CN107428202B - 充气子午线轮胎 - Google Patents
充气子午线轮胎 Download PDFInfo
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- CN107428202B CN107428202B CN201680011470.5A CN201680011470A CN107428202B CN 107428202 B CN107428202 B CN 107428202B CN 201680011470 A CN201680011470 A CN 201680011470A CN 107428202 B CN107428202 B CN 107428202B
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Classifications
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- B60C2009/2214—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel the plies being arranged with all cords disposed along the circumference of the tyre characterised by the materials of the zero degree ply cords
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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Abstract
本发明的目的在于，提供一种兼顾轻型化和高速耐久性的充气子午线轮胎。素数充气子午线轮胎的特征在于具有带束增强层(7)和胎面橡胶(9)，带束增强层(7)由将一根芳香族聚酰胺的纤维帘线以及一根脂肪族聚酰胺的纤维帘线捻合在一起的复合纤维帘线(8)构成，复合纤维帘线(8)的总细度为1800～3200dtex，施加2.0cN/dtex的载荷时的伸长率为3.0～4.0％，构成胎面橡胶(9)的橡胶组合物通过在二烯类橡胶100重量份中配合氮吸附比表面积为100m2/g以上的二氧化硅10～110重量份而成，60℃的损耗柔量为45Pa‑1以下。
Description
技术领域
本发明涉及一种充气子午线轮胎，更详细而言涉及一种在谋求轻型化的同时，将高速耐久性提高至以往水平以上的充气子午线轮胎。
背景技术
以往，为了提高充气子午线轮胎的高速耐久性或降低负载噪声，有时通过在带束层的外周侧设置在轮胎周向卷缠有机纤维帘线的带束增强层，赋予对于带束层的环箍效果。作为有机纤维帘线，提出使用由芳纶纤维帘线以及尼龙纤维帘线构成的三根捻合的复合纤维帘线等(例如参照专利文献1)。
近年来，为了提高充气子午线轮胎的燃料效率性能，要求加氢轮胎重量。当为了使轮胎轻型化而将构成带束增强层的三根捻合的复合纤维帘线变更为两根捻合的复合纤维帘线时，还期待减少跑气并减少中频区域的节点噪声的效果。但是，当通过两根捻合的复合纤维帘线来构成带束增强层时，存在对带束层的环箍效果变弱且高速耐久性降低的问题。因此，难以通过由两根捻合的复合纤维帘线构成的带束增强层来兼顾轮胎的轻型化和高速耐久性。
现有技术文献
专利文献
专利文献1：日本特开2011-68275号公报
发明内容
发明要解决的问题
本发明的目的在于提供一种在谋求轻型化的同时，将高速耐久性提高至以往水平以上的充气子午线轮胎。
技术方案
达成所述目的的本发明的充气子午线轮胎在一对胎圈之间装架有胎体层，在胎面部的所述胎体层的外周侧具有带束层，在该带束层的外周侧具有带束增强层以及胎面橡胶，其特征在于，所述带束增强层由将一根芳香族聚酰胺的纤维帘线以及一根脂肪族聚酰胺的纤维帘线捻合在一起的复合纤维帘线构成，该复合纤维帘线的总细度为1800～3200dtex，施加2.0cN/dtex的载荷时的伸长率为3.0～4.0％，并且，构成所述胎面橡胶的橡胶组合物通过在二烯类橡胶100重量份中配合氮吸附比表面积为100m2/g以上的二氧化硅10～110重量份而成，该橡胶组合物的60℃的损耗柔量为45Pa-1以下。
