CN1856399A - 层压物及使用其的充气轮胎 - Google Patents
层压物及使用其的充气轮胎 Download PDFInfo
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- CN1856399A CN1856399A CNA2004800278238A CN200480027823A CN1856399A CN 1856399 A CN1856399 A CN 1856399A CN A2004800278238 A CNA2004800278238 A CN A2004800278238A CN 200480027823 A CN200480027823 A CN 200480027823A CN 1856399 A CN1856399 A CN 1856399A
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Images
Classifications
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Abstract
防止空气透过层/粘合剂层的层压物,具有包括热塑性弹性体组合物的防止空气透过层,所述组合物包含热塑性树脂作为连续相,和橡胶组合物,其分散在其中,作为分散相,并且设置在防止空气透过层的一个表面上,层压物还具有厚度为100μm或以下的粘合剂组合物层,其自粘性小于5N,对未硫化的、基于二烯的橡胶的粘性为5N或以上,包含100重量份的热塑性弹性体,其包含50重量份或以上的环氧改性的、基于苯乙烯-丁二烯的嵌段共聚物,从而总量为30~200重量份的萜烯树脂和芳香改性的萜烯树脂,其重均分子量Mw为1000或以下,软化点为60~120℃,0.1~3重量份的内部脱模剂和0.1~2重量份的有机过氧化物。
Description
技术领域
本发明涉及防止空气透过层/粘合剂(或增粘剂,以下相同)层的层压物及使用该层压物的充气轮胎。更具体地,本发明涉及防止空气透过层/粘合剂层的层压物,其对硫化橡胶等具有较好的粘合性,较好的可加工性,并适合于降低充气轮胎的重量,还涉及使用该层压物的充气轮胎。
背景技术
使用热塑性弹性体用于充气轮胎的防止空气透过层的技术在本领域是已知的(例如,参见日本专利2999188)。例如,当在圆筒形状的两层中,与粘合剂层一起挤出热塑性弹性体时,如果设置在外侧的粘合剂层太粘,成型时它将粘在收取(或卷取)的辊子上,并且严重降低可加工性。而且,这要求收取时在管状材料之间插入释放纸,Mylar等,这是成本和运输重量方面的问题。而且,如果粘合剂层不足够粘,在轮胎生产时,存在这样的问题,即防止空气透过层从轮胎胎体(carcase)剥离,由此无法成型。而且,如果粘合剂组合物中的交联剂的量太大,存在这样的问题,即在高温下与热塑性弹性体组合物共挤出的过程中发生过早硫化(scorching)。应注意到日本专利公开(A)11-240108提出了热塑性树脂/橡胶的层压物,但是本发明涉及目标及其构成中的不同技术。
发明公开
因此,本发明的目的是解决上述防止空气透过层/粘合剂层的层压物的现有层压物的问题,并提供防止空气透过层/粘合剂层的层压物,其能够提高充气轮胎生产中的可加工性,并且例如,具有较好的与轮胎胎体的粘合性,有利于降低轮胎重量。
