CN1285777A - 改进了粘合性的多组分结构 - Google Patents
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Abstract
本发明提供了含卤聚物的多组分结构,该结构包括至少一层卤聚物层和至少一层粘合层。该粘合层包括具有至少一种选自不饱和酸及其酐、胺和环氧化合物的官能部分的原料聚合物,其中所述粘合层具有D等级小于约25和A等级小于约75的ASTM D-2240肖氏硬度值。用这些粘合剂制备的多组分结构例如薄膜、管道、薄片以及注塑和吹塑制品显示出通常与含卤聚物的多组分结构有关的优越粘合性和极好的防渗性。还公开了改进卤聚物粘合性的方法。
Description
有关申请的相互参照
本申请要求保护1997年11月6日提交的美国临时专利申请系列号60/064,482的利益。
发明背景
1.发明领域:
本发明涉及多组分结构,且更特别涉及改进了粘合性的多组分结构。
2.现有技术的叙述:
利用结构中各种组分显示出不同特性的优点来生产多组分结构在本领域中是众所周知的。典型的多组分结构是其中的不同层具有特定特性的多层薄膜。
例如,在包装应用中,最好使用含氟聚合物,已知这类聚合物对多数化学品是惰性的,且耐高温以及摩擦系数较低。聚三氟氯乙烯(“PCTFE”)均聚物和共聚物以及乙烯-三氟氯乙烯(“ECTFE”)交替共聚物,由于它们具有极好的抗渗性因而都是特别优越的。然而,由于其成本较高,因而这类含氟聚合物的使用局限于特制包装方面的应用。
降低由昂贵聚合物生产的包装材料成本的适宜方法是形成其中的聚合物层与其他不太贵的聚合物层共挤出或层压的多层结构。这种方法对于含氟聚合物包装的应用是特别需要的,因为,往往需要薄层的含氟聚合物,以便利用含氟聚合物的理想特性使成本降到最低。然而,含氟聚合物与多数其他的聚合物粘附不牢固,事实上,多数含氟聚合物的非粘性是众所周知的。
使用官能化聚烯烃作为多组分结构中的粘合层已有叙述,参见例如美国专利4,677,017和5,139,878,兹将该专利公开的内容特别引入本文作为参考。虽然这些多层结构显示出极好的防潮层特性,但在许多情况下,它们缺乏足够的粘合强度因而没有任何重要用途。所以,在市场上还买不到共挤出的卤聚物薄膜。因此,为了提供适合于各种用途的优质多组分结构非常希望提供改进了粘合性的树脂。
发明概述
根据本发明,提供了一种包括至少一层卤聚物层和至少一层粘合层的多组分结构,其中该粘合层是软质改性聚合物,该聚合物包括具有选自不饱和酸及其酐、胺和环氧化合物的至少一种官能部分的原料聚合物,其中所述粘合层具有的ASTM D-2240肖氏硬度值D等级小于约25和A等级小于约75。优选该肖氏硬度值D等级小于约20和A等级小于约72。还优选该粘合剂是用官能部分高度改性的。在实施本发明时,用马来酸酐改性的粘合剂是特别优越的。在一个优选的实施方案中,多层结构是三层结构,最优选该结构是三层薄膜。
出乎意料地发现,当将具有高度改性的软质聚合物用作含卤聚物多组分结构中的粘合层时,在卤聚物和软质改性聚合物之间存在着高度的粘合性。
优选实施方案的叙述
本发明的粘合层由具有官能部分的原料聚合物形成,且具有D等级小于约25和A等级小于约75的ASTM D-2240肖氏硬度值,已将该聚合物用不饱和酸、酐、胺或环氧部分按该聚合物总重约0.1%至约20%的用量改性。在一个优选的实施方案中,该肖氏硬度值D等级小于约20和A等级小于约72。肖氏硬度值按美国标准测试方法(ASTM)D-2240测定,本领域的技术人员对该方法是熟知的。本文中所用的肖氏硬度值是根据肖氏硬度试验且基于在特定条件下将特定类型压针强迫针入特定材料时的针入度测定的。肖氏硬度值是取决于材料弹性模数和粘弹特性的压针延伸率的反函数。因此,材料越软质,肖氏硬度值越低。用于肖氏硬度试验的硬度计有不同的类型,其中,通常报道的是A型和D型。这两种类型的区别是基于压针的形状和施加的力量。例如,一种D型硬度计具有的针头(即,0.100±0.012mm R)比A型硬度计的(即,0.79±0.03mm R)更尖锐。