有益效果
本发明的充气子午线轮胎通过芳香族聚酰胺纤维以及脂肪族聚酰胺纤维帘线的两根捻合的复合纤维帘线来构成带束增强层，将其总细度设为1800～3200dtex，将2.0cN/dtex负载时的伸长率设为3.0～4.0％，并且，胎面橡胶用橡胶组合物通过在二烯类橡胶100重量份中配合氮吸附比表面积为100m2/g以上的二氧化硅10～110重量份而成，将60℃的损耗柔量设为45Pa-1以下，因此，能够在使充气子午线轮胎轻型化的同时，将高速耐久性提高至以往水平以上。
作为构成所述胎面橡胶的橡胶组合物，在所述二烯类橡胶100重量％中含有苯乙烯单元含量为30～45重量％、乙烯基单元含量为30～50重量％的末端改性溶聚丁苯橡胶50～90重量％，并将该橡胶组合物的100℃的100％变形时的拉伸应力设为2.0MPa以上为好。
附图说明
图1是表示本发明的充气子午线轮胎的实施方式的一例的轮胎子午线方向的剖面图。
具体实施方式
以下，参照附图说明本发明的构成。
在图1中，本发明的充气子午线轮胎包含胎面部1、侧壁部2以及胎圈部3，在左右一对胎圈5、5之间装架胎体层4a、4b，并且，在胎面部1的胎体层4a、4b的外周侧配置在层间使帘线方向交叉的至少两层带束层6a、6b。在该带束层6a、6b的外周侧配置通过相对于轮胎周向以0～5°的角度螺旋状地卷绕复合纤维帘线8而构成的带束增强层7。此外，在胎面部1的带束层6a、6b以及带束增强层7的外周侧配置胎面橡胶9。胎面橡胶9由胎面用橡胶组合物构成。
在本发明的充气子午线轮胎中，由将一根芳香族聚酰胺的纤维帘线以及一根脂肪族聚酰胺的纤维帘线捻合在一起的两根捻合的纤维帘线来形成构成带束增强层7的复合纤维帘线8。通过由两根捻合的复合纤维帘线来构成带束增强层7，与使用三根捻合的复合纤维帘线时相比，能够减轻轮胎重量。而且，能够减少中频的节点噪声。
作为芳香族聚酰胺的纤维帘线，可以使用通常用于充气子午线轮胎的芳香族聚酰胺纤维帘线，可以举例示出芳纶纤维帘线。
作为脂肪族聚酰胺的纤维帘线，可以使用通常用于充气子午线轮胎的脂肪族聚酰胺纤维帘线，可以举例示出例如尼龙66纤维帘线、尼龙6纤维帘线、尼龙6/66纤维帘线、尼龙610纤维帘线、尼龙612纤维帘线、尼龙46纤维帘线等。其中优选尼龙66纤维帘线、尼龙46纤维帘线等。
构成带束增强层7的复合纤维帘线8的总细度为1800～3200dtex，优选为2000～2500dtex。若复合纤维帘线8的总细度小于1800dtex，则帘线强度不足，高速耐久性不足。此外，当复合纤维帘线8的总细度超过3200dtex时，轮胎重量变重。
此外，对复合纤维帘线8施加2.0cN/dtex的载荷时的伸长率为3.0～4.0％，优选为3.2～3.8％。当复合纤维帘线8的2.0cN/dtex负载时的伸长率小于3.0％时，复合纤维帘线的耐疲劳性不足。当2.0cN/dtex负载时的伸长率超过4.0％时，不能得到减少中频的节点噪声的效果。在本说明书中，复合纤维帘线的2.0cN/dtex负载时的伸长率是从充气子午线轮胎提取复合纤维帘线并依据JIS L1017进行测定的。此外，复合纤维帘线的2.0cN/dtex负载时的伸长率能够通过总细度、捻度、纤维帘线的表面处理工序中的张力等进行调整。
在本发明的充气子午线轮胎中，构成胎面橡胶的橡胶组合物(以下，有时称为“胎面用橡胶组合物”)通过在二烯类橡胶100重量份中配合氮吸附比表面积为100m2/g以上的二氧化硅10～110重量份而成，该橡胶组合物的60℃的损耗柔量需在45Pa-1以下。
胎面用橡胶组合物由二烯类橡胶构成其橡胶成分。作为二烯类橡胶，可以举例示出天然橡胶、异戊二烯橡胶、丁二烯橡胶、丁苯橡胶、丙烯腈丁二烯橡胶、丁基橡胶、氯丁橡胶等。这些二烯类橡胶可以单独或者作为任意混合来使用。
在胎面用橡胶组合物中，作为优选的二烯类橡胶，可以列举出丁苯橡胶、丁二烯橡胶、天然橡胶等。其中优选溶聚丁苯橡胶，特别优选苯乙烯单元含量为30～45重量％、乙烯基单元含量为30～50重量％的末端改性溶聚丁苯橡胶。通过含有末端改性溶聚丁苯橡胶，提高与二氧化硅的亲和性，改善二氧化硅相对于二烯类橡胶的分散性。
