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CN1229463C - 以金属茂聚乙烯和共接枝lldpe、sbs和pe为基的共挤出粘合剂 - Google Patents

以金属茂聚乙烯和共接枝lldpe、sbs和pe为基的共挤出粘合剂 Download PDF

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CN1229463C
CN1229463C CNB031327532A CN03132753A CN1229463C CN 1229463 C CN1229463 C CN 1229463C CN B031327532 A CNB031327532 A CN B031327532A CN 03132753 A CN03132753 A CN 03132753A CN 1229463 C CN1229463 C CN 1229463C
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polyethylene
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metallocene
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CN1495243A (zh
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J·L·普拉德尔
J·帕斯卡
P·罗伯特
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Aiskai Zhixin Co ltd
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Abstract

本发明涉及一种共挤出粘合剂，它含有10-35重量%聚合物(A)，(A)本身由80-20重量%金属茂聚乙烯(A1)和20-80重量%非金属茂LLDPE聚乙烯(A2)混合物组成，聚合物(A1)和(A2)混合物用接枝单体共接枝；40-60重量%苯乙烯/丁二烯/苯乙烯嵌段共聚物(B)；20-35重量%PE(C)；其总和为100%，(A)、(B)和(C)混合物MFI或熔融态流动指数是0.1-10g/10min。本发明还涉及包括本发明粘合剂的多层结构以及包括这种结构的物品。

Description

以金属茂聚乙烯和共接枝LLDPE、 SBS和PE为基的共挤出粘合剂
                         发明领域
本发明涉及一种以金属茂聚乙烯和共接枝LLDPE、苯乙烯/丁二烯/苯乙烯嵌段共聚物(缩写为SBS)和PE为基的共挤出粘合剂，其中SBS含有50-90摩尔％，优选地60-80摩尔％苯乙烯，以及涉及含有这种粘合剂的多层结构与包括这样一种结构的物品。
                         背景技术
本申请人的文件FR2 806 734披露了一种组合物，它含有用稀释在SBS中的不饱和羧酸共接枝的金属茂PE和非金属茂LLDPE。该文件没有涉及包括PS层的多层结构。直到现在，包括至少一层PS的结构所用的共挤出粘合剂是用马来酸酐接枝的乙烯/醋酸乙烯共聚物。
本申请人现在发现，在SBS嵌段共聚物中，在一定苯乙烯量的范围内，可得到一种共挤出粘合剂，这种粘合剂能够有效地将PS层与例如PE、PA和EVOH之类的层连接起来，而超出这个范围就不是这种情况。
因此，这种粘合剂有可能制造各种结构，它们其中包括一层具有良好粘附力值的聚苯乙烯(PS)，这种粘合剂的优点是具有由该组合物苯乙烯部分带来的良好热稳定性。例如在制造这种结构时，或使用所述的结构采用热焊接制造物品时，或巴斯德灭菌时就可看到这个优点。本发明粘合剂的其它优点涉及它们的制造方法。采用熔融态混合方法，最经常地采用熔融态接枝方法可以制备这些粘合剂。在挤出机或任何其它等效设备的出口可回收颗粒状的粘合剂，本申请人发现，这种制粒比接枝乙烯/醋酸乙烯类粘合剂制粒容易得多。
                          发明内容
本发明的目的是一种共挤出粘合剂，它含有：
-10-35重量％聚合物(A)，它本身由80-20重量％密度0.865-0.915的金属茂聚乙烯(A1)和20-80重量％非金属茂LLDPE聚乙烯(A2)的混合物组成，聚合物(A1)和(A2)的混合物可用选自不饱和羧酸及其衍生物的接枝单体共接枝，在所述混合物中接枝单体的含量是30-100000ppm；
-40-60重量％苯乙烯/丁二烯/苯乙烯嵌段共聚物(B)，其苯乙烯为50-90摩尔％；
-20-35重量％PE(C)；
其总和为100％，(A)、(B)和(C)混合物是这样的，MFI或熔融态流动指数(ASTM D 1238-190℃-2.16Kg)是0.1-10g/10min。
根据一种实施方式，该粘合剂的特征在于(A2)的密度是0.900-0.950。
根据一种实施方式，该粘合剂的特征在于在聚合物(A1)和(A2)的混合物中接枝单体的比例是600-5000ppm。
