CN1116354C - 具有改进再注塑粘合力的热塑性高弹体组合物 - Google Patents
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Abstract
本发明涉及一种热塑性高弹体组合物,该组合物包括:一种氢化弹性体嵌段共聚物,该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部嵌段和聚合共轭二烯的弹性体中间嵌段;一种增塑剂;和一种用苯乙烯-丙烯腈接枝的乙烯-丙烯-二烯单体橡胶。本发明还涉及制备再注塑的极性聚合物型材的方法,涉及再注塑的极性聚合物型材,以及含有再注塑的极性聚合物型材的物件。
Description
本发明涉及一种具有良好再注塑粘合力的热塑性高高弹体组合物。具体说,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)具有良好粘合力的热塑性高弹体组合物。
弹性体嵌段共聚物已知可以和聚烯烃配伍,但由于嵌段共聚物和基材如聚碳酸酯或ABS之间的配伍性差,以致它们在极性母体/基材上使用得很有限。具体地说,很多情况下需要将软橡胶原料直接模制在硬的基材上,以提供一层软的覆面。然而,由于高弹体和基材之间不相配伍,因而许多不错的软像胶状高弹体受到使用上的限制。橡胶涂布层与基材不能很好地粘合,使用时会脱落。人们希望有一种软的橡胶状的热塑性高弹体组合物,它能够和硬的(极性)基材如聚碳酸酯和ABS粘合。
这种组合物目前已令人意想不到地发现了。因此,本发明涉及了这种热塑性高弹体组合物,该组合物包括:
一种氢化弹性体嵌段共聚物,该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部嵌段和聚合共轭二烯的弹性体中间嵌段;
一种增塑剂;和
一种用苯乙烯-丙烯腈接枝的乙烯-丙烯-二烯单体橡胶。
具体地说,本发明的组合物包括:32-65%重量的氢化弹性体嵌段共聚物,该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部嵌段和一个聚合共轭二烯的弹性体中间嵌段;20-45%重量的增塑剂,所述增塑剂选自石蜡油、植物油和动物油或其衍生物以及氢化油;和5-20%重量的用苯乙烯-丙烯腈接枝的乙烯-丙烯-二烯单体橡胶。
申请人发现将苯乙烯-丙烯腈(SAN)接枝的乙烯-丙烯-二烯单体橡胶(EPDM)和氢化弹性体嵌段共聚物结合会得到具有改进粘合性的热塑性高弹体组合物,特别对极性基材如极性聚合物具有改进的粘合性,即那些聚合物比聚烯烃更具极性。
适用于本发明的弹性体嵌段共聚物是本领域已知的,例如在US5,194,530中就有所公开。弹性体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部嵌段,和1个聚合共轭二烯的弹性体中间嵌段,由此分别提供树脂性链段和提供弹性体链段。该嵌段共聚物可以是线性的,如A-B-A或(A-B)nX,也可以是径向的如(A-B)pX。这些式中,A表示聚合单乙烯基芳族嵌段,B表示聚合共轭二烯嵌段;X表示偶合剂;n为2而p大于2,优选3-20,更优选3-6。
适宜的单乙烯基芳族化合物包括那些具有8-20碳原子的化合物,举例如苯乙烯和苯乙烯同系物,如α-甲基苯乙烯和对-甲基苯乙烯。特别优选的是苯乙烯。
适宜的共轭二烯包括那些具有4-8碳原子的二烯。举例说明有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。优选共轭二烯是丁二烯和异戊二烯,最优选丁二烯。还可以用两种或多种不同共轭二烯单体形成共轭二烯嵌段。
嵌段共聚物的重均分子量一般为至少50,000。对线性聚合物而言,重均分子量一般为50,000-300,000范围。事实上,上限是考虑到粘度而确定出来的,使其高到可被允许同时仍具可加工性。线性共聚物的最优选重均分子量为50,000-185,000。对径向聚合物而言,由于这些聚合物在一定的总分子量下粘度较低,所以其重均分子量可以大很多。因此径向聚合物的重均分子量一般为50,000-1,000,000,优选100,000-500,000。
最好使用不同嵌段共聚物的混合物,如第一和第二嵌段共聚物的混合物,其中第一嵌段共聚物具有50,000-180,000范围优选小于175,000的重均分子量,且优选是线性的,而第二嵌段共聚物具有大于第一嵌段共聚物重均分子量的重均分子量。第二嵌段共聚物优选具有至少100,000、优选100,000-500,000、更优选至少175,000-300,000、甚至更优选大于180,000-300,000的重均分子量。优选第二嵌段共聚物是线性的。