末端改性溶聚丁苯橡胶的苯乙烯单元含量优选为30～45重量％，更优选为35～45重量％。当苯乙烯单元含量小于30重量％时，不能充分得到提高橡胶组合物的刚性以及强度的效果。当苯乙烯单元含量超过45重量％时，玻化温度(Tg)上升，粘弹性特性的平衡变差，难以得到降低发热性的效果。需要说明的是，丁苯橡胶的苯乙烯单元含量是通过红外光谱分析(汉普顿法)进行测定的。
此外，末端改性溶聚丁苯橡胶的乙烯基单元含量优选为30～50重量％，更优选为30～40重量％。当乙烯基单元含量小于30重量％时，丁苯橡胶的Tg变低，作为湿地性能的指标的0℃的动态粘弹性特性的损耗角正切(tanδ)降低。当乙烯基单元含量超过50重量％时，玻化温度(Tg)上升，作为低滚动性能的指标的60℃的tanδ变大，低滚动性能恶化。需要说明的是，丁苯橡胶的乙烯基单元含量是通过红外光谱分析(汉普顿法)进行测定的。
末端改性溶聚丁苯橡胶的含量在二烯类橡胶100重量％中优选为50～90重量％，更优选为60～85重量％，进一步优选为65～80重量％。当末端改性溶聚丁苯橡胶的含量小于二烯类橡胶中的50重量％时，未必能够充分得到与二氧化硅的亲和性。
胎面用橡胶组合物通过配合二氧化硅来减小其发热性并抑制行驶时变为高温。由此，能够提高高速耐久性。二氧化硅的配合量是相对于二烯类橡胶100重量为10～110重量份，优选为50～100重量份，更优选为60～90重量份。当二氧化硅的配合量小于10重量份时，橡胶组合物的硬度大大降低并且胎面部的橡胶变得更容易移动，因此，不能充分得到抑制发热性的效果。此外，当二氧化硅的配合量超过110重量份时，60℃的柔量上升，高速耐久性反而降低。
本发明中使用的二氧化硅的氮吸附比表面积N2SA为100m2/g以上，优选为100～250m2/g，更优选为150～250m2/g。通过将N2SA设为100m2/g以上，能够使橡胶组合物的硬度上升并抑制胎面部的橡胶的移动。二氧化硅的N2SA是依据JIS K6217-2进行测定的。
作为二氧化硅的种类，只要是通常用于充气子午线轮胎的二氧化硅即可，可以使用湿式法二氧化硅、干式法二氧化硅或对这些进行表面处理后的二氧化硅等。
在胎面用橡胶组合物中，在配合二氧化硅的同时，配合硅烷偶联剂，提高二氧化硅的分散性并使交联密度上升，并且硬度上升，由此，能够进一步减小发热性。关于硅烷偶联剂，相对于二氧化硅配合量，优选配合5～15重量％，更优选配合5～10重量％为好。在硅烷偶联剂的配合量小于二氧化硅重量的5重量％的情况下，不能充分得到提高二氧化硅的分散性的效果。此外，当硅烷偶联剂超过15重量％时，硅烷偶联剂彼此聚合，不能得到所期望的效果。此外，在制备橡胶组合物时，在滚筒机(roll)的滞留变多。
作为硅烷偶联剂，并不受特别限制，但是，优选含硫硅烷偶联剂，可以举例示出例如双-(3-三乙氧基甲硅烷基丙基)四硫化物、双(3-三乙氧基甲硅烷基丙基)二硫化物、3-三甲氧基甲硅烷基丙基苯并噻唑四硫化物、γ-巯丙基三乙氧基硅烷、3-辛酰基硫代丙基三乙氧基硅烷等。
在本发明中，胎面用橡胶组合物的60℃的损耗柔量需在45Pa-1以下。通过将60℃的损耗柔量设为45Pa-1以下，能够减小发热性并改善高速耐久性。60℃的损耗柔量优选为20～45Pa-1，更优选为25～40Pa-1。胎面用橡胶组合物的损耗柔量能够通过二氧化硅的配合量等进行调整。在本说明书中，损耗柔量LC通过下述通式(1)求得。
LC＝E”/(E＊)2 (1)
在算式(1)中，LC为损耗柔量[单位Pa-1]，E”为损耗弹性柔量[MPa]，E＊为复数弹性柔量[MPa]。
在本说明书中，胎面用橡胶组合物的复数弹性柔量E＊以及损耗弹性柔量E”是依据JIS K6394的规定，使用粘弹性谱仪(东洋精机制作所公司制)，在初始应变为10％、振幅为±2％、频率为20Hz、温度为60℃的条件下进行测定的。
胎面用橡胶组合物的100℃的100％变形时的拉伸应力优选为2.0MPa以上，更优选为2.0～3.0MPa。通过将100℃的100％变形时的拉伸应力设为2.0MPa以上，能够抑制胎面用橡胶组合物的反复变形并减小发热性。由此，能够进一步提高充气子午线轮胎的高速耐久性。在本说明书中，100℃的100％变形时的拉伸应力是依据JIS K6251，使用三号哑铃状试片，在100℃进行拉伸试验，测定100％变形时的拉伸应力而得到的。
