CN1117813C - 具有改进再注塑粘力的热塑性高弹体组合物 - Google Patents

具有改进再注塑粘力的热塑性高弹体组合物 Download PDF

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CN1117813C
CN1117813C CN97121420A CN97121420A CN1117813C CN 1117813 C CN1117813 C CN 1117813C CN 97121420 A CN97121420 A CN 97121420A CN 97121420 A CN97121420 A CN 97121420A CN 1117813 C CN1117813 C CN 1117813C
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M·J·莫迪克
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Abstract

本发明涉及一种热塑性高弹体组合物，包括一种氢化弹性嵌段共聚物，具有至少两个聚合单乙烯基芳族化合物的树脂状端基部嵌段和一个聚合共轭二烯的弹性中间嵌段；一种增塑剂；一种烯烃-丙烯酸聚合物；和一种聚烯烃。本发明还涉及一种制备再注塑的极性聚合物型材的方法；涉及一种再注塑的极性聚合物型材；涉及一种含有再注塑的极性聚合物型材的制品。

Description

具有改进再注塑粘力 的热塑性高弹体组合物
本发明涉及具有良好再注塑粘力。更具体地说，本发明涉及一种对极性基材如聚碳酸酯或丙烯腈-丁二烯-苯乙烯(ABS)具有良好粘力的热塑性高弹体组合物。
尽管已知高弹体型嵌段共聚物与聚烯烃相容，但由于嵌段共聚物与基材间相容性差，它们在极性母体/基材上的应用，例如聚碳酸酯或ABS，受到限制。特别是，在许多情况下希望直接在硬的基材上模塑一个软橡胶材料，由此提供一个软的覆面。然而，由于高弹体与基材间的不相容性，限制了许多不错的软橡胶状高弹体的使用。橡胶涂层将不能很好地粘附在基材上，且使用时脱落。
EP 0203425 A1描述了一种含有烯烃/丙烯酸酯共聚物和芳基乙烯与脂族二烯单体的嵌段共聚物的组合物，该组合物可用作芳族聚碳酸酯与聚烯烃间的粘结层。然而，仍可进一步改进粘结层与芳族聚碳酸酯间的粘附力。
人们希望有一种能较强粘附于硬(极性)基材例如聚碳酸酯和ABS的软的、橡胶状热塑性高弹体组合物。
这种组合物现已意想不到地被发现。因此，本发明涉及一种热塑性高弹体组合物，它含有：
一种氢化弹性体嵌段共聚物，它具有至少两个聚合单乙烯基芳族化合物的树脂状端部嵌段和一个聚合共轭二烯的弹性中间嵌段：
一种增塑剂；
一种烯烃-丙烯酸酯共聚物；和
一种聚烯烃。
具体地说，本发明的组合物包括：
15-60％重量的氢化弹性体嵌段共聚物，它具有至少两个聚合单乙烯基芳族化合物的树脂状端部嵌段和一个聚合共轭二烯的弹性体中间嵌段；15-45％重量的增塑剂，选自石蜡油、植物油和动物油或其衍生物以及氢化油；5-20％重量的烯烃-丙烯酸酯聚合物；和0.1-20％重量的聚丙烯。
申请人已发现该组合物，具体说是乙烯-丙烯酸酯共聚物和氢化弹性嵌段共聚物的组合产生具有改进粘附特性的，特别是粘附于极性基材如极性聚合物的热塑性高弹体组合物，即那些比聚烯烃更具极性的聚合物。
适合于本发明使用的弹性嵌段共聚物在现有技术中是已知的，例如在US 5,194,530中所公开的。弹性嵌段共聚物至少有两个聚合单乙烯基芳族化合物的树脂状端部嵌段，由此得到一个树脂状链段，以及一个聚合共轭二烯的弹性中间嵌段，由此得到一个弹性链段。嵌段共聚物可以是线性的，如A-B-A，或(A-B)nX或径向的，如(A-B)pX。在这些式子中，A代表聚合单乙烯基共轭二烯嵌段；X代表偶合剂；n是2而p大于2，优选3-20，更优选3-6。
适合的单乙烯基芳族化合物包括那些具有8-20个碳原子如以苯乙烯为例的化合物和苯乙烯同系物，如α-甲基苯乙烯和对-甲基苯乙烯。苯乙烯是特别优选的。
适合的共轭二烯包括那些具有4-8个碳原子的二烯。这样的共轭二烯的例子是1，3-丁二烯(丁二烯)、2-甲基-1，3-丁二烯(异戊二烯)、1，3-戊二烯(戊间二烯)、1，3-辛二烯和2-甲基-1，3-戊二烯。优选的共轭二烯是丁二烯和异戊二烯，最优选丁二烯。共轭二烯嵌段亦可由两个或多个不同共轭二烯的单体形成。
