CN101272902B - 低透气性树脂/橡胶组合物的低透气性橡胶叠层体及其制造方法 - Google Patents
低透气性树脂/橡胶组合物的低透气性橡胶叠层体及其制造方法 Download PDFInfo
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Abstract
本发明提供一种低透气性树脂/橡胶组合物的叠层体(F)及其制造方法,包括:使低透气性树脂(A)层与热塑性树脂组合物(B)层的叠层体(D)、按照成为(B)/(A)/(E)那样,与橡胶组合物(E)层进行叠层,硫化,仅使热塑性树脂组合物(B)从叠层体剥离,其中,所述低透气性树脂(A)层的透气系数为1.0×10-12cc·cm/cm2·sec·cmHg以下,并且平均厚度d(μm)为0.05<d<5。
Description
技术领域
本发明涉及低透气性橡胶叠层体及其制造方法,更详细地说,涉及在橡胶组合物的层上叠层平均厚度大于0.05μm、小于5μm的低透气性树脂层而成的防透气性和耐久性优异的低透气性橡胶叠层体及其制造方法,和由其获得的制品。
背景技术
在橡胶组合物层上被覆热塑性(或热固化性)树脂层(薄膜)、获得具有该树脂来源的机能的叠层体的技术,目前是已知的。作为其一例,对在橡胶组合物上涂布低透气性膜来用作充气轮胎的内衬层的方案,人们也进行了各种尝试。最近,例如在特开2002-79804号公报中,提出了以电子束交联聚乙烯醇、乙烯-乙烯醇共聚物等作为非透气层,将其叠层到弹性体辅助层中,用作充气轮胎的内衬层。其指出该非透气层的厚度为30μm以下,但是在其实施例中只记载了EVOH的厚度为20μm的例子。EVOH是拉伸弹性模量为2~3GPa的非常硬的树脂,因此当厚度为20μm时,如果进行拉伸,则容易产生颈缩变形,因应力集中而变得容易破断。因此,动态反复形变容易产生裂纹,出现从裂纹部剥离等的不良现象。另外,在特开2004-255937号公报中记载了,以5~100μm的厚度,使用电子束交联聚乙烯醇、乙烯-乙烯醇共聚物单层作为非透气层的支持体,以及充气性缺气保用轮胎(run-flat tire)。
发明内容
作为将低透气性树脂(A)的薄膜涂布在橡胶组合物层上的方法,有将树脂(A)的溶液、乳液涂布在橡胶组合物层上的方法,该方法在被覆10μm以上的比较厚的膜的情况下没有问题,但是,例如厚度小于5μm、进而为3μm以下的薄膜的均一性的控制很难,另外,存在下述问题:为了使其具有与橡胶组合物层的粘结性而用的底漆的涂布、溶剂的干燥等的工序增加。进而在要涂布于需要硫化工序的橡胶组合物上的情况下,为了使其具有与囊状(bladder)橡胶的脱离性,需要在叠层体表面涂布脱模剂等,进行硫化,此时,存在下述问题,即,有可能破坏涂布层,不能使其具有充分的阻气性。
因此,本发明的目的在于提供,可以解决上述问题的、将厚度小于5μm的低透气性树脂(A)层均一地叠层在橡胶组合物层上而成的低透气性橡胶叠层体,及其制造方法和制品。
根据本发明,可以提供一种低透气性橡胶叠层体(F),是将下述低透气性树脂(A)层叠层在橡胶组合物(E)层的一面上而成的,其中,所述低透气性树脂(A)层的透气系数为1.0×10-12cc·cm/cm2·sec·cmHg以下,并且平均厚度d(μm)为0.05<d<5。
根据本发明,可以提供一种在橡胶组合物(E)层的一面叠层有低透气性树脂(A)层的低透气性橡胶叠层体(F)的制造方法,该制造方法包括下述操作,即,使低透气性树脂(A)层与热塑性树脂组合物(B)层的叠层体(D)、按照成为(B)/(A)/(E)那样,与橡胶组合物(E)层进行叠层,硫化,使硫化后的低透气性树脂(A)层/橡胶组合物(E)层之间的剥离强度大于(A)层/(B)层之间的剥离强度,仅使热塑性树脂组合物(B)从叠层体剥离,其中,所述低透气性树脂(A)层的透气系数为1.0×10-12cc·cm/cm2·sec·cmHg以下,并且平均厚度d(μm)为0.05<d<5,所述热塑性树脂组合物(B)层处于与(A)层假粘结的状态并且在室温下与(A)层的剥离强度为0.001~10N/mm。
低透气性树脂(A),由于杨氏模量高,因此在叠层在反复接受动态形变的橡胶上来使用的情况下,出现树脂的材料破坏,树脂/橡胶界面出现剥离,与此相对,根据本发明,在将厚度小于5μm的低透气性树脂薄膜叠层在橡胶组合物层上而形成的叠层体中,不易出现弯曲龟裂,具有优异的耐弯曲疲劳性,也很难出现界面剥离。特别是在使用树脂中透气性最低的乙烯-乙烯醇共聚物的情况下,即使是厚度小于5μm的薄膜,在用作充气轮胎的内衬层时,也具有充分的阻气性,也可以使轮胎大幅度地轻量化。
具体实施方式
本说明书和权利要求书中使用的单数形式(a、an、the),表示包括多个对象的意思,从上下文能够明确的除外。
