CN112895665B - 高阻隔层叠体及其使用该层叠体的充气轮胎 - Google Patents

高阻隔层叠体及其使用该层叠体的充气轮胎 Download PDF

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CN112895665B
CN112895665B CN201911224012.1A CN201911224012A CN112895665B CN 112895665 B CN112895665 B CN 112895665B CN 201911224012 A CN201911224012 A CN 201911224012A CN 112895665 B CN112895665 B CN 112895665B
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周志峰
王清才
陈名行
赵天琪
李花婷
陈宏�
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Beijing Research and Design Institute of Rubber Industry
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Abstract

本发明公开了一种基于热塑性弹性体的柔性高阻隔层叠体及其用该层叠体制备的轮胎。发明的高阻隔层叠体是由橡胶组合物层和热塑性弹性体薄膜层复合而成，本发明提供了一种高阻隔层叠体及其制备方法，采用真空热压复合工艺，把热塑性弹性体阻隔层与混炼胶层热压复合，消除薄膜阻隔层与混炼胶层的剥离脱层和存气问题。用本发明制备的层叠体作为气密层部件可直接与胎体胶贴合成型，解决了薄膜与胎体胶之间的脱层存气等工艺问题。

Description

高阻隔层叠体及其使用该层叠体的充气轮胎
技术领域
本发明涉及一种具有柔软性和高气体阻隔性的层叠体材料。
背景技术
以TPV薄膜替代常用的卤化丁基橡胶组合物用于轮胎内衬层，重量更轻，气密性更优异，不仅保持更高的轮胎气压保持率，更能降低轮胎重量，达到降低滚动阻力效果。TPV薄膜是采用动态硫化技术，以聚酰胺树脂为连续相，橡胶为分散相的复合物，TPV的粘性很差，无法与胎体或胎体过渡层胶进行粘合。为克服这一缺点，通常在薄膜上涂覆粘合剂，但存在轮胎高温高压运行时粘合力下降的问题。另一技术方案是在薄膜和胎体过渡层胶中间增加一层粘合层。
CN 101277827A公开了一种热塑性弹性体组合物/粘结剂/二烯橡胶组合物的层叠体和使用它的充气轮胎。其中公开的热熔胶含有环氧化SBS和50～70质量份的增粘树脂，以片状形式粘接热塑性弹性体和二烯橡胶，存在粘接时的操作复杂性增加，以及硫化后与橡胶层剥离分层的问题。
CN 104602911A公开了一种包含粘结层的结构。该粘结层用于粘接基于热塑性聚酰胺弹性体防渗透膜。该粘结层包含100％至少一种卤化含异丁烯的弹性体和大约1～20份的至少一种增粘剂的混合物。由于该粘结层配料与现有的卤化丁基橡胶内衬层配料近似，且粘性更高，因此存在加工难度高及成本提高的问题。
CN 102481808A及CN 104411508A提供一种包含热塑性树脂或热塑性弹性体组合物的膜与橡胶层的层叠体作为内衬层材料的充气轮胎。其中的薄膜直接与橡胶层进行贴合硫化。所述的橡胶层与薄膜的粘性较低，成型加工过程中，存在薄膜在橡胶层上打折或偏移，从而导致硫化后薄膜贴合皱褶或剥离分层。
CN 102463846A公开了把DVA薄膜与橡胶层直接贴合硫化的技术方案，把薄膜直接附在胎体胶上，通过对胎体胶配方进行优化，以提高薄膜与胎体胶硫化后的粘合强度。
上述公开文献中主要开发新型粘合胶或粘合剂，用以解决TPV薄膜与橡胶硫化后的粘接强度。但TPV薄膜与胎体或过渡层混炼胶贴合成型时，即使TPV薄膜表面涂覆粘合剂，仍不可避免地出现TPV薄膜与橡胶脱层剥离及存有空气，造成轮胎硫化后薄膜皱褶甚至破裂。
发明内容
1.本发明的目的
本发明的目的是提供高阻隔层叠体及其制备方法，其中采用热压复合工艺，把热塑性弹性体阻隔层与含有与混炼胶层热压复合，阻隔层与混炼胶层无剥离脱层和存气现象，不仅兼顾硫化后薄膜与橡胶的粘接强度，也解决了硫化前薄膜与混炼胶之间的脱层存气问题，该层叠体可作为气密层部件与胎体胶直接贴合成型。本发明另一目的是提供该阻隔层叠体作为气密层部件制备的轮胎。
2.技术方案
本发明目的可以通过以下技术方案实现：
本发明所述的高阻隔层叠体主要是由热塑性弹性体阻隔膜层与橡胶组合物的层形成的叠层体构成。
本发明所述的热塑性弹性体层为溴化丁基橡胶/聚酰胺动态硫化热塑性弹性体膜，溴化丁基橡胶/聚酰胺热塑性弹性体是在210℃～230℃温度下，在双螺杆挤出机中，采用动态硫化技术把溴化丁基橡胶均匀分散在聚酰胺连续相中制备而成弹性体粒子，再用吹膜机把粒子加工成热塑性弹性体薄膜，薄膜厚度0.06～0.2mm
本发明所述的橡胶组合物包括天然橡胶，或顺丁橡胶、丁苯橡胶、异戊橡胶或溴化丁基橡胶；相对于100份橡胶，含有5～15份的官能团改性热塑性弹性体，官能团热塑性弹性体优选为马来酸酐SBS或环氧SBS。
本发明所述的增粘树脂为萜烯树脂、烷基酚乙炔树脂树脂一种或它们的混合物；相对于100份橡胶，萜烯树脂和烷基酚乙炔树脂树脂总量为5～40份。
本发明提供所述的高阻隔层叠体的制备方法。包括：(1)先将橡胶组合物所述组分按所述的比例混炼；(2)制备成规定厚度的混炼胶片；(3)在真空模压机中，按照牛皮纸/混炼胶片/阻隔层/牛皮纸顺序叠放，放置于模具中，然后进行热压，热压条件80～120℃，抽真空时间10～30s，热压时间30s～120s。
本发明中用该层叠体用作气密层部件，气密层部件的厚度0.2～1.5mm。
本发明提供了由该层叠体制备的轮胎。
3.有益效果
本发明提供了一种高阻隔层叠体及其制备方法，其中采用热压复合工艺，预先把热塑性弹性体阻隔层与混炼胶层热压复合，消除薄膜阻隔层与混炼胶层的剥离脱层和存气问题。用本发明制备的层叠体作为气密层部件可直接与胎体胶贴合成型，解决了薄膜与胎体胶之间的脱层存气等工艺问题。
具体实施方式
下面结合实施例进一步说明本发明目的，本发明的范围不受这些实施例的限制。
橡胶组合物的制备
各比较例和实施例的橡胶组合物的配方组成见表1，混炼胶的制备方法步骤如下：
在1.57L本伯里混炼机中，初始温度90℃，80转/分钟，投入除硫磺和促进剂外的所有组分混炼7分钟，排胶温度达到150℃以上排胶，冷却至室温在6寸开炼机上加入硫磺和促进剂，制成对比例和实施例的混炼胶。
层叠体制备
步骤1：把比较例和实施例中的橡胶组合物在开炼机上制成规定厚度的混炼胶片；
步骤2：按照牛皮纸/混炼胶片/薄膜/牛皮纸的顺序，依次叠放，然后把叠层放置于模具中；
步骤3：把步骤2中的层叠体放置于真空平板硫化机中，在100℃，2MPa的压力下，热压60s，制的本发明的薄膜-橡胶层叠体。
层叠体的评价
按照混炼胶-薄膜层叠体热压外观质量、层叠体与胎体贴合成型工艺、硫化后轮胎外观评价层叠体的质量。各对比例和实施例结果见表1。
表1比较例和实施例配方
Figure BDA0002301635840000051
说明
1)MAH-SBS，马来酸酐改性苯乙烯-丁二烯-苯乙烯嵌段共聚物，市售产品。
2)萜烯树脂，牌号PICCOLYTE S105，皮诺瓦公司产品。
3)增粘树脂，牌号Koresin，德国巴斯夫产品。
4)促进剂NS，N-叔丁基-2-苯并噻唑次磺酰胺，天津迈科化工。
根据表1结果可见：
1)比较例1～比较例2，比较例1采用薄膜直接与混炼胶片贴合，出现薄膜-混炼胶剥离存气现象，导致轮胎硫化后薄膜破裂。比较例2采用表面涂覆粘合剂薄膜，再与混炼胶片贴合，仍出现薄膜-混炼胶剥离存气现象，轮胎硫化薄膜破裂。比较例3未抽真空状态下热压，层叠体有少量气泡，层叠体与胎胚贴合成型，胎胚放置后，出现气泡扩大。
2)实施例1～实施3，采用真空热压工艺制备的薄膜-混炼胶层叠体表面无皱褶、无气泡，用该层叠体作为气密层部件，其橡胶面直接与胎体胶贴合成型，整个成型工艺正常，胎胚外观质量正常，薄膜与混炼胶无剥离存气，胎胚硫化后也无薄膜皱褶和破裂。

