CN101389495A - 低透气性橡胶叠层体和使用该叠层体的充气轮胎 - Google Patents
低透气性橡胶叠层体和使用该叠层体的充气轮胎 Download PDFInfo
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Abstract
本发明涉及一种低透气性橡胶叠层体，和内衬层使用了该叠层体的充气轮胎。所述低透气性橡胶叠层体含有平均厚度d满足0.05μm＜d＜5μm的至少1层低透气性树脂(A)的层和至少1层二烯类橡胶组合物(B)的层。所述低透气性树脂(A)含有乙烯组成比为20～50mol％、皂化度为90％以上的乙烯－乙烯醇共聚物，其接合性、气压保持性能和耐久性优异；所述二烯类橡胶组合物(B)，其相对于100重量份二烯类橡胶，含有1～25重量份的硅烷类偶联剂，该硅烷类偶联剂具有与橡胶有反应性的官能团，同时具有烷氧基甲硅烷基。
Description
技术领域
本发明涉及空气低透过性橡胶叠层体和使用该叠层体的充气轮胎，更详细地，涉及低空气透过性的乙烯-乙烯醇共聚物(EVOH)的薄膜与橡胶组合物叠层，提高了接合性、阻气性和耐久性，适合作为气密层(内衬层)使用的低空气透过性橡胶叠层体和使用该叠层体的充气轮胎。
背景技术
乙烯-乙烯醇共聚物(EVOH)，由于具有优异的阻气性，人们在研究将其作为气密层使用。例如，在特开平1-314164号公报中，公开了将EVOH与弹性体(橡胶)叠层得到的防止空气透过的结构体。但是，将EVOH与橡胶叠层的情况，尤其是将极性低的聚合物二烯类橡胶(例如SBR、NR、BR)，与极性非常高的EVOH直接接合是非常困难的。所以，有必要使用底胶和接合剂等来接合，但即使在这种情况下，接合性能、耐久性能仍不充分，进而还有生产工序变得繁琐等问题。
发明内容
所以，本发明的目的在于，为了能够将低空气透过性的乙烯-乙烯醇共聚物(EVOH)作为例如充气轮胎的气密层(内衬层)使用，提供含有EVOH层，接合性、耐久性和气压保持性能优异的低空气透过性橡胶叠层体。
根据本发明，提供一种低透气性橡胶叠层体，含有平均厚度d满足0.05μm<d<5μm的至少1层低透气性树脂(A)的层和至少1层二烯类橡胶组合物(B)的层，所述低透气性树脂(A)含有在30℃的空气透过系数(依照JIS K7126测定)为0.5×10-12cc·cm/cm2·sec·cmHg以下、乙烯组成比为20～50mol％、皂化度为90％以上的乙烯-乙烯醇共聚物；所述二烯类橡胶组合物(B)，相对于100重量份二烯类橡胶含有1～25重量份的硅烷类偶联剂，该硅烷类偶联剂具有与橡胶有反应性的官能团，同时具有烷氧基甲硅烷基。
根据本发明，还提供使用了上述叠层体为内衬层的充气轮胎。
本发明的叠层体，由于EVOH层与特定的橡胶组合物叠层，接合性良好，所以能够得到阻气性和耐久性优异的叠层体，适合作为充气轮胎的内衬层使用。
具体实施方式
本发明者们为了解决上述问题，即，改善以低透气性树脂(例如EVOH)作为气密层与橡胶叠层硫化的情况下EVOH薄膜与二烯类橡胶的接合性，提供具有优异的阻气性和耐久性(即对于动态形变也不剥离的特性)的低透气性橡胶叠层体，进行了深入研究。由于将作为几乎没有极性的聚合物的轮胎用二烯类橡胶(例如SBR、NR、BR等)，与极性非常高的EVOH直接接合是困难的，所以为了改良接合性，以往需要底胶和接合剂。本发明者等发现，不必使用这些底胶和接合剂，通过向轮胎用橡胶中配合含有与橡胶反应的官能团(例如硫元素)的硅烷类偶联剂，能够大幅改善与硫化后的EVOH的接合力。