嵌段共聚物的重均分子量一般至少是50,000。对于线性聚合物，重均分子量一般在50,000-300,000范围内。实际上，上限由粘度决定，可高达可允许的值同时仍可加工。线性嵌段共聚物最优选的重均分子量是50,000-185,000。对于径向聚合物，由于这些聚合物在给定的总分子量下具有低粘度，其分子量可较高。由此，对于径向聚合物，重均分子量一般在50,000-1,000,000的范围内，优选100,000-500,000。
用于本发明的嵌段共聚物可以是单一嵌段共聚物或嵌段共聚物的共混物。当本发明的嵌段共聚物含有至少一种重均分子量小于75,000的嵌段共聚物时，可看到粘附有所提高。
关于线性共聚物，当用于本文时，术语“分子量”是由凝胶渗透色谱法(GPC)测定的重均分子量，其中GPC系统已用聚苯乙烯标准适当地校正过。在阴离子聚合的线性聚合物中的聚合物基本上是单分散的，可既便于又充分描述以报告所观察到的窄分子量分布的峰分子量。这类方法是已知的，在包括U.S.5,229,464的专利中有描述。由于苯乙烯(如聚苯乙烯)用作校正标准，测量值直接给出苯乙烯端部嵌段的绝对分子量。已知所存在的苯乙烯的分子量和百分数，可计算出中间嵌段的绝对分子量。在试样上测量分子量，该试样在聚合的第一步之后除去，然后终止以使引发剂失活。
通过使用GPC测量最终偶合星形或径向共聚物的真正分子量就不那么简单了。星形分子不分离并不以和用于校正的线性聚合物的相同方式通过填充的GPC柱。因此，达到UV或折光率检测器的时间不是一个好的分子量直接标记。因此，可以使用光散射技术来代替GPC测量星形共聚物的重均分子量。将样品溶解于适当的溶剂至浓度小于每100毫升溶剂1克样品，然后使用注射器和孔径小于0.5微米的多孔膜滤器直接过滤进光散射池中。使用标准方法将光散射测量值作为散射角和聚合物浓度的函数。在用于光散射的相同的波长下和相同的溶剂中测量样品的差示折光指数(DRI)。结果产生大约等于径向共聚物重均分子量的分子量值。
对本说明书来说，这里所述的分子量值和范围是重均分子量值和范围。
将用于本发明的弹性嵌段共聚物氢化至这样的程度，即弹性嵌段的不饱和度显著地减少而树脂状嵌段成分的不饱和度没有显著的变化。一般地，至少90％的不饱和二烯中间嵌段被氢化。但不超过25％，优选小于10％的芳族不饱和被氢化。该氢化技术在现有技术中是已知的并有所公开，例如在US再颁布27，145中。既然将用于本发明的嵌段共聚物氢化以除去脂族不饱和，因此它们可被看作S-EB-S聚合物，或根据具体情况是(S-EB)(n或p)X，其中S是指单乙烯基芳族，一般是苯乙烯，端部嵌段EB表示乙烯/丁烯，它是由氢化聚合的1，3-丁二烯得到的结构，n.p和X是如前所述的。
本发明的组合物另外含有既可与弹性体嵌段共聚物相容又可与硬基材如聚碳酸酯或ABS相容的乙烯-丙烯酸酯聚合物。在马来酸酐或丙烯酸酯组合物存在下，乙烯-丙烯酸酯聚合物包括乙烯-丙烯酸甲酯、乙烯-丙烯酸乙酯、乙烯-丙烯酸丁酯、乙烯-甲基丙烯酸甲酯、乙烯-丙烯酸、乙烯-甲基丙烯酸、乙烯-甲基丙烯酸缩水甘油酯的共聚物和三元共聚物以及其混合物。当与用于本发明的嵌段共聚物一起使用时，含有丙烯酸甲酯的乙烯-丙烯酸酯的共聚物或三元共聚物提供了好的结果。乙烯-丙烯酸甲酯共聚物的例子是OPTEMA TC-221(OPTEMA是商标)，乙烯-丙烯酸甲酯共聚物含有大约30％W丙烯酸甲酯，且具有大约0.948g/cc的密度。乙烯-丙烯酸甲酯三元共聚物的例子是IGETABOND 7M (IGETABOND是商标)，乙烯-甲基丙烯酸缩水甘油酯-丙烯酸甲酯三元共聚物含有大约3％w甲基丙烯酸缩水甘油酯和大约30％w丙烯酸甲酯。IGETABOND 7M的密度大约0.964g/cc。丙烯酸酯含量一般大于10％w。
(中间嵌段)增塑剂包含于本发明的组合物中。所用增塑剂一般是可与弹性体嵌段共聚物的弹性中间嵌段相容的且不会趋向在显著的程度上进入芳族端部嵌段部分的油。因此，油可被看认为石蜡类。用于弹性组合物中的石蜡油应能够与其它弹性组合物的成分一起熔化加工而不降解。特别重要的是最终组合物具有熔化挤出的能力。优异的油是以DRAKEOL 34出售的白矿物油，可从Pennozoil公司的Pennreco部门购得(DRAKEOL是商标)。DRAKEOL 34在51℃下的比重是0.864-0.878，闪点238℃，在38℃下的粘度是370-420SUS(0.8-0.9cm2/sec)。适合的植物油和动物油或其衍生物亦可用作增塑剂。其它适合的油包括氢化原料，即氢化环烷类。起初实质上是芳族的原料应被氢化至它们显示出没有大量的芳族不饱和，或至多很低量，一般不大于5％。
已惊奇地发现加入与中间嵌段、端部嵌段或两者相容的聚合物，具体说是聚烯烃，优选聚丙烯，会获得改进的对极性基材的粘附力。本发明的组合物一般含有最多20wt％，优选0.1-20wt％，较优选3-15wt％，更优选5-10wt％的聚烯烃，优选聚丙烯。
