CN101351335B - 多层含氟聚合物膜 - Google Patents
多层含氟聚合物膜 Download PDFInfo
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- CN101351335B CN101351335B CN2006800495281A CN200680049528A CN101351335B CN 101351335 B CN101351335 B CN 101351335B CN 2006800495281 A CN2006800495281 A CN 2006800495281A CN 200680049528 A CN200680049528 A CN 200680049528A CN 101351335 B CN101351335 B CN 101351335B
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Abstract
本发明涉及一种具有至少一层含氟聚合物层的多层膜，用于高纯度接触应用。优选地，含氟聚合物层是聚偏二氟乙烯聚合物和共聚物。
Description
技术领域
本发明涉及一种具有至少一层含氟聚合物层的多层膜，用于高纯度接触应用。本发明还涉及用于高纯度接触应用的含氟聚合物单层膜。所述含氟聚合物层是可熔融加工性含氟聚合物，优选地是聚偏二氟乙烯聚合物或共聚物。
背景技术
高纯度操作需要清洁、纯净的工艺环境和容器。这种应用中的聚合物必须有强耐化学性并能容易地被灭菌。高纯度聚合物的应用包括袋子或其他容器，用于高纯度液体、生物学和生物医学介质，以及高纯度化学制品和试剂。
对于在生物学/生物化学反应器中用作一次性衬垫的聚合物袋，现有的袋子耐化学性有限，并且通常在装置外通过γ射线组装和灭菌。现有技术包括多层结构和具有接触层的单层膜，所述接触层由乙烯乙酸乙烯酯(EVA)和线性低密度聚乙烯(LLDPE)制成；100％聚氯三氟乙烯(PCTFE)膜或与热封性聚烯烃层共挤出的PCTFE膜。这些膜可包括增加强度的尼龙层和/或作为阻隔层的乙烯乙烯基醇。
一个问题是现有袋不能在蒸气压力罐中灭菌，因为它将融化在一起变无用。它也不易被热封，或需要额外的步骤以达到热封性，例如增加与聚烯烃层的共挤出。
含氟聚合物，和特别是聚偏二氟乙烯(PVDF)，已知具有强耐化学性。含氟聚合物可制成膜，包括美国专利申请10/678795中公开的多层(PVDF)/官能性聚甲基丙烯酸甲酯膜。这种膜不是纯PVDF层，而是PVDF和另一种聚合物的混合。
需要这样一种聚合物材料，它可提供高纯度接触表面，能用蒸气灭菌或γ射线灭菌，并且可热封。
令人惊讶的是，本发明发现，具有至少一层可熔融加工性含氟聚合物层的膜是一种可被蒸气灭菌或γ射线灭菌的高纯度材料。
发明概述
本发明涉及一种多层含氟聚合物膜，包括至少一层可熔融加工性含氟聚合物层，所述可熔融加工性含氟聚合物层形成接触液体和气体的接触层。
本发明还涉及一种用于生物或生物制药应用的膜，包括至少一层可熔融加工性含氟聚合物层，可直接被热封，不需要其他层。
详细描述
本发明涉及用于高纯接触应用的单层或多层膜，所述膜具有至少一层含氟聚合物，还涉及多层含氟聚合物膜。
这里用“多层膜”表示具有两层或更多层的膜。这种膜可由2、3、4、5、6或更多层粘合在一起组成。连接层和粘合层可以是膜结构的一部分，或者，不同的层可不通过粘合剂连接层而粘合在一起。
膜中至少有一层是可熔融加工性含氟聚合物。优选地，不止一层是可熔融加工性含氟聚合物。
