CN107250241B - 热膨胀性微囊复合体、其制造方法、配合有该复合体的橡胶组合物及使用了该组合物的充气轮胎 - Google Patents
热膨胀性微囊复合体、其制造方法、配合有该复合体的橡胶组合物及使用了该组合物的充气轮胎 Download PDFInfo
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- CN107250241B CN107250241B CN201680010516.1A CN201680010516A CN107250241B CN 107250241 B CN107250241 B CN 107250241B CN 201680010516 A CN201680010516 A CN 201680010516A CN 107250241 B CN107250241 B CN 107250241B
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Abstract
为了提高无钉轮胎在冰上的制动性,例如有在橡胶中配合中空粒子的技术,但这种情况下,存在耐磨耗性下降这样的问题。本发明中,为了提供可在维持耐磨耗性的同时、飞跃性地提高冰上性能的组合物,将通过下述方式得到的热膨胀性微囊复合体配合到橡胶成分中:制备浓度为1~30质量%的水溶性高分子的水溶液,相对于前述水溶液100质量份、添加纤维素纤维5~60质量份而制备分散液(1),向前述分散液(1)中添加热膨胀性微囊10~200质量份而制备分散液(2),使前述分散液(2)的水分蒸发。
Description
技术领域
本发明涉及热膨胀性微囊复合体、其制造方法、配合有该复合体的橡胶组合物及使用了该组合物的充气轮胎,详细而言,涉及可在维持耐磨耗性的同时、飞跃性地提高冰上性能的热膨胀性微囊复合体、其制造方法、配合有该复合体的橡胶组合物及使用了该组合物的充气轮胎。
背景技术
以往,为了提高无钉轮胎的冰上性能(在冰上的制动性),提出了多种手段。例如,已知下述方法(例如参见专利文献1):通过在橡胶中配合硬质异物、中空粒子,从而在橡胶表面形成微小的凹凸,由此,除去冰的表面上产生的水膜,提高冰上摩擦。另外,存在下述方法:减少橡胶组合物中的增强用填充剂的量,提高柔软性从而提高摩擦力的方法;在橡胶中配合形成孔隙的特殊的配合剂,吸收冰上路面上的水,提高橡胶与冰的密合性从而提高摩擦力的方法;等等。
然而,在橡胶中配合例如中空粒子时,存在在胎面橡胶中形成空洞,耐磨耗性下降这样的问题。
现有技术文献
专利文献
专利文献1:日本特开平11-35736号公报
发明内容
发明所要解决的课题
本发明的目的在于提供可在维持耐磨耗性的同时、飞跃性地提高冰上性能的热膨胀性微囊复合体、其制造方法、配合有该复合体的橡胶组合物及使用了该组合物的充气轮胎。
用于解决课题的手段
本发明人等反复进行了深入研究,结果发现,通过使用使多个热膨胀性微囊附着在纤维素纤维上而得到的复合体,能够解决上述课题,从而完成了本发明。
即,本发明如下所述。
1.一种热膨胀性微囊复合体,其特征在于,其具有在纤维素纤维上附着有多个热膨胀性微囊的结构。
2.根据前述1所述的热膨胀性微囊复合体,其特征在于,具有在前述纤维素纤维上多个前述热膨胀性微囊连结成线状、带状或簇状的结构。
3.根据前述1所述的热膨胀性微囊复合体,其特征在于,前述纤维素纤维为纤维素微纤丝。