为了解决上述课题,本发明者们进行了深入的研究,结果发现,通过使热塑性树脂组合物(B)/低透气性树脂(A)/任选使用的粘结剂(C)的2层或3层共挤出叠层体(D),与橡胶组合物(E)的层进行叠层,硫化,然后剥离热塑性树脂组合物(B)层,可以使低透气性树脂(A)层的厚度小于5μm的薄膜均一地被覆在橡胶组合物(E)层上,另外,该低透气性橡胶叠层体(F)具有优异的特性(阻气性、力学物性),从而完成了本发明。
如果是透气系数为1.0×10-12cc·cm/cm2·sec·cmHg以下(依据JISK7126(试验气体∶空气(N2∶O2=8∶2),30℃)进行测定,下同)的低透气性树脂(A)层的厚度小于5μm,优选1~3μm的薄膜,则不会损害橡胶的力学物性(断裂伸长率、拉伸和压缩永久变形等),可以大幅度改善氧气、臭氧等的气体的阻挡性。因此,可以大幅度改善橡胶的氧化劣化,除了内衬层之外,还可以适用于轮胎的胎侧橡胶。进而,厚度低于5μm的低透气性树脂(A)的薄膜具有耐弯曲疲劳性,因此上述低透气性橡胶叠层体(F)还可以适合用作必须具有耐弯曲疲劳性和阻气性的软管的例如内层、中间层和外层的至少1层。
即,根据本发明,通过使低透气性树脂(A)层与热塑性树脂组合物(B)层的叠层体(D)、与橡胶组合物(E)的层按照(B)/(A)/(E)的顺序进行叠层,硫化,按照硫化后的低透气性树脂(A)层/橡胶组合物(E)层之间的剥离强度大于(A)层/(B)层之间的剥离强度那样选择(A)、(B)和(E),仅使热塑性树脂组合物(B)层从叠层体的(A)层剥离,可以获得在橡胶组合物(E)的一面被覆(叠层)有(A)层的低透气性橡胶叠层体(F),其中所述低透气性树脂(A)层的透气系数为1.0×10-12cc·cm/cm2·sec·cmHg以下、优选0.001~0.1×10-12cc·cm/cm2·sec·cmHg,并且平均厚度d为0.05μm<d<5μm,优选1~3μm,所述热塑性树脂组合物(B)层处于与(A)层假粘结的状态(即,两层在通常的使用状态下粘结,但是在使两层剥离的情况下,仅通过人手拉伸就能够容易地剥离,通过简单的重合、挤压,不能再粘结的状态),并且,在室温下与(A)层的剥离强度为0.001~10N/mm,优选0.01~1N/mm(依据JIS6256进行测定,下同)。
上述低透气性树脂(A)层与热塑性树脂组合物(B)层的叠层体(D),例如可以为(A)和(B)的多层共挤出或多层吹胀成型物,该技术已经被广泛用于本技术领域,本发明也可以应用该通用技术。
在本发明中,作为可以用作低透气性树脂(A)的树脂,可以列举出,聚烯烃酮(POK)、聚乙烯醇(PVA)、乙烯-乙烯醇(EVOH)、尼龙MXD6,其中,从阻气性和柔软性的平衡、熔融成型加工性的观点出发,优选乙烯-乙烯醇共聚物。乙烯-乙烯醇共聚物中,从耐热性(熔点)、阻气性的观点出发,更优选乙烯组成比为50摩尔%以下。
在本发明中,可以用作热塑性树脂组合物(B)的树脂组合物,优选含有聚酰胺树脂和聚酯树脂的至少1种的组合物。具体的构成热塑性树脂组合物(B)的树脂,可以列举出,尼龙6、尼龙66、尼龙6/66、尼龙6/10、尼龙6/12、尼龙46、尼龙11、尼龙12、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚萘二甲酸乙二醇酯(PEN)等的至少1种,从与(A)层的脱离性(剥离强度小)的观点出发,特别优选使用尼龙11和尼龙12。
作为构成本发明中使用的橡胶组合物(E)的橡胶成分,没有特别的限定,可以使用目前一般用作轮胎用橡胶的任意的橡胶材料。作为这样的橡胶,可以列举出例如,天然橡胶(NR)、聚异戊二烯橡胶(IR)、聚丁二烯橡胶(BR)、苯乙烯-丁二烯共聚物橡胶(SBR)等的二烯类橡胶,卤化丁基、乙烯-丙烯共聚物等中添加炭黑、加工油、硫化剂等的配合剂而成的橡胶组合物。
作为本发明中可以任选使用粘结剂(C),有改性苯乙烯共聚物,具体来说,可以列举出,包括具有环氧基、羟基、氨基、羧基、酸酐基等的官能基的苯乙烯-乙烯-丙烯共聚物、苯乙烯-乙烯-丁二烯-苯乙烯共聚物、苯乙烯-乙烯-丁二烯共聚物、苯乙烯-丁二烯-苯乙烯共聚物和硫化促进剂、硫化剂、增粘剂(tackifier)的目前用于尼龙类热塑性弹性体的任意的粘结剂(参照特愿2003-208227、特愿2004-025782),其应用方法、应用量也与现有技术同样。
本发明涉及的上述低透气性橡胶叠层体(F)可以用于充气轮胎的内衬层、充气轮胎的胎侧部、以及低透气性软管等。对它们的制造方法没有特别的限制,可以利用目前的一般的方法。
本发明涉及的树脂组合物和橡胶组合物中,除了上述成分之外,可以配合这些组合物中目前一直使用的任意的添加剂、例如炭黑、二氧化硅等其它增强剂(填料)、硫化或交联剂、硫化或交联促进剂、各种油、防老化剂、增塑剂等的添加剂,该添加剂可以用一般的方法进行混炼,形成组合物,可以用于硫化或交联。这些添加剂的配合量可以在不违反本发明的目的的范围内,配合目前的一般的配合量。
