CN102218838A - 形成具有可变固化速率的分层橡胶制品的方法 - Google Patents
形成具有可变固化速率的分层橡胶制品的方法 Download PDFInfo
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Abstract
本发明描述形成包含两个或更多个橡胶层的胎面的方法。方法包括以下步骤:通过挤出机和齿轮泵挤出橡胶混合物,并与促进剂混合,然后将连续橡胶带直接施加到轮胎成型机,以形成具有第一固化速率的第一橡胶层;调节促进剂的量,以得到不同于所述第一固化速率的第二固化速率;然后将具有第二固化速率的橡胶带施加到轮胎成型机,其中固化速率之一快于另一固化速率。
Description
其它申请的交叉参考
本申请要求2009年12月23日提交的美国临时申请号61/289,679的权益,并通过引用该申请而将其结合到本文中。
技术领域
本发明主要涉及轮胎制造,更特别是,涉及连续制备定制橡胶混合物。
背景技术
现在越来越需要得到更好的轮胎性能,特别是较低滚动阻力。一般已知利用较低固化温度出现较低滚动阻力的性质。较低固化温度的缺点是模塑时间增加,导致较低的生产能力。为了消除由于较低固化温度所致的时间损失,一种解决方法可以是利用加快固化包(faster cure packages)。然而,在橡胶中使用加快固化包已证明是困难的,一般导致在班伯里混合机中经历处理的混合物焦化。
因此,需要一种改进的方法和设备,这种方法和设备基本减少使用班伯里混合机的需要,同时,通过两种或更多种混合物一起共混,并控制这些混合物和其它添加剂之比,提供在轮胎成型机准备定制混合的设备和技术。非生产性混合物和生产性混合物两者可一起共混。还需要在轮胎成型机具有一种系统,此系统提供用促进剂制备可定制混合物的能力。要解决的另一个问题是在轮胎成型机连续产生混合物。
定义
“高宽比”是指轮胎的截面高度与其截面宽度之比。
“轴向的”和“轴向地”是指平行于轮胎旋转轴的线或方向。
“胎圈”或“胎圈芯”一般指包括环形承拉构件的轮胎的那个部分,径向内部胎圈与将轮胎保持到胎圈轮缘(rim)相关,胎圈轮缘由帘布包裹并用或不用其它增强元件(reinforcement elements)成形,所述增强元件有例如钢丝圈包布(flipper)、切片包布(chipper)、三角胶(apex)或填料、护脚(toe guard)和胎圈包布(chafer)。
“带结构”或“增强带”是指织造或非织造、位于胎面下面、未锚接到胎圈并且与轮胎的赤道平面具有17°至27°左右两个帘线角(cord angles)的平行帘线的至少两个环形层或层片。
“缓冲层”或“轮胎缓冲层”意指与带或带结构或增强带相同。
“胎体”是指轮胎层片材料和切成适用于接合或已接合成圆筒形或复曲面形状的长度的其它轮胎元件的层压材料。另外的元件可在其被硫化产生模塑轮胎之前加到胎体中。
“圆周”是指沿着垂直于轴向的环形胎面的表面的周边延伸的线或方向,它也可以指其半径限定胎面的轴向曲率的多组相邻圆曲线的方向,如在横截面中见到的那样。
“帘线”是指用于增强层片的一个包括纤维的增强股(reinforcement strand)。
“无内胎轮胎衬里”是指形成无内胎轮胎的内表面并且在轮胎内包含充入流体的一层或多层弹性体或其它材料。
“插入物是指一般用于增强失压续跑型轮胎(runflat-type tires)的侧壁的加强筋(reinforcement),它也指位于胎面下的弹性体插入物。
“层片”指弹性体涂覆的帘线的帘线增强层。
“径向的”和“径向地”是指放射状地朝向或离开轮胎旋转轴的方向。
