CN109195813B - 用于由弹性体材料制成的制品的加强层以及充气车辆轮胎 - Google Patents

用于由弹性体材料制成的制品的加强层以及充气车辆轮胎 Download PDF

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CN109195813B
CN109195813B CN201780032827.2A CN201780032827A CN109195813B CN 109195813 B CN109195813 B CN 109195813B CN 201780032827 A CN201780032827 A CN 201780032827A CN 109195813 B CN109195813 B CN 109195813B
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沃尔夫冈·雷泽
托马斯·克拉默
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Continental Tire Germany Co ltd
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    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B60C15/06—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead
    • B60C15/0628—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead comprising a bead reinforcing layer
    • B60C15/0632—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead comprising a bead reinforcing layer using flippers in contact with and wrapped around the bead core and, at least partially, in contact with the bead filler
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    • B60C15/0628—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead comprising a bead reinforcing layer
    • B60C15/0635—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead comprising a bead reinforcing layer using chippers between the carcass layer and chafer rubber wrapped around the bead
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    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
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    • D—TEXTILES; PAPER
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    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/48—Tyre cords
    • D—TEXTILES; PAPER
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    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
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    • D—TEXTILES; PAPER
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    • D07B1/0606—Reinforcing cords for rubber or plastic articles
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    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/16—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics
    • D07B1/162—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics characterised by a plastic or rubber enveloping sheathing
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    • B60—VEHICLES IN GENERAL
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    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C2009/0071—Reinforcements or ply arrangement of pneumatic tyres characterised by special physical properties of the reinforcements
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C2009/0071—Reinforcements or ply arrangement of pneumatic tyres characterised by special physical properties of the reinforcements
    • B60C2009/0078—Modulus
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    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C2009/0071—Reinforcements or ply arrangement of pneumatic tyres characterised by special physical properties of the reinforcements
    • B60C2009/0092—Twist structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/18—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers
    • B60C9/20—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel
    • B60C2009/2074—Physical properties or dimension of the belt cord
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
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    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/18—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers
    • B60C9/20—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel
    • B60C2009/2074—Physical properties or dimension of the belt cord
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    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/18—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers
    • B60C9/20—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel
    • B60C2009/2074—Physical properties or dimension of the belt cord
    • B60C2009/208—Modulus of the cords
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    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/18—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers
    • B60C9/20—Structure or arrangement of belts or breakers, crown-reinforcing or cushioning layers built-up from rubberised plies each having all cords arranged substantially parallel
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Abstract

本发明涉及一种用于由弹性体材料制成的制品、优选用于车辆轮胎的用橡胶处理的加强层，其中该加强层具有多个彼此间隔开的平行的增强元件，每个增强元件由聚酰胺6.6组成并且具有×1构造，因此是聚酰胺6.6的加捻复丝纱线。聚酰胺6.6的原纱线具有在4％伸长率下在从1.35cN/分特克斯至1.60cN/分特克斯范围内的韧度；该复丝纱线具有在4％伸长率下在从2.0cN/分特克斯至2.8cN/分特克斯范围内的韧度，并且该帘线具有在177°下在4.0％‑7.0％的范围内的热收缩率，其中根据ASTM D885‑16的韧度和177℃下的热收缩率在0.045g/分特克斯的预加张力下用两分钟的暴露时间进行测定。