构成本发明所涉及的叠层体的层的低透气性树脂(组合物)(A)可以是满足上述要件的任意热塑性树脂，优选的是，作为树脂组合物，低透气性树脂组合物使用乙烯-乙烯醇共聚物(EVOH)，其乙烯组成比为20～50mol％，优选为25～40mol％，皂化度为90％以上，优选为95％以上，进而优选为99～100％，其平均厚度d为0.05μm<d<5μm，优选为1～3μm。如果该厚度薄，就不能获得充分的阻气性，所以不优选，相反如果厚，耐拉伸挠曲疲劳性就会变差，所以不优选。
在本发明中所使用的乙烯组成比为20～50mol％、皂化度为90％以上的乙烯-乙烯醇共聚物(EVOH)是公知的共聚物，可以通过例如将乙烯和乙酸乙烯酯进行自由基聚合，并将得到的乙烯-乙酸乙烯酯共聚物(EVA)水解(皂化)来制造。在本发明中，可以将エバ—ルL171B(乙烯组成比26mol％，クラレ制造)、エバ—ルH171B(乙烯组成比38mol％，クラレ制造)等市售品单独或者作为任意的混合物使用。
在本发明的叠层体的一层中所使用的低透气性树脂组合物(A)中，除了上述EVOH成分，还可以配合抗氧化剂、抗老化剂、着色剂、增塑剂、填充剂、加工助剂等在树脂组合物用途中一般配合的各种添加剂，该添加剂可以用一般的方法与树脂混合形成混合物，用于叠层。这些添加剂的配合量，只要不违反本发明的目的，可以采用以往一般的配合量。
构成本发明所涉及的叠层体的另外层的二烯类橡胶组合物(B)，可以由选自二烯类橡胶，例如天然橡胶(NR)、异戊二烯橡胶(IR)、丁二烯橡胶(BR)、卤化丁基橡胶(例如溴化丁基橡胶(Br-IIR)、氯化丁基橡胶(Cl-IIR))、乙烯-丙烯共聚物橡胶(EPM，EPDM)、苯乙烯类弹性体(例如苯乙烯-丁二烯橡胶(SBR)、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS))等中的至少1种构成。
在构成本发明所涉及的叠层体的上述层的二烯类橡胶组合物(B)中，相对于100重量份二烯类橡胶，配合1～25重量份，优选为2～15重量份的下述化合物，所述化合物是具有与橡胶有反应性的官能团，例如具有硫元素本身或者分子中含有硫原子的基团和键(例如巯基、多硫化物键(二硫化物、三硫化物、四硫化物))，同时具有烷氧甲硅烷基的化合物(即硅烷类偶联剂)。如果该配合量少，就不能维持与EVOH层充分的接合性，所以不优选，相反如果过多，橡胶的交联密度就会变高，造成橡胶的耐久性降低，所以不优选。上述硅烷类偶联剂是公知的化合物，例如可以使用作为双(三乙氧基硅丙基)四硫化物、3-巯基丙基甲基二甲氧基硅烷、3-巯基丙基三甲氧基硅烷等市售品。
在构成本发明所涉及的叠层体的层的橡胶组合物(B)中，除了上述橡胶成分，还可以配合碳黑、二氧化硅等其它增强剂(纤维)、硫化或交联剂、硫化或交联助剂、各种油、抗老化剂、增塑剂等在轮胎用途和其它橡胶组合物用途中一般配合的各种添加剂，该添加剂可以用一般的方法混炼制成组合物，用于硫化或交联。这些添加剂的配合量，只要不违反本发明的目的，可以采用以往一般的配合量。
实施例
以下，通过实施例更详细的说明本发明，但不言而喻，本发明的范围不受这些实施例限制。
按照表I所示的配合，将构成层(A)的EVOH组合物的配合和构成层(B)的橡胶组合物的配合示于表I。
实施例1～6和比较例1～7
按照以下方法制作低透气性树脂(EVOH)与橡胶的叠层体。将表I所记载的EVOH溶解到溶剂(水/异丙醇为50/50w/w的混合溶剂)中，制作浓度调整到10重量％的EVOH溶液。(＊在欲将硅烷偶联剂配合到EVOH的情况下，对该溶液配合一定量的硅烷偶联剂)
通过将上述EVOH溶液涂布到聚乙烯(PE)膜上，使溶剂挥发，获得了均匀厚度(表I所记载的厚度)的EVOH薄膜。接着，将与PE叠层的EVOH，与表I所示的厚度0.5mm的橡胶组合物，按照PE/EVOH/橡胶组合物的顺序叠层，揭去PE，从而制作EVOH/橡胶组合物叠层体，进而在EVOH一侧叠层0.5mm的橡胶组合物，制作由橡胶组合物/EVOH/橡胶组合物3层形成的低透气性橡胶叠层体。本EVOH/橡胶组合物的制作方法并不限于上述方法。接着，用该B层叠层体代替内衬层使用，在硫化温度190℃的条件下，制作轮胎(尺寸195/65R14(轮辋14×6JJ))。
