CN101659724A - 改性的乙烯-乙烯醇共聚物、阻气性树脂及其模制品 - Google Patents
改性的乙烯-乙烯醇共聚物、阻气性树脂及其模制品 Download PDFInfo
- Publication number
- CN101659724A CN101659724A CN200910159828A CN200910159828A CN101659724A CN 101659724 A CN101659724 A CN 101659724A CN 200910159828 A CN200910159828 A CN 200910159828A CN 200910159828 A CN200910159828 A CN 200910159828A CN 101659724 A CN101659724 A CN 101659724A
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- China
- Prior art keywords
- gas barrier
- ethylene
- vinyl alcohol
- alcohol copolymer
- modification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical class OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 title abstract description 6
- -1 methacryloxy group Chemical group 0.000 claims abstract description 27
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- 230000004048 modification Effects 0.000 claims description 61
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- 238000005452 bending Methods 0.000 abstract description 17
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- 229910000077 silane Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
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- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- 101000837805 Homo sapiens Testis-expressed protein 44 Proteins 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
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- 102100028514 Testis-expressed protein 44 Human genes 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
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- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
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- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
乙烯－乙烯醇共聚物有优良的阻气性，但其耐弯曲疲劳性差。本发明改进了耐弯曲疲劳性，并且不降低阻气性和耐热性。通过掺入0.01－1摩尔％的上式(3)表示的结构单元(3)改性乙烯含量为20－50摩尔％的乙烯－乙烯醇共聚物，其中n表示2－5的整数，m表示10－20的整数，R1表示C1－C20脂族烃基，条件是R1可以包含巯基、硫代酸酯基、亚磺酰胺基、乙烯基、甲基丙烯酰氧基或丙烯酰氧基。该改性的乙烯－乙烯醇共聚物可以用作阻气性树脂，可以成型或者层压该阻气性树脂并用在多种应用如充气轮胎和软管中。
