CN1270195A - 共挤出粘合剂、其用于多层结构的用途及由此获得的结构 - Google Patents
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Abstract
本发明涉及共挤出粘合剂,包括5—30份聚合物(A)和95—70份聚乙烯(B),其中(A)含有聚乙烯(A1)和选自弹性体、非常低密度聚乙烯和金属茂聚乙烯的聚合物(A2)的混合物,它们被不饱和羧酸共接枝;所述(A)和(B)的混合物的密度在0.910和0.930之间,接枝的不饱和羧酸的量在30和10000pppm之间,MFI在0.1和3克/10分钟之间。这样的粘合剂特别适用于制备汽油箱。
Description
本发明涉及共挤出粘合剂,其用于多层结构的用途,以及由此获得的结构。
更具体地说,本发明的共挤出粘合剂包括:--5-30份聚合物(A),其本身含有密度在0.910和0.940之间的聚乙烯(A1)和选自弹性体、非常低密度聚乙烯和金属茂聚乙烯的聚合物(A2)的混合物,上述(A1)和(A2)混合物被不饱和羧酸所共接枝;--95-70份密度在0.910和0.930之间的聚乙烯(B);--上述(A)和(B)混合物,使得:.其密度在0.910和0.930之间,.接枝的不饱和羧酸的量在30和10000ppm之间,.其MFI(ASTMD 1238;190℃/2.16千克)是在0.1和3克/10分钟之间,MFI表示熔体流动指数,以每10分钟的克数表示。
本发明还涉及一种多层结构,其中包括一层包含上面定义的共挤出粘合剂,和一层直接与其附着的含氮或含氧的极性树脂(E),例如一层聚酰胺树脂、一层脂肪族聚酮、一层皂化的乙烯-乙酸乙烯酯共聚物(EVOH),或者一层聚酯树脂,或者还有一层金属。
本发明还涉及一种结构,其中包括上述结构,并且在粘合剂一侧直接与其附着一层聚烯烃(F)或者一层选自(E)层树脂的树脂,或者还有一层金属。
本发明还涉及一种结构,分别地,包括一层聚烯烃(F)、一层如前述定义的粘合剂、一层聚酰胺树脂或者一层皂化的乙烯-乙酸乙烯酯共聚物(EVOH)、一层如前述定义的粘合剂和一层聚烯烃(F)。
这些结构适用于制备软包装或硬包装,例如袋子、瓶子或者容器。这些包装物可以通过共挤出、层压成型或共挤出-吹塑成型方法制得。
本发明特别适用于制备共挤出成型的软管或管子和用于制备汽车汽油箱。
汽油箱通常由5层组成,每层分别是:--高密度聚乙烯(PEGHD);--粘合剂;--聚酰胺(PA)或者具有乙烯单元和乙烯醇单元的共聚物(EVOH);--粘合剂;--PEHD。
在一层粘合剂和一层PEHD之间常常加入第六层。该第六层是由汽油箱模压过程中产生的废料或者极少量的、由没有用途的箱所组成。上述废料和这些没有用途的箱被压碎成颗粒。然后将反复磨碎的磨碎物在工厂中再熔融并且直接挤出,用于箱的共挤出。反复磨碎的磨碎物还可以在再使用之前通过挤出机例如双螺杆挤出机熔融并且再次造粒。
根据另一种形式,还可以将上述循环用产物与上述汽油箱的最外两层的PEHD共混。也可能例如将共混循环用产物的颗粒和新的这两层的PEHD颗粒相混合。也可以使用这些循环操作的所有组合。
循环用材料的量可以至多占所述汽油箱的总重量的50%。
因此所述第六层包含了所有多层结构的材料,即PEHD、粘合剂、PA或EVOH。
现有技术已经描述过多层汽油箱。欧洲专利文献EP834415描述了下面的结构:聚乙烯/粘合剂EVOH/粘合剂/聚乙烯。
上述粘合剂是熔体流动指数MF1为0.1-3,并且密度在0.920和0.930之间的被马来酸酐接枝的聚乙烯,并且它含有2-40%重量的在90℃不溶于正癸烷的材料。其解释了接枝的聚乙烯在140℃溶解于正癸烷并且冷却到90℃,并在该温度产生沉淀;然后过滤,不溶物含量以沉淀的重量百分比计,并且在90℃过滤收集。
如果该含量在2和40%之间,则粘合剂对汽油具有良好的抗耐性。
上述文献中没有一个实施例描述这样一种聚合物。然而,说明书详细说明了粘合剂实际上是2-30份具有0.930和0.980之间的密度的接枝聚乙烯和70-98份具有0.910和0.940之间的密度的未接枝聚乙烯的混合物。
申请人根据这样的教导,尝试制备本发明的粘合剂和相应的结构。其中发现粘合剂是不可重复生产的,也就是说以其密度选择产物是不够充分的指标。申请人还发现这些标准不足以使粘合剂耐受汽油。