Description

用于由弹性体材料制成的制品的加强层以及充气车辆轮胎
技术领域
本发明涉及一种用于由弹性体材料制成的制品、优选用于车辆轮胎的用橡胶处理的加强层，其中该加强层具有多个彼此间隔开的平行的增强元件，每个增强元件由聚酰胺6.6组成并且具有×1构造，因此是聚酰胺6.6的加捻复丝纱线。本发明进一步涉及一种包含这种加强层的充气车辆轮胎。
背景技术
用于由弹性体材料制成的制品(例如像工业橡胶产品和(充气)车辆轮胎)的加强层是极其重要的，并且是本领域技术人员的常识。这些加强层具有多个加强的线形元件(被称为增强元件)。将它们完全嵌入弹性体材料中。这些加强层的增强元件具有例如织物或压延的连续盘绕的增强元件的形式。
在充气车辆轮胎的情况下，例如在胎圈区域和带束箍带中，将复丝纱线用作增强元件。
在充气车辆轮胎中，并且特别是在高速使用的情况下，带束箍带用于防止由在驾驶操作中发生的离心力引起的轮胎的隆起。在充气车辆轮胎的情况下，该充气车辆轮胎总体上包含不透空气的内层、包含增强元件并且从该轮胎的胎冠经由胎壁延伸到胎圈区域的子午线胎体(该胎圈区域通常通过具有高拉张强度的胎圈芯的缠绕进行锚定)、具有胎面花纹沟(profile groove)的径向外部胎面以及带束，该箍带布置在带束与胎面之间。该带束箍带可以具有单层或多层构造；它至少覆盖带束边缘并且含有平行且基本上在圆周方向上延伸并且嵌入橡胶混合物中的增强元件。在轮胎制造期间，该带束箍带以具有嵌入未固化的橡胶混合物中的增强元件的多个层、条带或单独的增强元件的形式被应用，这些元件缠绕或盘绕到该带束上。将用于此多个层的增强元件嵌入橡胶中，例如像，一系列基本上平行的线形增强元件(一般来说，这些元件已经以本领域技术人员已知的方式热预处理和/或用浸渍预处理，以便更好地粘附到嵌入橡胶上)在纵向方向上穿过压延机或挤出机以便用橡胶混合物进行包裹。一种替代方案是使用已经进行粘附浸渍并且可以在没有压延的粘附混合物的情况下加工的增强元件。在轮胎的成型和固化中，与未固化的胎胚(当该胎胚缠绕在平坦的滚筒上时)相比，作为隆起的结果，轮胎总体上在胎肩区域中拉伸高达2％并且在中间区域中拉伸高达4％。因此，在带束箍带中使用的增强元件被认为有利地允许这种隆起，换言之，能够最初用相对低的施力拉伸，并且在此高达4％的初始拉伸之后，对于高速可操作性，能够仅用更高的施力拉伸。因此，在力-伸长率图中，直到4％的伸长率，增强元件都表现出相对平坦的曲线，并且之后具有更陡峭的曲线。
该带束箍带具有单层或多层构造，覆盖带束边缘，并且具有平行且近似地在圆周方向上延伸并且嵌入橡胶中的增强元件。“近似地在圆周方向上”是指相对于轮胎的圆周方向的0°至5°的角度。
由WO 2014182265 A1已知在带束箍带中具有聚酰胺6.6增强元件的一种充气车辆轮胎。
US 3,343,363 A披露了作为用作轮胎的增强元件的加强材料的加捻的聚酰胺6.6细丝、纱线和帘线，这些元件具有在室温下在25与60g/d之间的初始模量以及大于7.0g/d的韧度。初始模量值根据ASTM A1380-61T进行测定。
US 3,849,976 A披露了作为轮胎加强材料的具有两种或更多种L5模量大于60g/d的复丝纱线的聚酰胺6.6帘线，这些纱线已经通过高温下的高张力拉伸获得。
US 4,284,117 A披露了作为增强充气车辆轮胎的带束箍带的元件的加捻的尼龙、聚酯、人造丝和芳族聚酰胺纱线。
从现有技术中已知的做法是通过在相对高的温度下对聚酰胺增强元件进行热拉伸来增加聚酰胺增强元件的初始模量或LASE(特定伸长率下的负荷)。为了甚至在(在实验室条件下用自由切割端调节的)松弛之后保持所得到的特性，迄今为止必需将PA 6.6纱线或帘线暴露于高于250℃的温度条件下。然而，缺点是在上述条件下，纱线或帘线变硬/变脆，并且因此在暴露于压缩应力和弯曲应力的循环时更快地遭受疲劳。
发明内容
本发明的目的是提供一种用于弹性体材料的制品的加强层，该加强层具有由聚酰胺6.6制成的增强元件，这些增强元件具有从4％
伸长率的相对高的模量，但关于压缩应力和弯曲应力的循环是更耐疲劳的。此外，本发明的目的是提供一种充气车辆轮胎，其具有上述加强层并且表现出改进的高速特性和改进的滚动阻力。
关于加强层实现该目的，其中聚酰胺6.6的原纱线具有在4％伸长率下在从1.35cN/分特克斯至1.60cN/分特克斯范围内的韧度，其中该加捻的、经浸渍的、并且热拉伸的复丝纱线具有在4％伸长率下在从2.0cN/分特克斯至2.8cN/分特克斯范围内的韧度，并且其中该增强元件具有在177℃下在4.0％-7.0％的范围内的热收缩率，其中根据ASTMD885-16的韧度和177℃下的热收缩率在0.045g/分特克斯的预加张力下用两分钟的暴露时间下进行测定。
