JPH07119057A - Wire for reinforcing rubber and its production - Google Patents
Wire for reinforcing rubber and its productionInfo
- Publication number
- JPH07119057A JPH07119057A JP5258053A JP25805393A JPH07119057A JP H07119057 A JPH07119057 A JP H07119057A JP 5258053 A JP5258053 A JP 5258053A JP 25805393 A JP25805393 A JP 25805393A JP H07119057 A JPH07119057 A JP H07119057A
- Authority
- JP
- Japan
- Prior art keywords
- wire
- layer
- brass
- rubber
- plating
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 230000003014 reinforcing effect Effects 0.000 title abstract description 4
- 239000010410 layer Substances 0.000 claims abstract description 77
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910001369 Brass Inorganic materials 0.000 claims abstract description 36
- 239000010951 brass Substances 0.000 claims abstract description 36
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 30
- 239000010959 steel Substances 0.000 claims abstract description 30
- 238000005491 wire drawing Methods 0.000 claims abstract description 29
- 239000011247 coating layer Substances 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 23
- -1 triazine thiol Chemical class 0.000 claims description 20
- 239000011701 zinc Substances 0.000 claims description 15
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- HAZJTCQWIDBCCE-UHFFFAOYSA-N 1h-triazine-6-thione Chemical class SC1=CC=NN=N1 HAZJTCQWIDBCCE-UHFFFAOYSA-N 0.000 abstract description 5
- 238000007747 plating Methods 0.000 description 47
- 239000010949 copper Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 5
- 230000004927 fusion Effects 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910017518 Cu Zn Inorganic materials 0.000 description 2
- 229910017752 Cu-Zn Inorganic materials 0.000 description 2
- 229910002482 Cu–Ni Inorganic materials 0.000 description 2
- 229910017943 Cu—Zn Inorganic materials 0.000 description 2
- 229910000677 High-carbon steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 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
- Ropes Or Cables (AREA)
- Tires In General (AREA)
- Wire Processing (AREA)
- Reinforced Plastic Materials (AREA)
- Chemically Coating (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Metal Extraction Processes (AREA)
- Tyre Moulding (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、スチールラジアルタイ
ヤ、高圧ホース、ベルトコンベアなどに用いられるゴム
補強用ワイヤおよびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber-reinforcing wire used for steel radial tires, high-pressure hoses, belt conveyors and the like, and a method for producing the same.
【0002】[0002]
【従来の技術】スチールラジアルタイヤ、高圧ホース、
ベルトコンベアなどにゴム補強材として用いられるスチ
ールワイヤに関しては、加硫されたゴムとの接着性およ
びその持続性が重要である。従来より実用化されている
ゴム補強用ワイヤは、ゴムとの接着性を得るために、一
般に黄銅(ブラス)からなる被覆層を形成している。黄
銅層を形成する方法としては、シアン浴による共析めっ
きも用いられるが、シアンという毒物を使用するため公
害を防止する必要があり、しかもCu含有率の管理が比
較的困難である。このため、CuとZnとを順次めっき
した後、加熱拡散処理を施す拡散めっき法が主流になっ
てきている。加熱方法としては、通電加熱高周波加熱、
流動層炉加熱などがある。2. Description of the Related Art Steel radial tires, high pressure hoses,
Regarding the steel wire used as a rubber reinforcing material for a belt conveyor or the like, the adhesiveness with vulcanized rubber and its durability are important. The rubber-reinforcing wire that has been put into practical use has a coating layer generally made of brass in order to obtain adhesiveness with rubber. As a method for forming the brass layer, eutectoid plating using a cyan bath is also used, but it is necessary to prevent pollution because a poisonous substance called cyan is used, and it is relatively difficult to control the Cu content. For this reason, a diffusion plating method in which Cu and Zn are sequentially plated and then heat diffusion treatment is performed has become mainstream. As a heating method, energization heating high frequency heating,
Fluidized bed furnace heating etc.
【0003】黄銅中のCuは硫黄との反応性が良好であ
り、加硫時にゴムコンパウンド中の硫黄と反応してCu
の硫化物が生成する。一方、ZnはCuの硫黄に対する
反応性を低下させる。この結果、ワイヤの被覆層とゴム
との界面に適度な硫化物が生成し、ゴム接着性が得られ
ると考えられている。しかし、黄銅めっきの被覆層が形
成されたゴム補強用ワイヤは、湿潤雰囲気下におけるゴ
ムとの接着性(湿潤接着性)が劣るという欠点がある。
これはCuの反応性を低下させるというZnの効果が十
分ではなく、ワイヤとゴムとの接着界面に過剰な硫化物
が存在するためである。したがって、湿潤接着性を改善
するには、ワイヤとゴムとの接着界面における過剰な硫
化物生成を抑制することが好ましく、黄銅めっき層のC
u含有率が低い方が好ましいとされている。Cu in brass has a good reactivity with sulfur, and it reacts with sulfur in the rubber compound during vulcanization to form Cu.