现在详述本发明。
关于聚合物(A1),它是聚乙烯均聚物或乙烯与选自下面的共聚用单体的共聚物:-α-烯烃,优选具有3-30个碳原子的那些烯烃。
作为可能的共聚用单体的具有3-30个碳原子的α-烯烃,包括丙烯、1-丁烯、1-戊烯、3-甲基-1-丁烯、1-己烯、4-甲基-1-戊烯、3-甲基-1-戊烯、1-辛烯、1-癸烯、1-十二烯、1-十四烯、1-十六烯、1-十八烯、1-二十烯、1-二十二烯、1-二十四烯、1-二十六烯、1-二十八烯和1-三十烯。这些α-烯烃可以单独使用,或以其中两者或多者的共混物来使用。-不饱和羧酸的酯,例如(甲基)丙烯酸烷基酯,其中烷基具有1-24个碳原子。
可以使用的丙烯酸烷基酯或甲基丙烯酸烷基酯包括,甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯和丙烯酸2-乙基己酯。-饱和羧酸的乙烯酯,例如乙酸乙烯酯或丙酸乙烯酯。
(A1)的密度优选在0.915和0.925之间。
(A1)的MFI是0.1-8克/10分钟。
(A1)优选是LLDPE(线型低密度聚乙烯)型的乙烯/α-烯烃共聚物。
作为弹性体(A2)的实例,可以提到乙烯/丙烯(EPR)、乙烯/丙烯/二烯、乙烯/1-丁烯、乙烯/1-丁烯/二烯、乙烯/丙烯/1-丁烯/二烯和乙烯/4-甲基-1-戊烯共聚物和至少两种这些弹性体的混合物。
(A2)还可以是苯乙烯/丁二烯/苯乙烯嵌段共聚物(SBS)、苯乙烯/乙烯-丁烯/苯乙烯嵌段共聚物(SEBS)或苯乙烯/异戊二烯/苯乙烯嵌段共聚物(SIS)。
(A2)还可以是VLDPE(非常低密度聚乙烯)。这些是具有在0.860和0.910之间的密度的乙烯/α-烯烃共聚物。
(A2)还可以是金属茂聚乙烯。
上述术语“金属茂聚乙烯”应该理解为:通过乙烯和例如丙烯、丁烯、己烯或辛烯等α-烯烃,在一般由例如锆或钛的金属原子和与该金属连接的两个烷基环分子组成的单位点(monosite)催化剂存在下,共聚合作用得到的聚合物。更具体地说,金属茂催化剂通常由与金属连接的两个环戊二烯环组成。这些催化剂常常与作为共同催化剂或活化剂的铝氧烷,并优选甲基铝氧烷(MAO)一起使用。铪也可以用作环戊二烯连接的金属。其它金属茂可以包括IVA、VA和VIA族过渡金属。也可以使用镧系金属。
这些金属茂聚乙烯也可以以其Mw/Mn比例<3,并且优选<2作为特征。
(A2)的密度优选在0.860和0.880之间。
也就是说,(A2)代表从热塑性树脂至弹性体范围的聚合物。(A2)最好是弹性体,乙烯/丙烯、还有乙烯/辛烯和乙烯/己烯共聚物,并且其中乙烯/1-丁烯共聚物是最优选的。乙烯/丙烯共聚物和乙烯/1-丁烯共聚物最好具有0.1-20的熔体流动指数(根据ASTMD 1238-65T在190℃下测定),并且乙烯含量是60-90摩尔百分比。
一定要这样选择(A2)的密度,使得(A)(也就是说A1+A2)和(B)的共混物具有0.910和0.930之间的,优选0.915和0.920之间的密度。(A2)的MFI最好是0.1-20。
优选地,每40-10份的(A2)要使用60-90份的(A1)。
用不饱和的羧酸接枝(A1)和(A2)的混合物,也就是说(A1)和(A2)是被共同接枝。使用这些酸的官能衍生物也在本发明的范围内。
不饱和羧酸的实例是那些具有2-20个碳原子的酸类,例如丙烯酸、甲基丙烯酸、马来酸、富马酸和衣糠酸。这些酸的官能衍生物包括,例如,不饱和羧酸的酸酐、酯衍生物、酰胺衍生物、酰亚胺衍生物和金属盐(例如碱金属盐)。
具有4-10个碳原子的不饱和二羧酸及其官能衍生物,特别是其酸酐,是特别优选的接枝单体。
这些接枝单体包括,例如,马来酸、富马酸、衣糠酸、柠康酸、烯丙基琥珀酸、环己-4-烯-1,2-二羧酸、4-甲基环己-4-烯-1,2-二羧酸、双环[2.2.1]庚-5-烯-2,3-二羧酸和x-甲基双环[2.2.1]庚-5-烯-2,3-二羧酸、马来酸酐、衣糠酸酐、柠康酸酐、烯丙基琥珀酸酐、环己-4-烯-1,2-二羧酸酐、4-亚甲基环己-4-烯-1,2-二羧酸酐、双环[2.2.1]庚-5-烯-2,3-二羧酸酐和X-甲基双环[2.2.1]庚-5-烯-2,2-二羧酸酐。