“子午线帘布层片结构(Radial Ply Structure)”是指一个或多个胎体层片或其至少一层具有与轮胎赤道平面成65°和90°之间角度取向的增强帘线。
“子午线帘布层片轮胎(Radial Ply Tire)”是指其中从胎圈延伸到胎圈的帘布与轮胎赤道平面成65°和90°之间帘线角度布置的带束或圆周限制充气轮胎。
“侧壁”指胎面和胎圈之间的轮胎部分。
“层压结构”是指由一个或多个轮胎或弹性体元件层(如衬里、侧壁和任选的层片)制成的未硫化结构。
“生产性混合物”是指包含促进剂、硫和使橡胶固化所需的其它材料的橡胶混合物。
“非生产性混合物”是指不具有一种或多种以下项目的橡胶混合物:1)促进剂、2)硫;或3)固化剂。
附图简述
现在将通过实施例并参考附图描述本发明,其中:
图1为本发明的混合系统的示意图;
图2和3显示从混合系统的示例性输出;
图4显示本发明的胎面的横截面轮廓(profile);
图5显示本发明的胎面的横截面轮廓的第二实施方案;
图6为显示分解成网格点的胎面的示意图;和
图7显示本发明的连续分层胎面的第三实施方案。
本发明的具体实施方式
图1显示适用于制备轮胎或轮胎元件的橡胶组合物的连续混合系统所用方法和设备10的第一实施方案。连续混合系统不限于轮胎应用,并且可用于例如制造不涉及轮胎的其它橡胶元件,如输送带、软管、带等。混合系统可直接在轮胎成型机提供,用于将橡胶组合物直接施加到轮胎成型鼓或具有短停留时间优点的其它轮胎成型设备。
图1显示包括主挤出机20的本发明的连续混合设备10。挤出机20具有用于接收第一混合物A的入口22,第一混合物A可以为生产性或非生产性橡胶组合物或塑性组合物。挤出机可包括适用于处理橡胶或弹性体混合物的任何市售挤出机。挤出机可包括本领域的技术人员一般称为销钉型挤出机(pin type extruder)、双螺杆或单螺杆挤出机或环型挤出机的市售可获得的挤出机。一种适用的市售可获得的挤出机为VMI Holland BV,荷兰销售的多切转移混合(MCT)挤出机。优选挤出机的L/D为约8,但可以为约5至约25,优选10-15的范围。环型、销钉型或MCT型挤出机是优选的,但不限于此。挤出机工作将混合物A加热到约80℃至约150℃,优选约90℃至约120℃范围的温度,以根据需要塑炼(masticate)橡胶组合物。
混合物B也可包括生产性或非生产性橡胶组合物或塑性组合物。以下更详细描述混合物B组合物的实例。首先通过第二挤出机40和第二齿轮泵42挤出混合物B。挤出机40可以为常规销钉型、环型、双螺杆或单螺杆型挤出机。齿轮泵42作为计量装置和泵起作用,并且可具有齿轮,如行星齿轮、伞形齿轮或其它齿轮。挤出机40和齿轮泵42也可以为组合装置。
混合物B从齿轮泵42以控制量输出,并进料至主挤出机20的针孔。混合物A和混合物B一起以精确控制量共混。可任选通过油泵60将油注入主挤出机20。油控制复合混合物(compound mixture)的粘度。
设备10可还包括第一添加剂泵70,用于泵送一种或多种添加剂,如主促进剂,添加剂可任选在主挤出机20或主齿轮泵25加到混合物中。设备可还包括第二添加剂泵80,用于将一种或多种添加剂(如辅助促进剂)泵送输入主挤出机20或主齿轮泵25。设备可还包括第三添加剂泵90,用于将一种或多种添加剂(如第三促进剂)泵送输入主挤出机20或主齿轮泵25。添加剂泵70,80,90可以为齿轮泵、齿轮泵挤出机或文丘里泵或本领域的技术人员已知的其它泵送装置。
如果使用多于一种促进剂,它们可单独或一起加入到混合物中。例如,可加入主促进剂和辅助促进剂两者。促进剂用于控制硫化所需的时间和/或温度,并改善橡胶的性质。促进剂可以为粉末形式,或者可以为进入树脂或橡胶基质的包囊的粉末。以下更详细地描述促进剂组合物的实例。