Sulfides are generated. On the other hand, Zn reduces the reactivity of Cu with sulfur. As a result, it is considered that appropriate sulfides are generated at the interface between the coating layer of the wire and the rubber, and the rubber adhesiveness is obtained. However, the rubber-reinforcing wire on which the brass-plated coating layer is formed has a drawback in that it has poor adhesiveness (wet adhesiveness) to rubber in a wet atmosphere.
This is because the effect of Zn, which lowers the reactivity of Cu, is not sufficient, and excess sulfide is present at the bonding interface between the wire and rubber. Therefore, in order to improve the wet adhesion, it is preferable to suppress excessive sulfide formation at the adhesive interface between the wire and the rubber, and to improve the C content of the brass plating layer.
It is said that a lower u content is preferable.
【0004】一方、ワイヤの強度ひいてはゴムに対する
補強効果を高めるために、ゴム補強用ワイヤは冷間加工
特にダイスから引き抜く方法による伸線加工が施され
る。この伸線加工は非常に苛酷な条件で行われる。この
ため、黄銅めっきの変形能が低い場合には、摩擦熱によ
り著しく発熱する、伸線抵抗が高くなる、ダイスの寿命
が低下する、著しい場合には引抜き加工の際にワイヤが
断線するなど伸線加工性に問題が生じる。On the other hand, in order to enhance the strength of the wire and thus the reinforcing effect on rubber, the rubber-reinforcing wire is subjected to cold working, particularly wire drawing by a method of pulling out from the die. This wire drawing process is performed under extremely severe conditions. Therefore, if the deformability of brass plating is low, heat is generated remarkably due to frictional heat, wire drawing resistance is increased, die life is shortened, and if it is remarkable, wire breakage occurs during drawing, etc. There is a problem in wire workability.
【0005】黄銅めっきに関しては、結晶組織がβ相よ
りもα相の方が延展性がよい。これは、β相が体心立方
格子であるのに対して、α相は面心立方格子であり滑り
やすい面が多く存在することに起因している。したがっ
て、伸線加工性を改善するためには、黄銅めっき層中の
β相の比率が少ないことが好ましい。なお、拡散めっき
法を用いた場合には、加熱条件によっても結晶相に影響
が生じる。加熱温度が高く加熱時間が長いほど、融合拡
散が起こりやすく、β相が少なくなることが知られてい
るので、最適な条件が選択される。Regarding brass plating, the α phase has better spreadability than the β phase. This is because the β phase is a body-centered cubic lattice, whereas the α phase is a face-centered cubic lattice and has many slippery surfaces. Therefore, in order to improve the wire drawing workability, it is preferable that the proportion of β phase in the brass plating layer is small. When the diffusion plating method is used, the crystal phase is affected also by the heating conditions. It is known that the higher the heating temperature and the longer the heating time, the easier the fusion diffusion occurs and the β phase decreases, so the optimum conditions are selected.
【0006】しかし、上述したように湿潤接着性を改善
するために黄銅めっき層のCu含有率を低くすると、β
相が多くなることが知られている。このようにCu含有
率が低い場合には実用的な伸線加工が困難となるため、
工業生産の観点からは63%程度のCu含有率が下限で
あるとされている。以上のように、湿潤接着性と伸線加
工性の両者を同時に満たすことは困難である。However, if the Cu content of the brass plating layer is lowered to improve the wet adhesion as described above, β
It is known that there are many phases. As described above, when the Cu content is low, practical wire drawing becomes difficult.
From the viewpoint of industrial production, the Cu content of about 63% is the lower limit. As described above, it is difficult to simultaneously satisfy both wet adhesion and wire drawing workability.
【0007】[0007]
【発明が解決しようとする課題】そこで、黄銅に第3元
素(X)を添加した合金からなる被覆層を形成して、湿
潤接着性を改善する技術が提案されている。第3元素
(X)としては、例えばNi(特開昭55−10554
8号公報)、Co(特公平1−37411号公報)Fe
(特公平2−39599号公報)などが用いられる。こ
れらの技術では、Cu−X−Znの順にめっき層を積層
した後、加熱拡散させて被覆層を形成している。このよ
うな順に積層めっき層を形成するのは、Znめっきの上
にCuめっきを密着性よく積層することが困難なためで
ある。しかし、Cu−X−Znの構成において第3元素
の融点が高い場合には、第3元素のめっき層がCuとZ
nとの融合拡散を阻害する障壁層となるため、β相が多
く生成しやすい。このため、ワイヤの伸線加工性が阻害
される。Therefore, there has been proposed a technique for improving wet adhesion by forming a coating layer made of an alloy in which a third element (X) is added to brass. Examples of the third element (X) include Ni (Japanese Patent Laid-Open No. 55-10554).