亦可加入流动促进剂或端部嵌段树脂。流动促进剂提供较好的热塑性高弹体的“浸润”，因此使高弹体和基材之间较好的接触导致改进的粘附。优选流动改进剂是苯乙烯类树脂，较优选主要是(即大于50wt％)α-甲基苯乙烯树脂。已产生好的结果的流动促进剂的例子是KRISTALEX 1120(KRISTALEX是商标)。KRISTALEX 1120是主要从α-甲基苯乙烯衍生得到的水白色、低分子量热塑性烃类树脂。KRISTALEX 1120在25/25℃下的比重是1.07，闪点是236℃，在25℃下的粘度为50cm2/sec(沲)。0-10wt％，优选3-10wt％的流动促进剂的加入量提供了好的结果。
因此，本发明的组合物包含氢化弹性嵌段共聚物，乙烯-丙烯酸酯共聚物或三元共聚物及增塑剂。优选的混合物含15-60wt％，较优选35-60wt％嵌段共聚物，15-45wt％增塑剂和5-20wt％，较优选10-20wt％乙烯-丙烯酸酯聚合物，所有的百分数基于混合添加的总重量。
一般地，在组合物中不使用交联剂。当然这不排除用作正常稳定化目的的物料如稳定剂的存在。适合的稳定剂的例子公开在U.S.4,835,200中。特别优选的是受阻酚类，特别是挥发性低的受阻酚类，例如四[亚甲基(3，5-二-叔丁基-4-氢化肉桂酸酯)]甲烷，由Ciba Geigy出售，商标为IRGANOX1010，或与硫代增效剂如DLTDP(硫代二丙酸二月桂酯)混合使用。稳定剂的存在量一般为0.1-5wt％，优选0.5-2.5wt％。
可根据本领域技术人员公知的一般步骤制备热塑性高弹体组合物。
优选，首先在与其它成份掺混之前，将嵌段共聚物和增塑剂混合以制备本发明的热塑性高弹体组合物。
本发明特别用于在极性母体/基材物料如聚碳酸酯或ABS上直接再注塑。潜在的用途包括(没有限制)，汽车用仪表板、按钮、扣子、钢笔/铅笔夹，蜂窝式电话、牙刷、把手和工具夹。组合物亦可被共挤塑、共挤吹塑或双注塑。据认为在热的基材上再注塑和/或老化对于改进粘附是有帮助的。
根据另一方面，本发明涉及再注塑的极性聚合物型材的制备方法，该方法包括将本发明的热塑性弹性化合物挤压成挤压物；制作包括极性聚合性的型材；并且将挤压物注塑在极性聚合物上、制成再注塑的极性聚合物型材。
根据本领域人员公知的过程，将挤压物注射或模制在热的极性聚合物型材上。或者将挤压物和极性聚合物共挤压。
根据进一步的方面，本发明涉及一种再注塑的极性聚合物型材，它包括含有极性聚合物的第一层和在第一层上再注塑的含有热塑性高弹体组合的第二层，并涉及含有再注塑的极性聚合物型材制品。如果需要，再注塑的极性聚合物型材可经老化处理以提高粘附力。
实施例
制备14个具有不同量的嵌段共聚物、油、乙烯-丙烯酸酯共聚物或三元共聚物、聚丙烯和流动促进剂的试验组合物。首先用手或用混合器将嵌段共聚物(以碎片形式)和油一起混合。一旦油被碎片吸附，加入剩余成份，将全部混合物用转鼓或混合机混合。然后将混合物加到挤出机料斗中并向啮合同向旋转双螺杆挤出机供料。混合物在300rpm下被挤出，熔化温度230℃-240℃。通过线料切割，挤出物成为粒料。
用以制作再注塑粘附试样的注塑机装有能够模塑两个不同厚度板的镶嵌模具。首先，将所需的基材物料(例如聚碳酸酯，ABS)模塑成0.32cm(0.125英寸)的板。然后将镶嵌模具改装成能模塑一个较厚的板。将蒙版粘带的条状料以平行于模塑方向模置在预模塑的板的一端。然后将预模塑的基材板重新放回镶嵌模具中，将试验组合物注塑进模腔，形成大约0.25cm(0.100英寸)覆盖基材物料的厚度。
然后垂直于流动方向将再注塑的板切割成2.54cm(1英寸)宽的条状物，用于进行90°粘附剥离试验。在试验过程中，将在板上放置蒙版粘带的区域充当固定再注塑板的复合部分。
由针对试样尺寸(1”×6”(2.54×15.24cm)，与1”×8”相反)和实验速度(2英寸/分5.08cm/min)进行改进的ASTMD-903进行试验。在室温(大约75°F-78°F(23.9-25.6℃))下于INSTRON(INSTRON是商标)试验机上进行试验。测量初始剥离和平均剥离。在由于开始剥离粘附试验曲线上，在曲线突然改变斜率的那个点处测量初始剥离。平均剥离是在大部分剥离过程中基本上水平的斜率的平均数。实施例1
在具有中分子量或高分子量的嵌段共聚物的组合物上进行第一组试验，并改变乙烯-丙烯酸酯共聚或三元共聚物的加入量。试验组合物和粘附试验结果列于表1中。