在本发明中，可以在胎面用橡胶组合物中添加所述以外的其他配合剂。作为其他配合剂，可以举例示出二氧化硅以外的其他增强填充剂、硫化或交联剂、硫化促进剂、抗老化剂、液态聚合物、热固化性树脂、热可塑性树脂等一般用于充气轮胎的各种配合剂。只要不违反本发明的目的，这些配合剂的配合量可以采用以往一般的配合量。此外，作为混炼机，可以使用通常的橡胶用混炼机械，例如，班伯里密炼机、混碾机(kneader)、滚筒机等。
作为其他增强填充剂，可以举例示出例如炭黑、黏土、云母、滑石、碳酸钙、氢氧化铝、氧化铝、氧化钛等。其中优选炭黑。
以下，通过实例进一步说明本发明，但本发明的范围不限于这些实例。实例
以表2所示的配合剂为通用配合，使用1.7L的密闭式班伯里密炼机，对由表1所示的配合构成的胎面用橡胶组合物(实例1～3、比较例1～4)中除硫磺以及硫化促进剂以外的成分进行混炼，经过规定时间后，从密炼机排出并进行室温冷却。将其投入1.7L的密闭式班伯里密炼机，加入硫磺以及硫化促进剂并进行混合，由此制备胎面用橡胶组合物。需要说明的是，在表1的二烯类橡胶(SBR1、SBR2)栏中，除了产品的配合量，括号内还记载有除充油成分以外的SBR的净配合量。此外，表2记载的配合剂的配合量以表1记载的相对于二烯类橡胶100重量份的重量份来表示。
在规定的模具(150mm×150mm×2mm)中，以160℃的温度对所得到的胎面用橡胶组合物进行加压硫化20分钟，制作硫化试片。通过下述方法对损耗柔量以及拉伸应力(100％、100℃)进行测定。
损耗柔量(60℃)
使用所得到的胎面用橡胶组合物的硫化试片，依据JIS K6394：2007，使用粘弹性谱仪(东洋精机制作所公司制)在初始应变为10％、振幅为±2％、频率为20Hz、温度为60℃的条件下，对复数弹性模量E＊以及损耗弹性模量E”进行测定，通过所述算式(1)算出60℃的损耗柔量。所得到的结果在表1的“损耗柔量”栏中示出。
拉伸应力(100％、100℃)
依据JIS K6251，从所得到的硫化试片切出JIS3号哑铃型试片。依据JIS K6251，在500mm/分钟的拉伸速度、环境温度100℃的条件下，对100％变形时的拉伸应力进行测定。所得到的结果在表1的“拉伸应力(100％、100℃)”栏中示出。
将通过上述方法得到的胎面用橡胶组合物用于胎面橡胶，对由表1所示的胎面用橡胶组合物以及复合纤维帘线形成带束增强层的七种充气子午线轮胎(轮胎尺寸215/55R17)进行了硫化成型。需要说明的是，表1记载的复合纤维帘线的构造表示芳纶纤维帘线以及尼龙66纤维帘线的细度，比较例1的复合纤维帘线意味着两根芳纶纤维帘线(1670dtex)和一根尼龙66纤维帘线(1400dtex)的三根捻合。此外，在比较例2～4以及实例1～3的复合纤维帘线的构造中，第一个数表示芳纶纤维帘线的细度(dtex)，第二个数表示尼龙66纤维帘线的细度(dtex)，意味着它们是两根捻合的纤维帘线。
对于所得到的七种充气子午线轮胎，通过后述方法对高速耐久性进行评价。此外，从七种充气子午线轮胎提取带束增强层，通过下述的评价方法对带束增强层的重量以及复合纤维帘线的施加2.0cN/dtex的载荷时的伸长率进行测定。
2.0cN/dtex负载时的伸长率
从提取自充气子午线轮胎的带束增强层采样十根复合纤维帘线，依据JIS L1017对施加2.0cN/dtex的载荷时的伸长率进行测定。得到的结果在表1的“2.0cN/dtex负载时的伸长率”栏中示出。
带束增强层的重量
对从充气子午线轮胎提取的带束增强层的单位长度的重量进行测定。得到的结果以将比较例1的值设为100的指数表示，并在表1的“带束增强层的重量”栏中示出。该指数越小，意味着带束增强层越轻，能够对轮胎进行轻型化。
高速耐久性
将所得到的充气子午线轮胎组装于标准轮辋(尺寸17×7JJ)，填充气压230MPa。将该轮胎装于室内转鼓试验机(转鼓直径1707mm)，进行JATMA规定的高速耐久性试验。该高速耐久性试验结束后，每次将试验速度提高50km/小时，继续试验直至轮胎破坏，对行驶距离进行测定。得到的结果以将比较例1的值设为100的指数表示，并在表1的“高速耐久性”栏中示出。该指数越大表示，高速耐久性越优异。