No. 8), Co (Japanese Patent Publication No. 1-37411) Fe
(Japanese Patent Publication No. 2-39959) is used. In these techniques, a coating layer is formed by laminating a plating layer in the order of Cu-X-Zn and then heating and diffusing it. The reason why the laminated plating layers are formed in this order is that it is difficult to laminate the Cu plating on the Zn plating with good adhesion. However, when the melting point of the third element is high in the structure of Cu-X-Zn, the plating layer of the third element contains Cu and Z.
Since it becomes a barrier layer that inhibits fusion diffusion with n, a large amount of β phase is likely to be generated. Therefore, the wire drawing workability of the wire is hindered.
【0008】Cu−Zn−Xの順にめっき層を積層した
後、加熱拡散させる方法も提案されている。このような
積層めっき層の構成では、第3元素のめっき層がCuと
Znとの融合拡散を阻害することはない。しかし、この
方法ではZn−Xの相が生成するため、この相の延展性
によっては、伸線加工性が著しく阻害される。また、例
えば第3元素としてCoを用いた場合、Coは最密六方
格子を持ち延展性が低いため、伸線加工で削られてしま
う。A method has also been proposed in which a plating layer is laminated in the order of Cu-Zn-X and then heated and diffused. In such a structure of the laminated plating layer, the plating layer of the third element does not hinder the fusion diffusion of Cu and Zn. However, since a Zn-X phase is generated by this method, the wire drawability is significantly impaired depending on the ductility of this phase. Further, for example, when Co is used as the third element, Co has a close-packed hexagonal lattice and has low malleability, and therefore Co is scraped by wire drawing.
【0009】X−Cu−Znの順にめっき層を積層した
後、加熱拡散させる方法も提案されている。このような
積層めっき層の構成では、第3元素のめっき層が単なる
下地層として作用し、黄銅めっきとの十分な合金化が期
待できず、第3元素の添加効果が発現しない。A method has also been proposed in which plated layers are laminated in the order of X-Cu-Zn and then heated and diffused. In such a structure of the laminated plating layer, the plating layer of the third element acts as a mere underlayer, cannot be expected to be sufficiently alloyed with the brass plating, and the effect of adding the third element is not exhibited.
【0010】第3元素としてNiを用い、Cu−Niを
共析めっきした後、Znめっきを施し、加熱拡散処理す
る方法も提案されている。この方法では、Cu−Niの
めっき条件によりNiの添加量を制御する必要がある
が、この制御は困難である。また、高融点のNiの影響
によりβ相が生成しやくなる。しかも、添加されたNi
は、Cu−Znとの融合により希釈されるため、湿潤接
着性を改善するためには添加量を多くする必要がある。
なお、Niは面心立方格子を持ち延展性にも優れている
が、Niを単独でめっきした場合には黄銅めっきほど伸
線加工性が良好ではないため、工業的な生産は困難であ
る。本発明の目的は、伸線加工性を損なわずに、ゴムと
の湿潤接着性が改善されたゴム補強用ワイヤを提供する
ことにある。A method has also been proposed in which Ni is used as the third element, Cu-Ni is subjected to eutectoid plating, and then Zn plating is performed, followed by heat diffusion treatment. In this method, it is necessary to control the amount of Ni added depending on the Cu-Ni plating conditions, but this control is difficult. Further, the β phase is easily generated due to the influence of Ni having a high melting point. Moreover, the added Ni
Is diluted by fusion with Cu-Zn, so it is necessary to increase the addition amount in order to improve the wet adhesion.
Although Ni has a face-centered cubic lattice and is excellent in spreadability, when Ni is plated alone, it is not as good in wire drawing workability as brass plating, so industrial production is difficult. An object of the present invention is to provide a rubber-reinforcing wire having improved wet adhesion with rubber without impairing wire drawing workability.