4.根据前述3所述的热膨胀性微囊复合体,其特征在于,前述纤维素微纤丝包含纳米结构体,所述纳米结构体由粗细为10nm~100nm、长度为100nm~500nm左右的纤维素晶体及/或粗细为3nm~100nm、长度为5μm以上的纤维素纳米纤维形成,作为该微纤丝纤维体的纤维宽度为0.1μm以上,长度为0.5μm以上。
5.一种制造前述1所述的热膨胀性微囊复合体的方法,所述方法具有下述工序:
制备浓度为1~30质量%的水溶性高分子的水溶液的工序,
相对于100质量份的前述水溶液、添加5~60质量份的纤维素纤维而制备分散液(1)的工序,
向前述分散液(1)中添加10~200质量份的热膨胀性微囊而制备分散液(2)的工序,和
使前述分散液(2)的水分蒸发的工序。
6.根据前述5所述的制造方法,其特征在于,在制备前述分散液(1)或前述分散液(2)的工序中,配合相对于前述热膨胀性微囊而言为1~10质量%的极性溶剂。
7.根据前述6所述的制造方法,其特征在于,前述极性溶剂为选自二甲基亚砜、次氮基三乙醇、碳酸亚丙酯、γ-丁内酯、N-甲基-2-吡咯烷酮、N,N-二甲基乙酰胺、二甲基甲酰胺、乙腈及二甲基亚砜中的至少1种。
8.根据前述5所述的制造方法,其中,使用相对于100质量份的不挥发性液状化合物、添加5~40质量份的前述水溶性高分子的水溶液及5~60质量份的纤维素纤维而得到的分散液(1’)来代替前述分散液(1)。
9.根据前述5所述的制造方法,其特征在于,前述水溶性高分子为选自聚丙烯酸、聚丙烯酰胺、聚环氧乙烷、聚乙烯醇、羧甲基纤维素、淀粉、琼脂、明胶及动物胶(glue)中的至少1种。
10.根据前述5所述的制造方法,其特征在于,前述纤维素纤维为纤维素微纤丝。
11.根据前述10所述的制造方法,其特征在于,前述纤维素微纤丝包含纳米结构体,所述纳米结构体由粗细为10nm~100nm、长度为100nm~500nm左右的纤维素晶体及/或粗细为3nm~100nm、长度为5μm以上的纤维素纳米纤维形成,作为该微纤丝纤维体的纤维宽度为0.1μm以上,长度为0.5μm以上。
12.一种橡胶组合物,其特征在于,相对于100质量份的橡胶成分,配合有1~30质量份的前述1所述的热膨胀性微囊复合体。
13.一种充气轮胎,其使用了前述12所述的橡胶组合物的硫化物。
14.根据前述13所述的充气轮胎,其胎面使用了前述12所述的橡胶组合物的硫化物。
15.根据前述14所述的充气轮胎,其是无钉轮胎。
发明的效果
本发明的热膨胀性微囊复合体具有在纤维素纤维上附着有多个热膨胀性微囊的结构,通过将具有该结构的热膨胀性微囊复合体配合到橡胶组合物中,从而能在维持耐磨耗性的同时、显著提高吸水作用,可提高冰上性能。
另外,通过本发明的制造方法,能简便并且低成本地制造本发明的热膨胀性微囊复合体。
附图说明
图1为实施例1中制备的热膨胀性微囊复合体的显微镜照片。
图2为实施例2中制备的热膨胀性微囊复合体的显微镜照片。
图3为实施例3中制备的热膨胀性微囊复合体的显微镜照片。
图4为实施例4中制备的热膨胀性微囊复合体的显微镜照片。
具体实施方式
以下,进一步详细地说明本发明。
本发明的热膨胀性微囊复合体具有在纤维素纤维上附着有多个热膨胀性微囊的结构,优选具有在纤维素纤维上多个热膨胀性微囊连结成线状、带状或簇状的结构。