这里使用的有关线性或嵌段共聚物的术语“分子量”,是指通过凝胶渗透色谱法(GPC)测定的重均分子量,其中GPC系统是用聚苯乙烯标准进行适当校准过的。阴离子聚合的线性聚合物中的聚合物基本上是单分散状,这样既便于报告所观察到的狭窄分子量分布的峰分子量,又具有足够的描述性。这种方法是公知的并且在包括US5,229,464的专利中有所描述。由于使用苯乙烯(如聚苯乙烯)作为校样标准,测定值可直接作为苯乙烯端部嵌段的绝对分子量。知道了分子量和苯乙烯存在的百分比,就可以计算出中间嵌段的绝对分子量。测定等分试样的分子量,等分试样是在聚合的第一步之后除去,然后终止以使引发剂失活。
GPC无法直接测定最终偶合星状或径向共聚物的实际分子量。星状分子无法像用于校准的线性聚合物那样以同样方式分离和通过填充GPC柱。由此,到达UV或折光率检测器的时间就不是一个好的分子量直接指示数。所以,光散射技术可以代替GPC用来测定星形共聚物的重均分子量。将样品溶于合适的溶剂,达到1克以下样品/100毫升溶剂的浓度,然后使用注射器和小于0.5微米孔径的多孔膜滤器将其直接过滤到光散射池。使用标准过程,将光散射测定值作为散射角和聚合物浓度的函数。在同样波长和用于光散射的同样溶剂中测定样品的差示折光率(DRI)。这样得到的分子量值接近于径向共聚物的重均分子量。
本说明书中,分子量的值和范围在此是指重均分子量的值和范围。
本发明使用的是氢化弹性体嵌段共聚物,氢化的程度是使弹性体嵌段的不饱和度大大得到减少,但树脂状嵌段成分的不饱和度没有明显改变。一般说来,氢化至少90%的不饱和二烯中间嵌段,但氢化不超过25%优选10%以下的芳族不饱和。本领域已知和公开了这种氢化技术,如US再颁布27,145中有所记载。由于本发明使用的嵌段共聚物是氢化的,除去了脂族不饱和官能键,因此,它们可以认为是S-EB-S聚合物或根据具体情况为(S-EB)(n或p)X,其中S指单乙烯基芳族端部嵌段,优选苯乙烯端部嵌段,EB代表乙烯/丁烯,其是由氢化1,3-丁二烯得到的结构,而n、p和X如前所述。
本发明的组合物还含有既可和弹性体嵌段共聚物相混又可和硬的基材如聚碳酸酯或ABS相配伍的SAN-接枝的EPDM。本发明组合物中发现好用的SAN-接枝EPDM有ROYALTUF372P20和ROYALTUF372C(ROYALTUF是商标)。ROYALTUF372P2C是一种用SAN树脂接枝的乙烯/丙烯/非共轭二烯(EPDM)高弹体。EPDM作为连续SAN中的细分散相存在,尽管双螺旋挤压机的强力处理可导致相转化。ROYALTUF 372P20大约是50/50的SAN/EPDM,具有0.98的比重,和在265℃21600g载荷下20g/10min的熔化指数。ROYALTUF372C除来自反应器粗屑外与ROYALTUF 372P20相似。SAN以连续EPDM中的分散相存在。ROYALTUF 372C在265℃ 21600g载荷下具有小于0.01g/10min的熔化指数。由于ROYALTUF 372P20容易混合以及它在化合物中的分散度,而成为优选者。
本发明的组合物包括一种(中间嵌段)增塑剂。所用增塑剂一般为可和弹性体嵌段共聚物的弹性体中间嵌段相容、且在任何明显程度上没有倾向进入芳族端部嵌段部分的油。由此,油可以认为是石蜡油。可以用于弹性体组合物的石蜡油应当能够和弹性体组合物的其它成分熔化加工而不会降解。特别重要的是最终的组合物能够被熔化挤压。出色的油是可从PennzoilCompany的Pennreco Division商购作为DRAKEOL 34出售的白色矿物油(DRAKEOL是商标)。DRAKEOL 34在51℃具有0.864-0.878的比重、238℃的闪点和38℃下的370-420SUS粘度(0.8-0.9cm2/sec)。适宜的植物油和动物油或它们的衍生物也可以作为增塑剂使用。其它适宜的油包括氢化料,即氢化环烷类。应当将原始是天然芳族的原料氢化至某种程度,致使它们不表现出明显含量的芳族不饱和度,或者说,非常低的含量,一般至多不超过5%wt。
还可以添加促流剂或端部嵌段树脂。促流剂提供热塑性弹性体较好的“浸湿”,由此使高弹体和基材较好地接触,导致改进的粘合性。促流剂优选是苯乙烯树脂,更优选主要是(即50%wt以上)α-甲基苯乙烯树脂。一种能够产生好效果的促流剂是KRISTALEX 1120(KRISTALEX是商标)。KRISTALEX 1120是主要衍生于α-甲基苯乙烯的水白色低分子量热塑性烃树脂。KRISTALEX 1120在25/25℃时的比重为1.07、闪点236℃、25℃下的粘度为50cm2/sec(沲)。添加3-10%wt的促流剂会得到好效果。