【0011】[0011]
【課題を解決するための手段と作用】本発明のゴム補強
用ワイヤは、スチールワイヤと、該スチールワイヤの表
面に形成された、銅、亜鉛およびニッケルの合金からな
り、ニッケル組成が表面側で高く内部に向かって低くな
っている被覆層と、該被覆層の表面に形成された、トリ
アジンチオール処理層とを具備したことを特徴とするも
のである。The rubber-reinforcing wire of the present invention comprises a steel wire and an alloy of copper, zinc and nickel formed on the surface of the steel wire, and has a nickel composition on the surface side. It is characterized by comprising a coating layer which is high and is lowered toward the inside, and a triazine thiol-treated layer formed on the surface of the coating layer.
【0012】また、本発明のゴム補強用ワイヤの製造方
法は、スチールワイヤの表面に黄銅層を形成する工程
と、該スチールワイヤの表面にニッケル層を形成する工
程と、該スチールワイヤをトリアジンチオール誘導体を
含有する伸線潤滑剤中でダイスから引き抜いて伸線加工
を施し前記黄銅層およびニッケル層を合金化させた被覆
層及びトリアジンチオール処理層を形成する工程とを具
備したことを特徴とするものである。Further, the method for producing a rubber-reinforcing wire of the present invention comprises the steps of forming a brass layer on the surface of a steel wire, forming a nickel layer on the surface of the steel wire, and adding the triazine thiol to the steel wire. Forming a coating layer and a triazinethiol-treated layer by alloying the brass layer and the nickel layer by drawing from a die in a wire drawing lubricant containing a derivative and subjecting to wire drawing. It is a thing.
【0013】本発明において、ワイヤの材質としては、
強度の点からC含有量が0.70%以上の高炭素鋼が好
ましい。本発明において、ワイヤの表面に黄銅層を形成
する方法は、拡散めっき法すなわちCuめっき層とZn
めっき層とを順次形成して加熱拡散させる方法、または
シアン浴を用いた共析めっき法が挙げられる。ただし、
共析めっき法ではシアンによる公害を防止する必要があ
り、しかもCu含有率の制御が困難であるため、拡散め
っき法を用いることが好ましい。黄銅層中のCu含有率
は63〜67%であることが好ましい。このような組成
の黄銅相は、延展性に優れた面心立方格子組織のα相の
みであり、延展性の悪い体心立方格子組織であるβ相を
含まない。In the present invention, as the material of the wire,
From the viewpoint of strength, a high carbon steel having a C content of 0.70% or more is preferable. In the present invention, the method for forming the brass layer on the surface of the wire is the diffusion plating method, that is, the Cu plating layer and the Zn layer.
Examples include a method of sequentially forming a plating layer and heat diffusion, or a eutectoid plating method using a cyan bath. However,
In the eutectoid plating method, it is necessary to prevent pollution due to cyanide, and it is difficult to control the Cu content. Therefore, it is preferable to use the diffusion plating method. The Cu content in the brass layer is preferably 63 to 67%. The brass phase having such a composition is only the α phase having a face-centered cubic lattice structure excellent in ductility, and does not include the β phase which is a body-centered cubic lattice structure having poor ductility.
【0014】本発明において、黄銅層上にNi層を形成
する方法としては、通常のめっき法が挙げられる。Ni
層の厚さは0.04〜0.20μmであることが好まし
い。この量は、従来のNi量に比べて非常に少量であ
る。また、Niは面心立方格子を有するため延展性に優
れている。したがって、黄銅層上にNi層を形成した段
階において、ワイヤの伸線加工性は黄銅層のみの場合と
同程度に良好である。In the present invention, the method of forming the Ni layer on the brass layer may be a usual plating method. Ni
The layer thickness is preferably 0.04 to 0.20 μm. This amount is much smaller than the conventional Ni amount. In addition, Ni has excellent spreadability because it has a face-centered cubic lattice. Therefore, at the stage of forming the Ni layer on the brass layer, the wire drawing workability of the wire is as good as that of the case of only the brass layer.
【0015】次に、黄銅およびNiの2層のめっき層が
形成されたワイヤをトリアジンチオール誘導体を含有す
る伸線潤滑剤中でダイスから引抜いて伸線加工する。ト
リアジンチオール誘導体としては、下記一般式(1)で
示されるものが挙げられる。Next, the wire on which the two plated layers of brass and Ni are formed is drawn from a die in a wire drawing lubricant containing a triazine thiol derivative and drawn. Examples of the triazine thiol derivative include those represented by the following general formula (1).