作为纤维素纤维,没有特别限制,例如,可使用将木材、竹、麻、黄麻、洋麻、再生纸浆、废纸、细菌纤维素等作为原料、利用公知的方法得到的纤维素纤维,优选使用纤维素微纤丝。纤维素微纤丝的制备方法是公知的,例如,可举出下述方法:用氢氧化钠等药品对上述原料进行化学处理,然后,利用精制机(refiner)、双螺杆混炼机(双螺杆挤出机)、双螺杆混炼挤出机、高压均化器、介质搅拌磨、石磨、磨床、振动磨、砂磨机等进行机械地磨碎或打浆的方法。
纤维素微纤丝包含纳米结构体,所述纳米结构体由粗细为10nm~100nm、长度为100nm~500nm左右的纤维素晶体及/或粗细为3nm~100nm、长度为5μm以上的纤维素纳米纤维等形成,关于作为该微纤丝体的纤维宽度,期望的是,为0.1μm以上,优选为1.0μm~20μm左右,作为该纤维体的长度,为0.5μm以上,优选为5μm~300μm。该粗细及长度可利用各种显微镜照片的图像分析以其平均值的形式测定。
需要说明的是,也可使用市售的纤维素纤维,例如可适当采用ダイセルファインケム(株)制的商品名セリッシュシリーズ。
热膨胀性微囊由在由热塑性树脂形成的壳材料中内含热膨胀性物质的结构形成。热膨胀性微囊的壳材料可由腈系聚合物形成。
另外,在微囊的壳材料中内含的热膨胀性物质具有在热的作用下发生气化或膨胀的特性,例如,可例举选自异烷烃、正烷烃等烃中的至少1种。作为异烷烃,可举出异丁烷、异戊烷、2-甲基戊烷、2-甲基己烷、2,2,4-三甲基戊烷等,作为正烷烃,可举出正丁烷、正丙烷、正己烷、正庚烷、正辛烷等。这些烃分别可单独使用,也可组合多种而使用。作为热膨胀性物质的优选方式,优选使常温下为气体的烃溶解于常温下为液体的烃中而得到的物质。通过使用这样的烃的混合物,从而在未硫化轮胎的硫化成型温度区域(150℃~190℃),从低温区域至高温区域可得到充分的膨胀力。
作为这样的热膨胀性微囊,例如,可使用瑞典的Expancel公司制的商品名“EXPANCEL 091DU-80”或“EXPANCEL 092DU-120”等、或松本油脂制药公司制的商品名“マツモトマイクロスフェアーF-85D”或“マツモトマイクロスフェアーF-100D”等。
接下来,对制造本发明的热膨胀性微囊复合体的方法进行说明。
该制造方法中,首先,制备浓度为1~30质量%的水溶性高分子的水溶液。水溶性高分子作为纤维素纤维和热膨胀性微囊之间的粘结剂发挥作用,可提高两者的附着强度。
作为水溶性高分子,只要能达成上述目的即可,没有特别限制,例如,优选为选自聚丙烯酸、聚丙烯酰胺、聚环氧乙烷、聚乙烯醇、羧甲基纤维素、淀粉、琼脂、明胶及动物胶中的至少1种。
另外,该水溶液中的水溶性高分子的浓度进一步优选为1~10质量%。
接下来,相对于制备的前述水溶液100质量份,添加纤维素纤维5~60质量份,制备分散液(1)。通过该工序,使水溶性高分子附着于纤维素纤维。另外,该工序可使用公知的搅拌机实施。需要说明的是,分散液(1)中,进一步优选相对于前述水溶液100质量份,配合纤维素纤维5~30质量份。
接下来,向制备的前述分散液(1)中添加热膨胀性微囊10~200质量份,制备分散液(2)。通过该工序,多个热膨胀性微囊以沿着纤维素纤维上的方式附着,典型地,多个热膨胀性微囊连结成线状、带状或簇状。另外,该工序可使用公知的搅拌机实施。需要说明的是,分散液(2)中,进一步优选相对于前述水溶液100质量份,配合热膨胀性微囊20~100质量份。
进而,接下来使制备的前述分散液(2)的水分蒸发。干燥方法采用公知的方法即可,例如,可使用热风喷射干燥器等进行。
