CN105636769B - 自密封轮胎密封剂和充气车辆轮胎 - Google Patents
自密封轮胎密封剂和充气车辆轮胎 Download PDFInfo
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Abstract
本发明涉及一种自密封轮胎密封剂以及一种充气车辆轮胎,该充气车辆轮胎在其内部具有预先施用到与胎面相反的内表面上的一种自密封轮胎密封剂。该轮胎密封剂含有膨胀的固体的片段和/或残余物,特别是膨胀的微球和/或膨胀的石墨的片段和/或残余物。该充气车辆轮胎在其内部在该与胎面相反的内表面上包括该轮胎密封剂。
Description
技术领域
本发明涉及一种自密封轮胎密封剂并且涉及一种充气车辆轮胎,该充气车辆轮胎具有预先在该轮胎内部施用到与胎面相反的内表面上的一种自密封轮胎密封剂。
背景技术
已知的惯例是装备充气车辆轮胎,其方式为使得如果轮胎被刺破\损坏,它们表现得自密封。
因此,例如,US 4068027和US 4113799公开了一种基于交联丁基橡胶的轮胎密封剂。在这些情况中的轮胎密封剂由两种组分组成。然而,在那些情况中,所使用的橡胶使用溶剂稀释,这些溶剂是可燃的并且对健康有害。
DE 102007035192 A1,出于避免这些缺点的目的,描述了一种轮胎密封剂,该轮胎密封剂包括作为密封剂组分的一种填充剂,该填充剂的密封效应产生自其结构,该填充剂在行进的过程中通过离心力被压靠在轮胎内壁上,并且在该过程中在损伤部位或切口部位上和/或内和/或上方形成的层中发生构建。白云母云母作为填充剂用于DE 102007035192A1中。然而,这种类型的填充剂,特别是云母,具有以下缺点,作为相对大表面积层状硅酸盐,它们损害已经穿透的异物与该密封剂之间的粘附。此外,在大多数情况下,该填充剂的更大密度(相比于该密封剂)增加了轮胎的质量,进而导致高速度下的降低的性能。
发明内容
本发明的一个目的是提供一种自密封轮胎密封剂,该密封剂与现有技术相比具有低的密度(质量/单位体积)和高的密封效应/单位质量。密封效应指的是通过流入一个缺陷部位(例如,产生自用钉子对轮胎的损坏),并且封闭此缺陷部位的密封,以及还有气密性。
根据本发明通过该轮胎密封剂实现所述目的,该密封剂包含膨胀的固体的片段和/或残余物,这些固体选自下组,该组包含可膨胀的石墨和微球。
进一步可想到该固体包括玻璃珠。
“膨胀的固体的片段”在本发明的上下文中是指这些固体在已经膨胀之后不再处于与它们在膨胀之前的形式相同的形式,而是代替地是,由于三维膨胀,处于固体片段的形式。
“膨胀的固体的残余物”在本发明的上下文中是指这些固体在已经经历了膨胀之后不再以与在膨胀之前的形式相同的形式存在,而是代替地是,由于三维膨胀,处于一种改变的形式,但是不具有任何片段。因此,例如,在膨胀微球的情况下,可以想到外壳已经经历了三维膨胀而没有破碎成片段,因为,如下面所阐明,用于本发明的目的该微球外壳是可拉伸的并通过发泡气体的膨胀扩展。
这些固体优选选自下组,该组由以下各项组成:可膨胀的石墨和微球。因此,该轮胎密封剂优选包括膨胀微球的片段和/或残余物和/或膨胀的可膨胀石墨的片段和/或残余物,或该轮胎密封剂优选包括膨胀的微球和/或膨胀的可膨胀石墨。结果,该轮胎密封剂在轮胎的应用中具有较低的密度以及因此较低的重量,这进而带来就燃料消耗而论的优点。此外,一种含有本发明的轮胎密封剂的充气车辆轮胎的特征为,借助于使用相对于现有技术的密封剂的相同的层厚度或更厚的可能性对于相同重量的密封剂相等的或甚至改进的密封效应,特别是气密性和密封效应。取决于密封剂的层厚度,因此该轮胎有可能被更经济地设计和/或设计有就密封效应而论更好的性能。