根据一种实施方式，该粘合剂的特征在于该接枝单体是马来酸酐。
根据一种实施方式，该粘合剂的特征在于PE(C)的密度是0.870-0.935，它是LLDPE或金属茂PE。
本发明还有一个目的是一种多层结构，其特征在于它包括一层含有前面所述粘合剂的层(L)，和一层与所述层(L)两个面中的一个面直接连接的层(E)，所述的层(E)是苯乙烯均聚物或共聚物层。
根据一种实施方式，该多层结构的特征在于层(F)直接与层(L)的第二个面连接，该层(L)在层(E)与(F)之间呈夹层状，所述的层(F)是一层选自聚酰胺、聚脂族酮、皂化的乙烯与醋酸乙烯共聚物(EVOH)、聚乙烯、聚酯和聚苯乙烯的聚合物层或者金属层。
此外，本发明涉及包括例如上述结构的物品。
                       具体实施方式
现在详细地描述本发明。
关于(A1)，金属茂聚乙烯系指在单位点催化剂(catalyseur monosite)存在下，由乙烯和α-烯烃共聚合所得到的聚合物，α-烯烃例如像丙烯、丁烯、己烯或辛烯，所述的催化剂一般由例如可以是锆或钛的金属原子和两个与该金属连接的环烷基分子构成。更确切地，金属茂催化剂通常是由两个与金属连接的环戊二烯环组成的。这些催化剂经常与作为助催化剂或活化剂的铝氧烷(aluminoxane)，优选地甲基铝氧烷(MAO)一起使用。铪也可以作为固定环戊二烯的金属使用。其它的金属茂可以包括第IVA、VA和VIA族过渡金属。还可以使用镧系金属。
这些金属茂聚乙烯的特征还在于它们的Mw/Mn比＜3，优选地＜2，其中Mw和Mn分别代表重均摩尔质量与数均摩尔质量。金属茂聚乙烯还代表其MFR(熔体流动比或流动指数比)小于6.53，Mw/Mn比高于MFR减去4.63的那些聚乙烯。MFR代表MFI10(在10Kg负载下的MFI)与MFI2(在2.16Kg负载下的MFI)的比。其它的金属茂聚乙烯可用等于或高于6.13的MFR，低于或等于MFR减去4.63的Mw/Mn比定义。
有利地，(Al)的密度是0.870-0.900。
关于(A2)，聚合物(A2)是LLDPE(线型低密度聚乙烯)类的乙烯和α-烯烃的共聚物，并且不是金属茂的。α-烯烃有利地有3-30个碳原子。
作为任选共聚单体的有3-30个碳原子的α-烯烃实例包括丙烯、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、1-十二碳烯、1-十四碳烯、1-十六碳烯、1-十八碳烯、1-二十碳烯、1-二十二碳烯、1-二十四碳烯、1-二十六碳烯、1-二十八碳烯、1-三十碳烯。这些α-烯烃可以单个使用或两种或两种以上混合使用。
有利地，(A2)的密度是0.900-0.950。
(A2)的MFI或熔融态流动指数是0.1-8g/10min(190℃-2.16Kg)。
聚合物(A1)和(A2)的混合物用不饱和羧酸接枝，即聚合物(A1)和(A2)共接枝。使用这种酸的官能衍生物没有超出本发明的范围。
不饱和羧酸的实例是有2-20个碳原子的不饱和羧酸，例如丙烯酸、甲基丙烯酸、马来酸、富马酸和衣康酸。这些酸的官能衍生物例如包括这些不饱和羧酸的酸酐、酯衍生物、酰胺衍生物、酰亚胺衍生物与金属盐(例如碱金属盐)。
有4-10个碳原子的不饱和羧酸及其官能衍生物，特别是它们的酸酐，是特别优选的接枝单体。
这些接枝单体例如包括下述酸及其官能衍生物：马来酸、富马酸、衣康酸、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、x-甲基双环(2，2，1)-庚-5-烯-2，3-二羧酸、马来酸酐、衣康酸酐、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-2，3-二羧酸酐。
其它接枝单体实例包括不饱和羧酸的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、衣康酸单甲酯和衣康酸二乙酯；不饱和羧酸酰胺衍生物，例如丙烯酰胺、甲基丙烯酰胺、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；不饱和羧酸酰亚胺衍生物，例如马来酰亚胺、N-丁基马来酰亚胺和N-苯基马来酰亚胺；以及不饱和羧酸金属盐，例如丙烯酸钠、甲基丙烯酸钠、丙烯酸钾和甲基丙烯酸钾。优选马来酸酐。
可以使用各种已知的方法将接枝单体接枝在聚合物(A1)和(A2)的混合物上。该混合物可以含有使用聚烯烃时通常使用的添加剂，其含量为10-50000ppm，其中例如以取代苯酚分子为基的抗氧化剂、UV保护剂、加工助剂，例如脂肪酰胺、硬脂酸及其盐、作为避免出现挤出缺陷剂的已知含氟聚合物、胺基防雾剂、抗粘连剂，例如二氧化硅或滑石，有着色剂的母炼胶混合物和成核剂。
例如，在有或没有溶剂的存在下，有或没有自由基引发剂时，在高温，约150℃-300℃下加热聚合物(A1)和(A2)混合物可以实现这种接枝。在这个反应中，可以使用的合适溶剂其中是苯、甲苯、二甲苯、氯代苯、枯烯。可以使用的合适自由基引发剂包括叔丁基过氧化氢、枯烯过氧化氢、过氧化氢二异丙基苯、过氧化二叔丁基、过氧化叔丁基-枯烯、过氧化二枯烯、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、过氧化双-3，5，5-三甲基-己酰和过氧化甲乙酮。
