CN1185298C - 具有改进粘合性能的热塑性弹性体 - Google Patents
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Abstract
包括热塑性弹性体和嵌段共聚物的粘合剂组合物,嵌段共聚物含有刚性乙烯基芳族嵌段和二烯和乙烯基芳族单体的非刚性嵌段。
Description
发明领域
本发明总体上涉及热塑性弹性体(TPE)材料。热塑性弹性体广泛地定义为橡胶状材料,与常规的硫化橡胶不同,它可以象热塑性材料那样加工和回收,在工作温度下,还具有相似于硫化橡胶的性能和特性。本发明更具体地涉及已经通过加入特定的乙烯基芳族嵌段共聚物改性的热塑性弹性体。本发明的组合物对于聚合物基材,特别是对于工程塑料具有改进粘合性能。
现有技术的描述
一般通过如下方式获得具有热塑性和弹性性能两者的共混物:以一定的方式将热塑性树脂与弹性体材料结合,使得弹性体紧密而均匀地以离散粒子相在热塑性连续相中分散。采用弹性体相的硫化的早期工作在U.S.Pat.No.3,037,954中找到,它公开了静态硫化,以及动态硫化,其中将可硫化弹性体分散入树脂性热塑性聚合物中并将弹性体固化(交联),同时连续混合和剪切共混物。
U.S.Pat.No.4,130,535公开了通过动态硫化制备的,包括热塑性烯烃树脂和烯烃共聚物橡胶的热塑性弹性体组合物,其中将橡胶组分硫化到基本不溶于常规橡胶溶剂的程度。没有给出关于这些组合物粘合性能的详细情况,但已知未改性的非极性热塑性弹性体一般粘合不到工程树脂上。
已经通过向共混物中引入官能化热塑性树脂,进行改进热塑性弹性体的粘合性能的努力。一种方案描述在U.S.Pat.No.4,957,968中,该文献公开了加入官能化聚烯烃以改进对金属和极性聚合物的粘合。U.S.Pat.No.5,843,577描述了聚酰胺和官能化聚烯烃的共聚物的引入,以改进对酰胺的粘合。U.S.Pat.No.5,852,118公开了官能化烯烃的嵌段共聚物、热塑性聚氨酯、共聚酯或共聚酰胺,和异氰酸酯的加入。
然而,达到热塑性弹性体对聚合物基材,特别是对极性工程热塑性基材的良好粘合,还没有由这些方案克服或技术对于实际应用过于复杂。
发明概述
本发明基于如下发现:通过向TPE中引入柔性嵌段共聚物而提供具有改进粘合的热塑性弹性体组合物,该柔性嵌段共聚物由乙烯基芳族单体的嵌段和二烯烃和乙烯基芳族单体的嵌段组成,并具有特定的分子结构。详细地,本发明涉及一种热塑性弹性体组合物,包含:
(a)25-90wt%热塑性弹性体,和
(b)10-75wt%嵌段共聚物,嵌段共聚物包含玻璃化转变温度高于25℃的乙烯芳族单体的刚性嵌段(S)和玻璃化转变温度低于25℃并至少包含嵌段结构S-B/S-S的二烯烃和乙烯基芳族单体的非刚性嵌段(B/S),并且其中二烯烃含量小于总嵌段共聚物的40wt%且非刚性嵌段B/S等于总嵌段共聚物的至少50wt%,
基于(a)+(b)的总重量。
本发明的另一实施方案涉及一种粘合剂组合物,包含:
(a)50-75wt%热塑性弹性体,包含聚丙烯和动态硫化的乙烯-丙烯-非共轭二烯烃三元共聚物橡胶的共混物,和
(b)25-50wt%嵌段共聚物,包含玻璃化转变温度高于25℃的苯乙烯的刚性嵌段和玻璃化转变温度低于25℃并至少包含嵌段结构苯乙烯-1,3-丁二烯/苯乙烯-苯乙烯的1,3-丁二烯和苯乙烯的非刚性嵌段,其中1,3-丁二烯含量小于总嵌段共聚物的40wt%和非刚性嵌段等于总嵌段共聚物的至少50wt%,