根据本发明的一个优选的实施例,在该轮胎密封剂中的膨胀的固体总量是1至20wt%,更优选1至10wt%。
用于本发明的目的的微球是颗粒,这些颗粒的直径是在微米的范围内。本领域技术人员知道一致地实心微球和内部空心微球二者。出于本发明的目的,仅考虑空心微球,这些空心微球在外侧具有可拉伸外壳且在内侧具有至少一种气体。在这些微球内部的气体或气体混合物也被称为发泡剂。
这些空心微球可以被细分为可膨胀的或膨胀的微球。
本发明的轮胎密封剂,根据一个特别优选的实施例,包含膨胀的微球,其中该发泡剂由于例如在先的加热已经经历膨胀,并且因此使微球的外壳扩张。其结果是,该轮胎密封剂具有闭合的和/或打开的孔,这些孔包含至少一种气体。该气体是空气和发泡剂以及还有,任选地,该发泡剂的化学衍生物的一种混合物。在膨胀之前,存在于该轮胎密封剂中的微球优选具有的直径为0.5至50μm(微米),更优选0.5至40μm,非常优选1至40μm,进而非常优选10到30μm。
存在于本发明的轮胎密封剂中的微球的外壳优选地由至少一种聚合物构造并且更优选包括一种丙烯腈和丙烯酸甲酯的共聚物。这些微球的外壳可以进一步包括氧化镁(MgO)。因此,当微球存在时,该轮胎密封剂具有丙烯腈和丙烯酸甲酯的微球的膨胀的外壳的片段和/或残余物以及还有,任选地,MgO。在此可以想到膨胀的微球的外壳以片段的形式存在以及该外壳以一致的外壳形式作为一种残余物存在二者。
在本发明的轮胎密封剂的情况下,膨胀的微球的外壳可以通过该轮胎密封剂的硫网络被化学地附接到该轮胎密封剂的聚合物基质中。可替代地,微球的外壳可以是这样的,即,它不再可以经由交联附接到该轮胎密封剂的网络中。
存在于该轮胎密封剂中的微球的外壳的厚度,在膨胀之前,优选是0.1至5μm(微米)。
存在于本发明的轮胎密封剂中的微球的发泡剂优选包括异丁烷和/或异戊烷。
在本发明的上下文中,可以想到本发明的轮胎密封剂包括一种微球的混合物,这些微球具有不同的直径并且从它们的原始直径开始,已经经历膨胀至不同的程度,还可以想到一些微球已经经历很少或不膨胀并且因此保留它们的初始直径。因此,在膨胀之后,这些微球的直径是0.5至250μm,优选0.5至100μm,更优选80至100μm。这意味着特别优选所有微球都是膨胀的。
在膨胀时,这些微球表面上实体结构仍然完全和/或部分地处于圆滑。这意味着该外壳是可拉伸的并且由于通过加热的气体传播被加宽,例如-换句话说,这些微球经受三维膨胀。
当本发明的轮胎密封剂仅包括膨胀的微球作为膨胀的固体时,微球的量,基于该轮胎密封剂的总量,是0.5至3wt%,优选0.5至2.5wt%,更优选1.0至2.5wt%,非常优选1.8至2.2wt%。通过这种手段,实现的密封效应是特别良好的,结合有本发明的轮胎密封剂的低密度。
出于本发明的目的可膨胀石墨指的是具有一个层晶格结构的石墨,其中原子或分子、更具体地硫化合物或氮化合物被结合,换言之插入这些层之间。优选至少硫酸分子(这些是具有实验式H2SO4的分子)被插入该可膨胀的石墨中。
根据在线百科全书(Online Lexikon),版本3.36“石墨烯是碳原子的一种平面的、六边形排列,在其结构上对应于石墨的一个单分子层(蜂窝状结构)”。
