CN100467713C - 橡胶增强用钢丝帘线、橡胶增强用钢丝帘线的制造方法及充气轮胎 - Google Patents
橡胶增强用钢丝帘线、橡胶增强用钢丝帘线的制造方法及充气轮胎 Download PDFInfo
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Abstract
公开了一种橡胶增强用钢丝帘线、其制法和使用该钢丝帘线的充气轮胎。所述橡胶增强用钢丝帘线具有实施镀覆含铜的金属、而且在表面具有含钴化合物的油层(2)的钢丝(1),其制法包括:在实施镀覆含铜的金属的钢丝或者钢丝帘线上涂布含有钴化合物的油的涂布过程,以及将钢丝绞合的绞合过程。
Description
发明领域
本发明涉及在实施镀覆含铜的金属的钢丝表面涂布的油中含有钴化合物、既维持和橡胶的粘合、又防止橡胶老化、进而提高轮胎的耐久性并且降低成本的橡胶增强用钢丝帘线、其制造方法和充气轮胎.
背景技术
在轮胎等橡胶制品的增强中使用的钢丝帘线,为了形成和橡胶的复合体,需要和橡胶的良好粘合性.因此,为了得到钢丝帘线和橡胶的良好粘合性,已公开了许多技术.
例如,在特开平6-49786号公报中公开了,在构成钢丝帘线的钢丝上被覆润滑油,与此同时,在各钢丝的空隙间存在吸水性聚合物的技术.
另外,在特开平1-153783号公报中公开了,在钢丝帘线上涂布以有机羧酸钴·硼金属皂为主成分的反应混合物的方法.
此外,在特开平4-11637号公报中公开了,在橡胶成分中含有钴金属盐、硫和双马来酰亚胺化合物的同时,在钢丝帘线的表面设置钴镀层的技术.
但是,按照上述的技术,在良好地担保橡胶和钢丝帘线的粘合性的同时,提供使用该钢丝帘线的经济的轮胎是困难的.
于是提出了在钢丝帘线的表面实施镀黄铜,另一方面,在橡胶组合物中,作为粘合助剂添加钴金属盐等,使两者粘合.
但是,实施镀黄铜的钢丝帘线在运送中或轮胎制造过程中,存在钢丝帘线表面生锈,或由于镀层表面的氧化变质,降低和橡胶的粘合性等的问题.
另外,如果在橡胶中配合钴化合物,在未加硫状态,橡胶的分子链往往断开,还存在配合成本非常高的问题.
发明内容
本发明的目的在于,在提供和橡胶的粘合性提高的钢丝帘线的同时,提供该钢丝帘线的制造方法,而且提供使用该钢丝帘线的经济的轮胎.
本发明的橡胶增强用钢丝帘线,是具有实施镀覆了含铜的金属、而且在表面涂布含有钴化合物的油的钢丝的橡胶增强用钢丝帘线.
另外,本发明的上述橡胶增强用钢丝帘线,是上述油为矿物油的橡胶增强用钢丝帘线.
此外,本发明的橡胶增强用钢丝帘线的制造方法包括:在实施镀覆含铜的金属的钢丝上涂布含有钴化合物的油的涂布过程,以及将上述钢丝绞合的绞合过程。
另外,本发明的充气轮胎是以上述橡胶增强用钢丝帘线作为增强元件使用的充气轮胎.
本发明的上述和其他目的、特征、方面及优点,通过阅读本发明的以下的详细描述和附图,会更清楚.
附图说明
图1是本发明的钢丝的剖面图.
图2是本发明的钢丝帘线的剖面图.
图3是说明制造本发明的钢丝帘线的过程的图.
最佳实施方式
有关本发明的橡胶增强用钢丝帘线,以实施镀覆含铜的金属、而且在表面涂布含有钴化合物的油的钢丝作为构成要素.再者,作为镀覆含铜的金属,最好是镀铜和锌的黄铜,但不限于此.作为其他的金属,也考虑镍、钴等.本发明人基于在实施镀覆含铜的金属的钢丝表面设置含有钴化合物的油层,将该钢丝绞合而制成钢丝帘线,由此在能够良好地担保钢丝帘线和橡胶的粘合特性的同时,也能够抑制高价的钴化合物的使用量的新认识,完成了本发明.
作为钴化合物,能适合使用硬脂酸钴、环烷酸钴、油酸钴、亚油酸钴、香茅酸钴等有机酸钴.因为有机酸钴使油和橡胶的亲和性良好,而且能够良好地担保钢丝帘线和橡胶的粘合性。
再者,作为橡胶,可以使用二烯系橡胶,具体地说,可以使用天然橡胶、聚异戊二烯橡胶、聚丁二烯橡胶、苯乙烯-丁二烯共聚橡胶等.另外,根据需要,也可以添加碳黑、二氧化硅、碳酸钙、操作油、硫、加硫促进剂、老化防止剂等配合剂.