                                               表1
 组合物  高分子量嵌段共聚物1(％w)  低-中分子量嵌段共聚物2(％w)    油3(％w)    聚丙烯(％w)  乙烯-丙烯酸酯三元共聚物4(％w)  乙烯-丙烯酸酯共聚物5(％w)  粘附于ABS初始/平均值(pli)6   粘附于PC7  初始/平均值(pli)
   1*2*3*45*678     42.542.542.542.542.542.5------       ------------------54.254.2    42.542.542.537.542.537.520.820.8     15----10--101010        --1515815------15        ---------151515--      1.8/1.8(0.1/0.1)16.1/19.6(0.9/1.1)8.9/10.7(0.5/0.6)21.4/21.4(1.2/1.2)12.5/12.5(0.7/0.7)19.6/17.9(1.1/1.0)21.4/30.4(1.2/1.7)25.0/28.6(1.4/1.6)        (0.1/0.1)1.8/1.8(1.7/2.4)30.4/42.9(1.1/1.1)19.6/19.6(3.7/4.0)66.1/71.4(4.2/4.0)75.0/71.4(4.2/3.9)75.0/69.6(5.9/5.8)105.4/103.6(7.0/6.7)125.0/119.6
1KRATON G1651(Shell)，平均分子量约181,000的S-EB-S嵌段共聚物2KRATON G1650(Shell)，平均分子量约66,700的S-EB-S嵌段共聚物3DRAKOL 34(Pennzoil)，4IGETABOND7M(Sumitomo Chemical)，含有大约3％w甲基丙烯缩水甘油酯和大约30％w丙烯酸甲酯的乙烯-甲基丙烯酸缩水甘油酯-丙烯酸甲酯三元共聚物5OPTEMATC221(Exxon)，含大约30％w丙烯酸甲酯的乙烯-丙烯酸甲酯共聚物6pli＝每线性英寸磅(＝1b/in)7PC＝聚碳酸酯8用IGETABONDE代替8 IGETABOND7M，含大约12％甲基丙烯酸缩水甘油酯的乙烯-甲基丙烯酸缩水甘油酯共聚物*＝对比实验
已发现，通过加入乙烯-丙烯酸酯共聚物或三元共聚物和聚丙烯(组合物4和6-8)得到了显著改进的粘附力。还注意到采用少量油(实验4，和6-8)以及高熔流共聚物(组合物7和8)往往导致更高更均匀的粘附值。
实施例2
对具有不同共聚物混合物和流动促进剂加入量的组合物进行第二组试验。表2给出了粘附试验的试验组合物和结果。
                                                    表2
  组合物  低分子量共聚物1(％w)  高分子量共聚物2(％w)  官能化的共聚物3(％w)   油4(％w)  苯乙烯类树脂5(％w)   聚丙烯(％w)  乙烯-丙烯酸酯共聚物6(％w)     粘附于ABS初始/平均值(pli)7kg/m       粘附于PC8初始/平均值(pli)kg/m     MFI9(g/10min)
   691011121314 22.515.015.016.516.420.9    37.5------22.525.024.613.9     ---1522.5------------   37.537.537.537.537.541.033.8     ------------------7     1010101010109.4      151515158815      19.6/17.0(1.1/1.0)55.4/58.9(3.1/3.3)69.6/71.4(3.9/4.0)37.5/48.2(2.1/2.7)35.7/35.7(2.0/2.0)30.4/37.5(1.7/2.1)117.9/128.6(6.6/7.2)       75.0/69.6(4.2/3.9)123.2/128.6(6.9/7.2)114.3/123.2(6.4/6.910)141.1/141.1(7.9/7.910)110.7/125.0(6.2/7.010)142.9/141.1(8.0/7.910)146.4/157.2(8.2/8.810)     0.7599.4134.9104.876.8104.343.3