根据本发明,提供了防止空气透过层/粘合剂层的层压物,具有(I)包括热塑性弹性体组合物的防止空气透过层,所述组合物包含热塑性树脂作为连续相,和分散在其中的橡胶组合物,作为分散相,并且设置在防止空气透过层的一个表面上,(II)厚度为100μm或以下的粘合剂组合物层,由粘合剂组合物形成,所述组合物自粘性小于5N,对未硫化的、基于二烯的橡胶的粘性为5N或以上,包含(i)总量为100重量份的热塑性弹性体,其包含50重量份或以上的环氧改性的、基于苯乙烯-丁二烯的嵌段共聚物,从而环氧乙烷氧含量变为1~3重量%,(ii)总量为30~200重量份的萜烯树脂(A)和芳香改性的萜烯树脂(B),其重均分子量Mw为1000或以下,软化点为60~120℃,(A)∶(B)的比例=100∶0~50∶50(重量比),(iii)0.1~3重量份的内部脱模剂和(iv)0.1~2重量份的有机过氧化物,其一分钟半衰温度为160℃或以上,并且提供了使用所述层压物的充气轮胎。
附图简述
图1是吹胀成型机的图解图,其用于评价本说明书中的实施例和对比例中粘合剂组合物的测试。
实施本发明的最佳方式
根据本发明,可能获得粘合剂组合物和热塑性弹性体防止空气透过层的层压物,该粘合剂组合物使聚合物的自粘性(粘合剂互相的粘性)和与金属或硫化橡胶的粘性保持低,以提高可加工性,其在形成轮胎时表现出足够的与未硫化橡胶的粘性,并且其不会过早硫化,甚至当在200℃或以上的温度下与热塑性弹性体共挤出时也是如此。通过使用该层压物,可能获得较好的粘合性,并且可能获得重量轻的充气轮胎而不影响其它性质。
本说明书和附加的权利要求中使用的单数形式(例如“一个(a)”、“一个(an)”和“那个(the)”)应该被理解为包括复数形式,除了从上下文清楚看出是别的方式之外。
根据本发明,在一个表面上提供由热塑性弹性体组合物组成的防止空气透过层和粘合剂组合物层,以形成防止空气透过层/粘合剂层的层压物,该热塑性弹性体组合物具有热塑性树脂作为连续相,和橡胶组合物作为分散相,该粘合剂组合物层的自粘性小于5N,优选1~4N,对未硫化的、基于二烯的橡胶的粘性为5N或以上,优选7~20N,厚度为100μm或以下,优选5~70μm。
本发明中使用的防止空气透过层是已知的,其由热塑性弹性体组合物组成,该组合物具有热塑性树脂作为连续相,和橡胶组合物作为分散相。例如,可使用日本未审查专利公开(A)2002-80644等中描述的那些。
可在本发明中使用的粘合剂组合物包含(i)总量为100重量份的热塑性弹性体,其包含50重量份或以上,优选60~100重量份的,环氧改性的(或环氧化的)、基于苯乙烯-丁二烯的嵌段共聚物,从而使环氧乙烷氧含量变为1~3重量%,优选1.2~2.8重量%,(ii)总量为30~200重量份,优选40~120重量份的萜烯树脂(A)和芳香改性的萜烯树脂(B),萜烯树脂(A)的重均分子量Mw为1000或以下,优选500~900,软化点为60~120℃,优选80~110℃,萜烯树脂(B)的重均分子量Mw为1000或以下,优选500~900,软化点为60~120℃,优选80~110℃,(A)∶(B)的比例=100∶0~50∶50,优选100∶0~70∶30(重量比),(iii)0.1~3重量份,优选0.2~2重量份的内部脱模剂和(iv)0.1~1重量份,优选0.3~1重量份的有机过氧化物,其一分钟半衰温度为160℃或以上,优选165~190℃。
如以上说明的,可在本发明的粘合剂组合物中使用的热塑性弹性体,必须包含具有指定环氧乙烷氧浓度的、环氧改性的、基于苯乙烯-丁二烯的嵌段共聚物(ESBS)。可通过使用过酸或氢过氧化物,使例如基于苯乙烯-丁二烯的嵌段共聚物(SBS)环氧化,来进行这种环氧改性。作为过酸,可提及过甲酸、过乙酸、过苯甲酸、三氟过乙酸等。而且,作为氢过氧化物,可提及过氧化氢、叔丁基氢过氧化物、过氧化枯烯等。如果这样获得的环氧化SBS共聚物(ESBS)的环氧乙烷氧含量太低,与防止空气透过层的粘合性易于变差,因此这不是优选的,然而相反地,如果它太高,与轮胎橡胶的粘合性易于变差,因此这也不是优选的。而且,如果热塑性弹性体中ESBS共聚物的含量太小,与防止空气透过层的粘合性易于变差,因此这不是优选的。