本发明的制造方法中,优选在制备前述分散液(1)或前述分散液(2)的工序中,配合相对于热膨胀性微囊为1~10质量%的极性溶剂。通过该操作,使热膨胀性微囊的表面被一定程度地溶解,多个胶囊彼此变得容易连结。作为这样的极性溶剂,例如,可举出二甲基亚砜、次氮基三乙醇、碳酸亚丙酯、γ-丁内酯、N-甲基-2-吡咯烷酮、N,N-二甲基乙酰胺、二甲基甲酰胺、乙腈、二甲基亚砜等。这些溶剂可单独使用,也可组合2种以上而使用。
另外,本发明的制造方法中,也可使用相对于不挥发性液状化合物100质量份、添加前述水溶性高分子的水溶液5~40质量份及纤维素纤维5~60质量份而得到的分散液(1’)来代替前述分散液(1)。所谓不挥发性液状化合物,是指在随后的水分的蒸发工序时实施的加热温度下为不挥发性的液状化合物,例如,优选石油系的不挥发性溶剂,可例举液体石蜡、各种蜡类。另外,也可使用油、增塑剂、低聚物等不挥发性液状化合物。通过该操作,从而获得使随后的水分的蒸发工序容易进行的效果。
通过前述制造方法,可得到具有在纤维素纤维上多个热膨胀性微囊连结成线状、带状或簇状的结构的复合体。
另外,本发明的橡胶组合物中,相对于橡胶成分100质量份,配合有前述热膨胀性微囊复合体1~30质量份、优选1~15质量份。
关于本发明的橡胶组合物中可使用的橡胶成分,例如,可举出轮胎用橡胶组合物中可使用的各种二烯系橡胶,例如,可举出天然橡胶(NR)、异戊二烯橡胶(IR)、丁二烯橡胶(BR)、苯乙烯-丁二烯共聚物橡胶(SBR)、丙烯腈-丁二烯共聚物橡胶(NBR)、乙烯-丙烯-二烯三元聚合物(EPDM)等。它们可单独使用,也可并用2种以上。另外,其分子量、微观结构没有特别限制,可被胺、酰胺、甲硅烷基、烷氧基甲硅烷基、羧基、羟基等进行末端改性,也可被环氧化。
这些中,从冰上性能变得更良好的理由考虑,优选并用NR及BR。
本发明的橡胶组合物中,可配合硫化或交联剂;硫化或交联促进剂;炭黑、二氧化硅、粘土、碳酸钙之类的各种填充剂;防老化剂;增塑剂等通常在橡胶组合物中配合的各种添加剂,所述添加剂可利用常规方法进行混炼而制成组合物,用于进行硫化或交联。这些添加剂的配合量也是只要不违反本发明的目的,则可为以往的常规的配合量。
另外,本发明的橡胶组合物可按照以往的充气轮胎的制造方法,经硫化工序而制造充气轮胎,优选用于无钉轮胎的、胎面、尤其是胎面冠部。
实施例
以下,利用实施例及比较例进一步说明本发明,但本发明不受下述例子的限制。
热膨胀性微囊复合体的制造
实施例1
在水120g中溶解聚丙烯酸1.2g,向其中投入80g含有15%纤维素微纤丝的制品:セリッシュKY110N(ダイセルファインケム公司制),用带有分散器的搅拌装置以600rpm的转速进行5分钟搅拌。接下来,投入2,2,2-次氮基三乙醇5g,进一步在相同条件下进行5分钟搅拌,然后,从带有分散器的搅拌装置移至蝴蝶型搅拌机,投入80g热膨胀微囊:マツモトマイクロスフェアーF(松本油脂制药(株)制),以36rpm的转速进行2分钟搅拌。通过将得到的液状物利用喷射干燥机于90℃的热风温度进行喷射干燥,从而得到白色粉末。将得到的白色粉末的显微镜照片示于图1。
实施例2