术语“含氟单体”或“氟化单体”表示具有至少一个连接在参与聚合的烯烃双键上的氟原子、氟化烷基、或氟化烷氧基的可聚合的烯烃。术语“含氟聚合物”表示由至少一种含氟单体聚合而成的聚合物，它包括均聚物、共聚物、三元共聚物和高聚物，它们都具有热塑性，也就是说，它们能够受热塑变而形成有用的零件，就如成型和挤塑工艺中所做的那样。本发明中有用的含氟聚合物是那些可熔融加工性的。可熔融加工性含氟聚合物的例子包括，但不限于：聚偏二氟乙烯和其共聚物(PVDF和co-PVDF)、乙烯-四氟乙烯(ETFE)、乙烯-氯三氟乙烯(ECTFE)、聚氟化乙烯丙烯(FEP)、四氟乙烯-全氟乙烯基丙醚(PFA)、和多种单体(至少其中之一被氟化)的任意组合。所述例子还包括EFEP(乙烯、六氟丙烯、四氟乙烯)，PVDF与六氟丙烯、全氟乙烯基甲基醚或丙基醚、乙烯、四氟乙烯、氟乙烯、三氟乙烯(vinyl trifluoride)、乙烯等，以及官能性单体(例如顺丁烯二酐、甲基丙烯酸缩水甘油酯等)的共聚物。一些含氟聚合物因可熔融加工性差而不在本发明的范围内，包括但不限于丙烯氯三氟乙烯(PCTFE)和聚四氟乙烯。
本发明优选的含氟聚合物是1，1-二氟乙烯(VDF)的均聚物和1，1-二氟乙烯的共聚物、三元共聚物和高聚物，其中1，1-二氟乙烯单元占聚合物中单体单元总重量的大于70％，更优选地，占单元总重量的大于75％。1，1-二氟乙烯的共聚物、三元共聚物和高聚物可由1，1-二氟乙烯与一种或多种单体反应而成，所述单体选自：氟乙烯、三氟乙烯、四氟乙烯、一种或多种部分氟化或全氟化α烯烃(例如3，3，3-三氟-1-丙烯、1，2，3，3，3-五氟丙烯、3，3，3，4，4-五氟-1-丁烯和六氟丙烯)、部分氟化的烯烃六氟异丁烯、全氟化乙烯醚(例如全氟甲基乙烯醚、全氟乙基乙烯醚、全氟正丙基乙烯醚、和全氟-2-丙氧丙基乙烯醚)、氟化间二氧杂环戊烯(例如全氟(1，3-间二氧杂环戊烯)和全氟(2，2-二甲基-1，3-间二氧杂环戊烯))、烯丙基、部分氟化烯丙基或氟化烯丙基单体(例如2-羟乙基烯丙基醚或3-烯丙基丙二醇)以及乙烯或丙烯。优选的是与氟乙烯、三氟乙烯、四氟乙烯(TFE)、和六氟丙烯(HFP)形成的共聚物或三元共聚物。
优选的共聚物是1，1-二氟乙烯(VDF)的共聚物，包含约71％至约99％(重量)的VDF及相应地，约1％至约29％的TFE；约71％至99％重量的VDF及相应地，约1％至约29％的HFP(如专利号为3,178,399的美国专利中公开的)；和约71％至约99％重量的VDF及相应地，约1％至约29％重量的四氟乙烯。
优选的三元共聚物是VDF、HFP和TFE的三元共聚物和VDF、三氟乙烯和TFE的三元共聚物，特别优选的三元共聚物含有至少71％(重量)的VDF以及其他单体，其他单体可为不同比例，但总量占三元共聚物的29％(重量)。
聚偏二氟乙烯也可以是官能化的PVDF，通过共聚时官能化或聚合后官能化而生成。
含氟聚合物层可以是单层膜。在多层膜中，含氟聚合物可存在于结构中任何地方。在优选的实施例中，含氟聚合物层是与介质或液体接触的层。在另一实施例中，多层膜中的所有层都是含氟聚合物，并且优选PVDF均聚物和共聚物。一种特别优选的膜具有这样的结构：其中PVDF均聚物作为接触层且PVDF共聚物共挤出或层合其上。优选的是，至少一层PVDF层是100％PVDF，无其他聚合物混合。
在多层膜中，除含氟聚合物层之外，还可以有其他聚合物层、连接层和粘合层。特别有用的层包括但不限于：聚烯烃，例如聚乙烯(PE)，包括线性低密度聚乙烯(LLDPE)、低密度聚乙烯(LDPE)、中密度聚乙烯(MDPE)，聚丙烯(PP)和含有接枝或反应官能团(例如顺丁烯二酐或甲基丙烯酸缩水甘油酯(glycidalmethacrylate))的官能性聚乙烯(FPO)；乙烯乙酸乙烯酯(EVA)；聚酰胺(PA)；和高温聚烯烃，例如4-甲基-1-戊烯。还可用聚乙烯醇作为多层结构中的阻隔层。
本发明中有用的多层膜的一些例子如下所示。本领域技术人员可想到其他类似结构，根据特定终端应用的需求对其进行调制。这些例子包括：
1.PVDF均聚物/PVDF共聚物(非均相的或均相的，记为CoPVDF)。例如KYNAR 720/KYNAR 3120-10(阿科玛股份有限公司(Arkema Inc.))为例，其中，可对膜层进行调节以改变膜的阻隔性能和/或物理性质。它可包括VF2与TFE、HFP、CTFE、PPVE、PMVE等的共聚物。它也可含有官能性单体或其他非含氟单体组分。来自阿科玛股份有限公司的市售材料的一个例子是采用KYNAR弗莱克斯(Flex)2850或KYNAR2800或KYNAR 3120作为一层并采用KYNAR 740或KYNAR 720或Kynar 710作为第二层。