基于(a)+(b)的总重量。
此外,本发明涉及一种粘合剂组合物的制备方法,包括共混热塑性弹性体和嵌段共聚物的步骤,该嵌段共聚物包括玻璃化转变温度高于25℃的乙烯基芳族单体的刚性嵌段(S)和玻璃化转变温度小于25℃且至少包含嵌段结构S-B/S-S的二烯烃和乙烯基芳族单体的非刚性嵌段(B/S),其中二烯烃含量小于总嵌段共聚物的40wt%并且非刚性嵌段B/S等于总嵌段的共聚物的至少50wt%。
本发明的又一实施方案涉及包括至少一层热塑性基材的成型制品,基材至少部分与上述组合物粘合接触。
优选的实施方案是从属权利要求的证据。
热塑性弹性体组分(a)可以是烯烃热塑性弹性体,其中在热和剪切条件下,在固化剂存在下,共混热塑性烯烃聚合物和烯烃橡胶,以至少部分硫化(交联)橡胶组分以形成热塑性硫化橡胶(TPV)。热塑性弹性体组分(a)也可以是苯乙烯类嵌段共聚物,或烯烃类和苯乙烯类热塑性弹性体的混合物。
在本发明的另外实施方案中,热塑性聚氨酯也可以引入到组合物中。
优选实施方案的描述
烯烃类热塑性弹性体
热塑性烯烃聚合物组分
适用于本发明组合物的聚烯烃包括热塑性、结晶聚烯烃均聚物和共聚物。它们需要从含有2-7个碳原子的单烯烃单体,如乙烯、丙烯、1-丁烯、异丁烯、1-戊烯、1-己烯、1-辛烯、3-甲基-1-戊烯、4-甲基-1-戊烯、5-甲基-1-己烯、这些单烯烃的混合物制备,和是这些单烯烃与(甲基)丙烯酸和/或醋酸乙烯酯的共聚物。然而,优选是含有3-6个碳原子的单体,最优选是丙烯。在说明书和权利要求中使用的术语聚丙烯包括丙烯均聚物以及丙烯的反应器和/或无规共聚物,它可包含1-30wt%乙烯和/或4-16个碳原子的α-烯烃,及其混合物。聚丙烯可具有不同类型的结晶结构如等规或间规,和不同的结晶度,包括具有高百分比无定形结构的材料,如“弹性”聚丙烯。可用于本发明的另外聚烯烃是高、低、线性低和极低密度聚乙烯,和乙烯与(甲基)丙烯酸和/或醋酸乙烯酯的共聚物。
上述聚烯烃可以使用常规Ziegler/Natta催化剂体系或通过单中心催化剂体系制备。市售聚烯烃可用于本发明的实施。
发现提供有用的热塑性弹性体组合物的热塑性聚烯烃用量为8-90wt%,条件是聚烯烃和烯烃类橡胶的总量是35wt%,基于热塑性聚烯烃、烯烃橡胶和任选的添加剂的总重量。优选,热塑性聚烯烃含量为10-60wt%。
烯烃橡胶组分
合适的单烯烃共聚物橡胶包括两种或多种α-单烯烃,优选与至少一种多烯烃,通常是二烯烃共聚的非极性、橡胶状共聚物。可以使用饱和单烯烃共聚物橡胶,例如乙烯-丙烯共聚物橡胶(EPM)。然而,不饱和单烯烃橡胶如EPDM是更合适的。EPDM是乙烯,丙烯和非共轭二烯烃的三元共聚物。令人满意的非共轭二烯烃包括5-亚乙基-2-降冰片烯(ENB)、1,4-己二烯、5-亚甲基-2-降冰片烯(MNB)、1,6-辛二烯、5-甲基-1,4-己二烯、3,7-二甲基-1,6-辛二烯、1,3-环戊二烯、1,4-环己二烯、二环戊二烯(DCPD)、和乙烯基降冰片烯(VNB)。
丁基橡胶也用于热塑性弹性体组合物。如在说明书和权利要求中使用的术语丁基橡胶包括异烯烃和共轭单烯烃的共聚物、异烯烃与或不与共轭单烯烃,二乙烯基芳族单体的三元共聚物和这样共聚物和三元共聚物的卤化衍生物。本发明烯烃橡胶范围内的另一种合适共聚物是C4-7异单烯烃和对烷基苯乙烯的共聚物,和优选它的卤化衍生物。在共聚物中,主要在对烷基苯乙烯中的卤素数量,为0.1-10wt%。优选例子是异丁烯和对甲基苯乙烯的溴化共聚物。天然橡胶也是适用于热塑性弹性体组合物的烯烃橡胶。