作为根据本发明的、由热塑性弹性体组成的粘合剂组合物的母体聚合物,除了环氧化SBS共聚物,可使用各种SBS共聚物、各种苯乙烯-异戊二烯嵌段(SIS)共聚物和各种它们的部分氢化物等。
根据本发明的粘合剂组合物,可包含指定的萜烯树脂(A)或萜烯树脂(A)和芳香改性的萜烯树脂(B)的混合物。
此处,“萜烯”是具有异戊二烯单元的化合物系列的通用术语。“萜烯树脂”是主要由从松树树脂或柑橘类水果皮获得的油(例如α-蒎烯、β-蒎烯、二戊烯(苧烯)等)组成的均聚或共聚产物。与聚合物的溶解度和软化点可根据这些单体的比例和分子量(即聚合度)以及分子量分布而改变。从赋予粘合性的角度来看,可在本发明中使用的萜烯树脂(A)优选为β-蒎烯和二戊烯的共聚物或二戊烯的均聚物。二戊烯的均聚物是更优选的。
可通过使萜烯树脂(A)与苯酚、烷基苯酚等共缩合来生产芳香改性的萜烯树脂(B)。也可使用商业可获得的产品。芳香改性的萜烯树脂(B)的芳香改性量并不具体限制,但是优选为基于萜烯树脂重量的约1~20重量%。
本发明中基于萜烯的树脂(A)/芳香改性的萜烯树脂(B)的比例,可根据工作环境条件(例如温度、湿度等)和轮胎组件的粘性程度而改变。如果萜烯树脂的比例较大,自粘性和对金属或未硫化橡胶的粘性降低,并且可加工性提高,然而相反地,如果芳香改性的萜烯树脂的比例较大,对未硫化橡胶组件的粘性提高。从这一点来看,本发明人发现,如果(A)∶(B)为100∶0~50∶50(重量比),优选100∶0~70∶30,可获得其良好的平衡。而且,如果粘合剂层的厚度超过100μm,重量增加,耐久性往往变差,因此这不是优选的。
为了进一步调节粘性,根据本发明的粘合剂组合物其中可包含内部脱模剂,其量为0.1~3重量份,优选0.1~1重量份,基于总共100重量份的热塑性弹性体。作为内部脱模剂,例如,可使用通常使用的硬脂酸或油酸和它们的金属盐等。通过以这种方式混合内部脱模剂,尤其可能降低自粘性。通过调节粘性时合适地调节混合量从而与空气温度等的变化相对应,可能保持粘性的最佳状态。
在本发明中,作为交联剂,有机过氧化物用于交联,其一分钟半衰温度为160℃或以上,优选165~190℃,其量为0.1~2重量份,优选0.3~1重量份。作为这种有机过氧化物,具体地,例如可使用过氧化二枯基、过氧化二叔丁基、过氧化叔丁基枯基、过氧化苯甲酰、2,5-二甲基-2,5-二(叔丁基过氧化)己炔-3、2,5-二甲基-2,5-二(叔丁基过氧化)己烷、1,3-二(叔丁基过氧化异丙基)苯、4,4-二-过氧化叔丁基-缬草烯酸酯-正丁基酯(4,4-di-t-butylperoxy-valerenate-n-butyl ester)等。
根据本发明,粘合剂组合物可置于热塑性弹性体组合物与基于二烯的橡胶之间,以形成用于充气轮胎的层压物。
因此,提供防止空气透过层/粘合剂的层压物,其整体上形成圆筒(管状)形状,在内侧具有热塑性弹性体组合物的防止空气透过层,该组合物包含热塑性树脂作为连续相,和橡胶组合物作为分散相,在外侧具有粘合剂组合物,其具有较好的与轮胎胎体的粘合性,并有利于降低轮胎重量。
作为基于二烯的橡胶,可提及可用于轮胎的任何基于二烯的橡胶,例如,天然橡胶(NR)、聚异戊二烯橡胶(IR)、各种类型的苯乙烯-丁二烯共聚物橡胶(SBR)、各种类型的聚丁二烯橡胶(BR)、丙烯腈-丁二烯共聚物橡胶(NBR)、以及乙烯-丙烯-二烯共聚物(EPDM),(卤化)丁基橡胶等。这些橡胶可单独使用或以其任何共混物使用。