其它接枝单体的例子包括不饱和羧酸的C1-C8烷基酯或缩水甘油酯衍生物,例如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、马来酸单乙酯、马来酸二乙酯、富马酸单甲酯、富马酸二甲酯、衣糠酸单甲酯、衣糠酸二乙酯;不饱和羧酸的酰胺衍生物,例如丙烯基酰胺、甲基丙烯基酰胺、马来酸单酰胺、马来酸二酰胺、马来酸N-单乙基酰胺、马来酸N,N-二乙基酰胺、马来酸N-单丁基酰胺、马来酸N,N-二丁基酰胺、富马酸单酰胺、富马酸二酰胺、富马酸N-单乙基酰胺、富马酸N,N-二乙基酰胺、富马酸N-单丁基酰胺和富马酸N,N-二丁基酰胺;不饱和羧酸的酰亚胺衍生物,例如马来酰亚胺、N-丁基马来酰亚胺、N-苯基马来酰亚胺;和不饱和羧酸的金属盐,例如丙烯酸钠、甲基丙烯酸钠、丙烯酸钾和甲基丙烯酸钾。其中优选马来酸酐。
可以使用多种已知方法将接枝单体接枝到(A1)和(A2)的混合物上。该混合物可以以10ppm和5%之间的水平含有通常用于聚烯烃加工的添加剂,例如以取代的酚分子等为基础的抗氧化剂、紫外保护剂、加工助剂,例如脂肪酰胺、硬脂酸和硬脂酸的盐,已知防止挤出缺陷的氟化聚合物,以胺类为基础的防雾剂、防粘剂,例如二氧化硅或滑石,带有染料的母炼胶、成核剂等等。
例如,这可以通过在有或没有溶剂存在和用或没用自由基引发剂的条件下,将聚合物(A1)和(A2)加热至大约150℃至300℃的高温进行反应。在该反应中可以使用的合适的溶剂是苯、甲苯、二甲苯、氯苯、枯烯等。可以使用的自由基引发剂包括叔丁基氢过氧化物、氢过氧化枯烯、氢过氧化二异丙基苯、二叔丁基过氧化物、叔丁基枯基过氧化物、二枯基过氧化物、1,3-双(叔丁基过氧异丙基)苯、过氧化乙酰、过氧化苯甲酰、过氧化异丁酰、双(3,5,5-三甲基己酰)过氧化物和甲基乙基酮过氧化物。
据上述方法获得的接枝改性的(A1)和(A2)混合物中,接枝单体的量可以以合适的方法选择,但是以接枝的(A1)和(A2)的重量计,优选是0.01-10%,并以600ppm至6%为宜。
通过IRTF分光分析琥珀官能团来测定被接枝单体的量。
(A),也就是说已经共同接枝的(A1)和(A2)的MFI是0.1-10。关于聚乙烯(B),它是聚乙烯均聚物或者还可以是选自乙烯与选自α-烯烃、不饱和羧酸的酯或饱和羧酸的乙烯酯的单体的共聚物。这些单体已经在(A1)和(A2)的定义中提到。
(B)最好是LLDPE或乙烯/α-烯烃共聚物。
(B)的MFI优选在0.1和3之间。
根据本发明的优选方案,其中的粘合剂含有95-80份的(B)和5-20份的(A)。
根据本发明的优选方案,(A1)的共聚用单体与(B)的共聚用单体是相同,并且最好是选自1-己烯、1-辛烯和1-丁烯。
根据本发明的一个具体方案,聚合物(A),也就是说已经共同接枝的(A1)和(A2)是:
(A1)包括至少75摩尔%的乙烯并且具有其绝对值大于15的MFI2/[η]-8.77比例;
(A2)包括至少50摩尔%的乙烯;
(A2)具有绝对值大于15的MFI2/[η]-8.77比例;
其乙烯含量不少于70摩尔%;
MFI10/MFI2之比在5和20之间,其中MFI2是根据ASTMD1238测定的2.16千克负载下的在190℃中的熔体流动指数,MFI10是根据ASTMD1238测定的10千克负载下的在190℃中的熔体流动指数,特性粘度[η]是指在135℃萘烷溶液中测定的以dl/克表示的聚合物的粘度系数。
本发明的多层结构包括:含有上述粘合剂的一层和一层含氧或含氮的极性树脂层(E),或者一层金属。
除粘合剂外的层中,优选的极性树脂可以是聚酰胺树脂、脂肪族聚酮、皂化的乙烯-乙酸乙烯酯共聚物和聚酯。
更具体地说,它们包含:主链中具有酰胺基结构单元的长链合成聚酰胺,例如PA-6、PA-6,6、PA-6,10、PA-11、PA-6/6,6,和PA-12;一种通过皂化具有大约15-60摩尔百分比乙烯含量的乙烯/乙酸乙烯酯共聚物而得到、具有大约90-100摩尔%皂化程度的皂化的乙烯/乙酸乙烯酯共聚物;聚酯,例如聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚环烷酸乙酯,这些树脂的混合物,或者还有芳香族聚酯,例如液晶聚合物。
上述金属层可以是金属,如铝、铁、铜、锡和镍或者含有至少一种这样的金属作为主要成分的合金的薄片、膜或箔。膜的厚度或者箔的厚度可以适当地选择,大约为0.01至大约0.2毫米。实际上在将本发明粘合剂层压到其上之前通常将金属层表面脱脂。上述的含氧或者含氮极性树脂层(E)还可以含有常规量的已知的添加剂。