Description
技术领域
本发明涉及一种改性的乙烯-乙烯醇共聚物，更特别地涉及一种包含该改性的乙烯-乙烯醇共聚物的阻气性树脂及用该阻气性树脂生产的模制品，尤其是充气轮胎和软管。
背景技术
乙烯-乙烯醇共聚物有优良的阻气性，但缺点是其差的耐弯曲疲劳性。已知有一种用环氧化合物改性乙烯-乙烯醇共聚物的方法来克服该缺点。参见日本未审查专利公开No.2003-231715。
发明内容
技术问题
然而如果用环氧化合物改性乙烯-乙烯醇共聚物，则将改进耐弯曲疲劳性，但阻气性和耐热性(熔点)将有下降趋势。本发明致力于克服乙烯-乙烯醇共聚物的缺点也就是改进耐弯曲疲劳性，同时不降低阻气性和耐热性。
解决问题的方案
本发明是一种改性的乙烯-乙烯醇共聚物，其包含20-50摩尔％的下式(1)表示的结构单元(1)
-CH2-CH2- (1)
下式(2)表示的结构单元(2)
和0.01-1摩尔％的下式(3)表示的结构单元(3)
其中n表示2-7的整数，m表示10-20的整数，R1表示C1-C20脂族烃基或者用巯基、硫代酸酯基、亚磺酰胺基、乙烯基、甲基丙烯酰氧基或丙烯酰氧基取代的脂族烃基。
优选通过熔体混合乙烯-乙烯醇共聚物和下式(4)表示的烷基聚醚硅烷制备改性的乙烯-乙烯醇共聚物：
其中R2是甲基或乙基，R1、n和m与以上相同。
本发明还是一种包含该改性的乙烯-乙烯醇共聚物的阻气性树脂。
该阻气性树脂优选包含100重量份该改性的乙烯-乙烯醇共聚物和5-120重量份用酸酐改性的软树脂。
本发明还是一种包含该阻气性树脂的模制品。
本发明还是一种包含一层该阻气性树脂和一层除该阻气性树脂之外的树脂和/或弹性体的层压材料。
除该阻气性树脂之外的树脂优选是至少一种选自聚烯烃、聚酰胺、聚酯、聚苯乙烯、聚氨酯、聚偏1，1-二氯乙烯、聚氯乙烯、聚丙烯腈和聚碳酸酯的树脂。
除该阻气性树脂之外的弹性体优选选自基于二烯的弹性体、基于氨基甲酸酯的弹性体、基于烯烃的弹性体和基于苯乙烯的弹性体。
本发明是一种包含该阻气性树脂或该层压材料作为空气阻隔层的的充气轮胎。
本发明还是一种包含该阻气性树脂或该层压材料作为空气阻隔层的软管。
本发明的有利效果
本发明改性的乙烯-乙烯醇共聚物有优良的阻气性、耐热性和耐弯曲疲劳性。因为本发明改性的乙烯-乙烯醇共聚物有优良的阻气性、耐热性和耐弯曲疲劳性，其适合用作阻气性树脂以及用在要求阻气性的模制品尤其是充气轮胎和软管中。
具体实施方式
本发明改性的乙烯-乙烯醇共聚物包含结构单元(1)、结构单元(2)和结构单元(3)。
结构单元(1)是下式(1)表示的所谓乙烯单元：
-CH2-CH2- (1)，
结构单元(2)是下式(2)表示的所谓乙烯醇单元：
结构单元(3)是下式(3)表示的在其侧链上包含烷基聚醚甲硅烷基的结构单元：
其中n表示2-7的整数，优选4-6的整数，更优选5，m表示10-20的整数，优选11-18的整数，更优选12-16的整数，并且R1表示具有1-20个碳原子，优选2-10个碳原子，更优选3-5个碳原子的脂族烃基。然而R1可以包含巯基、硫代酸酯基、亚磺酰胺基、乙烯基、甲基丙烯酰氧基或丙烯酰氧基。R1尤其优选3-巯基丙基。
该改性的乙烯-乙烯醇共聚物包含20-50摩尔％，优选30-45摩尔％，更优选35-40摩尔％的结构单元(1)。如果结构单元(1)的含量太低，则耐弯曲疲劳性有不充分的倾向，另一方面如果其太高，则阻气性有变得不充分的倾向。
该改性的乙烯-乙烯醇共聚物包含0.01-1摩尔％，优选0.03-0.5摩尔％，更优选0.05-0.25摩尔％的结构单元(3)。如果结构单元(3)的含量太低，则耐弯曲疲劳性有不充分的倾向，另一方面如果其太高，则阻气性有变得不充分的倾向。
在组成该改性的乙烯-乙烯醇共聚物的结构单元中除了结构单元(1)和结构单元(3)之外优选有结构单元(2)。也就是该改性的乙烯-乙烯醇共聚物优选包含49.9-79摩尔％的结构单元(2)。然而该改性的乙烯-乙烯醇共聚物在不妨碍本发明效果的范围内可以包含除结构单元(1)、结构单元(2)和结构单元(3)之外的结构单元。注意，可以用NMR测量该改性的乙烯-乙烯醇共聚物中每种结构单元的含量。