在以上述方式得到的采用接枝方法改性的聚合物(A1)和(A2)混合物中，可以适当选择接枝单体的量，但该量优选地是以接枝(A1)和(A2)重量计为0.01-10重量％，优选地600-5000ppm。
采用IRTF光谱测定琥珀酸官能就可确定接枝单体的量。(A)，即已接枝的(A1)和(A2)混合物的MFI有利地是0.1-10g/10min。
关于SBS(B)嵌段共聚物，它涉及有苯乙烯和丁二烯嵌段的共聚物，在该共聚物中苯乙烯的比例是50-90重量％，优选地60-80重量％。
关于聚乙烯(C)，它涉及乙烯的均聚物和与选自下列的单体的共聚物：α-烯烃、不饱和羧酸酯或饱和羧酸乙烯酯。α-烯烃在前面有关(A2)的部分中定义过。不饱和羧酸酯例如是(甲基)丙烯酸烷基酯，其烷基有1-24个碳原子。可使用的丙烯酸烷基酯或甲基丙烯酸烷基酯实例具体地是甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸-2-乙基己酯。饱和羧酸乙烯酯例如是醋酸乙烯酯或丙酸乙烯酯。聚合物(C)可以是HDPE、LDPE、LLDPE、VLDPE或金属茂聚乙烯。
聚合物(C)也可以是具有弹性体特性的聚合物，即它可以是(i)ASTM D412意义上的弹性体，即一种在室温下可以拉伸到其两倍长度的材料，如此保持5分钟，然后放松时，它可回复到比其开始长度短约10％，或(ii)一种严格地没有这些上述特性，但可以拉伸，并且基本回复到其开始长度的聚合物。
有利地，(C)是LLDPE聚乙烯或金属茂PE，其密度为0.870-0.935。
本发明的粘合剂可用于多层结构，例如像膜、箔、管和中空物品，例如油箱。
本发明的多层结构包括一层含有上述粘合剂的层(L)，和一层直接与所述层(L)的第一个面连接的层(E)。层(E)是苯乙烯均聚物或共聚物层。
层(F)还可以直接与层(L)的第二个面连接，层(L)在层(E)与(F)之间呈夹层状，所述的层(F)是选自聚酰胺、脂族聚酮、皂化乙烯和醋酸乙烯共聚物(EVOH)、聚乙烯、聚酯和聚苯乙烯的聚合物层，或者是金属层。
然而，该多层结构还可以包括一层(L)，它含有在两层(F)之间呈夹层状的粘合剂。
作为实例可以列举下述结构，PS代表聚苯乙烯，PA代表聚酰胺，L代表粘合剂，PE代表聚乙烯和EVOH代表皂化乙烯和醋酸乙烯共聚物：
·层(E)层(L)/层(F)类结构：PS/L/PE，PS/L/EVOH/PS，PS/L/PA；
·层(E)层(L)/层(F)和层(F)/层(L)/层(F)类结构：PS/L/PA/L/PE和PS/L/EVOH/L/PE。
更特别地，聚酰胺是具有长链的合成聚酰胺，在其主链中有酰胺基团结构单元，例如PA-6、PA-6.6、PA-6.10、PA-11、PA-6/6.6和PA-12。皂化乙烯和醋酸乙烯共聚物的皂化度约90-100摩尔％，是皂化其乙烯含量约15-60摩尔％的乙烯/醋酸乙烯共聚物得到的。聚酯选自聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘酸乙二醇酯及其混合物，或芳族聚酯，例如聚合物液晶。
金属层例如可以是例如铝、铁、铜、锡和镍之类的金属，或含有这些金属中至少一种金属作为基本组分的合金的箔、薄膜或箔。薄膜或箔的厚度通常可以加以选择，例如厚度是约0.01-0.2mm。通常实际上在将本发明的粘合剂层压在金属层上之前应该对该层表面进行去脂。
本发明结构的不同层可以含有添加剂，例如填料、稳定剂、光滑剂、抗静电剂、防火剂。
可以采用已知共挤出、吹挤塑、热塑技术的方法生产本发明的结构。
下 表1汇集了本发明(实施例1-4)和对比(Comp1-10)的粘合剂组合物。
下 表2汇集了在t0(时间＝0)和在t8(相应于8天)时剥离力F。在粘合剂层(L)与PS层之间和在粘合剂层(L)与EVOH层之间进行剥离试验后测量了这些力。这些试验使用的膜是由3层构成的共挤出膜，例1：PS层/粘合剂层(L)/PA层，其厚度分别为75/5/70(以微米表示)，由5层构成的共挤出膜，例2：PE层/粘合剂层(L)/EVOH层/粘合剂层(L)/PE层，其厚度分别为20/10/10/10/80(以微米表示)。
这个试验是在温度T 25℃与剥离速度200mm/min条件下进行的。为制造这些膜使用了BASF公司的PA ultramid B36FN、ATOFINA公司的PS 7240和PE 1020FN24和38％乙烯的EVOH。符号s相应于标准偏差。
其目的是证明根据实施例1-4的组合物都能够达到在PS与EVOH上合理粘附力。
在 表3的情况下，测量了由5层构成的膜在t＝0和t＝8天时的剥离力：PS层/粘合剂层(L)/EVOH层/粘合剂层(L)/PS层，这些层在该表中提到界面处的厚度分别是50/5/10/5/20。
其目的是证实，在前面提到的同时含有PS和EVOH的结构的观察结果。
表1
     实施例1        实施例2         实施例3        实施例4***
 接枝聚合物(A)的特征   PE类型   PEm   LLDPE   PEm   LLDPE   PEm   LLDPE   PEm   LLDPE