本发明还涉及各自包括一层聚烯烃(F)、一层本发明的粘合剂和一层含氮或者含氧极性树脂(E)或者一层金属的一种结构。根据另一个具体实施方案,本发明涉及各自包括一层PEHD、一层本发明粘合剂、一层EVOH(或者一层EVOH合金)、一层本发明粘合剂和一层PEHD的一种结构。它最好是具有0.1-200升容积的刚性空心体形式。它的总厚度在0.2和20毫米之间,其中EVOH占该厚度的0.5-15%,各粘合剂层分别占0.2-10%,其余的厚度是两层PEHD。
PEHD的MFI最好是在190℃/21.6千克条件下测定为3-17克/10分钟。
EVOH的MFI最好是在190℃/2.16千克条件下测定为1-10克/10分钟。
PEHD外层最好可以被两层取代,外面一层是由任选有色的新制备的PEHD制成,而另一层是由来自这些空心体挤出-吹塑成型的废料和切削料的循环用产物制成。加到循环用材料层厚度的PEHD外层的厚度基本上与单一PEHD外层情况下的厚度是相同。
这些结构适用于制备汽油箱或者用于灌注汽油箱的管子。
本发明结构的各层可以含有添加剂,例如填料、稳定剂、滑移剂、抗静电剂和阻燃剂。
本发明的结构可以通过热塑领域中公知的共挤出和挤出-吹塑方法来制备。实施例
实施例描述通过下面条件经过挤出-吹塑制备的瓶的5-层结构。瓶的结构:-3种组分,五层;-PEHD/粘合剂/EVOH/粘合剂/PEHD;-厚度:1.2/0.1/0.15/0.1/1.2毫米;-PEHD:密度=0.945-0.950和MFI=5-6克/10分钟(190℃/21.6千克);-EVOH:乙烯含量=29%MFI=1.7克/10分钟(190℃/2.16千克);瓶的类型:
具有两个平面,0.7升容量,高度=270毫米和重量=170克的圆筒(=70毫米)。挤出-吹塑条件温度曲线(℃): 顶部PEHD 200 210 220 230 230 230粘合剂 210 220 220 220 220 230EVOH 180 190 200 210 220 230工具 塑模的直径=20毫米
心轴的直径=12毫米
间隙=4毫米吹塑拉伸比:大约3。内层抗剥离强度的测定-从瓶的平面部分切下15×150毫米试验用片样,并且在23℃和50%RH条件下处理至少24小时;-在粘合剂和EVOH接触面的一面开始切割;-在50毫米/分钟直角机头速度下进行“T”剥离试验。通过排除起始峰的剥离力的平顶值给出以N/cm表示的剥离强度。下面的表1显示了其结果,其中“AM”指马来酸酐,并且共同接枝了的混合物的重量百分比表示了在A+B混合物中的A的比例。
表1
配方 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | |
聚合物A1 | 共聚用单体 | 1-辛烯 | 1-丁烯 | 1-己烯 | 1-辛烯 |
密度(g/cm3) | 0.919 | 0.917 | 0.918 | 0.919 | |
MF1(g/10min;2.16kg) | 4.4 | 2.5 | 3 | 4.4 | |
重量百分比 | 75 | 90 | 80 | 75 | |
聚合物A2 | 共聚用单体 | 丙烯 | 1-丁烯 | 1-辛烯 | 1-辛烯 |
密度(g/cm3) | 0.880 | 0.900 | 0.870 | 0.870 | |
MF1(g/10min;2.16kg) | 0.2 | 2.8 | 5 | 5 | |
重量百分比 | 25 | 10 | 20 | 25 | |
被接枝A共混物 | AM的含量(ppm) | 3800 | 7500 | 4000 | 8000 |
重量百分比 | 20 | 10 | 15 | 15 | |
共聚物B | 共聚用单体 | 1-辛烯 | 1-丁烯 | 1-己烯 | 1-辛烯 |
密度(g/cm3) | 0.919 | 0.919 | 0.921 | 0.920 | |
MF1(g/10min;2.16kg) | 1,1 | 1 | 0,5 | 1 | |
共混物A+B | 密度(g/cm3) | 0.917 | 0.919 | 0.919 | 0.918 |
MF1(g/10min;2.16kg) | 1.0 | 0.8 | 0.5 | 1.1 | |
AM的含量(ppm) | 760 | 750 | 600 | 1200 | |