1KRATON G1652(Shell)，分子量约50,000的S-EB-S嵌段共聚物2KRATON G1651(Shell)，分子量约181,000的S-EB-S嵌段共聚物3KRATON FG1901X(Shell)，分子量约50,000的马来S-EB-S嵌段共聚物(1.7％w马来酸酐)4DRAKOL 34(Pennzoil)5KRISTALEX 1120(Hercules)，由α-甲基苯乙烯衍生得到的低分子量苯乙烯类树脂6OPTEMATC221(Exxon)，含大约30％w丙烯酸甲酯的乙烯-丙烯酸甲酯共聚物7pli＝每线性英寸磅8PC＝聚碳酸酯9MFI＝在230℃/2.16kg下的熔流指数10内聚破坏
可以看出通过使用低分子量至中分子量的嵌段共聚物(组合物9-14)或官能化的嵌段共聚物(组合物9和10)或端部嵌段树脂(组合物14)，实现了化合物的改进的流动性。改进的流动性导致改进的再注塑粘附于ABS和聚碳酸酯。
尽管为了说明的目的详细地描述了本发明，但不能由此当作对其的限制，而且在本发明的精神和范围内覆盖所有的改变和改进。

Claims (11)

1.一种热塑性高弹体组合物，它包括：
15-60％重量的氢化弹体嵌段共聚物，它具有至少两个聚合单乙烯基芳族化合物的树脂状端部嵌段和一个聚合共轭二烯的弹体中间嵌段；
15-45％重量的增塑剂，选自石蜡油、植物油和动物油或其衍生物以及氢化油；
5-20％重量的烯烃-丙烯酸酯聚合物；和
0.1-20％重量的聚丙烯。
2.一种权利要求1的热塑性高弹体组合物，其中烯烃-丙烯酸酯聚合物是乙烯-丙烯酸酯聚合物。
3.一种权利要求2的热塑性高弹体组合物，其中乙烯-丙烯酸酯聚合物选自乙烯-丙烯酸甲酯、乙烯-丙烯酸乙酯、乙烯-丙烯酸丁酯、乙烯-甲基丙烯酸甲酯、乙烯-丙烯酸、乙烯-甲基丙烯酸、乙烯-甲基丙烯酸缩水甘油酯和其混合物的共聚物或三元共聚物。
4.一种权利要求3的组合物，其中乙烯-丙烯酸酯是乙烯-丙烯酸甲酯共聚物或三元共聚物。
5.一种权利要求1-4中任一热塑性高弹体组合物，其中所述树脂状端部嵌段包括聚合苯乙烯，所述的弹体中间嵌段包括氢化以除去脂族不饱和部分的聚合1，3-丁二烯，由此作为乙烯/丁烯出现。
6.一种权利要求1-4中任一热塑性高弹体组合物，其中
所述嵌段共聚物的重均分子量在50,000-500,0000范围内。
7.一种权利要求1-4中任一项的热塑性高弹体组合物，还包括流动促进剂。
8.一种权利要求1-4中任一热塑性弹性组合物，其中氢化弹性嵌段共聚物是嵌段共聚物的共混物，其中至少一种嵌段共聚物的重均分子量小于75,000。
9.制备再注塑的极性聚合物型材的方法，它包括挤出前述权利要求中任一热塑性高弹体组合物以形成挤出物；制成含有极性聚合物的型材；将挤出物模塑在极性聚合物之上以形成再注塑的极性聚合物型材。
10.再注塑的极性聚合物型材，包括含有极性聚合物的第一层和再注塑在第一层之上的含有上述权利要求1-8中任一热塑性高弹体组合物的第二层。
11.含有权利要求10的再注塑的极性聚合物型材的制品。
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Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5987688A (en) * 1995-11-09 1999-11-23 Gillette Canada Inc. Gum-massaging oral brush
US5911676A (en) * 1996-09-12 1999-06-15 Anthony; Phillip K. Low-speed trash belt for open-end spinning machine and method
US6886207B1 (en) * 1999-06-14 2005-05-03 The Procter & Gamble Company Toothbrush
FR2799199B1 (fr) * 1999-09-23 2005-02-25 Thermoplastiques Cousin Tessie Materiau polymerique thermoplastique presentant une memoire de forme, sans qu'il soit necessaire de le reticuler, article presentant une memoire de forme realise en ce materiau et procede de fabrication dudit article
JP2001261922A (ja) * 2000-03-14 2001-09-26 Tokai Rubber Ind Ltd 高減衰エラストマー組成物