在可膨胀石墨的情况下,因此,这些插入化合物位于单独的石墨烯层之间。理想地,该插入的化合物位于石墨的每个单层之间。然而,实际上,可以想到某些石墨层不具有插入的化合物。
在加热时,可膨胀石墨经历三维膨胀,其结果是该插入的化合物,优选至少一种氮或硫化合物,优选释放SO2和/或H2SO4,和/或其衍生物,并且此外,在该轮胎密封剂中形成石墨烯结构。因此,如果可膨胀石墨存在,则该轮胎密封剂包括石墨烯结构作为膨胀的可膨胀石墨的片段。换句话说,本发明的轮胎密封剂如果包括可膨胀石墨,则它包括膨胀的石墨烯。这些结构主要地理想地发生,尽管还可以想到形成以下结构,在这些结构中许多石墨层仍然是彼此粘住(参见上文),并且因此本发明的轮胎密封剂包括石墨和/或石墨烯。
本发明的轮胎密封剂,根据一个特别优选的实施例,包含膨胀的可膨胀石墨,其中该轮胎密封剂包含石墨烯结构,这些结构由于该可膨胀石墨的膨胀(通过加热,例如)形成。可替代地,预膨胀的石墨也可以混合到该轮胎密封剂中。
根据这些实施例存在于该轮胎密封剂中的石墨烯结构在该轮胎密封剂的部分上导致良好的气密性。
此外,可膨胀石墨具有阻燃性的优点。包含在本发明的轮胎密封剂中的可膨胀石墨优选地在130℃或更高、优选150℃或更高,更优选150℃至230℃,非常优选170℃至230℃的温度下进行膨胀。在本发明的方法中使用的可膨胀石墨优选具有0.5至1500μm(微米),更优选200至1500μm,非常优选200至1000μm的预膨胀粒度。存在于本发明的轮胎密封剂中的可膨胀石墨优选包括至少插入的硫酸,H2SO4。
当本发明的轮胎密封剂中仅有的膨胀的固体为膨胀的可膨胀石墨时,可膨胀石墨的量,基于该轮胎密封剂的总量,是0.5至10wt%,优选0.5至8wt%,更优选2.0至8wt%,非常优选3至8wt%。其结果是,实现的密封效应是特别良好的,结合有本发明的轮胎密封剂的低密度。
进一步可想到该轮胎密封剂,根据本发明的一个实施例,包含,例如,组合的微球和可膨胀的石墨。在这种情况下,微球和可膨胀石墨的特征同样服从在其他实施例中所述的优选特征,如膨胀温度范围和预膨胀粒度。
在本发明的上下文中讨论的这些微球的直径,以及该可膨胀石墨的粒度,通过光学显微镜法确定。粒度在此指的是在一种可膨胀石墨颗粒在光学显微镜之下的二维投影中的最大可能的间距。
由于微球是球形形式,在此直径同样是在光学显微镜之下的二维投影中的最大可能的间距。
本发明的密封剂包括至少一种聚合物。
该轮胎密封剂的聚合物可以是在现有技术中已知用于充气车辆轮胎的轮胎密封剂的任何聚合物。该聚合物优选包含聚氨酯(PU)和/或聚异丁烯(PIB)和/或聚丁烯(PB)和/或丁基橡胶(异丁烯-异戊二烯共聚物,IIR)和/或硅酮橡胶。特别优选本发明的轮胎密封剂包括至少丁基橡胶作为聚合物。其结果是,在本发明的其中该轮胎密封剂包括微球的那些实施例,这些微球能够通过它们的外壳和硫网络(在丁基橡胶的情况下存在)附接到该丁基橡胶基质,导致在该轮胎密封剂的部分上的改进的耐疲劳性。
本发明的轮胎密封剂包括至少一种交联剂。
所考虑的交联剂包括本领域技术人员已知的所有的交联剂。本发明的轮胎密封剂优选包括至少硫作为交联剂,特别是如果丁基橡胶被包括作为聚合物的话。
该轮胎密封剂可以进一步包括常规组分。这些包括,具体地,至少一种活化剂,如锌氧化物(ZnO),例如,和/或增塑剂,如石蜡油或环烷油,例如,和/或一种或多种加工助剂,如烷基树脂或者酚醛树脂,例如,和/或一种或多种填充剂,如炭黑或二氧化硅,例如,和/或一种或多种老化抑制剂,例如PPD。