该改性的乙烯-乙烯醇共聚物是用下式(4)表示的烷基聚醚硅烷改性的包含结构单元(1)和结构单元(2)的乙烯-乙烯醇共聚物：
其中R2表示甲基或乙基，R1、n和m与以上相同。
将乙烯-乙烯醇共聚物与式(4)所示的烷基聚醚硅烷熔体混合可以制备改性的乙烯-乙烯醇共聚物。通过在高于其熔融温度的温度下掺混包含20-50摩尔％结构单元(1)的乙烯-乙烯醇共聚物与式(4)所示的烷基聚醚硅烷，式(4)所示的烷基聚醚硅烷通过缩合与乙烯-乙烯醇共聚物的OH基团反应，从而除去醇并且形成结构单元(3)。乙烯-乙烯醇共聚物与式(4)所示烷基聚醚硅烷的混合比为基于乙烯-乙烯醇共聚物的总计100摩尔的结构单元(1)和结构单元(2)混合0.01-1摩尔式(4)中所示的烷基聚醚硅烷。对熔体混合的条件没有特别的限定，只要在这些条件中乙烯-乙烯醇共聚物和式(4)所示的烷基聚醚硅烷反应形成结构单元(3)，但例如可以使用双螺杆挤出机在200-270℃的温度下加工1-5分钟。
式(4)所示的烷基聚醚硅烷可以使用商品或者可以合成。商品实例是德固赛(Evonik Degussa)生产的VP Si363。合成可以如下进行。在反应容器内加入具有三烷氧基甲硅烷基的硅烷化合物(例如3-巯基丙基三甲氧基硅烷、3-巯基丙基三乙氧基硅烷、乙烯基三乙氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三乙氧基硅烷、3-丙烯酰氧基丙基三甲氧基硅烷和3-丙烯酰氧基三乙氧基硅烷)，加入十二烷基苯磺酸或其它酸催化剂，还加入2摩尔当量的聚氧乙烯烷基醚(例如聚氧乙烯十二烷基醚、聚氧乙烯鲸蜡醚、聚氧乙烯硬脂醚等等)，基于1摩尔当量硅烷化合物，使混合物在10-100℃，优选20-60℃温度下搅拌的同时在减压条件下反应数小时，得到烷基聚醚硅烷。
本发明阻气性树脂包含该改性的乙烯-乙烯醇共聚物。本发明阻气性树脂可以仅由该改性的乙烯-乙烯醇共聚物组成，然而它可以在不妨碍本发明效果的范围内包含其它物质。例如本发明阻气性树脂可以是包含除改性的乙烯-乙烯醇共聚物之外的酸酐改性的软树脂(下文也简称为“改性软树脂”)的混合物。也就是，本发明阻气性树脂可以是改性的乙烯-乙烯醇共聚物和改性软树脂的混合物。包含改性软树脂还可以改进耐弯曲疲劳性。所混合的改性软树脂的量优选为5-120重量份，基于100重量份该改性的乙烯-乙烯醇共聚物。如果改性软树脂的量太小，则对耐弯曲疲劳性的改进效果将更小，另一方面如果改性软树脂的量太大，则阻气性有变得不充足的倾向。
改性的乙烯-乙烯醇共聚物和改性软树脂的混合物优选是改性的乙烯-乙烯醇共聚物和改性软树脂的熔体混合物。改性的乙烯-乙烯醇共聚物和改性软树脂可以在高于其熔融温度的温度下熔体混合。对熔体混合条件没有特别的限定，然而例如使用双螺杆挤出机在200-270℃混合1-5分钟。
酸酐改性软树脂是用酸酐改性的软树脂。“软树脂”指室温下杨氏模量不超过100Mpa的树脂。软树脂的实例包括基于烯烃的聚合物、基于乙烯的聚合物、乙烯-α-烯烃共聚物、乙烯-丙烯共聚物、乙烯-丁烯共聚物和乙烯-丙烯橡胶。
通过用酸酐改性软树脂可以改进与该改性的乙烯-乙烯醇共聚物的相容性。可以合适地选择改性软树脂中的酸酐以得到与该改性的乙烯-乙烯醇共聚物的适当的相容性，然而酸酐的量优选为0.1-2重量％，基于改性软树脂的重量。
该酸酐改性软树脂包含无水马来酸改性的乙烯-α-烯烃共聚物。优选无水马来酸改性的乙烯-丙烯共聚物或乙烯-丁烯共聚物。这些物质可商购并且可以从三井化学公司(Mitsui Chemicals，Inc)以商标名
MP-0620(无水马来酸改性的乙烯-丙烯共聚物)和MP-7020(无水马来酸改性的乙烯-丁烯共聚物)得到。
本发明阻气性树脂如上提及可以在不妨碍本发明效果的范围内包含其它物质。该阻气性树脂可以是与除该改性软树脂之外的树脂如聚乙烯醇、乙烯-乙烯醇共聚物、聚酰胺、聚酯、聚烯烃、聚苯乙烯、聚氨酯树脂、聚偏1，1-二氯乙烯、聚氯乙烯、和聚碳酸酯等的混合物。此外除上述成分以外它还可以包含混合到其中的添加剂如炭黑、硅石和其它填料、硫化或交联剂、硫化或交联促进剂、不同类型的油、防老剂和其它各种类型的通常用于树脂用途和其它橡胶组合物用途而混合的添加剂。可通过常用方法捏合入这些添加剂以得到待硫化或交联的组合物。所混合的这些添加剂的量可以是传统用量，只要不违背本发明的目的。