其它添加剂包括固化剂或前体,这些也可通过添加剂泵90加入到混合机。固化剂的一个实例为硫。硫可以固体形式加入。
因此,本发明的设备制备混合物C的输出混合物,这种混合物为A和B混合物、任选的油和任选的促进剂和任选的添加剂的精确混合物。混合物C的输出混合物离开主挤出机20,并进入主齿轮泵25。主齿轮泵25优选位于邻近轮胎成型站95,用于直接施加到芯,用于翻新轮胎的轮胎坯(tire blank)缓冲胎体或轮胎成型鼓95上,如图1所示。齿轮泵25优选具有喷嘴92,喷嘴92将从齿轮泵25输出的混合物制剂直接施加到轮胎成型机95上的条中,条缠绕在轮胎成型鼓或芯上。
混合物A的体积流速与混合物B的体积流速之比由计算机控制器100精确控制,计算机控制器100控制混合物A的齿轮泵25的速度与混合物B的齿轮泵42的速度之比。例如,从系统10输出的混合物可包括20%体积混合物A和80%体积混合物B之比,如图2所示。或者,从系统输出的混合物可包括具有35%体积混合物B和65%体积混合物A之比的混合物D。或者,从系统输出的混合物可包括具有10%体积混合物B和90%体积混合物A之比的混合物Z。因此,混合物A与混合物B之比可以在0∶100%至100%∶0范围内。通过改变齿轮泵25和42的速度,可瞬时调节此比例。计算机控制器100可另外控制挤出机和齿轮泵操作参数,如操作压力、操作温度,泵或螺杆速度。
也可用计算机控制器控制混合物的固化速率。例如,可用添加剂泵70混合主促进剂与混合物A和混合物B的混合物。例如,参见图3。可通过计算机控制器控制促进剂的量。也可通过添加剂泵80向混合物A和混合物B的混合物加入辅助促进剂。通过用控制器控制泵的速度,可瞬时调节主促进剂和辅助促进剂的量。
优选计算机控制器100为各挤出机的出口压力设定压力目标值。挤出机速度通过控制器控制并改变,直到满足压力目标。压力目标值由引起挤出机中物质的回流影响混合品质。
在本发明的第一实施例中,形成具有如图4所示横截面轮廓的分层胎面200。分层胎面包含三层或更多层,其中各层具有不同的固化速率。径向最外层210优选由一种胎面混合物形成,这种胎面混合物通过添加剂泵70与促进剂以足以具有第一固化速率的量混合。
径向最内层220由一种胎面混合物形成,这种胎面混合物可以为与最外层210的混合物相同或不同的胎面混合物。主促进剂通过齿轮泵/挤出机70以足以具有相对于径向最外层210的固化速率较快固化速率的量加入到该混合物。径向最内层220的固化速率优选比径向最外层310快30-40%。辅助促进剂也可与主促进剂联合用于产生所需的固化速率。
在径向外层和径向内层之间形成任选的中间层230。中间层由一种所需混合物形成,这种混合物具有相对于径向最外层310的固化速率更快,但比径向最内层320较慢的固化速率。中间层330的固化速率优选比径向最外层310快10-30%。辅助促进剂也可与主促进剂联合用于产生所需的固化速率。
因此,图4的示例性胎面可由相同混合物形成,并且具有在径向变化的固化速率。胎面不限于此,并可包括具有在轴向不同固化速率的一种或多种胎面混合物。胎面也可包括具有在径向和轴向均不同的固化速率的结构。
在本发明的第二实施例中,形成具有如图5所示的横截面轮廓的分层胎面300。分层胎面包含三层或更多层。径向最外层310优选由一种具有高耐磨性的胎面混合物(混合物A)形成。高耐磨性胎面混合物倾向为具有高填料的硬混合物。促进剂通过齿轮泵/挤出机70以足以具有所需固化速率的量加入到混合物中。