该粘合层的官能部分占该聚合物总重的约0.2%至约15%(重量)、优选约0.5%至约10%(重量)、且最优选约1%至约5%(重量)。任一种不饱和酸或酐均可用作本发明的官能部分。适宜的酸包括不饱和羧酸例如马来酸、富马酸、巴豆酸、柠康酸和衣康酸。适宜的酐包括上述任一种酸的酐。其中,最优选的是马来酸酐。适宜的胺包括脂族或芳族的伯、仲和叔胺。具体的实例包括:2,4,6-三溴苯胺、甲胺、乙胺、丙胺、二甲胺-N-甲基苯胺、乙基甲基胺、2-(N-甲胺)庚烷、仲丁基二甲胺、N-乙基-N-甲基苯胺、三甲胺和N,N-二甲基苯胺。适宜的环氧化合物是具有约2至约20个碳原子的那些环氧化合物。在一个特别优选的实施方案中,该粘合层包括约1%至约5%的马来酸酐。
用于制备粘合层的原料聚合物包括但不限于聚(α-烯烃)均聚物、共聚物及其混合物和包括苯乙烯嵌段共聚物、烯属弹性体、弹性体合金、热塑性聚氨酯、弹性聚酯和弹性聚酰胺的热塑性弹性体。
聚(α-烯烃)均聚物可以由具有约2至约10且优选约2至约6个碳原子的α-烯烃制备,并包括聚乙烯(包括超低密度、低密度、线型低密度、中密度、高和超高密度)、聚丙烯、聚丁烯、聚丁烯-1、聚戊烯-1、聚-3-甲基丁烷-1、聚-4-甲基戊烯-1和聚己烯。两种或多种上述α-烯烃或α-烯烃和其他单体例如α,β-乙烯属不饱和羧酸的烷基酯的共聚物可用于实施本发明,参见例如美国专利5,139,878,兹将该专利公开的内容特别引入本文作为参考。
苯乙烯嵌段共聚物可以是直链或支链的且包括苯乙烯和丁二烯(SBS)、苯乙烯和异戊二烯、苯乙烯和乙烯-丁烯(SEBS)以及苯乙烯和乙烯-丙烯。
适宜的烯属热塑性弹性体包括三元乙丙橡胶(EPDM)和乙丙橡胶。
适宜的弹性体合金包括可熔融加工的橡胶、热塑性硫化橡胶,例如乙丙橡胶或丁腈橡胶和聚烯烃,其中硫化橡胶均质地分散在聚烯烃基质中,以及乙烯共聚体例如与聚丙烯或聚乙烯合金的聚乙烯,此处聚乙烯是交联的。
适宜的弹性聚酯包括聚酯和聚醚的共聚物。适宜的聚酯包括聚(对苯二甲酸乙二醇酯)(PET)、聚(对苯二甲酸丁二醇酯)(PBT)和PET/PBT共聚物。适宜的聚醚是具有约2至约20个碳原子的那些聚醚。
适宜的热塑性聚氨酯包括聚酯基或聚醚基的聚氨酯。具体的实例包括全部可从B.F.Goodrich买到的Estane 58113(聚酯基)、Estane58013(聚醚基)和Estane 58880(聚醚基)和可从Dow ChemicalCompany买到的Pellethane 2103-70A(聚醚基)弹性体。
适宜的弹性聚酰胺包括聚酰胺和聚醚的共聚物。适宜的聚酰胺包括尼龙6、尼龙11、尼龙12、尼龙6,6、尼龙4,6、尼龙6,9、尼龙6,10、尼龙6,12和尼龙6,6T。适宜的醚类是具有约2至约20个碳原子的那些醚。
优选的原料聚合物包括烯属热塑性弹性体和聚(α-烯烃)均聚物、共聚物及其混合物。
这些原料聚合物可以在任一位置上用以下任一种化合物取代:卤素(包括氯、氟和溴)、氧和氮。
特别有效的组合物是用约2%至约4%马来酸酐改性的、在整个组合物中包含约80%乙烯组分和20%丙烯组分的乙烯-丙烯弹性体(EP橡胶)。乙烯-丙烯弹性体可以是共聚物或具有不同含量的E/P组合物和/或E/P序列的混合物,其中,将该混合物中的至少一种组分用不饱和羧酸和酐改性。一个实例是双组分混合物,其中一种组分基本上是未作任何改性的EP无规共聚物或乙烯-α-烯烃共聚物,而其他的是EP嵌段共聚物或用高含量马来酸酐改性的结晶聚乙烯。后一种组分也可以是由乙烯、丙烯和马来酸酐组成的三元共聚物。
本发明的软质、改性聚合物可以采用本领域中众所周知的包括但不限于共聚合和接枝法的常规方法制备。参见例如美国专利3,481,910、3,480,580、4,612,155和4,751,270,兹将该专利公开的内容特别引入本文作为参考。
可与软质、改性聚合物一起使用的卤聚物在本领域中是众所周知的且均可在市场上买到。它们包括但不限于具有约2至约20个碳原子的含氟聚合物、含氯聚合物和含氟氯聚合物,其中,该聚合物中的至少一个碳原子被至少一个卤素原子取代。