本发明阻气性树脂可以用作各种阻气性材料。
本发明阻气性树脂可用于各种模制品。该模制品的形状包括，但不限于膜形状、圆柱形状等。对成型方法没有特别的限定，可以使用常用方法。可以使用T模挤出机、吹胀机等将本发明阻气性树脂制成膜，该膜因为其优良的阻气性、耐热性和耐弯曲疲劳性而可适合用作充气轮胎的内衬。另外圆柱形模制品还可适合用作软管。
可以将本发明阻气性树脂(下文也简称为“阻气性树脂”)层压到除本发明阻气性树脂之外的树脂(下文也简称为“其它树脂”)或者除本发明阻气性树脂之外的弹性体(下文也简称为“弹性体”)上以形成层压材料。包含阻气性树脂层和其它树脂和/或弹性体层的层压材料指包含阻气性树脂层和其它树脂层的双层层压材料，包含阻气性树脂层和弹性体层的双层层压材料，包含阻气性树脂层、其它树脂层和弹性体层的三层层压材料，包含一层或多层阻气性树脂层和一层或多层其它树脂层的多层层压材料，包含一层或多层阻气性树脂层和一层或多层弹性体层的多层层压材料，或者包含一层或多层阻气性树脂层、一层或多层其它树脂层和一层或多层弹性体层的多层层压材料。
其它树脂包括聚烯烃、聚酰胺、聚酯、聚苯乙烯、聚氨酯、聚偏1，1-二氯乙烯、聚氯乙烯、聚丙烯腈和聚碳酸酯。这些可以单独使用，或者可以使用其两种或多种的混合物。
弹性体包括基于二烯的弹性体、基于氨基甲酸酯的弹性体、基于烯烃的弹性体和基于苯乙烯的弹性体。这些可以单独使用，或者可以使用其两种或多种的混合物。还可以将该其它树脂和弹性体混合在一起使用。
作为生产层压材料的方法，可以生产每个层(膜)，并且将它们彼此粘结，或者可以通过共挤出生产层压材料，然而优选后者。对于共挤出可以使用通常使用的方法。例如可以使用共挤吹胀和共挤吹塑。
可以在要求阻气性的各种应用中使用包含阻气性树脂层和其它树脂层和/或弹性体层的本发明层压材料。例如可以使用这些层压材料作为空气阻隔层生产充气轮胎或软管。
可以使用常用方法作为使用本发明层压材料作为空气阻隔层生产充气轮胎的方法。例如当将内衬安排在胎体层内侧时，将本发明的层压材料放置在圆柱形的成胎转筒上，将胎体层、带束层、胎面层和由正常轮胎生产中使用的未硫化橡胶制成的其它元件按该顺序叠加，然后拔出转筒，得到生胎。接着根据普通方法硫化该生胎以生产期望充气轮胎。
可以使用常用方法作为使用本发明阻气性树脂生产软管的方法。例如可以如下制备软管。首先通过十字头挤出方法预先使用本发明阻气性树脂颗粒将热塑性弹性体组合物从树脂挤出机挤出在涂布有脱模剂的心轴上，从而形成内管。此外可以将本发明的另一阻气性树脂或常用的热塑性弹性体挤出在内管之上以形成内管外层。接着，如果必要，通过涂布或喷淋将粘合剂应用到内管上。此外可以用编织机在内管之上编织加强纱或加强钢丝。如果必要，将粘合剂涂布在加强层之上用于与外管粘结，然后使用与本发明阻气性树脂或其它常用的热塑性弹性体组合物相同的方式从十字头树脂挤出机中挤出树脂，以形成外管。最后取出心轴，可得到软管。涂布在内管或加强层上的粘合剂包括基于异氰酸酯的、基于氨基甲酸酯的、基于酚树脂的、基于间苯二酚的、基于氯化橡胶的和基于HRH的粘合剂，然而特别优选基于异氰酸酯的和基于氨基甲酸酯的粘合剂。
实施例
实施例1-6和对比实施例1-3
为了生产改性的乙烯-乙烯醇共聚物，使用可乐丽工程公司(KurarayCo.，Ltd)生产的含有38摩尔％结构单元(1)的EVAL-H171B作为乙烯-乙烯醇共聚物，使用式(5)的三种类型的烷基聚醚硅烷作为烷基聚醚硅烷：
其中n＝5并且m＝12(下文称为“烷基聚醚硅烷1”)，n＝5并且m＝16(下文称为“烷基聚醚硅烷2”)，以及n＝5并且m＝18(下文称为“烷基聚醚硅烷3”)。
将表1中类型和数量的乙烯-乙烯醇共聚物和烷基聚醚硅烷加料到双螺杆捏合机(日本制钢所(Japan Steel Works)生产的TEX44)中并且在230℃熔体捏合3分钟，得到改性的乙烯-乙烯醇共聚物(实施例1-6)。注意，对比实施例1是未改性的乙烯-乙烯醇共聚物，对比实施例2和3是分别使用2摩尔％和4摩尔％缩水甘油代替烷基聚醚硅烷生产的改性的乙烯-乙烯醇共聚物。
以线材形式从挤出机中连续地排出每种改性的乙烯-乙烯醇共聚物，用水冷却，用切割机切割为丸状，然后通过T模挤出机(220℃)成型为膜，得到厚度为25μm的膜。
使用下述测试方法测试改性的乙烯-乙烯醇共聚物。
[弯曲疲劳]
