用意し、各線材
に、Cu：62 wt%及びZn：38 wt%を含有する組成のブラス
めっきを施し、次いで燐酸亜鉛を主成分とする潤滑剤を
供給しながら、0.175 〜0.36mmまで縮径した、各スチー
ルワイヤを撚り合わせてなるスチールコードを、それぞ
れゴムで被覆して加硫成形した後、ゴム接着性試験に供
した。なお、被覆ゴムの組成は、天然ゴム：100 重量部
に対し、カーボンブラック：50重量部、亜鉛華：５重量
部、ステアリン酸：２重量部、老化防止剤：１重量部、
ナフテン酸コバルト：２重量部、加硫促進剤：1.5 重量
部及び硫黄：４重量部である。EXAMPLE A plurality of 1.24 mmφ steel wires were prepared, and each wire was subjected to brass plating with a composition containing 62 wt% of Cu and 38 wt% of Zn, and then a lubricant containing zinc phosphate as a main component. While supplying the steel cords, steel cords each having a diameter reduced to 0.175 to 0.36 mm and formed by twisting steel wires were respectively coated with rubber, vulcanized and then subjected to a rubber adhesion test. The composition of the coated rubber is as follows: 100 parts by weight of natural rubber, 50 parts by weight of carbon black, 5 parts by weight of zinc white, 2 parts by weight of stearic acid, 1 part by weight of an antioxidant,
Cobalt naphthenate: 2 parts by weight, vulcanization accelerator: 1.5 parts by weight and sulfur: 4 parts by weight.
【００１５】ここで、ゴム接着性試験は、初期接着性、
熱経時接着性及び湿熱経時接着性についてそれぞれ行っ
た。すなわち初期接着性はゴム被覆コードを145 ℃で30
分間加圧加硫した後室温ではく離試験を行って評価し、
熱経時接着性は同様に145 ℃で600 及び1200分間加熱し
た後室温ではく離試験を行って評価し、そして湿熱経時
接着性は145 ℃で30分間加硫した後、試料を75℃、95％
RHの条件で所定時間放置した後室温ではく離試験を行っ
て評価した。[0015] Here, the rubber adhesion test was carried out to determine the initial adhesion,
The thermal aging adhesiveness and the wet thermal aging adhesiveness were respectively performed. In other words, the initial adhesion was 30 minutes at 145 ° C
After pressure vulcanization for minutes, perform a peel test at room temperature to evaluate,
After thermal aged adhesion was evaluated by a peeling test at room temperature after heating 600 and 1200 minutes likewise 145 ° C., and the humidity thermal aged adhesion was vulcanized for 30 minutes at 145 ° C., the sample 75 ° C., 95 %
After leaving for a predetermined time under RH conditions, a peeling test was performed at room temperature to evaluate.
【００１６】また、ブラスめっき表面のＰの付着量の制
御は、潤滑剤の燐酸亜鉛濃度及び温度と伸線ダイスの数
及び１ダイス当たりの加工減面率とを調整して行い、ス
チールワイヤの表面粗さは線引きダイスの形状、潤滑剤
などを変更することによって制御した。The amount of P deposited on the surface of the brass plating is controlled by adjusting the zinc phosphate concentration and temperature of the lubricant, the number of drawing dies, and the processing reduction rate per die. The surface roughness was controlled by changing the shape of the drawing die, the lubricant, and the like.