2.所述结构可包含三个层，例如PVDF/CoPVDF/PVDF或CoPVDF/PVDF/CoPVDF。作为一种选择，这种结构可包含多于三个的层。这种结构可以是A/B/A或A/B/C型结构，其中每个字母代表一种不同的PVDF或CoPVDF。
3.所述PVDF或CoPVDF可以是官能化的，其中官能度来自共聚过程或聚合后。所得产物记为PVDF-X。
4.所述结构可包含聚烯烃，例如MDPE或LLDPE或EVA。这种结构的选择之一可以是：PVDF/PVDF-X/FPO/PE，其中FPO是官能性聚烯烃，例如洛泰德AX8900(Lotader AX8900)。这种结构可制成两面均为PVDF，例如：PVDF/PVDF-X/FPO/PE/FPO/PVDF-X/PVDF。在一些应用中这种结构可以是PVDF-X/FPO/PE。
5.所述结构可包含其他含氟聚合物作为接触层。这可以是EFEP或其他含氟聚合物(ETFE，FEP，PFA，ECTFE，PCTFE)，其中的官能团通过共聚掺入产物。例如，EFEP可以与聚酰胺或与烯烃共挤出以形成多层产物。
6.在这些结构中，如果想提高强度，可以添加聚酰胺。一个例子是有或没有其他层的PVDF/PVDF-X/聚酰胺。
7.为得到最佳的阻隔性能，可添加EVOH到多层结构中。一个例子是：PVDF/PVDF-X/FPO-GMA-洛泰德(Lotader)/FPO-奥瑞瓦克(Orevac)/EVOH/FPO-奥瑞瓦克(Orevac)/PE或PVDF/PVDF-X/PA6/EVOH/PA6。另一个例子可以是PVDF/PVDF-X/EVOH/PVDF-X/PVDF。另一个例子可以是PVDF-X/EVOH/PVDF-X。所述PA6也可以是其他PA与PA6的PA6共聚物或混合物或“合金”(alloy)。这种结构中PVDF可以是PVDF共聚物。一种相似的结构可以用EFEP(或官能化ETFE)制得，例如：EFEP/PA6或EFEP/PA6/EVOH/PA6。所述PA6可以用其他聚酰胺代替。另两种结构可以是PVDF/PVDF-X/EVOH/PA6或PVDF/PVDF-X/EVOH/FPO-奥瑞瓦克(Orevac)/PE。所述PA6也可以是其他PA与PA6的PA6共聚物或混合物或“合金”。这些结构中PVDF可以是PVDF共聚物。
8.PVDF/PVDF-X/FPO-洛特(Lot)/PE可以代替PVC用于血袋或温室膜。
9.可在各种聚合物膜上以溶液涂覆的方式加以丙烯酸聚合物薄层。这些膜已经有售。这些膜的例子是与聚甲基丙烯酸甲酯(PMMA)薄层层合的PET或PVDC。PMMA与PVDF完全相容。可以通过在热层合工艺中将PVDF与这些膜层合来制成多层膜。因为这种技术能够设计以PET、PVDC、尼龙等为一面而PVDF在另一面的膜。在这种情况下，PMMA或丙烯酸类聚合物作为连接层。
优选的实施例之一是与PVDF共聚物(例如KYNAR 3120、KYNAR 2800或KYNAR 2850)共挤出的均聚物PVDF(例如KYNAR 710、KYNAR 720、KYNAR740和KYNAR 760)。优选地，由于其强耐化学性、高渗透性和高熔点，PVDF均聚物形成与液体或介质接触的表面。具有良好阻隔性能的另一优选的实施例是PVDF/EVOH/顺丁烯二酐接枝的PVDF膜袋。
可以在膜的外表面上添加金属层作为阻隔层。这也可以是与箔层层合。这还可以具有非金属化材料的窗口区。
多层膜可用本领域已知的手段来制成。多层膜可通过共挤塑、层合或其他可制备这种膜的工艺制成。这些膜可通过挤塑、铸膜、吹制膜和导向膜后再层合而制得。也可采用连接层来粘接各层。
本发明中多层膜的总厚度是1至50密耳，优选地是2至30密耳，更优选地是3至15密耳，最优选地是4至10密耳。各种层的层厚取决于应用中的性能需求(阻隔性能、弹性、硬度等)。如果整体膜太薄，它可能不能提供所需的阻隔性能或完整性，如果它太厚，采用传统膜焊接技术的可焊性可能受限。