【0016】[0016]
【化1】 [Chemical 1]
【0017】式(1)中、Rは−OR’、−SR’、−
NHR’又は−N(R’)2 ;R’はH、アルキル基、
アルケニル基、フェニル基、フェニルアルキル基、アル
キルフェニル基、又はシクロアルキル基であり、Mは
H、Na、Li、K、 1/2Mg、 1/2Ba、 1/2Ca、
脂肪族1級、2級もしくは3級アミン、第4級アンモニ
ウム塩、又はホスホニウム塩である。In the formula (1), R is -OR ', -SR',-.
NHR 'or -N (R') 2 ; R'is H, an alkyl group,
An alkenyl group, a phenyl group, a phenylalkyl group, an alkylphenyl group, or a cycloalkyl group, and M is H, Na, Li, K, 1 / 2Mg, 1 / 2Ba, 1 / 2Ca,
It is an aliphatic primary, secondary, or tertiary amine, a quaternary ammonium salt, or a phosphonium salt.
【0018】トリアジンチオール誘導体を用いてスチー
ルワイヤの表面に処理する方法は湿潤接着性を改善する
のに有効であり、黄銅めっきスチールワイヤやNiめっ
きスチールワイヤのいずれにも適用できる(特開平2−
212524号公報など)。The method of treating the surface of a steel wire with a triazine thiol derivative is effective in improving wet adhesion and can be applied to both brass-plated steel wire and Ni-plated steel wire.
No. 212524, etc.).
【0019】本発明において、伸線加工による減面率
は、90%以上98%未満であることが好ましい。伸線
加工後のワイヤの表面には、黄銅めっき層及びNiめっ
き層が機械的に混合され合金化された被覆層と、トリア
ジンチオール骨格を有するポリマーからなるトリアジン
チオール処理層とが形成される。被覆層中のNiの組成
は、平面的には均一であるが深さ方向では表面ほどNi
が多い。このことから、添加されたNiは部分的な融合
拡散を起こしているものと考えられる。この場合、伸線
加工の度合が増すほど、深さ方向の組成が均質化する傾
向が認められる。なお、Niめっき層が厚い場合には、
2層のめっき層の混合作用が少なく、Niが筋状に分布
するため好ましくない。In the present invention, the area reduction rate due to wire drawing is preferably 90% or more and less than 98%. A coating layer in which a brass plating layer and a Ni plating layer are mechanically mixed and alloyed with each other and a triazinethiol-treated layer made of a polymer having a triazinethiol skeleton are formed on the surface of the wire after wire drawing. The composition of Ni in the coating layer is uniform in the plan view, but the Ni in the depth direction is closer to the surface.
There are many. From this, it is considered that the added Ni causes partial fusion diffusion. In this case, as the degree of wire drawing increases, the composition in the depth direction tends to be homogenized. If the Ni plating layer is thick,
It is not preferable because the mixed action of the two plating layers is small and Ni is distributed in a streak pattern.
【0020】Ni単独ではゴムに対する接着性を示さな
いが、黄銅めっき層及びNiめっき層が合金化された被
覆層はゴムに対する接着性を示す。また、黄銅中には極
めて微量のNiが添加されるだけであるため、黄銅の結
晶相が影響を受けることはない。そして、添加されたN
iは、Cuの硫黄との反応性を抑制する作用があると考
えられる。このため、本発明のワイヤは、湿潤雰囲気下
でも被覆層とゴムとの界面に適度な硫化物が生成し、湿
潤接着性が改善される。Although Ni alone does not exhibit adhesiveness to rubber, the coating layer in which the brass plating layer and the Ni plating layer are alloyed exhibits adhesiveness to rubber. Further, since only a very small amount of Ni is added to brass, the crystal phase of brass is not affected. And added N
It is considered that i has the effect of suppressing the reactivity of Cu with sulfur. Therefore, in the wire of the present invention, an appropriate sulfide is generated at the interface between the coating layer and the rubber even in a wet atmosphere, and the wet adhesion is improved.
【0021】さらに、被覆層中のNiやCuと伸線潤滑
剤中のトリアジンチオール誘導体との反応により形成さ
れた処理層によりゴムとの接着性を改善できる。しか
も、トリアジンチオール処理層を形成した場合には、ゴ
ムに対する接着性を示さないNiの組成がある程度高く
とも湿潤接着性を補うことができる。したがって、銅、
亜鉛及びNiの合金からなる被覆層の組成範囲を広げる
ことができる。Further, the adhesion to rubber can be improved by the treatment layer formed by the reaction of Ni or Cu in the coating layer with the triazine thiol derivative in the wire drawing lubricant. Moreover, when the triazine thiol-treated layer is formed, wet adhesion can be supplemented even if the composition of Ni, which does not exhibit adhesion to rubber, is high to some extent. Therefore, copper,
The composition range of the coating layer made of an alloy of zinc and Ni can be expanded.