  密度(g/cm3)   0.87   0.92   0.87   0.92   0.87   0.92   0.87   0.92
  共聚单体   1-辛烯   1-丁烯   1-辛烯   1-丁烯   1-辛烯   1-丁烯   1-辛烯   1-丁烯
  组成   50％   50％   50％   50％   50％   50％   50％   50％
  接枝率        0.9％         0.9％         0.9％          0.9％
  接枝单体        MAH         MAH         MAH          MAH
  MFI(g/10min)190℃-2.16kg        0.7         0.7         0.7          0.7
    (A)的比例        25％         25％         25％          15％
 聚合物(B)的特征   PS类型        SBS         SBS         SBS          SBS
  组成        S的73％         S的73％         S的73％          S的73％
  密度(g/cm3)        1.01         1.01         1.01          1.01
  MF(g/10min)190℃-2.16kg        7.5         7.5         7.5          7.5
    (B)的比例        40％         40％         40％          50％
 (C)的特征   PE类型        LLDPE         LLDPE         PEm          LLDPE
  共聚单体        CA         CA         C8          C4
  密度(g/cm3)        0.910         0.910         0.870          0.810
  MF(g/10min)190℃-2.16kg        6.6         3         5          3
    (C)的比例        35％         35％         35％          35％
***熔点＝119℃和Vicat点＝75℃。
(续)
         Comp1         Comp2           Comp3   Comp4          Comp5
  PEm   LLDPE   PEm   LLDPE   PEm   LLDPE   EVA   PEm   LLDPE
  0.87   0.92   0.87   0.92   0.87   0.92   0.95   0.87   0.92
  1-辛烯   1-丁烯   1-辛烯   1-丁烯   1-辛烯   1-丁烯   醋酸乙烯   1-辛烯   1-丁烯
  50％   50％   50％   50％   50％   50％   100％   50％   50％
         0.9％          0.9％           0.9％   0.2％          0.9％
         MAH          MAH           MAH   MAH          MAH
         0.7          0.7           0.7   3          0.7
         30％          25％           25％   50％          50％
         SBS          SBS           SBS   SBS          SBS
         S的73％          S的40％           S的40％   S的73％          S的40％
         1.01          0.96           0.96   1.01          0.96
         7.5          8.5           8.5   7.5          8.5
         40％          40％           40％   50％          50％
         EVA          LLDPE           LLDPE   -          -
         醋酸乙烯          C4           C4   -          -
         0.95          0.910           0.911   -          -
         5          6           3   -          -