适宜的卤聚物的具体实例包括:PCTFE均聚物和共聚物、ECTFE共聚物、乙烯四氟乙烯共聚物、氟化的乙丙共聚物(FEP)、全氟烷氧基聚合物(PFA)、聚(偏二氟乙烯)、聚(氟乙烯)、聚(偏二氯乙烯)、聚氯乙烯、四氟乙烯的共聚物或混合物和偏二氟乙烯的共聚物或混合物以及两种或多种上述的混合物。
优选的卤聚物包括PCTFE均聚物和共聚物、ECTFE共聚物、乙烯四氟乙烯共聚物、氟化的乙丙共聚物(FEP)、四氟乙烯的共聚物或混合物以及偏二氟乙烯的共聚物或混合物。
软质改性聚合物可与卤聚物一起用来制备包括例如薄膜和管道的共挤出制品、例如薄膜和薄片的层压制品以及注塑和吹塑制品的多组分结构。
根据本文讲述的方法生产的软质改性聚合物适合于生产多组分结构,特别是多层薄膜。可以采用本领域中众所周知的方法制备多层薄膜,(参见例如美国专利4,677,017和上述实例,兹将该专利公开的内容特别引入本文作为参考)且可按一个方向或两个方向定向,或不定向(参见美国专利4,362,585,兹将该专利公开的内容特别引入本文作为参考)。多层薄膜包括至少一层卤聚物层和至少一层与该卤聚物层邻接的粘合层。适宜的薄膜结构包括但不限于:A/B/C、A/B/C/B/A和C/B/A/B/C,其中A是卤聚物,B是粘合层和C是热塑性聚合物。在一个更优选的实施方案中,该薄膜结构具有至少三层:一层卤聚物层,一层与该卤聚物邻接的粘合层以及一层与软质改性聚合物邻接的热塑性聚合物层。PCTFE是优选用于这三层薄膜的卤聚物。这种薄膜特别适用于例如要求硬质泡沫塑料衬垫包装的药品和其他物料的包装。
可以添加到卤聚物/增粘层结构的热塑性聚合物包括聚酰胺例如结晶的和无定形的尼龙例如尼龙6和MXD6(可从Mitsubishi GasChemical Company,Inc.买到);聚酯例如聚(对苯二甲酸乙二醇酯)、1,4-环己烷二甲醇改性的聚(对苯二甲酸乙二醇酯)、聚(对苯二甲酸-1,4-环己二亚甲酯)、聚(对苯二甲酸丁二醇酯)、聚(萘二甲酸乙二醇酯)和聚(萘二甲酸丁二醇酯);聚烯烃例如聚乙烯、聚丙烯和聚丁烯以及上述与原料聚合物有关的其他聚烯烃;聚丙烯腈、聚苯乙烯、聚丙烯酸酯、聚(氯乙烯)、聚(偏二氯乙烯)、乙烯乙酸乙烯酯、聚氨酯及其共聚物或混合物。
当然,其他通常包含在多组分结构中的添加剂可以包含在本发明的结构中。它们包括紫外线吸收剂和稳定剂、填料、滑爽剂、抗氧化剂以及热稳定剂。
如上所述,本发明的材料可以用来制备除薄膜以外的多组分结构。这些结构可以采用共挤出、层压、注塑和吹塑法制备。所有这些方法在本领域中是众所周知的,参见例如美国专利5,139,878、4,677,017和4,510,301,兹将该专利公开的内容特别引入本文作为参考。例如本发明的多组分结构可以用来制备对称或不对称的包括至少一层卤聚物层和至少一层与该卤聚物层邻接的粘合层的多组分管道。在一个优选的实施方案中,该管道包括至少一层卤聚物层、至少一层与该卤聚物层邻接的粘合层以及至少一层与该粘合层邻接的热塑性聚合物层。用于该管道的适宜结构包括但不限于:A/B/C、A/B/C/B/A和C/B/A/B/C,其中A是卤聚物,B是粘合层和C是热塑性聚合物层。
在另一个实施方案中,本发明涉及改进多组分结构中卤聚物与其他聚合物粘合性的方法,该方法包括将软质改性的聚合物用作卤聚物和其他聚合物之间的粘合层。
出乎意外地发现,根据本文讲述的方法生产的多组分结构比现有技术采用粘合用树脂的多组分结构显示出更优良的中间层粘合性。
兹提出以下实施例以便更充分地理解本发明。所陈述的具体方法、条件、材料特性以及报道的数据是用以举例说明本发明的原理和实践,而不应理解为是对本发明范围的限制。
实施例1