“原纱线”是指尚未经历热拉伸的复丝纱线。
“复丝纱线”是指被加捻并且因此作为具有×1构造的增强元件并且已经经历热拉伸操作(包括浸渍)的复丝纱线。
所提供的加强层具有聚酰胺6.6的复丝纱线，这些复丝纱线具有在4％伸长率下比可比较复丝纱线更高的弹性模量，但关于压缩应力和弯曲应力的循环是更抗疲劳的。这些特性尤其适用于这种用于车辆轮胎的加强层，更特别地作为带束箍带，因为轮胎制造保留了高达约3％的必需伸长率，而在较大的伸长率的情况下，必须施用较高的力，这对于轮胎的高速操作是有利的。
出人意料地，获得用于本发明的加强层的聚酰胺6.6的复丝纱线，其中所使用的聚酰胺6.6原纱线具有在4％伸长率下在从1.35cN/分特克斯至1.60cN/分特克斯的范围内的韧度，并且其中此原纱线在230℃与250℃之间的温度下在大于5％且小于12％的范围内拉伸，并且以在150g与500g/增强元件之间的张力盘绕到合适的线轴上。其结果是，通过拉伸操作获得的特性甚至保持在缠绕到线轴上的增强元件中，因为增强元件不能松弛并且可以在轮胎中使用而不松弛，松弛总是引起模量损失。
在线轴上将纱线在24℃和55％的相对大气湿度下调节24小时之后，根据D885-16测定纱线的力-伸长率数据。在经调节后，在从线轴退绕后1分钟内测试纱线。
这些复丝纱线具有在4％伸长率下从2.0cN/分特克斯至2.8cN/分特克斯的韧度以及在177℃下从4％至7％的热收缩率。在4％伸长率下从2.0cN/分特克斯至2.8cN/分特克斯的韧度对应于51g/分特克斯至71.4g/分特克斯(56.7g/d至79.3g/d)的模量。
如下计算模量值：在4％伸长率下的韧度×25，以得到100％伸长率所需的韧度。
在4％伸长率下的韧度[cN/分特克斯]为：在4％伸长率下的张力[cN]/线密度[分特克斯]，使用整个增强元件的线密度。
使用来自制造商Testrite的收缩测量装置在0.045g/分特克斯的预加张力下在177℃下用2分钟的暴露时间测定纱线和帘线的热收缩率。
如果聚酰胺6.6的原纱线具有在4％伸长率下在从1.35cN/分特克斯至1.50cN/分特克斯的范围内的韧度，则是有用的。如果力甚至更大，则这可能在模具引入期间导致问题。
如果复丝纱线具有从300至4000分特克斯的线密度，则是有用的。此线密度范围代表一方面强度与另一方面滚动阻力和成本之间的有利平衡。如果线密度太低，即，如果复丝纱线太稀疏，则所得强度将太低。如果复丝纱线太稠密，则这对轮胎的滚动阻力不利并且对成本不利。
如果该复丝纱线的捻系数α是在从30至50的范围内、优选在从35至45的范围内，则是有利的，其中α＝捻度[t/m]·(线密度[特克斯]/1000)1/2。捻系数是相对于复丝纱线的线密度的每米复丝纱线的捻度的量度。此捻度系数代表在抗疲劳性与强度之间的有利平衡。较低的捻系数将对抗疲劳性是不利的；较高的捻系数将表示增强元件的一部分上的强度较低。
具体实施方式
在本发明的第一特别合适的实施例中，该加强层的增强元件是具有940分特克斯的纱线线密度的复丝纱线，其中该纱线具有在4％伸长率下在从2.0cN/分特克斯至2.8cN/分特克斯范围内的韧度，并且其中该复丝纱线优选以100epdm的密度安排在加强层中。由于与现有技术相比PA6.6增强元件的模量增加，可以将其以更低的密度布置在加强层中，从而简化了此层的生产并且同样由于减少使用增强元件而实现成本优势。同样，半成品在切割成所需条带宽度期间受损的风险较低。
在本发明的第二特别合适的实施例中，该加强层的增强元件是具有1400的纱线线密度的复丝纱线，其中该纱线具有在4％伸长率下在从2.0cN/分特克斯至2.8cN/分特克斯范围内的韧度，并且其中该复丝纱线优选以90epdm的密度安排在加强层中。由于与现有技术相比PA6.6增强元件的模量增加，可以将其以更低的密度布置在加强层中，从而简化了此层的生产并且同样由于减少使用增强元件而实现成本优势。同样，半成品在切割成所需条带宽度期间受损的风险较低。
如果该加强层是带束箍带层，则是有利的，其中这些增强元件以用橡胶处理的织物条带的形式或作为用橡胶处理的织物缠绕或者以加捻的单独复丝纱线的形式或作为具有多个平行的单独复丝纱线的用橡胶处理的条带螺旋盘绕。聚酰胺6.6复丝纱线具有使其特别适用于带束箍带的物理特性。
然而，替代地，该加强层同样可以是胎圈加强物，如胎跟加强层(chipper)或胎圈芯包布(flipper)。
通过包含上述用橡胶处理的加强层的所述轮胎关于充气车辆轮胎实现本发明。充气车辆轮胎具有改善的滚动阻力，并且，给定带束箍带中的增强元件的合适密度，具有改善的高速性能。