另外,作为含有钴化合物的介质的油,可以使用矿物油.因为矿物油和橡胶的亲和性良好。作为矿物油,能适合使用环烷系操作油、芳香族系操作油等.
油中的钴化合物的浓度最好是0.3~10质量%.因为钴化合物的浓度如果低于0.3质量%,钢丝帘线和橡胶的粘合强度变弱,另一方面,钴化合物的浓度如果超过10质量%,伴随钴化合物的含量增加,制造成本上升.
图1是说明构成有关本发明的橡胶增强用钢丝帘线的钢丝剖面图.在钢丝1的外周面设置油层2.
图2是说明有关本发明的橡胶增强用钢丝帘线的剖面图.将3根钢丝1绞合构成橡胶增强用钢丝帘线10.再者,钢丝1的绞合的根数不限于3根。
有关本发明的橡胶增强用钢丝帘线的制造方法包括:在实施镀覆含铜的金属的钢丝上涂布含有钴化合物的油的涂布过程,以及将上述钢丝绞合的绞合过程.
在涂布过程中,至少在1根钢丝上涂布含有钴化合物的油.即,在绞合钢丝帘线之前,为了提高绞合作业性,通常,在至少1根钢丝上涂布油.这里,将钴化合物加到油中,然后在钢丝上涂布含有该钴化合物的油.但也可以在绞合钢丝的绞合过程后涂布油.
图3是说明制造有关本发明的橡胶增强用钢丝帘线的过程的图.本发明中的钢丝帘线称为将1根以上的钢丝绞合的钢丝帘线.设置3个卷出辊4,在各个卷出辊上准备好钢丝.在从卷出辊4至转筒5的通过生产线A中,在至少1根钢丝上涂布含有钴化合物的油。在转筒5中,3根钢丝被绞合,制造钢丝帘线。此后,钢丝帘线经过转筒6,通过转筒7、转筒8,卷取在卷取转筒9上.
作为在钢丝上涂布含有钴化合物的油的方法,可以采用浸涂、喷涂、刷涂等.但是,也可以在绞合钢丝后涂布油.
另外,有关本发明的充气轮胎是以本发明的橡胶增强用钢丝帘线用作增强元件的轮胎.本发明的橡胶增强用钢丝帘线,无论在使用增强元件的哪个部分都能够使用,例如,能够在胎体、胶带层、带束层等中使用。
实施例
(实施例1)
在拉伸成直径0.27mm的钢丝上,在实施铜为63质量%、锌为37质量%的镀黄铜,喷涂含有0.6质量%环烷酸钴的矿物油后,通过将3根钢丝绞合制成钢丝帘线.作为矿物油使用サンオイル(株)サンセン310.
作为钢丝帘线的被覆橡胶,使用由表1所示的配合物构成的橡胶组合物.
表1
配合物 | 质量份数 |
天然橡胶 | 100 |
碳黑(HAF) | 60 |
锌白 | 8 |
老化防止剂<sup>*1</sup> | 2 |
矿物油 | 2 |
加硫促进剂<sup>*2</sup> | 1 |
硫 | 5 |
环烷酸钴 | 0 |
*1 2,2,4-三甲基-1,2-二氢喹啉聚合物
*2 DZ:N,N-二环己基-2-苯并噻唑次磺酰胺
然后,用上述的橡胶组合物被覆钢丝帘线,在165℃的温度条件下,进行18分钟加硫,制成湿热粘合用试样.接着,在80℃、相对湿度95%的烘箱中,将制成的湿热粘合用试样放置120小时后,进行剥离试验.剥离试验,也在制成的湿热粘合用试样放置0小时后进行.
基于下述,作为小数点的数字表示剥离试验的评价标准.
5 用橡胶完全覆盖,看不到钢丝帘线的镀覆面.
4 看到3~6处钢丝帘线的镀覆面.
3 看到13处钢丝帘线的镀覆面.
2 看到13处以上的钢丝帘线的镀覆面,但作为全体,用橡胶覆盖60%以上.
1 钢丝帘线用橡胶覆盖的部分不到30%.
实施例1的剥离试验的结果示于表3中.
(实施例2)
除了在钢丝帘线上喷涂含有1.0质量%的环烷酸钴的矿物油以外,实施例2使用和实施例1完全相同的条件.实施例2的剥离试验的结果示于表3中.