由聚(三氟氯乙烯)(PCTFE)均聚物(密度:2.11 gm/cc,熔点:211℃,Aclar_HP,AlliedSignal Inc.生产)、线型低密度聚乙烯(“LLDPE”)(密度:0.920 gm/cc,熔体指数:按照ASTM D-1238,在190℃下为1.0 gm/10 min,由Dow Chemical Company生产)和粘合层共挤出三层薄膜。该粘合层包括(1)官能化聚烯烃(密度:0.89gm/cc,熔体指数:在190℃下为1.0 gm/10 min,D等级的肖氏硬度为21和A等级的肖氏硬度为76,含有68%(重量)乙烯、25%(重量)丙烯、7%(重量)乙酸乙烯酯和小于1%(重量)马来酸酐,MitsuiChemicals America Inc.生产)(Admer SF 700 A)作为对比例;(2)75%官能化聚烯烃(1)、15%另一低熔体指数的官能化聚烯烃(Admer AT1276)(密度:0.888 gm/cc,熔体指数:0.4 gm/10 min,D等级的肖氏硬度为25和与(1)的组成相同,也是Mitsui Chemicals AmericaInc.生产的)和10%苯乙烯-乙烯-丁烯-苯乙烯线型嵌段共聚物(密度:0.92 gm/cc,A等级的肖氏硬度为65,Shell Chemical Company生产)(Kraton G 1657)(这种混合物具有列于表1中的肖氏硬度)的混合物也作为对比例;或(3)高度官能化聚烯烃弹性体(密度:0.884gm/cc,熔体指数:0.4 gm/10 min,D等级的肖氏硬度为20和A等级的肖氏硬度为72,含有78%乙烯、19%丙烯和约2-4%马来酸酐,Mitsui Chemicals America Inc.生产)(Admer AT 1293)。
通过将PCTFE在121℃下干燥4小时并将其通过直径为3.2cm(1.26英寸)、装配有三个加热区和两个适配器的Killon单螺旋挤出机(L/D=24/1)挤出,制备卤聚物层。挤出温度分布对1-3区分别设定为277℃、282℃和288℃。适配器保持在288℃。熔融温度为286℃。
将聚乙烯通过直径为3.8 cm(1 1/2英寸)、装配有三个加热区和两个适配器的Killon单螺旋挤出机(L/D=24/1)挤出,制备包括乙烯和辛烯-1共聚物、具有密度为0.920且190℃下的熔体指数(ASTMD-1238)为1.0 gm/10min的LLDPE层。将加热区1-3分别保持为238℃、249℃和260℃。适配器保持在260℃。熔融温度为256℃。
将增粘树脂通过3.2 cm(1.26英寸)、装配有四个加热区和两个适配器的Killon单螺旋挤出机挤出。将加热区1-4分别保持为238℃、249℃、260℃和266℃。适配器保持在266℃。所产生的熔融温度为263℃。
多层结构以LLDPE/粘合层/卤聚物结构的形式共挤出,并在温度保持为62°F(17℃)的压延辊上、继之以温度保持为约80°F(27℃)的冷却辊上压延。
所得数据列于下表1:
表1
粘合强度gm/in(gm/cm) | |||||
粘合剂 | 肖氏硬度值D等级 | 肖氏硬度值A等级 | 马来酸酐改性的% | 仅在PCTFE一侧粘贴 | 在两侧粘贴 |
对比例1 | 21 | 76 | <1% | 81(32) | 238(94) |
对比例2 | 21 | 75 | <1% | 182(72) | 486(191) |
3 | 20 | 72 | 2-4% | 321(126) | 561(221) |
这些数据表明中间层的粘合性与“软质度”(D等级和A等级的肖氏硬度值)和粘合层的马来酸酐改性程度有关。对软质的材料而言,由于A等级较好鉴别,因而肖氏硬度值均按A等级而不是按D等级报道。在这种情况下,与用具有低度(即,<1%)酐改性的“硬”粘合剂制备的薄膜相比,用具有A等级肖氏硬度小于75(且D等级的肖氏硬度小于25)的粘合层制备的薄膜在中间层的粘合性表现出显著的改进。实施例2
用ECTFE(另一种共聚物,即,50%乙烯和50%三氟氯乙烯,密度:1.68 gm/cc,熔点:240℃Ausimont USA,Inc.生产)作为卤聚物并以实施例1中所述的对比粘合剂(2)和粘合剂(3)作为粘合层制备实施例1中所述的多组分薄膜。
所得数据列于表2:表2
粘合强度gm/in(gm/cm) | |||||
粘合剂 | 肖氏硬度值D等级 | 肖氏硬度值A等级 | 马来酸酐改性的% | 仅在PCTFE一侧粘贴 | 在两侧粘贴 |
对比例2 | 21 | 75 | <1% | 350(138) | 550(217) |
3 | 20 | 72 | 2-4% | 400(157) | >650(>256) |