Claims (4)

1.一种高阻隔层叠体，是由热塑性弹性体膜阻隔层与橡胶组合物的层形成的叠层体，其特征在于：橡胶组合物包含橡胶、官能团改性热塑性弹性体、增粘树脂以及硫化剂；所述阻隔层为基于动态硫化技术制备的溴化丁基热塑性弹性体薄膜，厚度0.06～0.2mm；所述官能团改性热塑性弹性体为马来酸酐改性热塑性弹性体为马来酸酐改性苯乙烯-丁二烯-苯乙烯嵌段共聚物(MAH-SBS)、马来酸酐改性苯乙烯-异戊二烯-苯乙烯嵌段共聚物(MAH-SIS)、马来酸酐改性苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物(MAH-SEBS)、马来酸酐改性乙烯-乙酸乙烯基酯共聚物(MAH-EVA)中一种或它们任意几种的混合物；所述的官能团改性热塑性弹性体可以为环氧化改性SBS、环氧化改性SIS、环氧化改性SEBS；所述增粘树脂为萜烯树脂、松香树脂、石油树脂、烷基酚乙炔树脂中的一种或它们任意几种的混合物。
2.根据权利要求1所述的高阻隔层叠体的制备方法，其特征在于：采用真空热压复合工艺制备，先将橡胶组合物的组分按比例混炼，然后把混炼胶与薄膜层叠放置于真空模压机中，在80℃～120℃温度下，进行热压复合，制备的层叠体表面无剥离、无皱褶、无存气。
3.一种充气轮胎用气密层 部件，其特征在于：由权利要求1中所述的层叠体制成，该气密层部件厚度0.2～1.5mm。
4.一种充气轮胎，其特征在于：使用了权利要求1中的层叠体作为气密层。
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US20150183270A1 (en) * 2012-07-27 2015-07-02 Bridgestone Corporation Laminate for inner liner, and tyre using same
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