(比较例1)
除了在钢丝帘线上喷涂不含环烷酸钴的矿物油,以及作为和钢丝帘线粘合的橡胶组合物,使用由下述表2所示的配合物构成的橡胶以外,比较例1使用完全和实施例1相同的条件.比较例1的剥离试验的结果示于表3中。
表2
配合物 | 质量份数 |
天然橡胶 | 100 |
碳黑(HAF) | 60 |
锌白 | 8 |
老化防止剂<sup>*1</sup> | 2 |
矿物油 | 2 |
加硫促进剂<sup>*2</sup> | 1 |
硫 | 5 |
环烷酸钴 | 1 |
*1 2,2,4-三甲基-1,2-二氢喹啉聚合物
*2 DZ:N,N’-二环己基-2-苯并噻唑次磺酰胺
接着,将比较例1中制成的钢丝帘线埋设在表1所示的橡胶中,制成带束层.同样,用表1所示的橡胶组合物被覆在实施例2中制成的钢丝帘线,制成带束层.
然后使用各个带束层制轮胎,评价轮胎的高速耐久性.轮胎的制造条件如下所示.
胎体:1670分特/2 聚酯(50经线(ends))
1枚相对圆周方向的帘线角度 90°
带束层:钢丝帘线 2枚(40经线)
相对圆周方向的帘线角度 +20°,-20°
轮胎尺寸 195/65R15
再者,经线意味着每5厘米帘布层的钢丝帘线的埋入根数.
高速耐久性试验,在下述所示的条件进行。即,使用转筒试验机,环境温度调整至25±5℃,将试制的轮胎安装在轮圈上,在内压280kPa、载荷492kgf下,以行走速度170km/h,每隔10分钟使行走速度每10km/h的阶段地上升,行走至发生故障为止.而且,以比较例1作为100的相对指数表示至发生故障时的行走距离.相对指数越大,高速耐久性越优良.实验结果示于表3中.
表3
根据剥离试验的结果可知,本发明的橡胶增强用钢丝帘线和橡胶的粘合性良好.另外,根据高速耐久性试验的结果可知,使用本发明的橡胶增强用钢丝帘线的充气轮胎,耐久性优良。再者,在表3中,对于绞合的钢丝帘线来说,所谓1×3×0.27意味着将直径0.27mm的钢丝绞合3根形成的钢丝帘线.
再者,这里公开的实施方式和实施例,应该认为在所有的方面都是例示,不是限制.本发明的范围包括上述未说明的、而权利要求的范围表示的、和权利要求的范围均等的意义及范围内的全部变更。
本发明的钢丝帘线,采用称为实施镀覆含铜的金属而且在表面涂布含有钴化合物的油的钢丝进行绞合而制成的独特的构成,利用这种构成,改进了和橡胶的粘合性.另外,使用本发明的钢丝帘线的充气轮胎是经济且耐久性优良的轮胎.
以上所示的实施方式或实施例,应该认为在所有的方面都是例示,不是限制.本发明的范围包括不是以上的实施方式或实施例、根据权利要求的范围表示的、和权利要求的范围均等的意义及范围内的全部修正或变更.
Claims (14)
1.橡胶增强用钢丝帘线,具有实施镀覆含铜的金属、而且在表面涂布含有钴化合物的油的钢丝,所述油中的钴化合物的浓度为0.3-10质量%,并且当涂布所述油时,所述镀覆了含铜的金属的钢丝没有被拉伸。
2.根据权利要求1所述的橡胶增强用钢丝帘线,其中,上述油是矿物油。
3.权利要求1的橡胶增强用钢丝帘线的制造方法,包括:
在实施镀覆含铜的金属的钢丝上涂布含有钴化合物的油的涂布过程,所述油中的钴化合物的浓度为0.3-10质量%,以及
将上述钢丝绞合的绞合过程。
4.使用权利要求1所述的橡胶增强用钢丝帘线作为增强元件的充气轮胎。
5.权利要求4的充气轮胎,其中所述油是矿物油。
6.权利要求1的橡胶增强用钢丝帘线,其中所述钴化合物选自硬脂酸钴、环烷酸钴、油酸钴、亚油酸钴和香茅酸钴。
7.权利要求1的橡胶增强用钢丝帘线,其中所述钴化合物是环烷酸钴。
8.权利要求6的橡胶增强用钢丝帘线,其中所述油是矿物油。
9.权利要求4的充气轮胎,其中所述钴化合物选自硬脂酸钴、环烷酸钴、油酸钴、亚油酸钴和香茅酸钴。
10.权利要求4的充气轮胎,其中所述钴化合物是环烷酸钴。
11.权利要求3的方法,其中所述油是矿物油。
12.权利要求3的方法,其中所述钴化合物选自硬脂酸钴、环烷酸钴、油酸钴、亚油酸钴和香茅酸钴。
13.权利要求3的方法,其中所述钴化合物是环烷酸钴。
14.橡胶增强用钢丝帘线,具有实施镀覆含铜的金属,而且在表面涂布含有钴化合物的油的钢丝,所述油中的钴化合物的浓度为0.3-10质量%。
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JP166262/2001 | 2001-06-01 | ||
JP2001166262A JP4015379B2 (ja) | 2001-06-01 | 2001-06-01 | ゴム補強用スチールコード、ゴム補強用スチールコードの製造方法、および、空気入りタイヤ |
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CN100467713C true CN100467713C (zh) | 2009-03-11 |
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US (1) | US7152644B2 (zh) |
EP (1) | EP1262592B1 (zh) |
JP (1) | JP4015379B2 (zh) |
CN (1) | CN100467713C (zh) |
DE (1) | DE60225624T2 (zh) |
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US6896932B2 (en) * | 2001-03-16 | 2005-05-24 | The Goodyear Tire & Rubber Company | Method of treating metallic cord |
JP5037947B2 (ja) | 2004-12-02 | 2012-10-03 | 株式会社ブリヂストン | ゴム組成物と黄銅製又は黄銅メッキが施された被着物との加硫接着方法、ゴム物品用補強材、ゴム−補強材複合体及び空気入りタイヤ |