本发明的另一个目的是提供一种充气车辆轮胎,该充气车辆轮胎具有预先在其内部、在与胎面相反的内表面上施用的一种自密封轮胎密封剂,所述轮胎与现有技术相比具有更低的重量,意图是该密封效应不应消极地受损和/或应改进。其他特性,例如,具体地,磨损行为和/或湿制动和/或干制动和/或操作行为,和/或撕裂特性,和/或滚动阻力行为,不被有害地影响。
根据本发明通过该充气车辆轮胎实现所述的目的,该充气车辆轮胎在其内部,在与胎面相反的内表面上具有以上描述的本发明的轮胎密封剂。上述所有特征和实施方式在此适应于该轮胎密封剂。
本发明的充气车辆轮胎,在该轮胎密封剂中包括膨胀的固体的片段和/或残余物,因此凭借该轮胎密封剂的较低密度具有较低的轮胎重量。这些膨胀的固体优选是膨胀的可膨胀石墨的片段,即,石墨烯结构,和/或如以上描述的膨胀的微球的片段和/或残余物。
此外,在其中该膨胀的固体包括可膨胀石墨的实施例中,本发明的充气车辆轮胎的特征为与现有技术相比改进的阻燃性,如果断裂发生由于该可膨胀石墨和/或石墨烯或由其形成的石墨烯状结构的良好的气密性具有相同的或改善的密封效应。
此外,在其中该膨胀的固体包括微球的实施例中,本发明的充气车辆轮胎具有与现有技术相比相同或改进的密封效应。
本发明的充气车辆轮胎的轮胎密封剂的层厚度是现有技术中已知的层厚度。根据本发明实施的充气车辆轮胎因此具有比其轮胎密封剂是没有气体-填充的孔构造的充气车辆轮胎更低的重量,其中相对于现有技术密封效应是相同的和/或改进的。
该轮胎密封剂的层厚度优选是在0.5mm与8mm之间。这些层厚度对应于在现有技术中已知用于充气车辆轮胎中的轮胎密封剂的层厚度。
该轮胎密封剂施加到其上的充气车辆轮胎的内表面优选是一种内层的气密实现方式(在本领域中也称为内衬(inner liner)或内衬(innerliner))或径向地最内的胎体帘布层。对于该充气车辆轮胎的部分上的充分气密性,本发明的充气车辆轮胎具有优选在该气密内层上的轮胎密封剂。
具体实施方式
以下参照充气车辆轮胎的工作实例阐明本发明。在此,标记为“C”的实例是对比实例,而标记为“I”的实例是本发明的实例。
C1:
从两种组分A和B生产轮胎密封剂,使用在现有技术中已知的所指出的量的物质:
生产组分A:使用如在WO 2008/141848 A1中描述的装置和方法步骤,混合丁基橡胶,硫(交联剂)和石蜡油。
组分B:使用如在WO 2008/141848 A1中描述的装置和方法步骤,使聚丁烯溶液和氧化锌(活化剂)彼此混合。
使用如在WO 2008/141848 A1中描述的装置和方法步骤,在100℃至140℃的温度下使组分A和B彼此混合。
经由喷嘴将该A和B的混合物(轮胎密封剂)喷涂到一种硫化的充气车辆轮胎的内部表面(与胎面相反)上,以4mm的层厚度施用该密封剂。
C2:
与C1类似,除了在施用后轮胎密封剂的层厚度是2.4mm。
I1:
与C2类似,其区别在于在组分B中,将微球(2wt%的微球,基于该轮胎密封剂的总质量,换言之基于A和B中组分的总量),商品名Expancel 031 DUX 40,混合到该聚丁烯溶液中。在微球膨胀(通过热的膨胀,该热在混合组分A和B的过程中产生)后的层厚度是与来自C1的层厚度可比较的。
C3:
与I1类似,其区别在于该轮胎密封剂包括4wt%的微球(基于该轮胎密封剂的总质量,换言之基于A和B中组分的总量)以及在膨胀之前的层厚度是1.5mm。在膨胀之后,层厚度是与来自C1和I1的层厚度可比较的。
称量所有的充气车辆轮胎并且测试它们的气密性。在这种情况下,使用钉子损坏每个轮胎并且在轮胎试验台上测量其压力损失。在没有压力损失的情况下,该轮胎评估为是气密的,因为轮胎密封剂密封该缺陷部位(轮胎气密性:是)。
表1
单位 | C1 | C2 | I1 | C3 | |
微球在轮胎密封剂中 | wt% | - | - | 2 | 4 |
膨胀之前的层厚度 | mm | 4.0 | 2.4 | 2.4 | 1.5 |
膨胀之后的层厚度 | mm | 4.0 | 2.4 | 3.7 | 3.6 |
充气车辆轮胎的重量 | kg | 11.2 | 10.8 | 10.7 | 10.4 |
轮胎密封剂的密度 | g/cm3 | 0.95 | 0.95 | 0.81 | 0.52 |
充气车辆轮胎气密性 | 是/否 | 是 | 否 | 是 | 否 |
如从表1中明显的,与对比实例C1相比,在可比较的轮胎密封剂层厚度下(在存在于I1中的微球膨胀之后),本发明的充气车辆轮胎I1具有更低的轮胎重量。重量降低可归因于本发明实例的轮胎密封剂的更低的密度。
如由对比实例C2所示,在不加入微球下的轮胎密封剂的层厚度的减少没有导致足够的气密性。微球的量太大降低了密封效应,由于轮胎密封剂的流变学的改变,如从对比实例C3明显的。
Claims (4)
1.一种自密封轮胎密封剂,其特征在于它包括膨胀的固体的片段和/或残余物,这些膨胀的固体选自膨胀的微球,微球的量基于该轮胎密封剂的总量是0.5至3重量%,这些微球具有一个丙烯腈和丙烯酸甲酯的至少一种共聚物的外壳,在膨胀之后微球的直径是0.5至100μm,膨胀的微球的外壳通过该轮胎密封剂的硫网络被化学地附接到该轮胎密封剂的聚合物基质中。
2.如权利要求1所述的自密封轮胎密封剂,其特征在于这些微球包括至少异丁烷和/或异戊烷作为发泡剂。
3.一种充气车辆轮胎,其特征在于在其内部,在与胎面相反的内表面上,它具有如权利要求1所述的自密封轮胎密封剂。
4.如权利要求3所述的充气车辆轮胎,其特征在于该轮胎密封剂的层厚度是0.5至8mm。
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- 2014-07-31 US US15/025,773 patent/US20160236428A1/en not_active Abandoned
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EP3052308B1 (de) | 2020-04-29 |
US20160236428A1 (en) | 2016-08-18 |
EP3052308A1 (de) | 2016-08-10 |
US20170144491A1 (en) | 2017-05-25 |
DE102013110977A1 (de) | 2015-04-02 |
US9802446B2 (en) | 2017-10-31 |
WO2015049070A1 (de) | 2015-04-09 |
CN105636769A (zh) | 2016-06-01 |
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