热塑性弹性体中的烯烃橡胶一般为70-10wt%,条件是热塑性聚烯烃和烯烃橡胶的总量为至少35wt%,基于聚烯烃、橡胶和任选的添加剂的重量。优选烯烃橡胶含量为50-10wt%。
添加剂
热塑性弹性体可任选地包含增强和非增强填料、增塑剂、抗氧剂、稳定剂、橡胶加工油、增量油、润滑剂、防粘连剂、抗静电剂、蜡、发泡剂、颜料、阻燃剂和在橡胶混炼领域已知的其它加工助剂。这样的添加剂可构成总组合物的至多65wt%,更优选至多50wt%。可以采用的填料和补充剂包括常规无机物如碳酸钙、粘土、二氧化硅、滑石、二氧化钛、炭黑等。橡胶加工油一般是衍生自石油馏份的链烷烃、环烷烃或芳族油。该油选自通常与组合物中特定的橡胶或橡胶组分结合使用的那些。
加工
尽管依赖于橡胶相对于热塑性树脂的数量和(若有的话)橡胶的硫化程度,共连续形态或相反转也是可能的,但烯烃类热塑性弹性体的烯烃橡胶组分一般以连续聚烯烃基体中小的,即微尺寸的粒子存在。优选,橡胶至少是部分硫化的,和最优选它是完全硫化的(交联的)。
可以通过向热塑性烯烃聚合物和烯烃橡胶的共混物中加入合适的橡胶硫化剂,和在硫化条件下硫化橡胶到所需程度,而达到部分或完全交联。优选通过动态交联的方法交联橡胶。如在说明书和权利要求中使用的术语动态交联表示硫化或交联(硫化)方法,其中在剪切条件下,在大于聚烯烃组分熔点的温度下硫化橡胶。
本领域技术人员会理解硫化剂的合适数量和类型,和要求达到所需硫化的条件。可以使用任何已知的交联体系,只要它在弹性体组分的硫化条件下是合适的并且它与组合物的热塑性烯烃聚合物组分相容。交联(硫化)剂包括硫、硫给体、金属氧化物、酚醛树脂体系、马来酰亚胺、过氧化物基体系、氢化硅烷化体系、高能辐射等,两者都含有和没有促进剂和助剂。
如在此使用的术语完全硫化或全部硫化表示组合物的烯烃橡胶组分已经交联到这样的状态,其中除热塑性弹性体组合物之外,交联橡胶的弹性体性能相似于橡胶在它的常规硫化态的性能。橡胶的交联(或硫化)程度也可以按照凝胶含量,交联密度或未交联橡胶数量表达,未交联橡胶可由橡胶溶剂萃取。所有这些描述在本领域是公知的。
每100重量份要硫化的橡胶组分,通常使用5-20重量份交联剂或体系。
苯乙烯类热塑性弹性体
用于本发明的另一种热塑性弹性体是苯乙烯/共轭二烯烃/苯乙烯的嵌段共聚物,共轭二烯烃任选地被完全或部分氢化,或它们的混合物。一般情况下此嵌段可包含10-50wt%,更优选25-35wt%苯乙烯和90-50wt%,更优选75-35wt%共轭二烯烃,基于该嵌段共聚物。然而,更优选的是包含30wt%苯乙烯和70wt%共轭二烯烃的嵌段共聚物。共轭二烯烃选自丁二烯、异戊二烯或其混合物。苯乙烯/共轭二烯烃/苯乙烯类型的具体嵌段共聚物是SBS、SIS、SIBS、SEBS和SEPS嵌段共聚物。这些嵌段共聚物在本领域是已知的和市售的。
任选地嵌段共聚物可以进一步与聚烯烃或通常的添加剂或其混合物混炼。因此,苯乙烯类热塑性弹性体任选地进一步包括至多60wt%这样的聚烯烃均聚物或共聚物,或添加剂或其混合物,基于嵌段共聚物和聚烯烃和/或添加剂的总重量。优选,苯乙烯类热塑性弹性体包括至少10wt%聚烯烃。热塑性聚烯烃选自在烯烃类热塑性弹性体上下文中提及的那些。
本发明的热塑性弹性体组分也可以是烯烃类热塑性弹性体(包括聚烯烃,橡胶和任选的添加剂)和苯乙烯类热塑性弹性体(包括嵌段共聚物,任选的聚烯烃和/或添加剂)的共混物。优选的共混物分别包含5-95wt%烯烃类热塑性弹性体和95-5wt%苯乙烯类热塑性弹性体,基于热塑性弹性体组分的总重量。这些共混物可以通过本领域已知的通常共混工艺制备。