径向最内层320优选由具有低或超低滚动阻力的混合物(混合物B)形成。径向最内层320可由100%混合物B形成。具有低滚动阻力的混合物一般为具有低填料的软混合物。低滚动阻力混合物倾向于具有高磨损率。主促进剂通过齿轮泵/挤出机70以足以具有相对于径向最外层310的固化速率更快的固化速率的量加入到该混合物中。径向最内层320的固化速率优选比径向最外层310快30-40%。辅助促进剂也可与主促进剂联合用于产生所需的固化速率。
在径向外层和径向内层之间形成任选的中间层330。中间层330优选由选自径向最外层310(混合物A)和径向最内层320(混合物B)的混合物的共混物形成。共混比可根据需要在10%-90%混合物A与90%-10%混合物B的范围内变化。主促进剂通过添加剂泵70以足以具有相对于径向最外层310的固化速率较快的固化速率,但比径向最内层320较慢的固化速率的量加入到该混合物中。中间层330的固化速率优选比径向最外层310快10-30%。辅助促进剂也可与主促进剂联合用于产生所需的固化速率。
通过改变促进剂的量,或者通过组合使用主促进剂和辅助促进剂,可改变各层的固化速率。通过改变每层使用的促进剂的组成或类型,也可改变固化速率。
为了形成胎面,将第一混合物A层挤到成形机或轮胎成型机上。胎面可以带的形式被挤到轮胎成型机上。可利用图1的混合系统,并将所需混合物A和所述量的选择的所需促进剂进料至挤出机20。混合物A离开齿轮泵25,并通过喷嘴92送到轮胎成型鼓95上。混合物A以所需的分布被挤到轮胎鼓上。
为了形成中间层230,将混合物A与混合物B以所需的量与所需量的主促进剂和/或辅助促进剂共混。在选择所需的共混比后,将混合物A与混合物B用得到精确混合物比的齿轮泵速度比共混。然后将共混物以所需的分布挤到轮胎成型鼓上。
下一步,通过将混合物B以所需的分布挤到轮胎成型鼓上的中间层上,可形成外层。外层也可以为混合物A与混合物B的共混物,以达到所需的性质。
图7显示分层胎面轮廓400的第三实施方案。胎面在径向的混合物组成和固化速率两方面均发生改变。径向外表面405由100%混合物A形成,并且具有第一固化速率。在此实施例中,选择具有高耐磨性的混合物A。高耐磨性胎面混合物倾向为具有高填料的硬混合物。径向最内层410由混合物B形成。混合物B选择成具有低滚动阻力性质,虽然可选择其它混合物性质。径向最内层也具有最快的固化速率。胎面还包括多个中间层,这些中间层在混合物A至混合物B的组成上逐渐变化,随着层径向向外推进,混合物A的量增加,而混合物B的量减少。多个中间层的固化速率也逐渐变化,从径向最内层的最快固化速率,随着层径向向外推进而逐渐减慢。
为了形成胎面,可利用图1的混合系统,将所需的混合物A进料至挤出机20。计算机控制器100也通过齿轮泵70控制加入到混合物的主促进剂的量,以产生第一固化速率。输出混合物离开齿轮泵25,并通过喷嘴92送到轮胎成型鼓95上,并挤入轮胎鼓上形成第一层。然后,第二层挤出到第一层上,如图6中所示。第二层由混合物A和混合物B的共混物形成。在一个实施例中,第二层可由10%混合物A与90%混合物B形成。混合系统的计算机控制器调节各齿轮泵25,42的速度,以控制输出混合物具有10%混合物A与90%混合物B。计算机控制器也通过齿轮泵70控制加入到混合物的主促进剂的量,以产生不同于所述第一速率且优选较快的第二固化速率。然后,将第三层挤出到第一层上。第三层可包含20%混合物A与80%混合物B,并且具有不同于所述第一或第二速率且优选甚至更快的第三固化速率。然后,可将第四层挤出到第三层上,第四层具有30-70的比例,并且具有不同于所述第一或第二速率且优选甚至更快的第四固化速率。可重复此过程,直至外层由100%混合物A形成。