作为根据本发明的层压物的热塑性弹性体的树脂组分,可提及例如基于聚酰胺的树脂(例如,尼龙6(N6)、尼龙66(N66)、尼龙11(N11)、尼龙12(N12)、尼龙610(N610)、尼龙612(N612)等)、基于聚酯的树脂(例如,聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸乙二醇酯(PET)、聚间苯二甲酸乙二醇酯(PEI)等)、基于聚腈的树脂(例如,聚丙烯腈(PAN)、聚甲基丙烯腈等)、基于聚甲基丙烯酸酯的树脂(例如,聚甲基丙烯酸甲酯(PMMA)、聚甲基丙烯酸乙酯等)、基于聚乙烯的树脂(例如,乙酸乙烯酯、聚乙烯醇(PVA)、聚偏二氯乙烯(PDVC)、聚氯乙烯(PVC)等)、基于纤维素的树脂(例如,醋酸纤维素和纤维素乙酸酯丁酸酯)、基于氟的树脂(例如,聚偏二氟乙烯(PVDF)、聚氟乙烯(PVF)等)、基于酰亚胺的树脂(例如,芳香聚酰亚胺(PI))等。
通过混合热塑性树脂和弹性体,来获得可用于根据本发明的层压物的热塑性弹性体。作为弹性体,可提及例如基于二烯的橡胶及其氢化物(例如,NR、IR、SBR、BR、NBR等)、基于烯烃的橡胶(例如,乙烯丙烯橡胶(EPDM、EPM)、IIR等)、丙烯酸酯橡胶(例如,ACM)、卤化橡胶(例如,Br-IIR、CI-IIR、溴化异丁烯对甲基苯乙烯共聚物(Br-IPMS)等)、硅橡胶(例如,甲基乙烯硅橡胶、二甲基硅橡胶等)、含硫橡胶(例如聚硫橡胶)、氟橡胶(例如,基于偏二氟乙烯的橡胶、基于乙烯醚的含氟橡胶)、热塑性弹性体(例如,基于苯乙烯的弹性体、基于烯烃的弹性体、基于酯的弹性体、基于聚氨酯的弹性体或基于聚酰胺的弹性体)等。这些橡胶可单独使用,或以任何两种或多种类型的任何共混物使用。
当与热塑性树脂混合时,弹性体组分可被动态硫化。此处,“动态硫化”是指热塑性树脂、弹性体组分和交联剂被进料到例如双螺杆混合器等中,并熔融混合混合物,同时弹性体组分被硫化。在动态硫化的情况下,应该根据加入的弹性体组分的组成,合适地确定硫化剂、硫化辅剂、硫化条件(例如,温度和时间)等,并且没有特别限制。作为硫化剂,可使用一般的橡胶硫化剂(或交联剂)。具体地,作为基于硫的硫化剂,可使用硫粉末、沉淀硫等,用量为例如0.5~4phr[基于100重量份橡胶组分(聚合物)的重量份]。
而且,作为基于有机过氧化物的硫化剂,具体地,可提及例如过氧化二枯基、过氧化二叔丁基、过氧化叔丁基枯基、过氧化苯甲酰、2,5-二甲基-2,5-二(过氧化叔丁基)己炔-3、2,5-二甲基-2,5-二(叔丁基过氧化)己烷、1,3-二(叔丁基过氧化异丙基)苯、4,4-二-叔丁基过氧化-缬草烯酸酯-正丁基酯(4,4-di-t-butylperoxy-valerenate-n-butyl ester)等。作为基于硫脲的硫化加速剂,可提及乙烯硫脲、二乙基硫脲等。
而且,使用配合剂,弹性体组分可与一般的橡胶一起使用。例如,可使用锌白、硬脂酸和油酸及其金属盐等。热塑性弹性体组合物的生产方法包括,用双螺杆捏合机/挤出机等提前熔融混合热塑性树脂组分和弹性体组分(在未硫化的橡胶的情况下),以使弹性体组分在形成连续相(即母体相)的热塑性树脂中分散为分散相(即区域(domain))。当硫化弹性体组分时,可加入硫化剂,同时混合,从而导致弹性体组分的动态硫化。而且,在混合过程中可加入各种用于热塑性树脂或弹性体组分的配合剂(而不是硫化剂),但是优选在混合之前将它们混合。用于混合热塑性树脂和弹性体组分的捏合机没有特别限制。可使用螺杆挤出机、捏合机、班伯里密炼机、双螺杆捏合机/挤出机等。作为熔融捏合条件,温度应该为至少热塑性树脂熔融的温度。而且,混合时的剪切速度优选为1000~7500秒-1。整个混合时间优选为30秒~10分钟。当加入硫化剂时,加入后的硫化时间优选为15秒~5分钟,然后挤出或压延由该方法制备的热塑性弹性体组合物,以形成像薄片的膜。膜的形成方法可基于通常热塑性树脂或热塑性弹性体形成为膜的方法。