热塑性弹性体组合物还可以含有烯烃聚合物。一般说来,烯烃聚合物可和至少嵌段共聚物的一个嵌段相容。
优选的烯烃聚合物是聚丙烯。如果存在的话,烯烃聚合物一般含有组合物的最多20%wt,优选最多15%wt,更优选3-15%wt,特别优选5-10%wt。
由此可见,本发明的组合物含有氢化弹性体嵌段共聚物、SAN-接枝EPDM和(中间嵌段)增塑剂。优选的混合物是25-45%wt优选35-45%wt嵌段共聚物、35-45%wt增塑剂(具体说是油)、和5-20%wt优选6-18%wt更优选10-18%wt的SNA-接枝EPDM,所有百分数皆基于添加物混合的总重量。可以添加优选3-15%wt更优选5-10%wt的聚丙烯。还可添加促流剂如KRISTALEX 1120,添加量优选3-10%wt。
组合物中一般不使用交联剂。当然,这不妨碍用于常规稳定作用的原料的存在,如稳定剂。适宜的稳定剂于US4,835,200中有所记载。具体说,优选受阻酚,特别是低挥发性受阻酚,如可单独使用汽巴嘉技(Ciba Geigy)出售的商品名为IRGANOX 1010的四[亚甲基(3,5-二叔丁基-4-羟基氢化肉桂酸酯)甲烷,或者和硫代协合剂如DLTDP(硫代二丙酸二月桂酯)结合使用,稳定剂一般存在的量为0.1-5%wt,优选0.5-25%wt。
热塑性高弹体组合物可以根据本领域技术人员公知的一般过程来制备。
制备本发明热塑性高弹体组合物时,优选在嵌段共聚物和其它成分混合之前,先和增塑剂混合。
本发明特别适合用于直接再注塑在极性母体1基材材料之上,如聚碳酸酯或ABS。潜在的作用包括(但不是限定)自动仪器底座、捏手、按钮、钢笔/铅笔夹、多孔耳机、牙刷、手柄和工具把手。组合物还可以进行共挤压、共挤压吹塑、双注塑、镶嵌模塑或夹芯注塑。据信,在热基材再注塑并且/或者老化有助于提高粘合性。
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高弹体组合物挤压成挤压物;制作包括极性聚合物的型材;并且将挤压物模制在极性聚合物上,制成再注塑的极性聚合物型材。
将挤压物根据本领域技术人员公知的过程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。
根据另外一方面,本发明涉及包括每一层和第二层的再注塑的极性聚合物型材,其中第一层含有极性聚合物,第二层再注塑在第一层之上,含有本发明的热塑性高弹体组合物;本发明还涉及含有再注塑的极性聚合物型材的物件。如果需要的话,可以将再注塑的极性聚合物材进行老化处理,以提高粘合性。
本发明通过下面的实施例进一步说明。
实施例
制备十六种不同量嵌段共聚物、油、SAN-接枝EPDM、聚丙烯和促流剂的试验用组合物。首先将嵌段共聚物(粗屑状)和油通过手或者混合机混合在一起。当油被屑吸收时,加入剩下的成分,并且将整个混合物转鼓混合。然后将混合物添加到挤压进料斗中,并填入同向旋转啮合式双螺旋挤压机。在300rpm下挤压混合物,熔化温度230℃-240℃。将挤压物线材切割制成丸粒状。
使用注模设备制作再注塑的粘合试样,设备装配有能够模制两种不同厚度板的镶嵌模具。首先将所需的基材原料(如聚碳酸酯或ABS)模制成0.32cm(0.125英寸)厚的片。然后改装镶嵌模具,使其能够模制较厚的板。平行于模制方向将一条状蒙版粘带横置在预模板的一端。然后将预模制的基材板放回镶嵌模具中,并且将试验用组合物注入到模腔中,形成大约0.25cm(0.100英寸)覆盖在基材材料上的厚度。
然后,将再注塑的板沿垂直于流动方向切割成2.54cm(1英寸)宽的条,用于90°剥离粘合试验。蒙版粘带放置于板上的区域在试验过程中充当固定再注塑板的复合部分。
按ASTM D-903进行试验,但这个ASTM D-903是根据试样大小(1”×6”(2.54×15.24cm),与1”×8”(2.54×20.32cm)不同)和试样速度(2英寸/分钟5.08cm/min经过改制的。试验在INSTRON(商标)测试设备上进行,试验温度为室温(约75°F-78°F(23.9-25.6℃))。测定初始剥离和平均剥离。在粘合试验曲线上,由于开始剥离而使曲线突然改变斜率的点处测定初始剥离。平均剥离是大部分剥离过程中基本水平的斜率的平均数。实施例1
对组合物进行第一组实验,该组合物具有相同的共聚物、和不同添加量的SAN-接枝EPDM以及聚丙烯。实验用组合物和粘合试验的结果见表1。