组合物的热塑性弹性体组分一般以25-90wt%的数量存在,基于热塑性弹性体和柔性嵌段共聚物的总重量。优选它为25-85wt%,和最优选50-75wt%。
热塑性聚氨酯
在本发明的进一步实施方案中,热塑性聚氨酯(TPU)可以包括在粘合剂组合物中。除了要求它在本质上是热塑性以外,关于它的配方TPU组分没有限制,这表示它从如下物质制备:基本二官能成分,即有机二异氰酸酯和在含活性氢基团中基本是二官能的组分。然而,通常可以采用官能度高于二的少部分成分。当使用增量剂如甘油、三羟甲基丙烷等时,特别如此。在本发明的范围之内,可以采用在本领域已知的任何TPU材料。
优选的TPU是从包括至少一种有机二异氰酸酯,至少一种聚合物二元醇和至少一种二官能补充剂的混合物制备的聚合物。TPU可以由预聚物,准预聚物或在本领域通常使用的一步法制备。
TPU组分可以按10-50wt%,和优选15-35wt%的数量引入,基于热塑性弹性体,TPU和柔性嵌段共聚物的总量。
柔性嵌段共聚物
本发明的组合物包括柔性嵌段共聚物组分,它由如下物质组成:包含乙烯基芳族单体的刚性嵌段(S)和二烯烃/乙烯基芳族单体的统计非刚性中等嵌段(B/S)的嵌段共聚物。这些嵌段共聚物至少包含嵌段结构S-B/S-S。嵌段S的玻璃化转变温度(Tg)一般大于25℃并且嵌段B/S的玻璃化转变温度(Tg)一般小于25℃。B/S嵌段由75-30wt%乙烯基芳族单体和25-70wt%二烯烃单体组成。特别优选的柔性B/S嵌段具有60-40wt%的乙烯基芳族单体含量和40-60wt%二烯烃单体含量。对于总嵌段共聚物组分,二烯烃含量小于40wt%,优选35wt%,且非刚性B/S嵌段部分至少等于50wt%,优选70wt%。嵌段共聚物组分具有低模量和屈服强度,和高伸长率。
合适的乙烯基芳族单体包括苯乙烯、烷基取代苯乙烯如对甲基苯乙烯、乙烯基甲苯,以及该混单体的混合物。优选的单体是苯乙烯。合适的二烯单体包括1,3-丁二烯、异戊二烯、1,3-戊二烯、苯基丁二烯、和该单体的混合物。优选的单体是1,3-丁二烯。共轭二烯烃单体也可以是完全或部分氢化的。
用于本发明热塑性弹性体组合物的嵌段共聚物在本领域是已知的,并进一步描述在如下文献中:加拿大Pat.No.2,193,264和国际专利申请WO96/20248、WO96/23823、WO98/12240和WO99/46330。它们一般通过丁基锂引发的序列阴离子聚合制备,但活性S-B/S二嵌段的偶合或二官能引发也是已知的方法。
嵌段共聚物组分在本发明组合物中的用量一般为10-75wt%,基于包括热塑性弹性体、添加剂和柔性嵌段共聚物组分的组合物总重量。柔性嵌段共聚物的优选用量为15-75wt%,最优选是25-50wt%。
实施例
如下通用步骤用于本发明热塑性弹性体的制备。尽管其它常规混合设备如Banbury混合机,Farrel连续混合机等也是令人满意的,在典型的热塑性混炼双螺杆挤出机中制备组合物。将嵌段共聚物的粒料与热塑性弹性体组分预共混,并使用失重带式给料机将共混物加入到挤出机中。调定挤出以达到至少为180℃但不高于220℃的熔体温度。一个挤出机排气口用作真空口以除去痕量挥发性物质和以防止挤出组合物中的空隙率。使用水下造粒机将组合物处理成球形粒料。在造粒之后,将组合物模塑成试片用于物理性能的测试或如下所述模塑用于剥离测试。