         30％          35％           35％   -          -
(续)
           Comp6            Comp8   Comp10
  PEm   LLDPE   PEm   LLDPE   EVA
  0.87   0.92   0.87   0.92   0.95
  1-辛烯   1-丁烯   1-辛烯   1-丁烯   醋酸乙烯
  50％   50％   50％   50％   100％
           0.9％           0.9％   0.2％
           MAH           MAH   MAH
           0.7           0.7   3
           50％           30％   100％
           SBS           PS   -
           S的73％           S的100％   -
           1.01           1.04   -
           7.5           5   -
           50％           50％   -
           -           PEm   -
           -           C8   -
           -           0.870   -
           -           5   -
           -           20％   -
表2
                        例1*                          例2**
  在t0的F用N/15mm表示   s   在t8的F用N/15mm表示   s   在t0的F用N/15mm表示   s   在t8的F用N/15mm表示   s
  实施例1   3.4   0.1   3.2   0.3   3.4   0.3   4.2   -
  实施例2   4.7   0.2   4.4   0.2   2.9   0.1   3.6   -
  实施例3   3   0.2   3   0.2   3   0.2   4.3   -
  实施例4***   3.4   0.1   3   0.2   3   0.2   3.2   -
  Comp1   1.2   -   1   0   0.3   0   0   -
  Comp2   0.2   0   0.1   0   5.4   0.1   8.2   -
  Comp3   0.3   0.1   0.1   0   5   0.1   6.6   -
  Comp4   6   0.8   4.3   0.5   0.4   0.2   2   0.1
  Comp5   2   0.2   1.9   0.3   6.1   0.6   6.7   0.3
  Comp6   9.1   1   7.1   2.2   2   0.1   2.4   0.1
  Comp8   0.6   0   0   0   0.5   0   0   -
  Comp10   2.8   0.1   2.0   0.1   3.4   0.1   4.0   0.1
*除了Comp1在PA层与粘合剂层(L)之间断裂外在PS层与粘合剂层(L)之间也断裂
**在PE80微米与粘合剂层(L)之间进行剥离试验
***熔点＝119℃，Vicat点＝75℃
表3
  在t0时F用N/15mm表示   s 在t8时F用N/15mm表示   s   界面
  实施例1   2.3   0.4   2.5   0.4   L/PS
  实施例2   3.3   0.2   5.2   0.2   L/EVOH
  实施例2   3.6   0.1   3.3   0   L/PS
  实施例3   3   0.1   3.3   0.2   L/PS
  实施例4***   1.9   0.1   2.6   0.1   L/EVOH
  Comp10   1.6   0   1.5   0   L/PS
***熔点＝119℃，Vicat点＝75℃

Claims (8)

1、共挤出粘合剂，它含有：
-10-35重量％聚合物(A)，它本身由80-20重量％密度0.865-0.915的金属茂聚乙烯(A1)和20-80重量％非金属茂的线形低密度聚乙烯的聚乙烯(A2)混合物组成，聚合物(A1)和(A2)混合物用选自不饱和羧酸及其衍生物的接枝单体共接枝，在所述混合物中接枝单体的含量是30-100 000ppm；
-40-60重量％苯乙烯/丁二烯/苯乙烯嵌段共聚物(B)，其苯乙烯为50-90摩尔％；
-20-35重量％聚乙烯(C)；
其总和为100％，(A)、(B)和(C)混合物是这样的，MFI或熔融态流动指数(ASTM D 1238-190℃-2.16Kg)是0.1-10g/10min。
2、根据权利要求1所述的粘合剂，其特征在于(A2)的密度是0.900-0.950。