Claims (12)

1.一种用于由弹性体材料制成的制品的加强层，所述加强层用于车辆轮胎的用橡胶处理，其中该加强层具有多个彼此间隔开的平行的增强元件，每个增强元件由聚酰胺6.6组成并且具有×1构造，因此是聚酰胺6.6的加捻复丝纱线，
其特征在于，聚酰胺6.6的原纱线具有在4％伸长率下在从1.35cN/分特克斯至1.60cN/分特克斯的范围内的韧度，
其特征在于，该加捻的、经浸渍的、并且热拉伸的复丝纱线具有在4％伸长率下在从2.0cN/分特克斯至2.8cN/分特克斯范围内的韧度，并且
其特征在于，该复丝纱线具有在177℃下在4.0％-7.0％范围内的热收缩率，
其中根据ASTM D885-16的韧度和177℃下的热收缩率在0.045g/分特克斯的预加张力下用两分钟的暴露时间进行测定。
2.如权利要求1所述的加强层，其特征在于，该复丝纱线具有从300至4000分特克斯的线密度。
3.如权利要求1所述的加强层，其特征在于，该复丝纱线的捻系数α是在从35至45的范围内，其中α＝捻度[t/m]·(线密度[特克斯]/1000)1/2。
4.如权利要求1所述的加强层，其特征在于，该聚酰胺6.6的原纱线具有在4％伸长率下在从1.35cN/分特克斯至1.50cN/分特克斯的范围内的韧度。
5.如权利要求4所述的加强层，其特征在于，该复丝纱线具有940分特克斯的纱线线密度，其特征在于，该纱线具有在4％伸长率下在从2.0cN/分特克斯至2.8cN/分特克斯范围内的韧度，并且其特征在于，该复丝纱线以高达210epdm的密度安排在该加强层中。
6.如权利要求5所述的加强层，其特征在于，该复丝纱线以100epdm的密度安排在该加强层中。
7.如权利要求4所述的加强层，其特征在于，该复丝纱线具有1400分特克斯的纱线线密度，其特征在于，该纱线具有在4％伸长率下在从2.0cN/分特克斯至2.8cN/分特克斯范围内的韧度，并且其特征在于，该复丝纱线以高达180epdm的密度安排在该加强层中。
8.如权利要求7所述的加强层，其特征在于，该复丝纱线以90epdm的密度安排在该加强层中。
9.如权利要求1至8中任一项所述的加强层，其特征在于，该复丝纱线具有在177℃下在5.0％-6.5％范围内的热收缩率。
10.如权利要求1所述的加强层，其特征在于，该加强层是胎圈加强物。
11.如权利要求1所述的加强层，其特征在于，该加强层是胎跟加强层或胎圈芯包布。
12.一种充气车辆轮胎，其具有如前述权利要求1至11中任一项所述的加强层。
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