需要说明的是，如下示出在表1中所使用的原材料的种类。
·SBR1：末端改性溶聚丁苯橡胶，日本瑞翁公司制SBR Ns460、在丁苯橡胶100重量份中配合油成分37.5重量份的充油产品，苯乙烯量为25重量％，乙烯基单元量为63重量％，重量平均分子量为78万
·SBR2：末端改性溶聚丁苯橡胶，旭化成公司制SBR E581、在丁苯橡胶100重量份中配合油成分37.5重量份的充油产品，苯乙烯量为40重量％，乙烯基单元量为44重量％，重量平均分子量为126万
·Br：丁二烯橡胶，日本瑞翁公司制Nipol BR1220
·二氧化硅：罗地亚公司制Zeosil 115GR，氮吸附比表面积为160m2/g
·偶联剂：含有硫磺的硅烷偶联剂，双(3-三乙氧基硅丙基)四硫化物，赢创公司制Si69
[表2]
如下示出在表2中所使用的原材料的种类。
·炭黑：东海碳素公司制SEAST6
·硬脂酸：日油公司制珠状硬脂酸
·氧化锌：正同化学工业公司制氧化锌三种
·抗老化剂：富莱克斯公司制Santoflex 6PPD
·香薰油：昭和壳牌石油公司制提取物(Extract)4号S
·硫磺：鹤见化学工业公司制含有金华印油的粉末硫磺
·硫化促进剂1：CBS、大内新兴化学公司制Nocceler CZ-G
·硫化促进剂2：DPG、住友化学工业公司制Soxinol D-G
根据表1已明确认定：通过实例1～3制造的充气子午线轮胎实现了带束增强层的轻型化，同时，高速耐久性优异。
由于比较例2的充气子午线轮胎的由两根捻合而成的复合纤维帘线的总细度小于1800dtex，且2.0cN/dtex负载时的伸长率超过4.0％，因此，高速耐久性差。
由于比较例3的充气子午线轮胎的由两根捻合而成的复合纤维帘线的2.0cN/dtex负载时的伸长率超过4.0％，因此，高速耐久性差。
由于比较例4的充气子午线轮胎的胎面橡胶的损耗柔量超过45Pa-1，因此，高速耐久性差。
Claims (2)
1.一种充气子午线轮胎，在一对胎圈之间装架有胎体层，在胎面部的所述胎体层的外周侧具有带束层，在所述带束层的外周侧具有带束增强层以及胎面橡胶，其特征在于，
所述带束增强层由将一根芳香族聚酰胺的纤维帘线以及一根脂肪族聚酰胺的纤维帘线捻合在一起的复合纤维帘线构成，所述复合纤维帘线的总细度为1800～3200dtex，施加2.0cN/dtex的载荷时的伸长率为3.0～4.0％，并且，构成所述胎面橡胶的橡胶组合物通过在二烯类橡胶100重量份中配合氮吸附比表面积为100m2/g以上的二氧化硅10～110重量份而成，所述橡胶组合物的60℃的损耗柔量为45Pa-1以下。
2.根据权利要求1所述的充气子午线轮胎，其特征在于，
构成所述胎面橡胶的橡胶组合物在所述二烯类橡胶100重量％中含有苯乙烯单元含量为30～45重量％、乙烯基单元含量为30～50重量％的末端改性溶聚丁苯橡胶50～90重量％，所述橡胶组合物的100℃的100％变形时的拉伸应力为2.0MPa以上。
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| WO2021079672A1 (ja) * | 2019-10-25 | 2021-04-29 | 住友ゴム工業株式会社 | タイヤ |
| JP6915719B1 (ja) * | 2020-04-07 | 2021-08-04 | 横浜ゴム株式会社 | 空気入りタイヤ |
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| EP3263363B1 (en) | 2022-07-13 |
| WO2016136575A1 (ja) | 2016-09-01 |
| KR20170085601A (ko) | 2017-07-24 |
| KR101784199B1 (ko) | 2017-10-11 |
| JP2016155522A (ja) | 2016-09-01 |
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| EP3263363A1 (en) | 2018-01-03 |
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