抗剥离强度 | (N/cm) | 50 | 47 | 45 | 49 |
Claims (9)
1.共挤出粘合剂,包括:
--5-30份聚合物(A),其本身含有密度在0.910和0.940之间的聚乙烯(A1)和选自弹性体、非常低密度聚乙烯和金属茂聚乙烯的聚合物(A2)的混合物,上述(A1)+(A2)混合物被不饱和羧酸所共接枝;
--95-70份密度在0.910和0.930之间的聚乙烯(B);
--上述(A)和(B)的混合物,使得:
.其密度在0.910和0.930之间,
.接枝的不饱和羧酸的量在30和10000ppm之间,
.其MFI(ASTMD 1238-190℃-2.16千克)是在0.1和3克/10分钟之间,MFI表示熔体流动指数。
2.根据权利要求1的粘合剂,其密度是在0.915和0.920之间。
3.根据权利要求1或2的粘合剂,其中(A1)的共聚用单体与(B)的共聚用单体是相同。
4.根据前述权利要求任一项的粘合剂,其中聚合物(A),也就是说已经共同接枝的(A1)+(A2)是:
(A1)包括至少75摩尔%的乙烯,并且具有其绝对值大于15的MFI2/[η]-8.77比例;
(A2)包括至少50摩尔%的乙烯;
(A2)具有绝对值大于15的MFI2/[η]-8.77比例;
其乙烯含量不少于70摩尔%;
MFI10/MFI2之比在5和20之间,其中MFI2是根据ASTMD 1238测定的2.16千克负载下的在190℃中的熔体流动指数,MFI10是根据ASTMD 1238测定的10千克负载下的在190℃中的熔体流动指数,特性粘度[η]是指在135℃萘烷溶液中测定的以dl/克表示的聚合物的粘度系数。
5.多层结构,其中包括一层含有据前述权利要求中任一项的粘合剂层,和一层直接与其附着的含氮或含氧的极性树脂(E),例如一层聚酰胺树脂、一层脂肪族聚酮、一层皂化的乙烯-乙酸乙烯酯共聚物(EVOH)或者一层聚酯树脂,或者还有一层金属。
6.根据权利要求5的结构,其中的一层聚烯烃层(F)或者一层选自(E)层的树脂的树脂层或者一层金属层是直接附着在粘合剂面上。
7.根据权利要求6的结构,各自包括一层PEHD、一层本发明的粘合剂、一层EVOH或者一层EVOH合金、一层本发明的粘合剂和一层PEHD。
8.具有权利要求5-7中任一项的结构的刚性空心体。
9.具有权利要求7的结构的汽油箱。
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CN1302082C (zh) * | 2002-09-27 | 2007-02-28 | 阿肯马公司 | 用于聚酯的基于共接枝线性低密度聚乙烯和茂金属聚乙烯以及茂金属聚乙烯的共挤出粘合剂 |
CN103443231A (zh) * | 2011-03-25 | 2013-12-11 | 三井化学株式会社 | 粘合性树脂组合物及使用其的多层结构体 |
CN105980504A (zh) * | 2013-12-18 | 2016-09-28 | 阿肯马法国公司 | 用于多层结构的粘结剂 |
CN107759893A (zh) * | 2017-11-17 | 2018-03-06 | 南京棠城塑胶有限公司 | 一种pbt/pe流延复合薄膜粘接用材料的制备方法 |
CN109796886A (zh) * | 2019-01-31 | 2019-05-24 | 华高科(宁波)集团有限公司 | 一种聚氯乙烯自粘防水卷材 |
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JP2002264669A (ja) * | 2001-02-28 | 2002-09-18 | Ti Group Automotive Systems Technology Center Gmbh | 多層構造の燃料タンク |
FR2844517B1 (fr) * | 2002-09-16 | 2004-10-15 | Atofina | Liant de coextrusion a base de polyethylene metallocene et lldpe cogreffes, de sbs et de pe |