US6553604B1 (en) 2000-03-16 2003-04-29 Gillette Canada Company Toothbrush
US6846571B1 (en) * 2002-10-03 2005-01-25 Raj K. Agrawal Polymer blend for automotive flooring applications
US20040177462A1 (en) 2003-03-14 2004-09-16 The Gillette Company Toothbrush head
US20060272112A9 (en) * 2003-03-14 2006-12-07 The Gillette Company Toothbrush
US20090044357A1 (en) * 2007-08-16 2009-02-19 The Procter & Gamble Company Electric toothbrushes
RU2314775C2 (ru) 2003-04-23 2008-01-20 Дзе Проктер Энд Гэмбл Компани Электрическая зубная щетка
US7941886B2 (en) 2003-09-19 2011-05-17 Braun Gmbh Toothbrushes
EP1582563A1 (en) * 2004-03-31 2005-10-05 KRATON Polymers Research B.V. Hydrogenated styrenic block copolymer compositions with improved high temperature overmolding properties
US20070129454A1 (en) * 2005-12-05 2007-06-07 Tsrc Corporation Thermoplastic elastomer foaming material and the manufacturing method thereof
US9260578B2 (en) * 2005-11-30 2016-02-16 Tsrc Corporation Thermoplastic elastomer foaming material
JP5543805B2 (ja) * 2010-03-04 2014-07-09 旭化成ケミカルズ株式会社 水性インク印刷性に優れた樹脂組成物
GB201007796D0 (en) 2010-05-10 2010-06-23 Bielskis Linas Motorcycle stand
EP2598331A1 (en) * 2010-07-30 2013-06-05 E.I. Du Pont De Nemours And Company Multilayer films containing a fluorinated copolymer resin layer and an encapsulant layer
WO2016002506A1 (ja) * 2014-07-02 2016-01-07 住友ゴム工業株式会社 トレッド用ゴム組成物及び空気入りタイヤ
BR112018076848B1 (pt) 2016-06-23 2023-02-23 Dow Global Technologies Llc Artigo de sobreinjeção para policarbonato
JP2018012818A (ja) * 2016-07-22 2018-01-25 横浜ゴム株式会社 タイヤ用ゴム組成物
CN106700247A (zh) * 2016-12-02 2017-05-24 芜湖天鸿汽车零部件有限公司 一种汽车把手注塑成型的模具材料及其制备方法
EP3668925A1 (en) * 2017-09-29 2020-06-24 Kraton Polymers LLC Elastomeric compositions providing improved wet grip
KR102570571B1 (ko) * 2018-10-31 2023-08-23 롯데첨단소재(주) 열가소성 수지 조성물 및 이를 이용한 성형품