【0022】以上のように、NiがCuの反応性を抑制
して過剰の硫化物生成を防止する作用を発現し、トリア
ジンチオール処理層がゴムとの湿潤接着性を改善する作
用を発現するため、本発明のゴム補強用ワイヤは非常に
優れた湿潤接着性を示す。As described above, Ni expresses the action of suppressing the reactivity of Cu and preventing the formation of an excessive sulfide, and the triazine thiol-treated layer exerts the action of improving wet adhesion with rubber. The rubber-reinforcing wire of the present invention exhibits very good wet adhesion.
【0023】[0023]
【実施例】以下、本発明の実施例を説明する。 実施例1〜5 スチールワイヤとして1.70mm径でC含有率0.8
2%の高炭素鋼を用いた。ピロりん酸銅浴にてCuめっ
き層を形成し、硫酸亜鉛浴にてZnめっき層を形成し
た。流動層炉中で熱処理を施して、CuとZnとを合金
化し、黄銅層を形成した。希硫酸中でエッチングして酸
化層を除去した。表1に示すように、この黄銅層に関し
ては、Cu含有率が65%、β相が0%、付着量が4.
0g/kgであった。次に、硫酸ニッケル浴にてNiめ
っき層を形成した。表1に示すように、Niめっき層の
厚みは、0.04〜0.20μmの範囲で変化させた。EXAMPLES Examples of the present invention will be described below. Examples 1 to 5 1.70 mm diameter as steel wire and C content 0.8
2% high carbon steel was used. A Cu plating layer was formed in a copper pyrophosphate bath, and a Zn plating layer was formed in a zinc sulfate bath. Heat treatment was performed in a fluidized bed furnace to alloy Cu and Zn to form a brass layer. The oxide layer was removed by etching in dilute sulfuric acid. As shown in Table 1, regarding this brass layer, the Cu content was 65%, the β phase was 0%, and the adhesion amount was 4.
It was 0 g / kg. Next, a Ni plating layer was formed in a nickel sulfate bath. As shown in Table 1, the thickness of the Ni plating layer was changed in the range of 0.04 to 0.20 μm.
【0024】さらに、各スチールワイヤをトリアジンチ
オール誘導体(前記式(1)においてRが−NHR’、
MがHのもの)を含む伸線潤滑剤中で超硬合金ダイスを
用いて0.30mmまで伸線加工を施し、黄銅とNiと
を機械的に合金化させて被覆層を形成するとともにトリ
アジンチオール処理層を形成した。Further, each steel wire is treated with a triazine thiol derivative (in the formula (1), R is —NHR ′,
(M is H)) and wire-drawing is performed to 0.30 mm using a cemented carbide die to mechanically alloy brass and Ni to form a coating layer and triazine. A thiol-treated layer was formed.
【0025】実施例6 共析めっきにより黄銅層を形成した以外は、実施例4と
同様の方法でスチールワイヤを作製した。Example 6 A steel wire was produced in the same manner as in Example 4 except that the brass layer was formed by eutectoid plating.
【0026】比較例1〜6 伸線加工時に用いた伸線潤滑剤中にトリアジンチオール
誘導体を添加しなかった以外は、それぞれ実施例1〜6
と同様にしてスチールワイヤを作製した。Comparative Examples 1 to 6 Examples 1 to 6 except that the triazine thiol derivative was not added to the wire drawing lubricant used during wire drawing.
A steel wire was prepared in the same manner as in.
【0027】比較例7 Cuめっき層およびZnめっき層を順次積層した後(N
iめっき層は積層せず)、加熱拡散させて黄銅層を形成
した。この黄銅層に関しては、Cu含有率が65%、β
相が0%、付着量が4.0g/kgであった。このスチ
ールワイヤをトリアジンチオール誘導体を含まない伸線
潤滑剤中で伸線加工した。Comparative Example 7 After a Cu plating layer and a Zn plating layer were sequentially laminated (N
The i-plated layer was not laminated) and was diffused by heating to form a brass layer. This brass layer has a Cu content of 65%, β
The phase was 0% and the adhesion amount was 4.0 g / kg. The steel wire was drawn in a drawing lubricant containing no triazine thiol derivative.
【0028】比較例8 Cuめっき層およびZnめっき層を順次積層した後(N
iめっき層は積層せず)、加熱拡散させて黄銅層を形成
した。この黄銅層に関しては、Cu含有率が61%、β
相が30%、付着量が4.0g/kgであった。このス
チールワイヤをトリアジンチオール誘導体を含まない伸
線潤滑剤中で伸線加工した。Comparative Example 8 After a Cu plating layer and a Zn plating layer were sequentially laminated (N
The i-plated layer was not laminated) and was diffused by heating to form a brass layer. Regarding this brass layer, the Cu content is 61%, β
The phase was 30% and the adhesion amount was 4.0 g / kg. The steel wire was drawn in a drawing lubricant containing no triazine thiol derivative.