用该轮胎进行室内轮胎行走试验(条件：气压140kPa，对转数相当于80km/h的速度的转鼓按压6kN负荷，行走5000km)。结果示于表I。
表I脚注
＊1：クラレ(株)制造エバ—ルL171B(皂化度99％以上)
＊2：クラレ(株)制造エバ—ルG156(皂化度99％以上)
＊3：信越シリコ—ン(株)制造KBM-803
＊4：PT.NUSIRA SIR20
＊5：旭化成ケミカルズ(株)制造タフデン1000R
＊6：昭和シエル石油(株)制造エキストラクト4号S
＊7：アクゾノ—ベル(株)制造クリステツクスHS OH20
＊8：大内新兴化学工业(株)制造ノクセラ—CZ-G
＊9：BF GOODRICH(株)制造硬脂酸
＊10：正同化学工业(株)制造氧化锌3种
＊11：新日化カ—ボン(株)制造HTC#G
＊12：信越シリコ—ン(株)制造KBM-803
＊13：デグサ(株)制造Si69
比较例1是将EVOH膜与没有配合硅烷类偶联剂的橡胶组合物叠层、硫化，从而得到的低透气性橡胶叠层体，该叠层体接合/密合性差，在轮胎行走试验后，出现界面剥离造成的橡胶层松动，不优选。比较例2～3是在EVOH溶液中配合巯基硅烷，将通过浇铸得到的膜与橡胶组合物叠层、硫化，从而得到的低透气性橡胶叠层体。该叠层体接合/密合性差，在轮胎行走后，出现界面剥离/橡胶松动，不优选。比较例4是在EVOH膜上涂布巯基硅烷，与橡胶组合物叠层、硫化得到的低透气性橡胶叠层体。但是，即使涂布巯基硅烷作为底胶，接合/密合性也差，在轮胎行走后，出现界面剥离造成的橡胶层的松动，不优选。比较例5在橡胶组合物中配合0.5重量份的巯基硅烷，但由于配合量过少，不能获得充分的接合性，出现界面剥离造成的橡胶层的松动，不优选。
实施例1～4是将在橡胶中配合混合巯基硅烷后的橡胶组合物与EVOH叠层、硫化，从而得到的低透气性橡胶叠层体，能够获得优异的接合性。
比较例6由于巯基硅烷的配合量过多，橡胶组合物的交联密度过高，橡胶层在行走中破裂，所以不优选；比较例7由于EVOH层过厚，所以出现破裂，还产生剥离，不优选。
实施例5～6是使用Si69为硅烷偶联剂，与EVOH叠层、硫化得到的低透气性橡胶叠层体的例子。这也显示了优良的接合性。
工业实用性
将作为几乎没有极性的聚合物的轮胎用二烯类橡胶(SBR、NR、BR)，与极性非常高的EVOH直接接合是困难的，以往需要底胶和接合剂，在本发明中，通过在轮胎用橡胶组合物中，配合具有与橡胶反应的官能团的硅烷类偶联剂，能够大幅度改善与硫化后的EVOH的接合力，所以能够得到具有优异的阻气性和耐久性(即对于动态形变也不剥离的特性)的低透气性橡胶叠层体。
Claims (7)
1.一种低透气性橡胶叠层体，含有平均厚度d满足0.05μm<d<5μm的至少1层低透气性树脂(A)的层、和至少1层二烯类橡胶组合物(B)的层，所述低透气性树脂(A)含有在30℃的空气透过系数为0.5×10-12cc·cm/cm2·sec·cmHg以下、乙烯组成比为20～50mol％、皂化度为90％以上的乙烯-乙烯醇共聚物，所述空气透过系数是依照JIS K7126测定的；所述二烯类橡胶组合物(B)，相对于100重量份二烯类橡胶含有1～25重量份的硅烷偶联剂，该硅烷偶联剂具有与橡胶有反应性的官能团，同时具有烷氧基甲硅烷基。
2.如权利要求1所述的低透气性橡胶叠层体，上述二烯类橡胶组合物(B)含有2～15重量份硅烷偶联剂。
3.如权利要求1或2所述的低透气性橡胶叠层体，上述橡胶组合物(B)含有天然橡胶(NR)、异戊二烯橡胶(IR)、丁二烯橡胶(BR)和苯乙烯-丁二烯橡胶(SBR)中的至少1种。
4.如权利要求1～3的任一项所述的低透气性橡胶叠层体，上述橡胶组合物(B)还含有硫化剂和硫化促进剂。