本发明的组合物是拉伸残余形变值约为50%或更小的橡胶性材料,它满足由ASTM D1566定义的橡胶标准。优选组合物具有65或以下的肖氏A硬度和/或1.86MPa(270psi)或更低的拉伸模量(100%)。
本发明的粘合剂组合物具有对如下热塑性基材的不可预料改进的粘合:如丙烯腈、丁二烯和苯乙烯的三元共聚物(ABS)、聚碳酸酯(PC)、ABS/PC合金和共混物、聚苯乙烯(PS)、高抗冲聚苯乙烯(HIPS)、聚苯醚、聚甲基丙烯酸甲酯(PMMA)、聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸乙二醇酯(PET)、丙烯腈苯乙烯丙烯酸(ASA)、聚丙烯聚乙烯和其它烯烃类聚合物,包括这些聚合物的共混物和合金,以及它们玻璃和矿物质填充的变化体。因此组合物可在通过如下常规工艺用于制备成形制品的工艺中使用:如共注塑、共挤塑、共吹塑(注射和挤出)、层压、压延、通过压挤和注射的重叠模塑、嵌件模压、和重叠挤出。由这些工艺获得的成形制品是多层制品,包括至少一层聚合物基材和至少一层根据本发明的粘合剂组合物。粘合剂组合物和从其制备的模塑和成形制品用于各种用途,如防滑柄、软触标签和涂层,和消费类电子产品、工具和器具部件。
在评价本发明实施例中使用如下测量方法:
断裂拉伸强度,拉伸变定,拉伸模量,断裂伸长率-ASTM D412(ISO37,类型2)
肖氏硬度-ASTM D2240
撕裂强度-ASTM D624
比重-ASTM D792
通过模仿ASTM D1876的剥离测试,测量本发明组合物的粘合力,改进之处在于使用硬和软基材代替两个软基材。同样,因为由于本发明组合物在基材界面处获得粘合,不存在单独的粘合剂层。为评价嵌件模压条件,将更硬的热塑性基材在“L”形模具腔室中生产,然后取出并冷却到环境温度。然后将成形塑料型材***另一个具有“T”形腔室的模具中,以占据腔室的一半。然后将熔融的本发明组合物注塑在现有的“L”上以生产“T-棒”制品。为评价压缩模塑条件,按所述生产热塑性“L”,但不从模具取出。通过旋转模具腔室到下一工段或通过使用滑动芯板,在“T”腔室中将模塑的“L”立即变成可及的并注入熔融的本发明组合物。然后使用标准张力计,通过在将每个向上“T”的耳柄放入单独的夹具中,以测量“T-棒”的剥离值。然后将夹具拉开180度。剥离的力依十字头行程(crosshead travel)做图,它也是向下的型材剥离长度。曲线典型地达到峰值而后下降到平稳段。平稳段的值记录为粘合力,表达为磅每直线英寸(pli)[牛顿/米(N/m)]。
本发明组合物的性能,和它们对ABS和PC基材的粘合力见表1和2。
表1
实施例No. | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
组分(wt%) | ||||||||||
SP8211·45W237 | 70 | 100 | ||||||||
SP9911·45W237 | 70 | 75 | 65 | 60 | 60 | 55 | 50 | 100 | ||
StyroflexBX6105 | 30 | 25 | 35 | 30 | 40 | 45 | 50 | 30 | ||
Septon 4055 | 10 | |||||||||
性能 | ||||||||||
硬度(肖氏A) | 52 | 51 | 55 | 58 | 60 | 61 | 63 | 55 | 45 | 45 |