这些数据也表明,卤聚物中间层的粘合性与“软质度”(D等级和A等级的肖氏硬度值)和软质、改性聚合物粘合剂的马来酸酐改性程度有关。即,软质改性粘合剂可显示出优良的粘合特性而与多组分结构中所用的卤聚物无关。因此,中间层的粘合性与卤聚物无关,而与粘合剂的类型有关。
实施例3
为了说明粘合强度与软质度之间的关系,用各种对比粘合剂制备实施例1中所述的多组分薄膜,所有粘合剂具有的D等级肖氏硬度值均大于25。用具有D等级肖氏硬度值为40的超低密度聚(乙烯)(“ULDPE”)作为粘合层(Flexomer DEFA 1373,可从Union Carbide买到,密度:0.903,维卡软化温度:53℃(ASTM D-1525),0.3-0.6%马来酸酐改性)制备的薄膜显示出190 gm/in(75 gm/cm)的粘合强度(在两侧粘贴)和75 gm/in(30 gm/cm)的粘合强度(仅在PCTFE一侧粘贴)。用具有D等级肖氏硬度值为46的线型低密度聚乙烯(“LLDPE”)作为粘合层(Admer NF500A,可从Mitsui ChemicalsAmerica,Inc.买到,密度:0.92 gm/in,维卡软化温度:86℃(ASTMD-1525),马来酸酐改性小于1%)制备的薄膜显示出150 gm/in(59gm/cm)的粘合强度(在两侧粘贴)和50 gm/in(20 gm/cm)的粘合强度(仅在PCTFE一侧粘贴)。用具有D等级肖氏硬度值为67的聚丙烯(“PP”)作为粘合层(Admer QF500A,可从Mitsui ChemicalsAmerica,Inc.买到,密度:0.90 gm/cc,维卡软化温度:143℃(ASTMD-1525),马来酸酐改性小于1%)制备的薄膜显示出100 gm/in(39gm/cm)的粘合强度(在两侧粘贴)和45 gm/in(18 gm/cm)的粘合强度(仅在PCTFE一侧粘贴)。具有由美国专利5,139,878中所述的Blend树脂(“Blend”)组成的、包括来自实施例1的60%对比增粘树脂1和40%乙基甲基丙烯酸酯共聚物(EMAC 2202,可从Chevron ChemicalCompany买到,密度:0.943,丙烯酸甲酯含量:21%(重量),维卡软化温度60℃(ASTM D-1525),没有用马来酸酐改性,D等级的肖氏硬度为38),且具有D等级肖氏硬度值为28的粘合层的薄膜显示出220 gm/in(87 gm/cm)的粘合强度(在膜的两侧粘贴)和75 gm/in(30gm/cm)的粘合强度(仅在PCTFE一侧粘贴)。具有包括乙烯乙酸乙烯酯(美国专利4,677,017中所述的马来酸酐改性的乙酸乙烯酯)(“EVA”)(Bynel 3101,可从E.I.du Pond de Nemours and Company买到,乙酸乙烯酯含量约为18%,密度:0.943 gm/cc,维卡软化温度:650℃(ASTM D-1525),马来酸酐改性小于1%)、A等级的肖氏硬度值为90和D等级的约为33的粘合层的薄膜显示出190 gm/in(75gm/cm)的粘合强度(在膜的两侧粘贴)和70 gm/in(28 gm/cm)的粘合强度(仅在PCTFE一侧粘贴)。表3概括了这些结果。表3
粘合强度gm/in(gm/cm) | |||||
粘合层 | 肖氏硬度值A或D等级 | 维卡软化温度(ASTM D)-1525) | 马来酸酐改性的% | 仅在PCTFE一侧粘贴 | 在两侧粘贴 |
ULDPE | D等级为40 | 53 | <1% | 75(30) | 190(75) |
LLDPE | D等级为46 | 86 | <1% | 50(20) | 150(59) |
PP | D等级为67 | 143 | <1% | 45(18) | 100(39) |
Blend | D等级为28 | - | <1% | 75(30) | 220(87) |
EVA | A等级为90D等级为33 | 65 | <1% | 70(28) | 190(75) |