PVDF多层膜能经受住压热器的作用(蒸气消毒)和γ射线消毒，并具有高纯度、强阻隔和强耐化学性。所述膜也可用射频射线消毒。因为在产品地就地消毒很容易，制造商可选择就地装配自己的系统并蒸气消毒。这样可缩短交货时间并为终端用户产品提高更高的灵活性。
由于本发明的多层膜可用γ射线消毒，终端用户由此可以仅进行一个系统的达标而非两个(一个用于蒸气消毒和一个用于γ射线消毒)。
本发明的PVDF膜具有良好的热封性，这是大部分其他含氟聚合物所没有的。膜的热封性使之可用于生产可高强度连接件。
本发明的膜可制成容器、零件、滤材、管和袋，由此可使得一个系统只采用一种液体接触材料。由于PVDF膜具有良好的耐化学性和惰性，这种膜可用于制备多种化学制剂。所述膜，无论单层膜和多层膜，可用作阻隔层/接触层-特别是用于生物学、生物医学、生物制药学的接触应用。
本发明的其他用途可包括气体样品袋-包括用于汽车排放用途，用于筒的耐化学性衬垫、温室罩等。
实施例
实施例1
以下多层膜在通过将两层KYNAR膜热层合在一起而制得。
膜层厚度，密耳
KYNAR 720 KYNAR 3120 KYNAR 2800
膜1 2 5
膜2 5 5
膜3 2 5
膜4 5 5
在下表1中，采用以下缩写：
2850、2750、3120-弗莱克斯(Flex)、2800-都是指相应级别KYNAR的10密耳单层膜(阿科玛公司)
表1
KYNAR10密耳膜的物理性质
| 样品 | 拉伸模量，切向，psi，ASTMD 882 | 拉伸屈服，psiASTM D882 | 拉伸断裂，psiASTM D882 | 延展屈服，％ASTM D882 | 延展断裂％，ASTMD 882 | 抗扯强度g/mil，ASTMD 1004 |
| 2850(横向) | 138630(4940) | 5230*(110) | 4470十(180) | 10.6(0.5) | 463.5(7.6) | 714(53) |
| 2850(纵向) | 144370(4180) | 5560*(170) | 5000十(270) | 11.4(0.3) | 486.7(62.9) | 653(38) |
| 2750(横向) | 52960(1250) | 2520十(60) | 7140*(750) | 14.9(0.5) | 937.0(47.6) | 435(34) |
| 2750(纵向) | 42300(970) | 2540十(100) | 7650*(320) | 18.3(0.6) | 837.3(14.4) | 419(26) |
| 3120 Flex(横向) | 96520(4250) | 3560十(160) | 5300*(850) | 9.6(0.3) | 753.3(97.2) | 527(42) |
| 3120 Flex(纵向) | 97640(4580) | 4040十(120) | 8070*(390) | 15.1(0.3) | 855.6(27.3) | (35)577 |
| 2800/720层合(横向) | 132490(4470) | 4760十(290) | 4410*(280) | 9.8(0.9) | 442.5(18.1) | 669(55) |
| 2800/720层合(纵向) | 116050(5810) | 4670十(200) | 7880*(1210) | 12.9(0.2) | 707.2(60.4) | 652(73) |
| 2500(横向) | 33220(1380) | 1930十(90) | 5250*(850) | 18.2(0.7) | 1000.6(70.1) | 401(37) |
| 2500(纵向) | 31570(1850) | 1930十(90) | 6410*(770) | 19.4(0.8) | 1004.6(41.0) | 386(27) |
| 2800(横向) | 72500(3620) | 3190十(150) | 6960*(710) | 13.4(0.5) | 962.1(34.3) | 511(58) |