断裂拉伸(psi)* | 580 | 540 | 610 | 930 | 920 | 1100 | 1210 | 610 | 475 | 500 |
断裂伸长率(%) | 590 | 590 | 640 | 710 | 740 | 770 | 780 | 540 | 500 | 450 |
拉伸模量(100%(psi) | 210 | 190 | 210 | 210 | 230 | 230 | 240 | 210 | 200 | |
拉伸残余形变(%) | 11 | 9 | 9 | 9 | 9 | 9 | 9 | 5 | ||
粘合力(pli) ** | ||||||||||
ABS(嵌件模塑) | 17 | 12 | 23 | 18 | 20 | 23 | 25 | 18 | <1 | <1 |
PC(嵌件模塑) | 28 | <1 | <1 | |||||||
ABS(压缩模塑) | 26 | |||||||||
PC(压缩模塑) | 37 |
*1psi=6874.8Pa
**1pli=175.2N/m
表2
实施例No. | 11 | 12 | 13 | 14 | 15 | 16 |
组分(wt%) | ||||||
SP8211-45W237 | 65 | 65 | 65 | 65 | 65 | |
Styroflex BX6105 | 35 | 25 | 17.5 | 25 | 17.5 | 35 |
Elastollan 1185 | 10 | 17.5 | ||||
Elastollan C85A | 10 | 17.5 | ||||
Thermolast K-TC6AAZ | 65 | |||||
粘合力(pli) * | ||||||
ABS | 19 | 16 | 7.5 | 20.5 | 17 | 8.5 |
PC | 26.5 | 20 | 13 | 22.5 | 12 | 15 |
*1pli=175.2N/m
通过共混65wt%SP8211-55W237热塑性弹性体和35wt%StyroflexBX6105柔性嵌段共聚物,制备本发明的粘合剂组合物。通过上述嵌件模压技术测试对各种聚合物基材的粘合力。剥离强度测试的结果见表3。在粘合模式的描述中,注释“内聚”表示在基材或本发明热塑性弹性体主体中发生的剥离或失效。注释“粘合剂”表示在基材和本发明热塑性弹性体之间界面发生的剥离或失效。
表3
基材 | 粘合力(pli)* | 粘合模式 |
聚碳酸酯(PC) | 29 | 内聚 |
丙烯腈/丁二烯/苯乙烯(ABS) | 21 | 粘合剂 |
PC/ABS共混物 | 29 | 内聚 |
PC-30%玻璃填充的 | 23 | 内聚 |
结晶聚苯乙烯(PS) | 29 | 内聚 |
高抗冲聚苯乙烯(HIPS) | 29 | 内聚 |
聚甲基丙烯酸甲酯(PMMA) | 19 | 粘合剂 |
丙烯酸类苯乙烯丙烯腈(ASA) | 15 | 粘合剂 |
ASA/PC | 17 | 粘合剂 |
PC/聚对苯二甲酸丁二醇酯(PBT) | 21 | 粘合剂 |
聚对苯二甲酸乙二醇酯(PET) | 17.5 | 粘合剂 |
聚丙烯(PP) | 25 | 内聚 |
聚苯醚(PPO) | 21 | 内聚 |
*1pli=175.2N/m
表中使用的缩写和产品名称定义如下:
SP8211-45W237-基于聚丙烯和硫化EPDM橡胶的Santoprene热塑性弹性体(Advanced Elastomer Systems,L.P.)