实施例
下面,通过实施例来进一步说明本发明,但是并不是说本发明的范围受这些实施例的限定。
实施例1~3和比较例1~3
使用带有3层模头的吹胀成型机,按照表I、表II、表III和表IV那样,制作热塑性树脂组合物(B)/低透气性树脂(A)/粘结剂(C)的圆筒状叠层体(D)。作为比较例3,制作由热塑性树脂组合物(B)低透气性树脂(A)的2层形成的叠层体(D)。另外,作为比较例4,制作由尼龙11(BESNO TL)/粘结剂的2层形成的叠层体(D)。
<作为轮胎内衬层的评价>
对应内衬层,使用所制作的叠层体(D),用一般的方法制作轮胎(尺寸165SR13(轮圈13×41/2-J))。在制作轮胎后,通过剥离(B)层,获得在轮胎最内面具有用乙烯-乙烯醇共聚物覆盖了的内衬层的轮胎。对这些轮胎进行室内轮胎运行试验,评价漏气性。
评价试验方法
剥离强度的测定
(A)/(B)间的剥离强度,是按照(B)/(A)/粘结剂(C)/橡胶组合物(E)的顺序进行叠层,硫化,使(A)/橡胶组合物间的粘结力充分强,形成能够使(A)/(B)间剥离的状态,然后依据JIS6256进行测定。
(A)/橡胶组合物(E)间的剥离强度测定,在(A)/(B)间的剥离强度小于(A)/橡胶组合物(E)间的剥离强度的情况下,(A)/(B)间剥离,所以有时不能测定。因此,(A)/橡胶组合物(E)间的剥离强度,可以通过制作(A)/粘结剂(C)的2层吹胀叠层体,然后按照(A)/粘结剂(C)/橡胶组合物(E)的顺序进行叠层,硫化,使(A)/橡胶组合物(E)间剥离,来求出。
室内轮胎评价
使用制作的165SR13钢丝子午线轮胎(轮圈13×41/2-J),在空气压200kPa下,在1500cc级别的乘用车中,加入相当于4个人乘坐时的负荷(65kg/人),在实际路上运行2万km。在运行后,从轮圈上卸下轮胎,目视观察轮胎内面的(A)层,将(A)层存在裂纹、(A)层出现剥离、突起物的情况判断为不合格,将不存在上述现象的情况判断为合格。
判断方法
良好:没有发现(A)层有裂纹和剥离
不良:发现(A)层有裂纹和剥离
漏气
使用165SR13钢丝子午线轮胎(轮圈13×41/2-J),在初期压力200kPa下,在无负荷条件下,在室温21℃放置3个月,每间隔4天,测定压力。将测定压力记作Pt、初期压力记作Po、经过天数记作t,回归为函数Pt/Po=exp(-αt),求出α值。使用所得到的α,将t=30代入下式,根据β=[1-exp(-αt)]×100,求出β值。将该β值作为每个月的压力降低率(漏气率)(%/月)。
漏气判断基准
良好:漏气率<2.5%/月
一般:2.5%/月<漏气率<4.0%/月
不良:漏气率>4.0%/月
在比较例1中,不能使(B)/(A)间剥离,因此使(B)层保持叠层的状态,进行室内轮胎运行试验。
在比较例3中,使用由热塑性树脂组合物(B)/低透气性树脂组合物(A)的2层形成的叠层体(D)。由于(A)/橡胶间剥离强度小于(B)/(A)间剥离强度,因此(A)层没有被覆在橡胶层上。
实施例4~6和比较例5~7
作为轮胎胎侧部的评价
如表VI所示那样,将叠层体(D)层叠层在胎侧橡胶复合物上,然后用现有的一般的方法制作轮胎。在轮胎硫化后,通过剥离(B)层,获得在胎侧被覆有EVOH薄膜的轮胎。结果表VI所示。
评价方法
剥离强度:与内衬层的情况同样。
氧劣化评价:使用制作的165SR13钢丝子午线轮胎(轮圈13×41/2-J),在空气压120kPa下,在1500cc级别的乘用车中,加入相当于4个人乘坐时的负荷(65kg/人),对轮胎的两胎侧照射臭氧,同时运行5000km。在运行后,目视观察确认轮胎的胎侧部的臭氧裂纹的发生。
判断方法
良好:没有发现在胎侧部有臭氧裂纹
不良:发现在胎侧部有臭氧裂纹
工业可利用性
如上所述,根据本发明,通过使低透气性树脂(A)的薄膜的厚度小于5μm,将低透气性树脂(A)的薄膜叠层在橡胶组合物(E)上而成的叠层体,很难产生弯曲龟裂,具有优异的耐弯曲疲劳性,也不易出现界面剥离,特别是如果使用树脂中透气性最低的乙烯-乙烯醇共聚物,则即使是厚度小于5μm,进而为3μm以下的薄膜,也具有用作充气轮胎的内衬层所需要的充分的阻气性,可以使轮胎大幅度地轻量化,进而,如果使用厚度小于5μm的薄膜,则不会损害橡胶的力学物性(断裂伸长率、拉伸和压缩永久变形等),可以大幅度改善氧气、臭氧等的气体的阻挡性,可以大幅度改善橡胶的氧化劣化,因此可以适合用作轮胎的胎侧橡胶等,另外,也适合用于需要耐弯曲疲劳性和阻气性的软管。
Claims (11)