这样获得的膜将热塑性树脂(A)的结构作为母体,其中弹性体组分(B)分散为分散相(即区域)。通过采用这种分散的结构,使热塑性加工变得可能,由于由树脂层构成的连续相的作用,由膜构成的防止空气透过层可被赋予足够的柔性和足够的刚性。在成型时,不管弹性体组分的量是多少,可获得与热塑性树脂的可加工性相等的可加工性。因此,通常的树脂成型机,即挤出或压延,可用来形成膜。
当混合热塑性树脂和弹性体时,热塑性树脂(A)和弹性体组分(B)的具体比例没有特别限制,并且应该由膜厚度、防止空气透过性质和柔性的平衡来适当地确定,但是优选的范围是,(A)/(B)重量比为10/90~90/10,更优选15/85~90/10。
除了以上基本组分,本发明中使用的粘合剂组合物可包含在常规粘合剂组合物中通常使用的各种添加剂,如氧化锌、抗氧化剂、着色剂。可通过常规方法使用这些添加剂。只要不有害地影响本发明的目的,这些添加剂的量可为混合的常规一般量。
实施例
现在将使用实施例来进一步解释本发明,但是本发明的范围不限于这些实施例。
实施例1~4和对比例1~6
如表I所示的每个配方的粘合剂组合物,由螺杆直径为40mmφ的单螺杆挤出机混合,并通过抗粘溶液,然后被切割机切成小球。另一方面,具有如表II所示配方的热塑性弹性体组合物,由双螺杆挤出机混合,然后在水中冷却,被切割机切成小球。使用50mmφ和75mmφ挤出机和圆筒形叠压口模将这些小球挤出成圆筒形状,厚度为50μm和150μm。这样获得的测试膜经受如表I所示的测试。
评价的测试方法
1)粘性测试
使用50mmφ和75mmφ挤出机和管状叠压口模,将如表I所示的每个配方的粘合剂组合物和如表II所示的热塑性弹性体薄片挤出成圆筒形状,厚度为50μm和150μm。将所得物切成宽度为1cm的带子,附着在粘性测试器的圆环部分,然后在自粘性的情况下,其被垂直压向从相同薄片上切下的10cm2片,在对胎体层的粘性的情况下,其被垂直压向未硫化的胎体元件。当剥离它时,测量力。在以下条件下,使用Toyoseiki PICMA粘性测试器进行测量。结果如表I所示。
测量条件
顶部样品的尺寸: 12.7mm×152mm
压力负荷: 4.90N
剥离速度: 120mm/min
加压时间: 0秒
温度: 20℃
相对湿度: 65%
2)圆筒形成型可加工性测试
由图1所示的吹胀方法,将如表I所示的每个粘合剂组合物和如表II所示的热塑性弹性体组合物挤出成两层管状形状,其在外侧具有粘合剂层。它被吹成直径为355mm,然后被夹送辊折叠,在那种状态下被收取(或卷取)。使用以下标准用于评价。结果如表I所示。
++:在挤出性能和收取上都没有问题
+:在挤出性能上没有问题,然而膜稍微倾向于粘在夹送辊上,但是这并不成为主要问题
±:在挤出性能上没有问题,但是膜粘在夹送辊上,并且收取困难
-:挤出不能良好进行
3)轮胎模压性能测试
每个由图1所示的吹胀机器制备的355mm热塑性弹性体/粘合剂膜层压物,被切成宽度为360mm,然后被插入轮胎形成转鼓,围绕胎体卷绕,形成胎缘(bead),并卷起。接着,使侧面(side)、加固带(belt)和帽(cap)粘附在一起,由此形成生轮胎(green tire)。形成之后,由以下标准肉眼观察管状膜和胎体结合的程度。结果如表I所示。
++:胎体橡胶很好地跟随形状,没有观察到高出部分和剥离
+:观察到一些高出部分,但是没有观察到从胎体的剥离
±:一些从胎体的剥离和高出,需要由手工缝合来校正
-:在基本上整个周缘上从胎体剥离,使得不可能传送到硫化步骤
4)粘合测试