表 1 1
SAN-接枝EPDM组合物 共聚物2 油3 聚丙烯 EPDM SAN 对ABS的初始粘合 对PC7的初始粘合性/
(wt%) (wt%) (wt%) 分散4 分散5 性/平均粘合性 平均粘合性
(wt%) (wt%) kg/m(pli)6 kg/m(pli)
1 42.5 42.5 15 -- -- 1.8/1.8(0.1/0.1) (0.1/0.1)1.8/1.8
2 42.5 42.5 7.5 7.5 -- 3.6/5.4(0.2/0.3) (0.7/0.9)12.5/16/1
3 42.5 42.5 -- 15 -- 87.5/NF(4.9/NF) (3.3/2.5)58.9/44.6
4 35 42.5 7.5 15 -- 17.9/17.9(1.0/1.0) (3.6/3.9)64.3/69.6
5 42.5 42.5 7.5 -- 7.5 14.3/12.5(0.8/0.7) (1.1/1.2)19.6/21.4
6 42.5 42.5 -- -- 15 60.7/62.5(3.4/3.5) (3.2/3.6)57.1/64.3
7 35 42.5 7.5 -- 15 25.0/25.0(4/1.4) (3.8/3.9)67.9/69.6
8 42.5 42.5 -- -- 15 60.7/62.5(3.4/3.5) (3.2/3.6)57.1/64.3
9 37.5 37.5 -- -- 25 41.1/64.3(2.3/3.6) (1.8/2.9)32.1/51.7
1所有实验用组合物中还存在一种增塑剂
2KRATON G1651(Shell),分子量约181,000的S-EB-S嵌段共聚物
3DRAKEOL 34(Pennzoil)
4ROYALTUF 372C(Uniroyal),265℃,21600g负载下熔化指数<0.01g/10min的SAN-接枝EPDM
5ROYALTUF 372P20(Uniroyal),265℃,21600g负载下熔化指数为20g/10min的SAN-接枝EPDM
6pli=每线形英寸磅数(=1b/in)
7PC=聚碳酸酯
KRATON,DRAKEOL和ROYALTUF为商标
可以看出随着SAN-接枝EPDM的加入,粘合性得到明显的改进(组合物2-9)。还可以看出的是当SAN-接枝EPDM含量的增加超过15wt%,无论是ABS还是聚酸酯没有达到进一步明显的改进(组合物6、8和9)。
实施例2
对组合物进行第二组实验,该组合物具有不同类型的共聚物,包括两种共聚物的混合物。实验用组合物和粘合试验的结果见表2。
表 2组合物 低分子量共 高分子量共 油1 SAN-接枝 对ABS的初始粘合性/ 对聚碳酸酯初始粘合性/平
聚物 聚物 (wt%) EPDM2 平均粘合性 均粘合性
(wt%) (wt%) (wt%) kg/m(pli)3 kg/m(pli)8 --- 42.54 42.5 15 60.7/64.3(3.4/3.6) (3.2/3.6)51.1/64.310 175 25.54 42.5 15 14.3/23.2(0.8/1.3) (2.5/2.8)44.6/50.011 176 25.54 42.5 15 35.7/46.4(2.0/2.6) (3.9/3.8)69.6/67.712 --- 42.57 42.5 15 30.4/42.9(1.7/2.4) (2.8/2.7)50.0/48.213 61.48 --- 23.6 15 44.6/46.4(2.5/2.6) (4.5/5.5)80.4/98.21DRAKEOL 34(Pennzoil)2ROYALTUF 372P20(Uniroyal),在265℃,21600g载荷下SAN接枝EPDM的熔化指数为20g/10min3pli=每线性英寸磅数(=1b/in)4KRATON G1651(Shell),分子量181,000的S-EBS嵌段共聚物5KRATON G1652(Shell),分子量约50,000的S-EBS嵌段共聚物6KRATON FG1901X(Shell),分子量约50,000的马来化S-EB-S嵌段共聚物(1.7%马来酸酐)7KRATON G1654(Shell),分子量约130,000的S-EB-S嵌段共聚物8KRATON G1650(Shell),分子量约67,000的S-EB-S嵌段共聚物DRAKEOL ROYALTUF和KRATON是商标
可以看出各种氢化苯乙烯-丁二烯共聚物和嵌段共聚物混合物可以用来生产对ABS和聚碳酸酯表现良好粘合性的化合物。实施例3