【００１７】上記の各評価結果を、各ワイヤの表面粗さ
及びＰの付着量に併せて表１〜８に示す。The results of the above evaluations are shown in Tables 1 to 8 together with the surface roughness of each wire and the amount of P attached.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【表２】 [Table 2]
【００２０】[0020]
【表３】 [Table 3]
【００２１】[0021]
【表４】 [Table 4]
【００２２】[0022]
【表５】 [Table 5]
【００２３】[0023]
【表６】 [Table 6]
【００２４】[0024]
【表７】 [Table 7]
【００２５】[0025]
【表８】 [Table 8]
【００２６】なお、同表における、表面粗さ及びＰ付着
量の測定とゴムはく離試験評価とは、次の(1) 〜(3) に
従って行った。 (1) 表面粗さの定量 ワイヤ表面のめっきを溶解し地鉄を露出させたワイヤ
に、粗さ測定機の触針を接触させ、次いで触針をワイヤ
の周線に沿って回転させて触針の運動軌跡を測定し、こ
の測定値から中心線平均粗さ(Ra)を求めた。 (2) ブラスめっきのＰの定量法 ５ｇのワイヤを採集し、1.2 Ｎの塩酸水溶液10ml中に室
温下で60秒間浸漬して表面のＰを溶解し、この溶液中の
溶質PO4 の定量を誘導結合高周波プラズマを光源とする
発光分光分析によって行い、得られた測定結果に基い
て、ブラス表面積当たりの付着量に換算した。 (3) ゴム接着性の評価 引き抜き試験では熱および湿熱によるゴムの老化により
引き抜き力が影響を受けるため剥離試験によりスチール
ワイヤおよびコード表面に接着しているゴムの状態をＡ
からＥまで５段階評価により判定した。Ａはもっとも良
好な接着状態、Ｅはスチールとゴムがまったく接着して
いない状態である。各試験条件とも５本の試料を剥離し
て５本のゴムの接着状態をそれぞれ判定した。The measurement of the surface roughness and the amount of P adhesion and the evaluation of the rubber peeling test in the same table were performed according to the following (1) to (3). (1) Quantitative determination of surface roughness The stylus of the roughness measuring instrument is brought into contact with the wire on which the plating on the wire surface has been dissolved to expose the ground iron, and then the stylus is rotated along the circumference of the wire to touch The movement locus of the needle was measured, and the center line average roughness (Ra) was determined from the measured value. (2) Method of quantifying P in brass plating 5 g of a wire was collected, immersed in 10 ml of 1.2 N hydrochloric acid solution at room temperature for 60 seconds to dissolve P on the surface, and the quantification of solute PO 4 in this solution was performed. Emission spectroscopy was performed using inductively-coupled high-frequency plasma as a light source, and the amount of adhesion per brass surface area was converted based on the obtained measurement results. (3) Evaluation of Rubber Adhesion In the pull-out test, the pull-out force is affected by the aging of the rubber due to heat and wet heat.
To E were evaluated by a five-step evaluation. A is the best adhesion state, and E is the state where steel and rubber are not bonded at all. Under each test condition, five samples were peeled, and the adhesion state of the five rubbers was determined.
【００２７】[0027]
【発明の効果】この発明によれば、特別なめっき組成と
か新たに装置を設置する等の工程変更を要することなし
に、スチールワイヤに優れたゴム接着性を付与すること
ができ、従来と同じ製造コストでゴム製品の耐久性の向
上に寄与するスチールワイヤ、さらにはスチールコード
を提供し得る。According to the present invention, excellent rubber adhesiveness can be imparted to a steel wire without requiring a special plating composition or a process change such as installation of a new apparatus. It is possible to provide a steel wire and further a steel cord that contribute to improving the durability of a rubber product at a manufacturing cost.
【図１】ワイヤ表面凹凸とＰの分布状態との関係を示す
模式図である。FIG. 1 is a schematic diagram showing a relationship between wire surface irregularities and a distribution state of P.
【図２】ワイヤ表面凹凸とＰの分布状態との関係を示す
模式図である。FIG. 2 is a schematic diagram showing the relationship between wire surface irregularities and the distribution of P.
【図３】各種径のワイヤにおける、表面粗さとゴム接着
性との関係を示すグラフである。FIG. 3 is a graph showing the relationship between surface roughness and rubber adhesion for wires of various diameters.