【0029】比較例9、10 伸線加工時に用いた伸線潤滑剤中にトリアジンチオール
誘導体を添加した以外は、それぞれ比較例7、8と同様
にしてスチールワイヤを作製した。Comparative Examples 9 and 10 Steel wires were produced in the same manner as in Comparative Examples 7 and 8 except that the triazine thiol derivative was added to the wire drawing lubricant used during wire drawing.
【0030】[評価試験]実施例1〜6および比較例1
〜10の各スチールワイヤから1×2の構成のスチール
コードを作製した。これらのスチールコードと工業ゴム
コンパウンドとを150℃で30分間加硫して、コード
−ゴム接着複合材を作製した。[Evaluation Test] Examples 1 to 6 and Comparative Example 1
Steel cords each having a configuration of 1 × 2 were prepared from each of the steel wires Nos. 10 to 10. These steel cords and industrial rubber compounds were vulcanized at 150 ° C. for 30 minutes to prepare cord-rubber adhesive composite materials.
【0031】各スチールワイヤについて、ダイス当たり
で正常に伸線された量を求め、比較例7を100として
伸線加工性を評価した。また、各コード−ゴム接着複合
材について、ASTM−2229−73に従い、1次接
着性および2次湿潤接着性を評価した。1次接着性に関
しては、12.7mm当たりの引抜き力と、コードへの
ゴム付着面積の割合を求めた。2次湿潤接着性に関して
は、1次加硫後の試料を120℃のスチーム中に12時
間保持し、前記と同様に引抜き力と、コードへのゴム付
着面積の割合を求めた。これらの結果を表2に示す。For each steel wire, the amount of normally drawn wire per die was determined, and the wire drawing workability was evaluated by setting Comparative Example 7 to 100. In addition, each cord-rubber adhesive composite material was evaluated for primary adhesiveness and secondary wet adhesiveness according to ASTM-2229-73. Regarding the primary adhesiveness, the ratio of the pulling force per 12.7 mm and the area of rubber adhesion to the cord was determined. Regarding the secondary wet adhesion, the sample after primary vulcanization was held in steam at 120 ° C. for 12 hours, and the pulling force and the ratio of the rubber adhesion area to the cord were determined in the same manner as above. The results are shown in Table 2.
【0032】[0032]
【表1】 [Table 1]
【0033】[0033]
【表2】 [Table 2]
【0034】これらの結果から以下のことがわかる。実
施例1〜6のスチールワイヤの伸線加工性は、Cu組成
が65%の通常の黄銅めっきスチールワイヤ(比較例
7)と比較して90%以内に保たれている。しかも、実
施例1〜6のスチールワイヤは、トリアジンチオール処
理層が形成されていないもの(比較例1〜6)およびN
iめっき層が形成されていないもの(比較例9)と比較
して、1次接着性が同等以上であり、2次接着性が著し
く改善されている。The following can be seen from these results. The wire drawability of the steel wires of Examples 1 to 6 is kept within 90% as compared with the ordinary brass-plated steel wire having a Cu composition of 65% (Comparative Example 7). Moreover, the steel wires of Examples 1 to 6 had no triazine thiol-treated layer (Comparative Examples 1 to 6) and N
The primary adhesiveness is equal to or higher than that of the case where the i-plated layer is not formed (Comparative Example 9), and the secondary adhesiveness is remarkably improved.
【0035】さらに、トリアジンチオール処理層を形成
していない場合にはNiめっき層の厚さが0.2μmと
比較的厚いと十分な1次接着性が得られない(比較例
5)のに対し、トリアジンチオール処理層を形成した場
合にはNiめっき層の厚さが0.2μmであっても十分
な1次接着性が得られている(実施例5)。Further, in the case where the triazine thiol-treated layer is not formed, if the Ni plating layer has a relatively large thickness of 0.2 μm, sufficient primary adhesion cannot be obtained (Comparative Example 5). When the triazine thiol-treated layer was formed, sufficient primary adhesiveness was obtained even when the Ni plating layer had a thickness of 0.2 μm (Example 5).