US7598308B2 (en) * | 2005-03-30 | 2009-10-06 | The Gates Corporation | Metal—elastomer compound |
JP5094319B2 (ja) * | 2007-10-09 | 2012-12-12 | 株式会社ブリヂストン | ゴム物品補強用スチールワイヤ及びその製造方法、スチールコード、ゴム複合体並びに空気入りタイヤ |
JP5415703B2 (ja) * | 2008-03-10 | 2014-02-12 | 株式会社ブリヂストン | スチールコード−ゴム複合体 |
JP5452875B2 (ja) * | 2008-03-10 | 2014-03-26 | 株式会社ブリヂストン | スチールコード−ゴム複合体 |
PT2516729E (pt) | 2009-12-23 | 2015-11-03 | Bekaert Sa Nv | Um fio de latão revestido com um gradiante de zinco no revestimento e o seu método de fabrico |
JP5995793B2 (ja) | 2013-06-26 | 2016-09-21 | 東京製綱株式会社 | ストリップ状スチールコード |
US10940718B2 (en) * | 2017-04-19 | 2021-03-09 | Sumitomo Rubber Industries, Ltd. | Composite and pneumatic tire |
CN113215843A (zh) * | 2021-05-06 | 2021-08-06 | 朱淑粉 | 一种钢绞线生产制造绞合加工机械及绞合加工方法 |
CN114151486A (zh) * | 2021-11-24 | 2022-03-08 | 重庆长安汽车股份有限公司 | 一种橡胶衬套及汽车悬架 |
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- 2001-06-01 JP JP2001166262A patent/JP4015379B2/ja not_active Expired - Lifetime
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2002
- 2002-05-23 DE DE60225624T patent/DE60225624T2/de not_active Expired - Lifetime
- 2002-05-23 EP EP02011361A patent/EP1262592B1/en not_active Expired - Fee Related
- 2002-05-31 CN CN02128626.4A patent/CN100467713C/zh not_active Expired - Fee Related
- 2002-05-31 US US10/157,995 patent/US7152644B2/en not_active Expired - Fee Related
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US3846160A (en) * | 1972-05-25 | 1974-11-05 | Yokohama Rubber Co Ltd | Process for enhancing the adhesion between steel cord and a rubber compound |
US5221559A (en) * | 1989-02-17 | 1993-06-22 | Compagnie Generale Des Etablissements Michelin-Michelin & Cie | Method of treating a metallic reinforcement so as to favor its adherence to a rubber base composition and of producing an article with said reinforcements; reinforcements and articles obtained by these |
US5118367A (en) * | 1989-09-25 | 1992-06-02 | The Goodyear Tire & Rubber Company | Process for treating a brass-plated steel wire |
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CN1392308A (zh) | 2003-01-22 |
DE60225624T2 (de) | 2009-04-23 |
US7152644B2 (en) | 2006-12-26 |
US20020189735A1 (en) | 2002-12-19 |
DE60225624D1 (de) | 2008-04-30 |
EP1262592A2 (en) | 2002-12-04 |
EP1262592B1 (en) | 2008-03-19 |
EP1262592A3 (en) | 2004-06-16 |
JP2002363874A (ja) | 2002-12-18 |
JP4015379B2 (ja) | 2007-11-28 |
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