每个热塑性弹性体膜与表I的粘合剂一起被挤出和成型,被放在如表III所示的2mm未硫化橡胶薄片上,在160℃下硫化20分钟以上。每个被切成宽度为25mm和长度为100mm的条。在宽度方向上,切到热塑性弹性体膜的中心,由此制备测试样品。它被放在Ueshima Seisakusho Demattia爆裂测试器中,并重复经受连续拉伸应力500,000次,卡盘距离为60mm,冲程为10mm,然后肉眼观察膜从切割部分的任何剥离。并用以下标准评价。结果如表I所示。
++:根本没有观察到膜的剥离
+:从切割部分观察到轻微剥离,但是是由于橡胶或粘合剂材料的破坏引起的
-:大量从切割部分的剥离,并形成界面剥离
表I.粘合剂组合物的配方
对比例1 | 对比例2 | 对比例3 | 对比例4 | 对比例5 | 对比例6 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | |
配方(重量份) | ||||||||||
E-GMA-VA(Bondfast 7B,Sumitomo Chemical)*1 | 60 | - | - | - | - | - | - | - | - | - |
环氧化SBS(Epofriend A1020,Daicel ChemicalIndustries)*2 | - | 50 | 10 | 50 | 50 | 50 | 50 | 80 | 50 | 50 |
SBS(Tufprene A,Asahi Kasei)*3 | 40 | 50 | 90 | 50 | 50 | 50 | 50 | 20 | 50 | 50 |
松香酯(Pensel AD,Arakawa Chemical)*4 | 70 | 70 | - | - | - | - | - | - | - | - |
萜烯树脂(YS树脂D-105,Yasuhara Chemical)*5 | - | - | 70 | - | 70 | 70 | 70 | 70 | 70 | 40 |
芳香改性的萜烯树脂(YS树脂TR-105,Yasuhara Chemical)*6 | - | - | - | 70 | - | - | - | - | - | 30 |
氧化锌(锌白#3,Seido Chemical) | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
硬脂酸(硬脂酸珠粒,Kao) | 1 | 1 | 1 | 1 | - | 1 | 1 | 1 | 1 | 1 |
有机过氧化物(Parkerdox 14,Kayaku Akzo) | - | - | - | - | - | 2.5 | 0.1 | 1 | 1 | 1 |
测试结果 | ||||||||||
自粘性(N) | 2.3 | 2.6 | 3.7 | 6.3 | 5.3 | 3.4 | 3.5 | 3.0 | 3.4 | 4.8 |
圆筒成型可加工性 | (+) | (+) | (+) | (±) | (±) | (-)*1 | (++) | (++) | (++) | (+) |
与胎体的粘性(N) | 3.8 | 4.0 | 7.7 | 4.6 | 8.0 | 7.4 | 5.9 | 7.4 | 10.1 | |
轮胎模压性能 | (-) | (-) | (+) | (±) | (++) | (+) | (+) | (+) | (++) | |
粘合测试 | (+) | (+) | (-) | (+) | (+) | (+) | (++) | (++) | (+) |
*1:成型是不可能的
表II.热塑性弹性体的配方
材料名称 | 产品名称 | 制造商 | 配方量(重量份 |
Br-IPMS | EXXPRO 89-4 | Exxon Mobil Chemical | 100 |