对组合物进行第三组实验,该组合物中包括促流剂。实验用组合物和粘合试验的结果见表3。
表 3组合 低嵌段 高嵌段 油3 苯乙烯 SAN-接枝 对ABS的 对聚碳酸酯的物 共聚物1 共聚物2 (wt%) 树脂4 EPDM5 初始粘合性 初始粘合性/
(wt%) (wt%) (wt%) (wt%) /平均粘性 平均粘合性
kg/m(pli)6 kg/m(pli)14 17 25.5 42.5 -- 15.0 15.3/22.2 (2.2/2.3)
(0.9/1.3) 37.5/39.215 16.3 24.5 40.8 4.0 14.4 22.2/29.0 (1.6/2.0)
(1.3/1.7) 27.3/34.116 15.7 23.5 39.2 7.8 13.8 42.6/49.5 (3.1/2.9)
(2.5/2.9) 52.9/49.5
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
3DRAKEOL 34(Pennzoil)
4KRISTALEX 1120(Hercules),衍生于α-甲基苯乙烯的低分子量苯乙烯树脂
5ROYALTUF372P20(Uniroyal),265℃,21600g负载下熔化指数为20g/10min的SAN-接枝EPDM
6pli=每线性英寸磅数(1b/in)
KRATON,DRAKEOL,KRISTALEX和ROYALTUF是商标。
随着促流剂量的增加,热塑性高弹体的流动有所增加(组合物14、15和16在230/2.16kg载荷下分别具有0.12、0.18和0.83g/10min的熔化流动指数)。可以看出流动性的改进提高了对基材的粘合性。
以上作了出于解释本发明目的的详细描述,虽不能受此限定的限制,但旨在本发明的实质和范围内覆盖所有的改变和改进。
Claims (12)
1.一种热塑性高弹体组合物,该组合物包括:
32-65%重量的氢化弹性体嵌段共聚物,该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部嵌段和一个聚合共轭二烯的弹性体中间嵌段;
20-45%重量的增塑剂,所述增塑剂选自石蜡油、植物油和动物油或其衍生物以及氢化油;和
5-20%重量的用苯乙烯-丙烯腈接枝的乙烯-丙烯-二烯单体橡胶。
2.根据权利要求1的热塑性高弹体组合物,其中所说的树脂状端部嵌段包括聚合的苯乙烯,所说的弹性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,因此以乙烯/丁烯形式出现。
3.根据权利要求1或2的热塑性高弹体组合物,其中氢化弹性体嵌段共聚物具有50,000-500,000范围的重均分子量。
4.根据权利要求1的热塑性高弹体组合物,还含有促流剂。
5.根据权利要求4的热塑性高弹体组合物,其中促流剂主要衍生于α-甲基苯乙烯。
6.根据权利要求4或5的热塑性高弹体组合物,其中促流剂存在的量为3-10%wt。
7.根据权利要求1的热塑性高弹体组合物,还含有烯烃聚合物。
8.根据权利要求7的热塑性高弹体组合物,其中烯烃聚合物存在的量为3-15%wt。
9.根据权利要求1的热塑性高弹体组合物,其中氢化嵌段共聚物是第一嵌段共聚物和第二嵌段共聚物的混合物,第一嵌段共聚物是线性的,且具有50,000-180,000的重均分子量,第二嵌段共聚物具有比第一嵌段共聚物重均分子量大的重均分子量。
10.制备再注塑的极性聚合物型材的方法,包括
将前述任一权利要求的热塑性高弹体组合物挤压成挤压物;
制成包括极性聚合物的型材,并且将挤压物模制在极性聚合物上形成再注塑的极性聚合物型材。
11.再注塑的极性聚合物型材,包括含有极性聚合物的第一层,和再注塑在第一层上的含有前述权利要求1-9中任一热塑性高弹体组合物的第二层。
12.含有根据权利要求11的再注塑的极性聚合物型材的物件。
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CN (1) | CN1116354C (zh) |
BR (1) | BR9704864A (zh) |
DE (1) | DE69708815T2 (zh) |
ES (1) | ES2168571T3 (zh) |
TR (1) | TR199701043A2 (zh) |