制备50张如上生产并且切割为21cm×30cm尺寸的单层膜，并且基于ASTM F 392-74，将它们弯曲50次、100次、200次、250次、1000次、10000次、20000次、50000次、75000次和100000次，然后使用Rigaku Kogyo生产的Gelbo Flex测试机测量针孔的数量。在每个弯曲次数上进行5次测量，将这些测量的平均值记录为针孔数量。将测量结果绘图，以弯曲次数(P)作为横坐标，针孔数量(N)作为纵坐标。通过外推到2位有效数字，确定产生一个针孔的弯曲次数。
[熔融温度]
通过热分析(DTA或DSC)测量比热的温度依赖性，记录峰值温度作为熔融温度。
[透气系数]
基于JIS K6404，制备样品并且于60℃测量透气性。结果显示为以对比实施例1的透气性系数值为100的值。该值越大则阻气性越好。
表1所示为得到的测试结果。清楚地看出，与未改性的乙烯-乙烯醇共聚物(对比实施例1)相比，本发明的烷基聚醚硅烷改性的乙烯-乙烯醇共聚物(实施例1-6)的耐弯曲疲劳性显著提高。另外现有技术的环氧改性的乙烯-乙烯醇共聚物的耐弯曲疲劳性(对比实施例2和3)也提高，但耐热性和阻气性下降，而本发明烷基聚醚硅烷改性的乙烯-乙烯醇共聚物(实施例1-6)提高了耐弯曲疲劳性，并且不降低耐热性和阻气性。
实施例7
将80重量份的无水马来酸改性的EPM(三井化学公司生产的
MP-0620)加入100重量份实施例3的改性的乙烯-乙烯醇共聚物中，并且熔体捏合以制备阻气性树脂。在评价时，树脂的耐弯曲疲劳数为52000，熔融温度为160℃并且透气性系数为32。
对比实施例4
使用与实施例7相同的方式生产阻气性树脂，不同的是使用实施例7中未改性的乙烯-乙烯醇共聚物(Kurarary Co.Ltd.生产的EVAL-H171B，其乙烯单元的含量为38摩尔％)代替实施例3中的改性的乙烯-乙烯醇共聚物。在评价时，树脂的弯曲疲劳数为340，熔融温度为161℃并且透气性系数为34。
从实施例7和对比实施例4的评价结果可以清楚地看出，与未改性的乙烯-乙烯醇共聚物相比，使用改性的乙烯-乙烯醇共聚物将使耐弯曲疲劳性显著提高。
Claims (10)
1.一种改性的乙烯-乙烯醇共聚物，其包含20-50摩尔％的下式(1)表示的结构单元(1)
-CH2-CH2- (1)、
下式(2)表示的结构单元(2)
和0.01-1摩尔％的下式(3)表示的结构单元(3)
其中n表示2-7的整数，m表示10-20的整数，R1表示C1-C20脂族烃基或者用巯基、硫代酸酯基、亚磺酰胺基、乙烯基、甲基丙烯酰氧基或丙烯酰氧基取代的脂族烃基。
2.如权利要求1所述的改性的乙烯-乙烯醇共聚物，其中通过熔体混合乙烯-乙烯醇共聚物与下式(4)表示的烷基聚醚硅烷来制备改性的乙烯-乙烯醇共聚物：
其中R2是甲基或乙基，R1、n和m与以上相同。
3.一种阻气性树脂，其包含权利要求1或2所述的改性的乙烯-乙烯醇共聚物。
4.如权利要求3所述的阻气性树脂，其包含100重量份所述改性的乙烯-乙烯醇共聚物和5-120重量份用酸酐改性的软树脂。
5.一种模制品，其包含权利要求3或4所述的阻气性树脂。
6.一种层压材料，其包含一层权利要求3或4所述的阻气性树脂和一层除该阻气性树脂之外的树脂和/或弹性体。
7.如权利要求6所述的层压材料，其中除该阻气性树脂之外的树脂是至少一种选自聚烯烃、聚酰胺、聚酯、聚苯乙烯、聚氨酯、聚偏1，1-二氯乙烯、聚氯乙烯、聚丙烯腈和聚碳酸酯的树脂。
8.如权利要求6或7所述的层压材料，其中除该阻气性树脂之外的弹性体选自基于二烯的弹性体、基于氨基甲酸酯的弹性体、基于烯烃的弹性体和基于苯乙烯的弹性体。
9.一种充气轮胎，其包含权利要求3或4所述的阻气性树脂或者权利要求6-8中任一项所述的层压材料作为空气阻隔层。
10.一种软管，其包含权利要求3或4所述的阻气性树脂或权利要求6-8中任一项所述的层压材料作为空气阻隔层。
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| JP2008215517A JP4488097B2 (ja) | 2008-08-25 | 2008-08-25 | ガスバリア樹脂成形品または積層体 |
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| EP (1) | EP2159234B1 (zh) |
| JP (1) | JP4488097B2 (zh) |