CN114573939B (zh) * 2022-03-08 2023-09-26 金发科技股份有限公司 一种热塑性弹性体组合物及其制备方法与应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4588777A (en) * 1982-10-21 1986-05-13 Dainippon Plastics Co., Ltd. Synthetic resin composition
EP0330151A2 (en) * 1988-02-23 1989-08-30 Nissho Corporation Bag for the storage of blood platelets
EP0409155A2 (en) * 1989-07-20 1991-01-23 Nissho Corporation Bag for storage of platelets and multiple bag system containing the bag

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
UST962011I4 (en) * 1977-04-25 1977-09-06 Shell Oil Company Coextruded laminate
US4397987A (en) * 1980-07-14 1983-08-09 Uniroyal, Inc. Nitrile rubber/EPDM graft blends
EP0082154A1 (en) * 1981-06-29 1983-06-29 Abbott Laboratories Clear, autoclavable thermoplastic formulation for medical liquid containers
US4391863A (en) * 1981-10-23 1983-07-05 Composite Container Corporation Peel resistant coextruded sheet
EP0096301A2 (de) * 1982-06-08 1983-12-21 Bayer Ag Einphasige Polymermischungen
US4444840A (en) * 1982-08-09 1984-04-24 Uniroyal, Inc. Calendered AES film
US4493921A (en) * 1982-09-24 1985-01-15 Uniroyal, Inc. Impact resistant blend
EP0107303B1 (en) * 1982-09-24 1988-07-06 UNIROYAL CHEMICAL COMPANY, Inc. Impact resistant blend and method for making it
USRE32217E (en) * 1982-11-12 1986-07-29 The Dow Chemical Company Graft copolymerization process
US4476283A (en) * 1982-11-12 1984-10-09 Uniroyal, Inc. Graft copolymerization process
US4550138A (en) * 1984-04-23 1985-10-29 Uniroyal, Inc. Polycarbonate compositions with improved low temperature impact strength
DE3429523A1 (de) * 1984-08-10 1986-02-20 Alkor GmbH Kunststoffe, 8000 München Schaumlaminatfolie oder -bahn
US4665125A (en) * 1984-11-20 1987-05-12 Mitsubishi Rayon Company Limited Thermoplastic resin composition of a polycarbonate and vinyl aromatic-vinyl cyanide comonomers/diene rubber graft copolymer
EP0203425A1 (en) * 1985-05-13 1986-12-03 General Electric Company Composition of a copolymer of an olefin and an acrylate monomer and a block copolymer of vinylaromatic and aliphatic diene