1.一种在橡胶组合物E层的一面叠层有低透气性树脂A层的低透气性树脂/橡胶组合物的叠层体F的制造方法,包括下述操作:使低透气性树脂A层与热塑性树脂组合物B层的叠层体D、按照成为B/A/E那样与橡胶组合物E层进行叠层,硫化,使硫化后的低透气性树脂A层/橡胶组合物E层之间的剥离强度大于A层/B层之间的剥离强度,从而仅使热塑性树脂组合物B从叠层体剥离,其中,所述低透气性树脂A层的透气系数为1.0×10-12cc·cm/cm2·sec·cmHg以下,并且平均厚度d为0.05μm<d<5μm,所述热塑性树脂组合物B层处于与A层假粘结的状态,并且在室温下与A层的剥离强度为0.001~10N/mm。
2.一种在橡胶组合物E层的一面叠层有低透气性树脂A层的低透气性树脂/橡胶组合物的叠层体F的制造方法,包括下述操作:使低透气性树脂A层与热塑性树脂组合物B层和粘结剂C按照B/A/C的顺序叠层而成的3层叠层体D,按照成为B/A/C/E那样与橡胶组合物E层进行叠层,硫化,使硫化后的低透气性树脂A层/橡胶组合物E层之间的剥离强度大于A层/B层之间的剥离强度,仅使热塑性树脂组合物B从叠层体剥离,其中,所述低透气性树脂A层的透气系数为1.0×10-12cc·cm/cm2·sec·cmHg以下,并且平均厚度d为0.05μm<d<5μm,所述热塑性树脂组合物B层处于与A层假粘结的状态,并且在室温下与A层的剥离强度为0.001~10N/mm。
3.根据权利要求1或2所述的低透气性树脂/橡胶组合物的叠层体F的制造方法,叠层体D是多层共挤出或多层吹胀成型物。
4.根据权利要求1或2所述的低透气性树脂/橡胶组合物的叠层体F的制造方法,上述低透气性树脂A层的平均厚度d为1~3μm。
5.根据权利要求1或2所述的低透气性树脂/橡胶组合物的叠层体F的制造方法,低透气性树脂A是乙烯-乙烯醇共聚物。
6.根据权利要求1或2所述的低透气性树脂/橡胶组合物的叠层体F的制造方法,乙烯-乙烯醇共聚物的乙烯组成比为50摩尔%以下。
7.根据权利要求1或2述的低透气性树脂/橡胶组合物的叠层体F的制造方法,热塑性树脂组合物B是选自聚酰胺树脂和聚酯树脂中的至少1种。
8.根据权利要求2所述的低透气性树脂/橡胶组合物的叠层体F的制造方法,热塑性树脂组合物B是选自尼龙11和尼龙12中的至少1种。
9.一种充气轮胎,在内衬层中使用了由权利要求1或2所述的方法获得的低透气性树脂/橡胶组合物的叠层体F。
10.一种充气轮胎,在胎侧部使用了由权利要求1或2所述的方法获得的低透气性树脂/橡胶组合物的叠层体F。
11.一种低透气性软管,在内层、中间层和外层的至少1层中使用了由权利要求1或2所述的方法获得的低透气性树脂/橡胶组合物的叠层体F。
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WO (1) | WO2007037541A1 (zh) |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1995079B1 (en) * | 2006-03-03 | 2011-06-29 | The Yokohama Rubber Co., Ltd. | Low permeable rubber laminate and pneumatic tire using same |
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 |
WO2008053815A1 (fr) * | 2006-11-02 | 2008-05-08 | The Yokohama Rubber Co., Ltd. | Procédé de production de stratifiés de caoutchouc de faible perméabilité à partir d'un film multicouche en résine de faible perméabilité |
WO2009014232A1 (ja) * | 2007-07-23 | 2009-01-29 | The Yokohama Rubber Co., Ltd. | 空気入りタイヤ |
WO2009041710A1 (ja) * | 2007-09-27 | 2009-04-02 | The Yokohama Rubber Co., Ltd. | 熱可塑性樹脂組成物及びそれを用いた空気入りタイヤ |
JP5417802B2 (ja) * | 2008-11-04 | 2014-02-19 | 横浜ゴム株式会社 | 空気入りタイヤの製造方法 |
JP5611233B2 (ja) * | 2009-12-01 | 2014-10-22 | 株式会社クラレ | 空気入りタイヤ用インナーライナー及びその製造方法 |