如同实施例1和2一样,这些数据表明,中间层的粘合性与“软质度”(肖氏硬度)和改性粘合层的酐改性程度有关。更具体而言,具有D等级肖氏硬度值大于25和低度马来酸酐改性(即,<1%)的改性粘合剂显示出低的粘合强度,即,小于220 gm/in(87 gm/cm)(在两侧粘贴),该粘合强度对于实际应用往往是不够的。经过对比,来自实施例1和2、具有D等级肖氏硬度值小于25和A等级为75且具有大于1%马来酸酐改性的粘合剂(3)显示出极好的粘合强度。因此,与其“较硬”的对应物相比,该软质改性粘合剂明显地表现出优良的中间层粘合性。
虽然不希望受特定理论的限制,但是可以认为卤聚物表面上的带负电的卤化物与水解酐的酸性之间的酸碱相互作用,使这些软质改性的聚合物成为良好的粘合剂。
已相当详细地对本发明作了叙述,应该理解的是,这些细节不一定都被完全附上,但是,对本领域中的技术人员而言,进一步的改变和修改均属由所附权利要求限定的本发明的范围之内。
Claims (35)
1.一种多组分结构,该结构包括:
a)至少一层卤聚物层;和
b)至少一层粘合层,其中所述粘合层包括具有选自不饱和酸或其酐、胺和环氧化合物的至少一种官能部分的原料聚合物,其中所述粘合层具有的ASTM D-2240肖氏硬度值为D等级小于约25和A等级小于约75。
2.权利要求1的多组分结构,其中所述多组分结构是三层结构。
3.权利要求1的多组分结构,其中所述多组分结构是三层薄膜。
4.权利要求1的多组分结构,其中所述粘合层的官能部分的含量占该粘合层总重的约0.1%至约20%(重量)。
5.权利要求1的多组分结构,其中所述粘合层的官能部分的含量占该粘合层总重的约0.2%至约15%(重量)。
6.权利要求1的多组分结构,其中所述粘合层的官能部分的含量占该粘合层总重的约0.5%至约10%(重量)。
7.权利要求1的多组分结构,其中所述粘合层的官能部分的含量占该粘合层总重的约1%至约5%(重量)。
8.权利要求1的多组分结构,其中所述粘合层的官能部分是不饱和羧酸。
9.权利要求1的多组分结构,其中所述粘合层的官能部分是不饱和羧酸的酐。
10.权利要求1的多组分结构,其中所述粘合层的官能部分是马来酸酐。
11.权利要求1的多组分结构,其中所述粘合层的官能部分选自脂族的伯、仲和叔胺以及芳族的伯、仲和叔胺。
12.权利要求1的多组分结构,其中所述粘合层的官能部分是具有约2至约20个碳原子的环氧。
13.权利要求1的多组分结构,其中所述粘合层的原料聚合物选自聚(α-烯烃)均聚物、共聚物及其混合物,和热塑性弹性体。
14.权利要求13的多组分结构,其中所述原料聚合物是具有约2至约10个碳原子的聚(α-烯烃)均聚物。
15.权利要求13的多组分结构,其中所述原料聚合物是具有约2至约6个碳原子的聚(α-烯烃)均聚物。
16.权利要求13的多组分结构,其中所述原料聚合物是选自苯乙烯嵌段共聚物、烯属弹性体、弹性体合金、热塑性聚氨酯、弹性聚酯和弹性聚酰胺的热塑性弹性体。
17.权利要求16的多组分结构,其中所述原料聚合物是选自直链和支链共聚物的苯乙烯嵌段共聚物。
18.权利要求16的多组分结构,其中所述原料聚合物是选自三元乙丙橡胶和乙丙橡胶的烯属热塑性弹性体。
19.权利要求16的多组分结构,其中所述原料聚合物是选自可熔融加工的橡胶、热塑性硫化橡胶和乙烯共聚体的弹性体合金。
20.权利要求16的多组分结构,其中所述原料聚合物是选自聚酯基聚氨酯和聚醚基聚氨酯的热塑性聚氨酯。
21.权利要求16的多组分结构,其中所述原料聚合物是聚酯与聚醚的共聚物的弹性聚酯。
22.权利要求16的多组分结构,其中所述原料聚合物是聚酰胺与聚醚的共聚物的弹性聚酰胺。
23.权利要求1的多组分结构,其中所述卤聚物是含氟聚合物。
24.权利要求23的多组分结构,其中所述含氟聚合物选自PCTFE均聚物和共聚物、ECTFE共聚物、乙烯四氟乙烯共聚物、氟化的乙烯丙烯共聚物、全氟烷氧基聚合物、聚(偏二氟乙烯)、聚(氟乙烯)、四氟乙烯的共聚物或混合物、偏二氟乙烯的共聚物或混合物以及上述两种或多种的混合物。
25.权利要求23的多组分结构,其中所述含氟聚合物是PCTFE均聚物或共聚物。
26.权利要求23的多组分结构,其中所述含氟聚合物是PCTFE均聚物。
27.权利要求1的多组分结构,该结构还包括至少一层热塑性层。