【0036】[0036]
【発明の効果】以上詳述したように本発明によれば、伸
線加工性を損なわずにゴムとの湿潤接着性が改善された
ゴム補強用ワイヤを提供できる。As described in detail above, according to the present invention, it is possible to provide a rubber-reinforcing wire having improved wet adhesion with rubber without impairing wire drawing workability.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 C08J 5/06 CEQ 7310−4F C23C 10/52 18/52 B D06M 13/358 // B29B 15/08 9350−4F ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location C08J 5/06 CEQ 7310-4F C23C 10/52 18/52 B D06M 13/358 // B29B 15 / 08 9350-4F
Claims (2)
表面に形成された、銅、亜鉛およびニッケルの合金から
なり、ニッケル組成が表面側で高く内部に向かって低く
なっている被覆層と、該被覆層の表面に形成された、ト
リアジンチオール処理層とを具備したことを特徴とする
ゴム補強用ワイヤ。1. A steel wire, a coating layer formed on the surface of the steel wire, comprising an alloy of copper, zinc and nickel, wherein the nickel composition is higher on the surface side and lower toward the inside, and the coating. A rubber-reinforcing wire comprising a triazine thiol-treated layer formed on the surface of the layer.
る工程と、該スチールワイヤの表面にニッケル層を形成
する工程と、該スチールワイヤをトリアジンチオール誘
導体を含有する伸線潤滑剤中でダイスから引き抜いて伸
線加工を施し前記黄銅層およびニッケル層を合金化させ
た被覆層及びトリアジンチオール処理層を形成する工程
とを具備したことを特徴とするゴム補強用ワイヤの製造
方法。2. A step of forming a brass layer on the surface of a steel wire, a step of forming a nickel layer on the surface of the steel wire, and the step of forming the steel wire from a die in a wire drawing lubricant containing a triazine thiol derivative. And a wire-drawing process to form a coating layer and a triazine thiol-treated layer that are alloyed with the brass layer and the nickel layer, and a method for producing a rubber-reinforcing wire.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP5258053A JP2863691B2 (en) | 1993-10-15 | 1993-10-15 | Rubber reinforcing wire and method of manufacturing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5258053A JP2863691B2 (en) | 1993-10-15 | 1993-10-15 | Rubber reinforcing wire and method of manufacturing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH07119057A true JPH07119057A (en) | 1995-05-09 |
JP2863691B2 JP2863691B2 (en) | 1999-03-03 |
Family
ID=17314889
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---|---|---|---|
JP5258053A Expired - Fee Related JP2863691B2 (en) | 1993-10-15 | 1993-10-15 | Rubber reinforcing wire and method of manufacturing the same |
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JP (1) | JP2863691B2 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997023311A1 (en) * | 1995-12-21 | 1997-07-03 | Bridgestone Metalpha Corporation | Steel wire for reinforcement of rubber articles, method of manufacturing the same, and steel cord using the same |
JPH09188982A (en) * | 1996-01-10 | 1997-07-22 | Tokyo Seiko Co Ltd | Production of element wire for steel cord |
JP2007131919A (en) * | 2005-11-10 | 2007-05-31 | Iwate Univ | Method for producing electroforming die |
JP2008036678A (en) * | 2006-08-08 | 2008-02-21 | Bridgestone Corp | Manufacturing method of brass-plated steel wire, steel cord and tire |
JP2011219836A (en) * | 2010-04-13 | 2011-11-04 | Nippon Steel Corp | Extra fine plated steel wire having excellent adhesiveness to rubber |
-
1993
- 1993-10-15 JP JP5258053A patent/JP2863691B2/en not_active Expired - Fee Related
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997023311A1 (en) * | 1995-12-21 | 1997-07-03 | Bridgestone Metalpha Corporation | Steel wire for reinforcement of rubber articles, method of manufacturing the same, and steel cord using the same |
US6203932B1 (en) * | 1995-12-21 | 2001-03-20 | Bridgestone Corporation | Steel wire for reinforcement of rubber articles, method of manufacturing the same, and steel cord using the same |
JPH09188982A (en) * | 1996-01-10 | 1997-07-22 | Tokyo Seiko Co Ltd | Production of element wire for steel cord |
JP2007131919A (en) * | 2005-11-10 | 2007-05-31 | Iwate Univ | Method for producing electroforming die |
JP2008036678A (en) * | 2006-08-08 | 2008-02-21 | Bridgestone Corp | Manufacturing method of brass-plated steel wire, steel cord and tire |
JP2011219836A (en) * | 2010-04-13 | 2011-11-04 | Nippon Steel Corp | Extra fine plated steel wire having excellent adhesiveness to rubber |
Also Published As
Publication number | Publication date |
---|---|
JP2863691B2 (en) | 1999-03-03 |
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