5.如权利要求1～4的任一项所述的低透气性橡胶叠层体，上述硅烷类偶联剂分子中含有硫。
6.如权利要求1～4的任一项所述的低透气性橡胶叠层体，上述硅烷类偶联剂分子中含有巯基。
7.一种充气轮胎，在内衬层中使用了权利要求1～6的任一项所述的低透气性橡胶叠层体。
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| CN102019733A (zh) * | 2009-09-10 | 2011-04-20 | 住友橡胶工业株式会社 | 制造气密层用聚合物薄片的方法及制造充气轮胎的方法 |
| CN102019733B (zh) * | 2009-09-10 | 2015-05-13 | 住友橡胶工业株式会社 | 制造气密层用聚合物薄片的方法及制造充气轮胎的方法 |
| CN102019702A (zh) * | 2009-09-18 | 2011-04-20 | 住友橡胶工业株式会社 | 制造充气轮胎的方法 |
| CN102234385A (zh) * | 2010-04-30 | 2011-11-09 | 横滨橡胶株式会社 | 橡胶组合物和使用它而成的充气轮胎 |
| CN102234385B (zh) * | 2010-04-30 | 2015-04-22 | 横滨橡胶株式会社 | 橡胶组合物和使用它而成的充气轮胎 |
| CN102482471A (zh) * | 2010-08-26 | 2012-05-30 | 横滨橡胶株式会社 | 热塑性弹性体组合物及使用该热塑性弹性体组合物的充气轮胎 |
| CN102482471B (zh) * | 2010-08-26 | 2015-01-14 | 横滨橡胶株式会社 | 热塑性弹性体组合物及使用该热塑性弹性体组合物的充气轮胎 |
| US8940835B2 (en) | 2010-08-26 | 2015-01-27 | The Yokohama Rubber Co., Ltd. | Thermoplastic elastomer composition and pneumatic tire using same |
| CN103842187A (zh) * | 2011-10-26 | 2014-06-04 | 横滨橡胶株式会社 | 充气轮胎 |
| CN110077172A (zh) * | 2011-10-26 | 2019-08-02 | 横滨橡胶株式会社 | 充气轮胎 |
| CN110077173A (zh) * | 2011-10-26 | 2019-08-02 | 横滨橡胶株式会社 | 充气轮胎 |
| CN110077174A (zh) * | 2011-10-26 | 2019-08-02 | 横滨橡胶株式会社 | 充气轮胎 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20080314490A1 (en) | 2008-12-25 |
| JP4278697B2 (ja) | 2009-06-17 |
| JPWO2007100159A1 (ja) | 2009-07-23 |
| EP1995079A1 (en) | 2008-11-26 |
| EP1995079A4 (en) | 2009-11-04 |
| CN101389495B (zh) | 2010-04-07 |
| EP1995079B1 (en) | 2011-06-29 |
| US8609232B2 (en) | 2013-12-17 |
| WO2007100159A1 (ja) | 2007-09-07 |
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