| KR (1) | KR20100024343A (zh) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107116869A (zh) * | 2011-05-31 | 2017-09-01 | 株式会社普利司通 | 多层结构体、充气轮胎用气密层以及充气轮胎 |
| CN109535707A (zh) * | 2012-05-28 | 2019-03-29 | 横滨橡胶株式会社 | 充气轮胎 |
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| JP4488097B2 (ja) * | 2008-08-25 | 2010-06-23 | 横浜ゴム株式会社 | ガスバリア樹脂成形品または積層体 |
| JP5440249B2 (ja) * | 2010-02-25 | 2014-03-12 | 横浜ゴム株式会社 | 変性エチレン−ビニルアルコール共重合体、その製造方法およびガスバリア樹脂組成物 |
| BR112014020182A8 (pt) | 2012-02-14 | 2017-07-11 | Bridgestone Corp | Pneu |
| JP5911731B2 (ja) * | 2012-02-14 | 2016-04-27 | 株式会社ブリヂストン | タイヤ |
| EP2969594A4 (en) | 2013-03-15 | 2016-10-26 | Bridgestone Americas Tire | LOW WEIGHT INTERNAL CHAMBER AND ASSOCIATED METHODS |
| JP6434266B2 (ja) * | 2013-12-17 | 2018-12-05 | 富士紡ホールディングス株式会社 | ラッピング用樹脂定盤及びそれを用いたラッピング方法 |
| DE102019203254A1 (de) * | 2019-03-11 | 2020-09-17 | CONTITECH KüHNER GMBH & CIE KG | Kältemittelschlauch |
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| US4650721A (en) * | 1983-12-23 | 1987-03-17 | Mobil Oil Corporation | Polypropylene barrier film and method of forming same |
| US5369168A (en) * | 1992-08-03 | 1994-11-29 | Air Products And Chemicals, Inc. | Reactive melt extrusion grafting of thermoplastic polyvinyl alcohol/polyolefin blends |
| JPH1076593A (ja) * | 1996-09-03 | 1998-03-24 | Daicel Chem Ind Ltd | バリア性複合フィルムおよびその製造方法 |
| WO1998051331A1 (en) * | 1997-05-13 | 1998-11-19 | Societe De Conseils De Recherches Et D'applications Scientifiques S.A. (S.C.R.A.S.) | Somatostatin and somatostatin agonists for decreasing body weight |
| JP2000071396A (ja) * | 1998-05-26 | 2000-03-07 | Nakato Kenkyusho:Kk | ガスバリアー性積層フィルム及びその製造方法 |
| CA2314480C (en) * | 1999-07-29 | 2007-01-02 | Kuraray Co., Ltd. | Fuel container |