EP1557256A1 (en) * | 2004-01-26 | 2005-07-27 | Arkema | Copolyester-based structure for manufacturing transparent hollow bodies by coextrusion blow-molding |
US20120046411A1 (en) * | 2010-08-20 | 2012-02-23 | Becton, Dickinson And Company | Recycled Resin Compositions And Disposable Medical Devices Made Therefrom |
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US4460745A (en) * | 1982-04-26 | 1984-07-17 | Chemplex Company | Adhesive three-component blends containing grafted HDPE |
US4460632A (en) * | 1982-04-26 | 1984-07-17 | Chemplex Company | Adhesive blends and composite structures |
EP0742236B1 (fr) * | 1995-05-09 | 2002-01-02 | Atofina | Liant de coextrusion à base de polyoléfines greffées |
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- 2000-04-06 US US09/544,613 patent/US6924013B1/en not_active Expired - Lifetime
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1302082C (zh) * | 2002-09-27 | 2007-02-28 | 阿肯马公司 | 用于聚酯的基于共接枝线性低密度聚乙烯和茂金属聚乙烯以及茂金属聚乙烯的共挤出粘合剂 |
CN103443231A (zh) * | 2011-03-25 | 2013-12-11 | 三井化学株式会社 | 粘合性树脂组合物及使用其的多层结构体 |
CN105980504A (zh) * | 2013-12-18 | 2016-09-28 | 阿肯马法国公司 | 用于多层结构的粘结剂 |
CN107759893A (zh) * | 2017-11-17 | 2018-03-06 | 南京棠城塑胶有限公司 | 一种pbt/pe流延复合薄膜粘接用材料的制备方法 |
CN109796886A (zh) * | 2019-01-31 | 2019-05-24 | 华高科(宁波)集团有限公司 | 一种聚氯乙烯自粘防水卷材 |
Also Published As
Publication number | Publication date |
---|---|
DK1043374T3 (da) | 2004-04-13 |
CA2304393C (fr) | 2007-08-07 |
EP1043374B1 (fr) | 2003-12-17 |
US6924013B1 (en) | 2005-08-02 |
KR20010020717A (ko) | 2001-03-15 |
JP2000355641A (ja) | 2000-12-26 |
ES2212972T3 (es) | 2004-08-16 |
CA2304393A1 (fr) | 2000-10-06 |
ATE256720T1 (de) | 2004-01-15 |
DE60007213D1 (de) | 2004-01-29 |
DE60007213T2 (de) | 2004-09-30 |
EP1043374A1 (fr) | 2000-10-11 |
PT1043374E (pt) | 2004-05-31 |
CN1174064C (zh) | 2004-11-03 |
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