3、根据上述权利要求中任一权利要求所述的粘合剂，其特征在于在聚合物(A1)和(A2)混合物中接枝单体的比例是600-5000ppm。
4、根据权利要求1或2所述的粘合剂，其特征在于该接枝单体是马来酸酐。
5、根据权利要求1或2所述的粘合剂，其特征在于PE(C)的密度是0.870-0.935，它是线形低密度聚乙烯或金属茂聚乙烯。
6、一种多层结构，其特征在于它包括一层含有根据上述权利要求中任一权利要求所述粘合剂的层(L)，和一层与所述层(L)两个面中的一个面直接连接的层(E)，所述的层(E)是苯乙烯均聚物或共聚物层。
7、根据权利要求6所述的多层结构，其特征在于层(F)直接与层(L)的第二个面连接，该层(L)在层(E)与(F)之间呈夹层状，所述的层(F)是选自聚酰胺、聚脂族酮、皂化的乙烯与醋酸乙烯共聚物、聚乙烯、聚酯和聚苯乙烯的聚合物层或者金属层。
8、包括根据权利要求6或7所述结构的物品。
CNB031327532A 2002-09-16 2003-09-16 以金属茂聚乙烯和共接枝lldpe、sbs和pe为基的共挤出粘合剂 Expired - Lifetime CN1229463C (zh)

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FR02/11438 2002-09-16
FR0211438A FR2844517B1 (fr) 2002-09-16 2002-09-16 Liant de coextrusion a base de polyethylene metallocene et lldpe cogreffes, de sbs et de pe

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FR2934599B1 (fr) 2008-07-29 2012-12-21 Arkema France Fabrication de polyethylene a partir de matieres renouvelables, polyethylene obtenu et utilisations
KR101006744B1 (ko) * 2010-05-25 2011-01-10 (주)해양연구개발 어장정화, 항로준설 및 다양한 준설사업 중 발생되는 준설 퇴적물에서 쓰레기, 자갈 및 모래를 빠른 속도로 분리하는 선별장치 및 방법
FR2994435B1 (fr) 2012-08-09 2014-10-24 Arkema France Composition de polymeres a base de pla
JP6291246B2 (ja) * 2013-12-17 2018-03-14 株式会社カネカ 接着性樹脂組成物および積層体
CN103709974B (zh) * 2013-12-31 2015-10-07 广州市合诚化学有限公司 一种低加工温度粘接树脂及其制备方法与应用
JP6864497B2 (ja) * 2017-02-24 2021-04-28 Ｍｃｐｐイノベーション合同会社 接着性樹脂組成物及びマスターバッチ、並びに、これらを用いた積層フィルム、延伸フィルム、及び多層成形体
CN114316862A (zh) * 2022-01-13 2022-04-12 广州鹿山新材料股份有限公司 用于多层阻隔片材的粘接树脂及其制备方法、阻隔结构

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EP1400566A1 (fr) 2004-03-24
IL157631A (en) 2008-11-03
CN1495243A (zh) 2004-05-12
ATE384765T1 (de) 2008-02-15
DE60318794T2 (de) 2009-01-22
DK1400566T3 (da) 2008-05-13
US20040105988A1 (en) 2004-06-03
FR2844517A1 (fr) 2004-03-19
KR100547457B1 (ko) 2006-01-31
US7074492B2 (en) 2006-07-11
AR041150A1 (es) 2005-05-04
TWI249557B (en) 2006-02-21
ES2300551T3 (es) 2008-06-16
BR0303422A (pt) 2004-09-08
SI1400566T1 (sl) 2008-06-30
KR20040024846A (ko) 2004-03-22
CA2441066C (fr) 2008-02-12
FR2844517B1 (fr) 2004-10-15
JP2004107662A (ja) 2004-04-08
DE60318794D1 (de) 2008-03-13
CA2441066A1 (fr) 2004-03-16
JP3965499B2 (ja) 2007-08-29
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