SP8211-55W237-基于聚丙烯和硫化EPDM橡胶的Santoprene热塑性弹性体(Advanced Elastomer Systems,L.P.)
SP9911-45W237-基于聚丙烯和硫化EPDM橡胶的Santoprene热塑性弹性体(Advanced Elastomer Systems,L.P.)
StyroflexBX6105-柔性苯乙烯-丁二烯嵌段共聚物(BASFAktiengesellschaft)
Septon4055-热塑性弹性体SEPS嵌段共聚物(Kuraray Co.,Ltd.)
Elastollan1185-聚醚基热塑聚氨酯(BASF Corp.)
ElastollanC85A-聚酯基热塑聚氨酯(BASF Corp.)
Thermolast KTM-基于SEBS的混炼TPE(Gummiwerk Kraiburg)
ABS-丙烯腈-丁二烯-苯乙烯三元共聚物树脂(Cycolac5600-GE)
PC-聚碳酸酯树脂(GE)
Claims (14)
1.一种粘合剂组合物,包含:
(a)25-90wt%热塑性弹性体,包括热塑性烯烃均聚物或共聚物和烯烃橡胶,与任选的添加剂的共混物,和
(b)10-75wt%嵌段共聚物,包含玻璃化转变温度高于25℃的乙烯芳族单体的刚性嵌段(S)和玻璃化转变温度低于25℃并至少包含嵌段结构S-B/S-S的二烯烃和乙烯基芳族单体的非刚性嵌段(B/S),其中二烯烃含量小于总嵌段共聚物的40wt%和非刚性嵌段B/S等于总嵌段共聚物的至少50wt%,
基于(a)+(b)的总重量。
2.权利要求1的组合物,进一步包括10-50wt%热塑性聚氨酯(c),基于(a)+(b)+(c)的总重量。
3.权利要求1的组合物,其中该共混物包括选自聚乙烯和聚丙烯的热塑性烯烃聚合物,和选自乙烯-丙烯共聚物橡胶和乙烯-丙烯-非共轭二烯烃三元共聚物橡胶的烯烃橡胶。
4.权利要求3的组合物,其中该烯烃橡胶至少是部分硫化的。
5.权利要求1的组合物,其中该热塑性弹性体(a)包括苯乙烯/共轭二烯烃/苯乙烯的苯乙烯类嵌段共聚物。
6.权利要求1的组合物,其中该嵌段共聚物(b)包括苯乙烯的刚性嵌段和1,3-丁二烯和苯乙烯的非刚性嵌段。
7.权利要求1的组合物,由ASTM D412测试的拉伸残余形变为50%或更小。
8.权利要求1的组合物,包括:
(a)50-75wt%热塑性弹性体,包含聚丙烯和动态硫化的乙烯-丙烯-非共轭二烯烃三元共聚物橡胶的共混物,和
(b)25-50wt%嵌段共聚物,包含玻璃化转变温度高于25℃的苯乙烯的刚性嵌段和玻璃化转变温度低于25℃并至少包含嵌段结构苯乙烯-1,3-丁二烯/苯乙烯-苯乙烯的1,3-丁二烯和苯乙烯的非刚性嵌段,其中1,3-丁二烯含量小于总嵌段共聚物的40wt%和非刚性嵌段等于总嵌段共聚物的至少50wt%,
基于(a)+(b)的总重量。
9.一种至少包括一层热塑性基材的成形制品,基材至少部分与权利要求1的组合物粘合接触。
10.一种权利要求1的粘合剂组合物的制造方法,包括共混热塑性弹性体和嵌段共聚物的步骤,其中热塑性弹性体包括热塑性烯烃均聚物或共聚物和烯烃橡胶,与任选的添加剂的共混物,且嵌段共聚物包括玻璃化转变温度高于25℃乙烯芳族单体的刚性嵌段(S)和玻璃化转变温度低于25℃并且至少包含嵌段结构S-B/S-S的二烯烃和乙烯基芳族单体的非刚性嵌段(B/S),其中二烯烃含量小于总嵌段共聚物的40wt%和非刚性嵌段B/S等于总嵌段共聚物的至少50wt%。
11.权利要求10的方法,其中该热塑性弹性体包括选自聚乙烯和聚丙烯的热塑性烯烃聚合物,和选自乙烯-丙烯共聚物橡胶和乙烯-丙烯-非共轭二烯烃三元共聚物橡胶的烯烃橡胶。
12.权利要求11的方法,其中热塑性弹性体包括热塑性烯烃基体,热塑性烯烃基体具有分散在其中的烯烃橡胶的离散粒子,烯烃橡胶已经通过动态硫化至少部分硫化。
13.权利要求10的方法,其中该热塑性弹性体包括苯乙烯/共轭二烯烃/苯乙烯的苯乙烯类嵌段共聚物。
14.权利要求10的方法,其中该嵌段共聚物包括苯乙烯的刚性嵌段和1,3-丁二烯和苯乙烯的非刚性嵌段。
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EP (1) | EP1261664B1 (zh) |
JP (1) | JP4799793B2 (zh) |
KR (1) | KR20020071977A (zh) |
CN (1) | CN1185298C (zh) |
AT (1) | ATE276311T1 (zh) |
AU (1) | AU776203B2 (zh) |
BR (1) | BR0107971A (zh) |
CA (1) | CA2397775A1 (zh) |
CZ (1) | CZ20022881A3 (zh) |