28.权利要求27的多组分结构,其中所述热塑性层选自聚酰胺、聚酯、聚烯烃、聚丙烯腈、聚苯乙烯、聚丙烯酸酯、聚(氯乙烯)、聚(偏二氯乙烯)、乙烯乙酸乙烯酯、聚氨酯以及上述两种或多种的共聚物或混合物。
29.权利要求27的多组分结构,其中所述热塑性层是聚烯烃。
30.权利要求1的多组分结构,其中所述粘合层具有的肖氏硬度值为D等级小于约20和A等级小于约72。
31.一种包括权利要求1的多组分结构的多层薄膜。
32.权利要求31的多层薄膜,其中所述多层薄膜是定向的。
33.一种多组分结构,该结构包括:
a)至少一层PCTFE均聚物或共聚物层;
b)至少一层粘合层,其中所述粘合层包括具有选自不饱和酸或其酐、胺和环氧化合物的至少一种官能部分的原料聚合物,其中所述粘合层具有的ASTM D-2240肖氏硬度值为D等级小于约25和A等级小于约75;和
c)至少一层烯属热塑性层。
34.一种包括权利要求33的多组分结构的多层薄膜。
35.一种改进多组分结构中卤聚物与其他聚合物粘合性的方法,该方法包括在卤聚物和其他聚合物之间使用粘合层,该粘合层包括具有选自不饱和酸及其酐、胺和环氧化合物的至少一种官能部分的原料聚合物,所述粘合层具有的ASTM D-2240肖氏硬度值为D等级小于约25和A等级小于约75。
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
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US6448297P | 1997-11-06 | 1997-11-06 | |
US60/064482 | 1997-11-06 | ||
US60/064,482 | 1997-11-06 | ||
US09/161,369 US6432542B1 (en) | 1997-11-06 | 1998-09-28 | Multicomponent structures having improved adhesion |
US09/161,369 | 1998-09-28 | ||
US09/161369 | 1998-09-28 |
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Publication Number | Publication Date |
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CN1285777A true CN1285777A (zh) | 2001-02-28 |
CN1171718C CN1171718C (zh) | 2004-10-20 |
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CNB988129655A Expired - Fee Related CN1171718C (zh) | 1997-11-06 | 1998-11-05 | 改进了粘合性的多组分结构 |
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US (1) | US6432542B1 (zh) |
EP (1) | EP1028843B1 (zh) |
JP (1) | JP4195186B2 (zh) |
KR (1) | KR100552571B1 (zh) |
CN (1) | CN1171718C (zh) |
AT (1) | ATE245526T1 (zh) |
AU (1) | AU1519299A (zh) |
BR (1) | BR9815433A (zh) |
CA (1) | CA2309188C (zh) |
DE (1) | DE69816646T2 (zh) |
DK (1) | DK1028843T3 (zh) |
ES (1) | ES2201561T3 (zh) |
FI (1) | FI119363B (zh) |
HU (1) | HUP0004910A3 (zh) |