在水100g中溶解1.5g的聚乙烯醇:ポバール115,向其中投入120g含有10%纤维素微纤丝的制品:セリッシュKY100G(ダイセルファインケム公司制),用带有分散器的搅拌装置,以600rpm的转速进行5分钟搅拌。接下来,投入2,2,2-次氮基三乙醇5g,进一步在相同条件下进行5分钟搅拌,然后,从带有分散器的搅拌装置移至蝴蝶型搅拌机,投入100g热膨胀微囊:マツモトマイクロスフェアーF(松本油脂制药(株)制),以36rpm的转速进行2分钟搅拌。通过将得到的液状物利用喷射干燥机于90℃的热风温度进行喷射干燥,从而得到白色粉末。将得到的白色粉末的显微镜照片示于图2。
实施例3
在水100g中溶解聚丙烯酸1.5g,向其中投入120g含有15%纤维素微纤丝的制品:セリッシュKY110N(ダイセルファインケム公司制),用带有分散器的搅拌装置,以600rpm的转速进行5分钟搅拌。接下来,投入5g二甲基亚砜:DMSO,进一步在相同条件下进行5分钟搅拌,然后,从带有分散器的搅拌装置移至蝴蝶型搅拌机,投入90g热膨胀微囊:マツモトマイクロスフェアーF(松本油脂制药(株)制),以36rpm的转速进行2分钟搅拌。通过将得到的液状物利用喷射干燥机于90℃的热风温度进行喷射干燥,从而得到白色粉末。将得到的白色粉末的显微镜照片示于图3。
实施例4
向液体石蜡100g中投入15%聚丙烯酸溶液10g和2,2,2-次氮基三乙醇8g,用带有分散器的搅拌装置,以600rpm的转速进行3分钟搅拌。接下来,投入120g含有15%纤维素微纤丝的制品:セリッシュKY110N(ダイセルファインケム公司制),用带有分散器的搅拌装置,以600rpm的转速进行5分钟搅拌。接下来,从带有分散器的搅拌装置移至蝴蝶型搅拌机,投入100g热膨胀微囊:マツモトマイクロスフェアーF(松本油脂制药(株)制),以36rpm的转速进行2分钟搅拌。然后,一边持续搅拌一边缓缓升温至90℃,持续90分钟搅拌后,得到稍湿的凝集粉末状的组合物。将得到的组合物的显微镜照片示于图4。
由图1~4的结果可知,通过上述各制造方法,可得到具有在纤维素纤维上多个热膨胀性微囊连结成线状、带状或簇状的结构的热膨胀性微囊复合体。
实施例5~9及比较例1~3
样品的制备
用1.7升的密闭式班伯里密炼机,将表1所示的配合(质量份)中除硫化促进剂和硫之外的成分混炼5分钟,然后将橡胶放出至密炼机外,进行室温冷却。接下来,向该班伯里密炼机中添加该橡胶、硫化促进剂及硫,进一步进行混炼,得到橡胶组合物。接着,在规定的模具中,对得到的橡胶组合物进行170℃、10分钟加压硫化,得到硫化橡胶试验片,利用以下所示的试验法,测定硫化橡胶试验片的物性。
冰上性能:将已将各种硫化橡胶试验片组入胎面的轮胎尺寸215/60R16的充气轮胎组装于16×7J的轮辋,填充空气压(220[kPa]),安装于试验车辆(日本产2升FF轿车)。接下来,在为结冰路的试验场地中,利用上述试验车辆,从40[km/h]的初速紧急制动,测定直至完全停车为止的制动距离。以将比较例1作为100时的指数表示结果。指数越大表示冰上性能越优异。
耐磨耗性:按照JIS K6264,在室温下进行测定。以将比较例1作为100时的指数表示结果。该值越大表示耐磨耗性越良好。
将结果合并示于表1。
[表1]
*1:NR(RSS#3)
*2:BR(日本ゼオン(株)制Nipol BR1220)
*3:炭黑(キャボットジャパン(株)制N339)
*4:二氧化硅(ローディア公司制ZEOSIL 1165MP)
*5:氧化锌(正同化学工业(株)制氧化锌3种)
*6:硬脂酸(日油(株)制ビーズステアリン酸)