DE (1) | DE60105559T2 (zh) |
ES (1) | ES2223776T3 (zh) |
IL (1) | IL150966A0 (zh) |
MX (1) | MXPA02007422A (zh) |
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2001
- 2001-01-25 BR BR0107971-9A patent/BR0107971A/pt not_active IP Right Cessation
- 2001-01-25 EP EP01903314A patent/EP1261664B1/en not_active Expired - Lifetime
- 2001-01-25 AU AU31146/01A patent/AU776203B2/en not_active Ceased
- 2001-01-25 JP JP2001561102A patent/JP4799793B2/ja not_active Expired - Lifetime
- 2001-01-25 DE DE60105559T patent/DE60105559T2/de not_active Expired - Lifetime
- 2001-01-25 CN CNB018043291A patent/CN1185298C/zh not_active Expired - Lifetime
- 2001-01-25 US US10/181,003 patent/US7381771B2/en not_active Expired - Lifetime
- 2001-01-25 AT AT01903314T patent/ATE276311T1/de not_active IP Right Cessation
- 2001-01-25 CZ CZ20022881A patent/CZ20022881A3/cs unknown
- 2001-01-25 CA CA002397775A patent/CA2397775A1/en not_active Abandoned
- 2001-01-25 WO PCT/US2001/002482 patent/WO2001055257A1/en not_active Application Discontinuation
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- 2001-01-25 PL PL01356831A patent/PL356831A1/xx not_active Application Discontinuation
- 2001-01-25 MX MXPA02007422A patent/MXPA02007422A/es not_active Application Discontinuation
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AU776203B2 (en) | 2004-09-02 |
BR0107971A (pt) | 2002-11-05 |
JP2003523473A (ja) | 2003-08-05 |
MXPA02007422A (es) | 2002-12-09 |
DE60105559T2 (de) | 2005-10-06 |
JP4799793B2 (ja) | 2011-10-26 |
EP1261664A1 (en) | 2002-12-04 |
PL356831A1 (en) | 2004-07-12 |
EP1261664B1 (en) | 2004-09-15 |
ATE276311T1 (de) | 2004-10-15 |
CA2397775A1 (en) | 2001-08-02 |
CN1396941A (zh) | 2003-02-12 |
WO2001055257A1 (en) | 2001-08-02 |
US7381771B2 (en) | 2008-06-03 |
AU3114601A (en) | 2001-08-07 |
IL150966A0 (en) | 2003-02-12 |
ES2223776T3 (es) | 2005-03-01 |
CZ20022881A3 (cs) | 2002-11-13 |
DE60105559D1 (de) | 2004-10-21 |
KR20020071977A (ko) | 2002-09-13 |
US20030083434A1 (en) | 2003-05-01 |
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