IL (1) | IL136003A0 (zh) |
MY (1) | MY132920A (zh) |
WO (1) | WO1999024242A1 (zh) |
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- 1998-11-05 HU HU0004910A patent/HUP0004910A3/hu unknown
- 1998-11-05 ES ES98959382T patent/ES2201561T3/es not_active Expired - Lifetime
- 1998-11-05 DK DK98959382T patent/DK1028843T3/da active
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- 1998-11-05 JP JP2000520290A patent/JP4195186B2/ja not_active Expired - Fee Related
- 1998-11-05 AU AU15192/99A patent/AU1519299A/en not_active Abandoned
- 1998-11-05 WO PCT/US1998/023581 patent/WO1999024242A1/en active IP Right Grant
- 1998-11-05 DE DE1998616646 patent/DE69816646T2/de not_active Expired - Lifetime
- 1998-11-05 CN CNB988129655A patent/CN1171718C/zh not_active Expired - Fee Related
- 1998-11-05 BR BR9815433A patent/BR9815433A/pt not_active Application Discontinuation
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CA2309188C (en) | 2007-03-27 |
CN1171718C (zh) | 2004-10-20 |
JP4195186B2 (ja) | 2008-12-10 |
JP2001522738A (ja) | 2001-11-20 |
EP1028843A1 (en) | 2000-08-23 |
FI119363B (fi) | 2008-10-31 |
HUP0004910A2 (hu) | 2001-05-28 |
ATE245526T1 (de) | 2003-08-15 |
WO1999024242A1 (en) | 1999-05-20 |
HUP0004910A3 (en) | 2005-06-28 |
EP1028843B1 (en) | 2003-07-23 |
KR100552571B1 (ko) | 2006-02-20 |
DE69816646T2 (de) | 2004-06-03 |
KR20010015797A (ko) | 2001-02-26 |
IL136003A0 (en) | 2001-05-20 |
ES2201561T3 (es) | 2004-03-16 |
US6432542B1 (en) | 2002-08-13 |
MY132920A (en) | 2007-10-31 |
BR9815433A (pt) | 2002-03-12 |
CA2309188A1 (en) | 1999-05-20 |
FI20001060A (fi) | 2000-06-21 |
DK1028843T3 (da) | 2003-09-15 |
AU1519299A (en) | 1999-05-31 |
DE69816646D1 (de) | 2003-08-28 |
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