US4638033A (en) * 1985-12-23 1987-01-20 General Electric Company Resinous composition of a carbonate resin and a grafted derivative of ethylene-propylene-diene terpolymer exhibiting improved resistance to organic solvents
US4814381A (en) * 1987-04-16 1989-03-21 Uniroyal Chemical Company, Inc. Impact resistant polyethylene terephthalate/polycarbonate blends
US4780506A (en) * 1987-04-16 1988-10-25 Uniroyal Chemical Company, Inc. Impact resistant polyethylene terephthalate/polycarbonate blends
US4822653A (en) * 1987-08-05 1989-04-18 National Starch And Chemical Corporation Recyclable hot melt adhesive compositions
GB2210047A (en) * 1987-09-18 1989-06-01 Evode Ltd Thermoplastic elastomers
US4895899A (en) * 1987-12-23 1990-01-23 Uniroyal Chemical Company, Inc. Impact resistant polyethylene terephthalate/polycarbonate/polyethylene graft copolymer blends
USH1022H (en) * 1991-01-09 1992-02-04 Shell Oil Company Soft paintable polymer composition
US5356705A (en) * 1992-01-09 1994-10-18 The Dow Chemical Company Laminated, weatherable film-capped siding structure

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4588777A (en) * 1982-10-21 1986-05-13 Dainippon Plastics Co., Ltd. Synthetic resin composition
EP0330151A2 (en) * 1988-02-23 1989-08-30 Nissho Corporation Bag for the storage of blood platelets
EP0409155A2 (en) * 1989-07-20 1991-01-23 Nissho Corporation Bag for storage of platelets and multiple bag system containing the bag

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EP0832930A1 (en) 1998-04-01
DE69704597D1 (de) 2001-05-23
EP0832930B1 (en) 2001-04-18
CN1178810A (zh) 1998-04-15
KR100515873B1 (ko) 2006-01-12
ES2158444T3 (es) 2001-09-01
DE69704597T2 (de) 2001-10-18
TW457271B (en) 2001-10-01
TR199701044A2 (xx) 1998-04-21
TR199701044A3 (tr) 1998-04-21
KR19980024907A (ko) 1998-07-06
US5723543A (en) 1998-03-03
JPH10130453A (ja) 1998-05-19

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