JP5702733B2 (ja) * | 2009-12-01 | 2015-04-15 | 株式会社クラレ | 多層構造体及びその製造方法 |
US9375980B2 (en) | 2010-07-16 | 2016-06-28 | Exxonmobil Chemical Patents Inc. | Adhesive extrusion for dynamically vulcanized thermoplastic elastomer laminates |
JP5583223B2 (ja) * | 2010-10-01 | 2014-09-03 | 株式会社クラレ | 多層構造体、これを用いたインナーライナー及び空気入りタイヤ |
JP5939734B2 (ja) * | 2010-11-02 | 2016-06-22 | 横浜ゴム株式会社 | 空気入りタイヤ |
US8454778B2 (en) | 2010-11-15 | 2013-06-04 | Ramendra Nath Majumdar | Pneumatic tire with barrier layer and method of making the same |
KR101475494B1 (ko) * | 2010-12-30 | 2014-12-31 | 코오롱인더스트리 주식회사 | 타이어 이너라이너용 필름 및 이의 제조 방법 |
US8534331B2 (en) | 2011-12-13 | 2013-09-17 | The Goodyear Tire & Rubber Company | Tire containing layered composite of sealant and air permeation resistant film |
JP5354057B2 (ja) * | 2012-05-08 | 2013-11-27 | 横浜ゴム株式会社 | 空気入りタイヤ |
CN102896974A (zh) * | 2012-10-25 | 2013-01-30 | 北京化工大学 | 耐臭氧老化的高性能轮胎及其制造方法 |
WO2014164054A1 (en) | 2013-03-13 | 2014-10-09 | Basf Se | Inner liner for a pneumatic tire assembly |
DE102013103663B4 (de) | 2013-04-11 | 2014-10-23 | Nora Systems Gmbh | Verfahren zum Herstellen eines eine Dekorschicht aufweisenden Elastomer-Bodenbelags und Elastomer-Bodenbelag mit einer Dekorschicht |
JP6115386B2 (ja) * | 2013-07-31 | 2017-04-19 | 横浜ゴム株式会社 | 熱可塑性樹脂組成物並びにそれを用いたタイヤ及びホース |
US20190152263A1 (en) * | 2016-06-30 | 2019-05-23 | Kolon Industries, Inc. | Pneumatic tire |
WO2018094026A1 (en) | 2016-11-17 | 2018-05-24 | Bridgestone Americas Tire Operations, Llc | Pneumatic tire having dampening element adhered to air barrier layer |
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CN1558819A (zh) * | 2001-09-28 | 2004-12-29 | ɽ����ʽ���� | 热压用缓冲材料及其制造方法 |
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IT1177047B (it) * | 1984-10-26 | 1987-08-26 | Carbolux Spa | Procedimento e apparecchiatura per l'accoppiamento, coadiuvato da un film ausiliario, di film protettivi a una lastra estrusa, tutti realizzati in materie plastiche e prodotto cosi' ottenuto |
JP3173740B2 (ja) | 1992-04-22 | 2001-06-04 | 日本合成化学工業株式会社 | エチレン−酢酸ビニル系共重合体ケン化物溶液及びその用途 |