TW (1) | TW527396B (zh) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU3821999A (en) * | 1998-04-20 | 1999-11-08 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of a polyvinylarene composition and polyvinylarene compositions |
US7196137B2 (en) | 2002-02-08 | 2007-03-27 | Teknor Apex Company | Polymer compositions |
EP1582563A1 (en) * | 2004-03-31 | 2005-10-05 | KRATON Polymers Research B.V. | Hydrogenated styrenic block copolymer compositions with improved high temperature overmolding properties |
EP2054227B1 (de) | 2006-08-10 | 2010-04-28 | Braun GmbH | Verfahren zur herstellung eines verbunderzeugnisses mit selektiver galvanisierung |
PL2616492T3 (pl) * | 2010-09-17 | 2016-05-31 | Saint Gobain Performance Plastics Corp | Elastyczny materiał i wytworzone z niego artykuły |
US9127153B2 (en) * | 2012-11-02 | 2015-09-08 | Henkel IP & Holding GmbH | Molding and overmolding compositions for electronic devices |
JP6964578B2 (ja) * | 2015-07-24 | 2021-11-10 | ダイナソル・エラストメロス・エセ・アDynasol Elastomeros S.A. | Tpe組成物における改善された性能を有する水素化ゴム |
CN108227380B (zh) * | 2016-12-12 | 2021-06-18 | 上海甚龙新材料技术有限公司 | 消除各向异性的感光树脂柔性版及其制成的柔性印刷版 |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US32217A (en) * | 1861-04-30 | Beehive | ||
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 |
DE3035637A1 (de) * | 1980-09-20 | 1982-05-06 | Basf Ag, 6700 Ludwigshafen | Thermoplastische formmasse, verwendung der formmasse, sowie formteile aus dieser |
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 |
EP0107303B1 (en) * | 1982-09-24 | 1988-07-06 | UNIROYAL CHEMICAL COMPANY, Inc. | Impact resistant blend and method for making it |
US4493921A (en) * | 1982-09-24 | 1985-01-15 | Uniroyal, Inc. | Impact resistant blend |
US4476283A (en) * | 1982-11-12 | 1984-10-09 | Uniroyal, Inc. | Graft copolymerization process |
USRE32217E (en) | 1982-11-12 | 1986-07-29 | The Dow Chemical Company | 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 |
US4780506A (en) * | 1987-04-16 | 1988-10-25 | Uniroyal Chemical Company, Inc. | Impact resistant polyethylene terephthalate/polycarbonate blends |