| EP1403289B8 (en) * | 2001-05-14 | 2010-05-12 | Kuraray Co., Ltd. | Modified ethylene -vinyl alcohol copolymer and method for the production thereof |
| JP3851218B2 (ja) | 2001-05-14 | 2006-11-29 | 株式会社クラレ | 変性エチレン−ビニルアルコール共重合体からなるガスバリア材 |
| EP1285926B1 (de) * | 2001-08-06 | 2004-05-12 | Degussa AG | Organosiliciumverbindungen |
| JP2006167919A (ja) * | 2004-12-10 | 2006-06-29 | Bridgestone Corp | 積層体、その製造方法及びそれを用いたタイヤ |
| JP2008523224A (ja) * | 2004-12-10 | 2008-07-03 | スリーエム イノベイティブ プロパティズ カンパニー | 充填剤入りポリマー複合材料 |
| DE102006008670A1 (de) * | 2006-02-24 | 2007-08-30 | Degussa Gmbh | Kautschukmischungen |
| WO2007100159A1 (ja) * | 2006-03-03 | 2007-09-07 | The Yokohama Rubber Co., Ltd. | 低透過性ゴム積層体及びそれを用いた空気入りタイヤ |
| CN101421102B (zh) * | 2006-04-18 | 2012-05-23 | 横滨橡胶株式会社 | 低透过性橡胶叠层体和使用了该低透过性橡胶叠层体的充气轮胎 |
| DE102006033310A1 (de) * | 2006-07-17 | 2008-01-31 | Evonik Degussa Gmbh | Gemische aus siliciumhaltigen Kopplungsreagentien |
| JP4488097B2 (ja) * | 2008-08-25 | 2010-06-23 | 横浜ゴム株式会社 | ガスバリア樹脂成形品または積層体 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107116869A (zh) * | 2011-05-31 | 2017-09-01 | 株式会社普利司通 | 多层结构体、充气轮胎用气密层以及充气轮胎 |
| CN107116869B (zh) * | 2011-05-31 | 2019-04-30 | 株式会社普利司通 | 多层结构体、充气轮胎用气密层以及充气轮胎 |
| CN109535707A (zh) * | 2012-05-28 | 2019-03-29 | 横滨橡胶株式会社 | 充气轮胎 |
| CN109535707B (zh) * | 2012-05-28 | 2021-05-25 | 横滨橡胶株式会社 | 充气轮胎 |
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| Publication number | Publication date |
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| US20130123428A1 (en) | 2013-05-16 |
| ATE521644T1 (de) | 2011-09-15 |
| KR20100024343A (ko) | 2010-03-05 |
| JP4488097B2 (ja) | 2010-06-23 |
| JP2010047733A (ja) | 2010-03-04 |
| EP2159234B1 (en) | 2011-08-24 |
| EP2159234A1 (en) | 2010-03-03 |
| US8969475B2 (en) | 2015-03-03 |
| US20100047586A1 (en) | 2010-02-25 |
| CN101659724B (zh) | 2013-08-07 |
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