JP3424844B2 (ja) | 1993-10-21 | 2003-07-07 | 日本合成化学工業株式会社 | エチレン−酢酸ビニル系共重合体ケン化物の水性分散液及びその用途 |
EP0706878B1 (en) * | 1994-09-13 | 2000-08-23 | Gunze Limited | Laminate |
US6079465A (en) * | 1995-01-23 | 2000-06-27 | The Yokohama Rubber Co., Ltd. | Polymer composition for tire and pneumatic tire using same |
JP2002052904A (ja) * | 2000-08-11 | 2002-02-19 | Kuraray Co Ltd | タイヤ内面用インナーライナー |
JP4450497B2 (ja) | 2000-09-07 | 2010-04-14 | 株式会社ブリヂストン | 空気入りタイヤ |
ES2305385T3 (es) * | 2002-11-13 | 2008-11-01 | Bridgestone Corporation | Revestimiento interno para cubierta de neumatico y cubierta de neumatico. |
JP2004255937A (ja) | 2003-02-25 | 2004-09-16 | Bridgestone Corp | 支持体および空気入りランフラットタイヤ |
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2006
- 2006-09-29 JP JP2007537779A patent/JP4412406B2/ja not_active Expired - Fee Related
- 2006-09-29 US US12/088,607 patent/US7976666B2/en not_active Expired - Fee Related
- 2006-09-29 WO PCT/JP2006/320022 patent/WO2007037541A1/ja active Application Filing
- 2006-09-29 EP EP06811349A patent/EP1930152B1/en not_active Expired - Fee Related
- 2006-09-29 CN CN2006800356556A patent/CN101272902B/zh not_active Expired - Fee Related
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2011
- 2011-05-16 US US13/108,298 patent/US20110217536A1/en not_active Abandoned
Patent Citations (1)
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CN1558819A (zh) * | 2001-09-28 | 2004-12-29 | ɽ����ʽ���� | 热压用缓冲材料及其制造方法 |
Also Published As
Publication number | Publication date |
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EP1930152B1 (en) | 2012-06-13 |
US20100147431A1 (en) | 2010-06-17 |
US20110217536A1 (en) | 2011-09-08 |
EP1930152A4 (en) | 2011-11-16 |
WO2007037541A9 (ja) | 2007-05-31 |
EP1930152A1 (en) | 2008-06-11 |
JP4412406B2 (ja) | 2010-02-10 |
WO2007037541A1 (ja) | 2007-04-05 |
JPWO2007037541A1 (ja) | 2009-04-16 |
CN101272902A (zh) | 2008-09-24 |
US7976666B2 (en) | 2011-07-12 |
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