PA6/66 | Ube尼龙5033B | Ube Industries | 30 |
PA 11 | Rilsan BESN O TL | Atofina Japan | 40 |
氧化锌 | 锌白#3 | Seido Chemical | 0.2 |
硬脂酸 | 硬脂酸珠粒 | Kao | 0.5 |
硬脂酸锌 | 硬脂酸锌 | Seido Chemical | 0.3 |
增塑剂 | BM-4 | Daihachi Chemical Industry | 10 |
抗氧化剂 | Irganox 1098 | Ciba Specialty Chemicals | 0.5 |
表III.橡胶配方
材料名称 | 产品名称 | 制造商 | 配方量(重量份) |
NR | RSS#3 | - | 60 |
SBR | Nipol 1502 | Nippon Zeon | 40 |
碳 | Seast 300 | Tokai Carbon | 60 |
氧化锌 | 锌白#3 | Seido Chemical | 5 |
硬脂酸 | 硬脂酸珠粒 | Kao | 1 |
抗氧化剂 | Nocrac RD | Ouchi Shinko Chemical Industrial | 1 |
芳香油 | 提取物#4S | Showa Shell Oil | 10 |
硫 | 油扩张的硫 | Karuizawa Refinery | 3 |
硫化加速剂 | Noccelar CZ | Ouchi Shinko Chemical Industrial | 1 |
表1的脚注
*1:常规粘合剂(主要成分:环氧改性的乙烯-乙酸乙烯酯共聚物)
*2:环氧改性的苯乙烯-丁二烯-苯乙烯嵌段共聚物
*3:苯乙烯-丁二烯-苯乙烯嵌段共聚物
*4:增粘树脂
*5:增粘树脂
*6:增粘树脂
在表I中,对比例1是这样的情况的实施例,即对于粘合剂的聚合物使用E-GMA-VA,对于增粘剂使用松香酯,对比例1存在与胎体的粘性不足的问题,并且不能成型轮胎。对比例2是这样的情况的实施例,即对于粘合剂的聚合物使用SBS体系,对于增粘剂使用松香酯体系,对比例2存在与胎体的粘性不足的问题,并且不能成型。对比例3是这样的情况的实施例,即其中环氧改性的苯乙烯-丁二烯-苯乙烯嵌段共聚物(ESBS)的量小于规定量,存在剥离测试中的差的结果的问题。对比例4是这样的情况的实施例,即对于增粘剂仅使用芳香改性的萜烯树脂,存在太多的自粘性的问题,很难模压。对比例5是这样的情况的实施例,即其中没有使用硬脂酸(即内部脱模剂),存在太多的自粘性的问题,很难模压。对比例6是这样的情况的实施例,即其中包含过量的交联剂即有机过氧化物,由于挤出过程中粘合剂的过早硫化,存在产生大量凝胶颗粒的问题。
与以上相反,实施例1和3是包含规定量的有机过氧化物即交联剂的实施例,在挤出加工过程中,粘合剂没有过早硫化,在自粘性和与胎体粘性的平衡方面较好,剥离测试结果也非常好。实施例2是其中增加环氧改性的SBS配方量的实施例,提高了粘合性。实施例4是这样的情况的实施例,即使得增粘剂为萜烯树脂和芳香改性的萜烯树脂的混合物,很大地提高了与胎体的粘性。
工业实用性
本发明的防止空气透过层/粘合剂层的层压物在轮胎生产中具有较好的可加工性,较好的与轮胎胎体的粘合性,有助于减少轮胎重量,适合于用作充气轮胎。
Claims (8)