１ ワイヤ ２ ブラスめっき 1 Wire 2 Brass plating
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ２５Ｄ 5/26 Ｃ２５Ｄ 5/26 Ｅ 7/06 7/06 Ｒ (56)参考文献 特開 昭62−288634（ＪＰ，Ａ) 特開 平３−130378（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) D07B 1/06 B29D 30/38 B60C 9/00 C08J 5/06 C25D 3/58 C25D 5/26 C25D 7/06 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI C25D 5/26 C25D 5/26 E 7/06 7/06 R (56) References JP-A-62-288634 (JP, A) JP-A-3-130378 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) D07B 1/06 B29D 30/38 B60C 9/00 C08J 5/06 C25D 3/58 C25D 5 / 26 C25D 7/06
Claims (1)
イヤであって、該ブラスめっきの表面に付着量：1.0mg/
m2〜3.0mg/m2のＰ（元素記号）を有し、かつブラスめっ
き層との境界をなすワイヤ周面の表面粗さが、ワイヤの
直径ｄ（mm）に関し、（0.019 ＋0.159 ｄ）μｍRa以下
であることを特徴とする、ゴム接着性に優れるゴム物品
補強用スチールワイヤ。1. A steel wire having a brass plating on a peripheral surface thereof, the amount of which is 1.0 mg /
m has a 2 ~3.0mg / m 2 of P (element symbol), and the surface roughness of the wire circumferential surface forming a boundary between the brass plated layer relates wire diameter d (mm), (0.019 +0.159 d) A steel wire for reinforcing a rubber article having excellent rubber adhesion, which is not more than μmRa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04194092A JP3096159B2 (en) | 1992-07-21 | 1992-07-21 | Steel wire for rubber article reinforcement with excellent rubber adhesion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04194092A JP3096159B2 (en) | 1992-07-21 | 1992-07-21 | Steel wire for rubber article reinforcement with excellent rubber adhesion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0649783A JPH0649783A (en) | 1994-02-22 |
| JP3096159B2 true JP3096159B2 (en) | 2000-10-10 |
Family
ID=16318821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04194092A Expired - Lifetime JP3096159B2 (en) | 1992-07-21 | 1992-07-21 | Steel wire for rubber article reinforcement with excellent rubber adhesion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3096159B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07268787A (en) * | 1994-03-25 | 1995-10-17 | Nippon Steel Corp | Highly strong steel wire excellent in fatigue characteristic and steel cord using the steel wire and rubber product using the steel wire or the steel cord |
| EP1365064B1 (en) | 2001-02-21 | 2016-06-15 | Bridgestone Corporation | Steel wire and steel cord for reinforcing rubber article, and tire |
| JP4497788B2 (en) * | 2002-04-09 | 2010-07-07 | 株式会社ブリヂストン | Steel wire for reinforcing rubber articles and steel cord and tire for reinforcing rubber articles |
| CN101326324B (en) | 2005-12-13 | 2012-10-31 | 住友橡胶工业株式会社 | Metallic cord, rubber/cord composite object, and pneumatic tire obtained using the same |
| ES2642918T3 (en) | 2012-02-06 | 2017-11-20 | Nv Bekaert Sa | Elongated steel element comprising a ternary or quaternary brass alloy coating and corresponding method |
| JP6040259B2 (en) * | 2012-02-06 | 2016-12-07 | ナムローゼ・フェンノートシャップ・ベーカート・ソシエテ・アノニムＮ Ｖ Ｂｅｋａｅｒｔ Ｓｏｃｉｅｔｅ Ａｎｏｎｙｍｅ | Ternary or quaternary alloy coatings for steam aging and post cure wet adhesion, elongated steel elements with ternary or quaternary brass alloy coatings, and corresponding methods |
| PL2877630T3 (en) | 2012-07-24 | 2019-04-30 | Bekaert Sa Nv | A steel cord for rubber reinforcement with selectively brass coated filaments |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2645457B2 (en) * | 1986-06-05 | 1997-08-25 | 住友電気工業株式会社 | Method of manufacturing steel wire and steel cord for reinforcing rubber articles |
| US5118367A (en) * | 1989-09-25 | 1992-06-02 | The Goodyear Tire & Rubber Company | Process for treating a brass-plated steel wire |
-
1992
- 1992-07-21 JP JP04194092A patent/JP3096159B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0649783A (en) | 1994-02-22 |
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