以上实施例的共混比可根据需要改变,并且不限于此。虽然此实施例已改变橡胶的组成和在径向的固化速率,但本发明不限于此。橡胶的组成可在轴向并且也在与径向的组合上变化。橡胶混合物的固化速率也可在轴向并且也在与径向的组合上变化。通过改变橡胶混合物在轴向的组成或共混比,也可形成这种胎面。通过根据需要改变橡胶混合物在轴向和径向两个方向的组成或共混比,也可形成所述胎面。图5显示分解成小递增的胎面轮廓的一部分。一旦已设计理想的胎面轮廓,就将胎面轮廓分解成小的递增区A,B,C,并为各递增区选择所需的共混比和固化速率。利用计算机控制,可将具有所需共混比和固化速率的一条或多条带施加到轮胎成型鼓上。共混比可根据需要在径向、轴向或两个方向上变化。
以下为可与本发明结合使用的示例性组合物。
I.促进剂组合物
在一个实施方案中,可使用单一促进剂系统,即主促进剂。主促进剂可以范围约0.5至约4或约0.8至约1.5phr的总量使用。在另一个实施方案中,可使用主促进剂和辅助促进剂的组合,辅助促进剂以较小量使用,例如约0.05至约3phr,以活化并改善硫化橡胶的性质。可预料这些促进剂的组合对最终性质产生协同作用,并且略好于使用单独的任何一种促进剂产生的作用。另外,可使用延迟作用的促进剂,这些促进剂不受一般处理温度的影响,但在一般硫化温度产生令人满意的固化。也可使用硫化延迟剂。可用于本发明的促进剂的适合类型为胺、二硫化物、胍、硫脲、噻唑、秋兰姆、次磺酰胺、二硫代氨基甲酸盐和黄原酸盐。在一个实施方案中,主促进剂为次磺酰胺。如果使用辅助促进剂,则辅助促进剂可以为胍、二硫代氨基甲酸盐或秋兰姆化合物。适合的胍包括二苯胍等。适合的秋兰姆包括二硫化四甲基秋兰姆、二硫化四乙基秋兰姆和二硫化四苄基秋兰姆。
II.橡胶组合物
可用于橡胶混合物的代表性橡胶包括丙烯腈/二烯共聚物、天然橡胶、卤化丁基橡胶、丁基橡胶、顺-1,4-聚异戊二烯、苯乙烯-丁二烯共聚物、顺-1,4-聚丁二烯、苯乙烯-异戊二烯-丁二烯三元共聚物、乙烯-丙烯三元共聚物(也称为乙烯/丙烯/二烯单体(EPDM)),且特别为乙烯/丙烯/二环戊二烯三元共聚物。可使用以上橡胶的混合物。各橡胶层可包含相同橡胶组合物,或者交替层可具有不同的橡胶组合物。
橡胶混合物可包含扁平状填料(platy filler)。扁平状填料的代表性实例包括滑石、粘土、云母及其混合物。在使用时,扁平状填料的量的范围为约25至150份/100重量份橡胶(以后称为phr)。优选橡胶混合物中扁平状填料的量为约30至约75phr。
可将各种橡胶组合物与常规橡胶混合成分混合。一般使用的常规成分包括炭黑、二氧化硅、偶联剂、增粘剂树脂、加工助剂、抗氧化剂、抗臭氧剂、硬脂酸、活化剂、蜡、油、硫化剂和胶溶剂。本领域的技术人员已知,根据所需的抗磨度和其它性质,一般以常规量使用某些上述添加剂。炭黑的一般加入量占橡胶重量约10至150重量份,优选50至100phr。二氧化硅的一般量在10至250重量份,优选30至80重量份的范围内,也包含二氧化硅和炭黑的共混物。增粘剂树脂的一般量占约2至10phr。加工助剂的一般量占1至5phr。抗氧化剂的一般量占1至10phr。抗臭氧剂的一般量占1至10phr。硬脂酸的一般量占0.50至约3phr。促进剂的一般量占1至5phr。蜡的一般量占1至5phr。油的一般量占2至30phr。硫化剂,如元素硫、二硫化胺、聚合性多硫化物、硫烯烃加合物及其混合物,以范围约0.2至8phr的量使用。胶溶剂的一般量占约0.1至1phr。
III.油