US4814381A (en) * | 1987-04-16 | 1989-03-21 | Uniroyal Chemical Company, Inc. | Impact resistant polyethylene terephthalate/polycarbonate blends |
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 |
FR2717487B1 (fr) * | 1994-03-16 | 1998-06-26 | Atochem Elf Sa | Composition de liant de coextrusion et complexe multicouche coextrudé dans lequel ladite composition est utilisée comme couche adhésive. |
US5814702A (en) * | 1996-02-20 | 1998-09-29 | General Electric Company | Elastomer composition and thermoplastic resin composition modified therewith |
-
1996
- 1996-09-26 US US08/721,644 patent/US5969034A/en not_active Expired - Lifetime
-
1997
- 1997-09-23 DE DE69708815T patent/DE69708815T2/de not_active Expired - Lifetime
- 1997-09-23 ES ES97202914T patent/ES2168571T3/es not_active Expired - Lifetime
- 1997-09-23 EP EP97202914A patent/EP0832931B1/en not_active Expired - Lifetime
- 1997-09-24 KR KR1019970048450A patent/KR100517297B1/ko not_active IP Right Cessation
- 1997-09-24 JP JP9259039A patent/JPH10101895A/ja active Pending
- 1997-09-24 BR BR9704864A patent/BR9704864A/pt not_active IP Right Cessation
- 1997-09-24 CN CN97121394A patent/CN1116354C/zh not_active Expired - Fee Related
- 1997-09-26 TR TR97/01043A patent/TR199701043A2/xx unknown
- 1997-09-26 TW TW086114063A patent/TW527396B/zh not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
ES2168571T3 (es) | 2002-06-16 |
TR199701043A3 (tr) | 1998-04-21 |
US5969034A (en) | 1999-10-19 |
DE69708815T2 (de) | 2002-09-26 |
BR9704864A (pt) | 1998-12-22 |
DE69708815D1 (de) | 2002-01-17 |
TW527396B (en) | 2003-04-11 |
KR100517297B1 (ko) | 2006-01-12 |
EP0832931B1 (en) | 2001-12-05 |
JPH10101895A (ja) | 1998-04-21 |
TR199701043A2 (xx) | 1998-04-21 |
EP0832931A1 (en) | 1998-04-01 |
CN1178809A (zh) | 1998-04-15 |
KR19980024906A (ko) | 1998-07-06 |
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