1、防止空气透过层/粘合剂层的层压物,具有(I)包含含有作为连续相的热塑性树脂和分散在其中作为分散相的橡胶组合物的热塑性弹性体组合物的防止空气透过层,并且设置在防止空气透过层的一个表面上,(II)厚度为100μm或以下的粘合剂组合物层,其由粘合剂组合物形成,所述组合物的自粘性小于5N,对未硫化的、基于二烯的橡胶的粘性为5N或以上,包含(i)总量为100重量份的热塑性弹性体,其包含50重量份或以上的环氧改性的、基于苯乙烯-丁二烯的嵌段共聚物,从而使环氧乙烷氧含量变为1~3重量%,(ii)总量为30~200重量份的萜烯树脂(A)和芳香改性的萜烯树脂(B),其重均分子量Mw为1000或以下,软化点为60~120℃,(A)∶(B)的比例=100∶0~50∶50(重量比),(iii)0.1~3重量份的内部脱模剂和(iv)0.1~2重量份的有机过氧化物,其一分钟半衰温度为160℃或以上。
2、如权利要求1所述的防止空气透过层/粘合剂层的层压物,在内侧包括热塑性弹性体组合物的防止空气透过层,所述组合物包含热塑性树脂作为连续相,和橡胶组合物作为分散相,在外侧包括粘合剂组合物,其整体上形成圆筒形状。
3、如权利要求1或2所述的层压物,其中所述的热塑性树脂为聚酰胺。
4、如权利要求1~3中任何一项所述的层压物,其中橡胶组合物是由异丁烯和对甲基苯乙烯的部分卤化共聚物组成的橡胶。
5、如权利要求1~4中任何一项所述的层压物,其中萜烯树脂为二戊烯树脂。
6、如权利要求5所述的层压物,其中芳香改性的萜烯树脂是根据权利要求5的萜烯树脂与芳香乙烯单体共聚的。
7、如权利要求1~6中任何一项所述的层压物,其中有机过氧化物为过氧化二枯基、2,5-二甲基-2,5-二(叔丁基过氧化)己烷或2,5-二甲基-2,5-二(叔丁基过氧化)己炔-3。
8、使用根据权利要求1~7中任何一项的层压物的充气轮胎。
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JP2003336057A JP4433744B2 (ja) | 2003-09-26 | 2003-09-26 | 積層体及びそれを用いた空気入りタイヤ |
JP336057/2003 | 2003-09-26 |
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EP (1) | EP1666242B1 (zh) |
JP (1) | JP4433744B2 (zh) |
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WO (1) | WO2005030479A1 (zh) |
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- 2004-09-08 US US10/572,549 patent/US7730919B2/en not_active Expired - Fee Related
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US20070031661A1 (en) | 2007-02-08 |
JP4433744B2 (ja) | 2010-03-17 |
EP1666242A4 (en) | 2008-04-23 |
CN100575069C (zh) | 2009-12-30 |
EP1666242B1 (en) | 2014-09-03 |
EP1666242A1 (en) | 2006-06-07 |
US7730919B2 (en) | 2010-06-08 |
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WO2005030479A1 (ja) | 2005-04-07 |
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