橡胶组合物也可包含最多70phr加工油。加工油可作为一般用于使弹性体增量的增量油包含于橡胶组合物中。通过在橡胶混合期间直接加入油,也可使加工油包含于橡胶组合物中。所用加工油可包含存在于弹性体的增量油和在混合期间加入的加工油两者。适合的加工油包括在本领域已知的各种油,包括芳族油、石蜡油、环烷油、植物油和低PCA油,如MES、TDAE、SRAE和重环烷油。适合的低PCA油包括具有通过IP346方法测定小于3%重量的多环芳族含量的那些油。IP346方法的步骤可发现于Standard Methods for Analysis & Testing of Petroleum and Related Products and British Standard 2000Parts,2003,62版,the Institute of Petroleum,United Kingdom出版。
本发明可根据本文提供的说明而变化。虽然已为了说明本发明展示了某些代表性实施方案和细节,但可在不脱离本发明的范围下对其中的内容进行各种变化和改进,这对本领域的技术人员而言将是显而易见的。因此,应了解,可在所述具体实施方案中作出变化,这些变化将在以下所附权利要求书限定的本发明的完全预定范围内。
Claims (7)
1.一种形成用于轮胎的由第一混合物和第二混合物形成的胎面的方法,所述胎面包含两个或更多个橡胶层,所述方法的特征在于包括以下步骤:
通过主挤出机和第一齿轮泵挤出第一橡胶混合物;
通过第二挤出机和第二齿轮泵挤出第二橡胶混合物,并进入所述主挤出机;
将促进剂泵入所述主挤出机;
通过调节第一齿轮泵的速度和第二齿轮泵的速度,改变所述第一混合物与所述第二混合物的共混比,然后将由所述第一混合物和所述第二混合物形成的橡胶带直接施加到轮胎成型机上,以形成具有第一共混比和第一固化速率的第一橡胶带;
调节第一齿轮泵和第二齿轮泵的速度,以得到第二共混比的所述第一混合物与所述第二混合物,同时调节促进剂的量,以得到不同于所述第一固化速率的第二固化速率,然后施加由所述第二共混比的第一混合物与第二混合物形成的橡胶带,以使具有第二固化速率的第二橡胶层形成到所述轮胎成型机上。
2.权利要求1的方法,其特征在于通过调节第一齿轮泵的速度和第二齿轮泵的速度,以提供第三共混比的所述第一混合物与所述第二混合物,同时调节促进剂的量,并加入辅助促进剂,以形成第三固化速率,然后将由所述第三共混比的第一混合物形成的橡胶带施加到轮胎成型机上,从而在第二层上形成第三橡胶层。
3.权利要求1的方法,其特征在于使齿轮泵与喷嘴组合使用,将连续橡胶带施加到轮胎成型机上。
4.权利要求1的方法,其特征在于第一混合物具有低滚动阻力性质。
5.权利要求1的方法,其特征在于第二混合物具有高耐磨性质。
6.一种形成包含两个或更多个橡胶层的胎面的方法,所述方法的特征在于包括以下步骤:
通过挤出机和齿轮泵挤出橡胶混合物,并与促进剂混合,然后将具有第一固化速率的一条或多条第一橡胶带直接施加到轮胎成型机上;
调节促进剂的量,以得到不同于所述第一固化速率的第二固化速率,然后将具有第二固化速率的一条或多条第二橡胶带直接施加到轮胎成型机上,其中固化速率之一快于另一固化速率。
7.一种形成由第一混合物和第二混合物形成的轮胎元件的方法,所述方法的特征在于包括以下步骤:
通过第一挤出机和第一齿轮泵挤出第一橡胶混合物;
通过第二挤出机和第二齿轮泵挤出第二橡胶混合物,然后进入所述第一挤出机;
将促进剂泵入所述第一挤出机,并使促进剂与所述第一和第二混合物混合,从而形成具有第一共混比和第一固化速率的第一橡胶混合物;并且
将由所述第一橡胶混合物形成的橡胶带直接施加到轮胎模芯上;
通过调节第一齿轮泵和第二齿轮泵的速度,以得到第二共混比的所述第一混合物与所述第二混合物,来形成第二橡胶混合物,同时调节促进剂的量,以得到不同于所述第一固化速率的第二固化速率,然后将由所述第二橡胶混合物形成的一条或多条橡胶带直接施加到轮胎模芯上。
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