*7:防老化剂(FLEXSYS制SANTOFLEX6PPD)
*8:蜡(大内新兴化学工业(株)制石蜡)
*9:硅烷偶联剂(エボニックジャパン(株)制Si69)
*10:热膨胀性微囊(松本油脂制药(株)制マツモトマイクロスフェアーF)
*11:热膨胀性微囊复合体-1(前述实施例1中制造的复合体)
*12:热膨胀性微囊复合体-2(前述实施例2中制造的复合体)
*13:热膨胀性微囊复合体-3(前述实施例3中制造的复合体)
*14:热膨胀性微囊复合体-4(前述实施例4中制造的复合体)
*15:油(昭和シェル石油(株)制エキストラクト4号S)
*16:硫(鹤见化学工业(株)制金华印油入微粉硫)
*17:硫化促进剂(大内新兴化学工业(株)制ノクセラーCZ-G)
如上述的表1所表明那样,可知实施例5~9中制备的橡胶组合物由于配合了本发明的热膨胀性微囊复合体,因此与作为以往的代表的比较例1相比,在维持耐磨耗性的同时,冰上性能显著提高。
与此相对,比较例2~3由于是未配合本发明的热膨胀性微囊复合体、仅配合了热膨胀性微囊的例子,因而不能同时实现耐磨耗性和冰上性能。
Claims (11)
1.一种制造其特征在于具有在纤维素纤维上附着有多个热膨胀性微囊的结构的热膨胀性微囊复合体的方法,所述方法具有下述工序:
制备浓度为1~30质量%的水溶性高分子的水溶液的工序,
相对于100质量份的前述水溶液、添加5~60质量份的纤维素纤维而制备分散液1的工序,
向前述分散液1中添加10~200质量份的热膨胀性微囊而制备分散液2的工序,和
使前述分散液2的水分蒸发的工序。
2.根据权利要求1所述的制造方法,其特征在于,在制备前述分散液1或前述分散液2的工序中,配合相对于前述热膨胀性微囊而言为1~10质量%的极性溶剂。
3.根据权利要求2所述的制造方法,其特征在于,前述极性溶剂为选自二甲基亚砜、次氮基三乙醇、碳酸亚丙酯、γ-丁内酯、N-甲基-2-吡咯烷酮、N,N-二甲基乙酰胺、二甲基甲酰胺、乙腈及二甲基亚砜中的至少1种。
4.根据权利要求1所述的制造方法,其中,使用相对于100质量份的不挥发性液状化合物、添加5~40质量份的前述水溶性高分子的水溶液及5~60质量份的纤维素纤维而得到的分散液1’来代替前述分散液1。
5.根据权利要求1所述的制造方法,其特征在于,前述水溶性高分子为选自聚丙烯酸、聚丙烯酰胺、聚环氧乙烷、聚乙烯醇、羧甲基纤维素、淀粉、琼脂、明胶及动物胶中的至少1种。
6.根据权利要求1所述的制造方法,其特征在于,前述纤维素纤维为纤维素微纤丝。
7.根据权利要求6所述的制造方法,其特征在于,前述纤维素微纤丝包含纳米结构体,所述纳米结构体由粗细为10nm~100nm、长度为100nm~500nm的纤维素晶体及/或粗细为3nm~100nm、长度为5μm以上的纤维素纳米纤维形成,作为该微纤丝纤维体的纤维宽度为0.1μm以上,长度为0.5μm以上。
8.一种橡胶组合物,其特征在于,相对于100质量份的橡胶成分,配合有1~30质量份的其特征在于具有在纤维素纤维上附着有多个热膨胀性微囊的结构的热膨胀性微囊复合体。
9.一种充气轮胎,其使用了权利要求8所述的橡胶组合物的硫化物。
10.根据权利要求9所述的充气轮胎,其胎面使用了权利要求8所述的橡胶组合物的硫化物。
11.根据权利要求10所述的充气轮胎,其是无钉轮胎。
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