| 2800(纵向) | 60600(1780) | 3130十(70) | 7210*(700) | 15.9(0.3) | 857.5(39.1) | 489(44) |
| 3120/720层合(横向) | 143480(5470) | 5190十(160) | 7040*(2050) | 10.8(0.3) | 710.4(186.6) | 681(101) |
| 3120/720层合(纵向) | 135600(5300) | 53001十(180) | 8600*(1610) | 13.0(0.4) | 745.5(67.0) | 695(19) |
所有的测试是在23℃和50％RH的条件下进行的。在测试前，所有的试样在50％RH和23℃的条件下适应超过24小时。括号内的值是标准偏差。试样从挤塑膜上冲压制得。在2”/min的十字头速度条件下测试试样。通过十字头移动测试延展性。对所有的数据点n＝5。
表2
耐穿孔性-落镖冲击试验仪(Dart Impact Tester){KOP Lab}测试
冲击速度：10.93ft/s
表3
收缩结果：135℃下2小时
*2500试样在100℃下测试-试样在135℃下开始熔化
表4
收缩结果：135℃下2小时
*2500试样在100℃下测试-试样在135℃下开始熔化
实施例2
以下多层膜采用多层吹制膜共挤塑技术制得
表5
拉伸性能
所有的测试是在23℃和50％RH的条件下进行的。在测试前，所有的试样在50％RH和23℃的条件下适应超过24小时。括号内的值是标准偏差。试样从挤塑膜上冲压制得。在2”/min的十字头速度条件下测试试样。通过十字头移动测试延展性。对所有的数据点n＝5。
表6
抗扯性能
实施例3
以下多层膜通过在涂有丙烯酸的聚酯膜上热层合Kynar而制得：
表7
拉伸性能
表8
抗扯性能
Claims (9)
1.一种多层膜在用于生物学、生物医学或生物制药学中的用途，所述多层膜包括至少一层用于与生物或生物制药化合物接触的可熔融加工性的聚偏二氟乙烯（PVDF）均聚物或共聚物层和至少一层其它层，其中所述PVDF是接触层，所述膜可被蒸气消毒或γ射线消毒，所述多层膜选自：a)两层或更多层的多层膜，其中所有层都是PVDF聚合物，所述PVDF聚合物选自PVDF均聚物、PVDF共聚物、官能化的PVDF均聚物、官能化的PVDF共聚物、和它们的混合物；b)这样一种多层膜，其包含所述PVDF液体接触层、任选的一层或更多层连接层和至少一层选自聚酰胺、聚烯烃、官能性聚烯烃和聚对苯二甲酸乙二酯的非含氟聚合物其他层。
2.如权利要求1所述的用途，其特征在于，它包括至少一层聚偏二氟乙烯均聚物或含有至少70重量％1,1-二氟乙烯单体单元的聚偏二氟乙烯共聚物层。
3.如权利要求2所述的用途，其特征在于，所述聚偏二氟乙烯聚合物或共聚物层完全由聚偏二氟乙烯均聚物或含有至少70重量％1,1-二氟乙烯单体单元的聚偏二氟乙烯共聚物组成，不混有任何其他聚合物。
4.如权利要求1所述的用途，其特征在于，所述膜的总厚度是1-50密耳。
5.如权利要求1所述的用途，其特征在于，它包括两层聚偏二氟乙烯均聚物或含有至少70重量％1,1-二氟乙烯单体单元的聚偏二氟乙烯共聚物层。
6.如权利要求1所述的用途，其特征在于，它由一层聚偏二氟乙烯均聚物层和一层含有至少70重量％1,1-二氟乙烯单体单元的聚偏二氟乙烯共聚物层构成。
7.一种形成如权利要求1所述的多层膜的方法，所述方法包括将含氟聚合物膜与有涂层或经预处理的底层膜层合的步骤。
8.如权利要求7所述的方法，其特征在于，采用官能化聚偏二氟乙烯，加用或不加用附加连接层，使所述含氟聚合物层可与阻隔层共挤出。
9.如权利要求7所述的方法，其特征在于，所述多层膜包括乙烯乙烯醇层。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US75478205P | 2005-12-29 | 2005-12-29 | |
| US60/754,782 | 2005-12-29 | ||
| PCT/US2006/048694 WO2007078972A2 (en) | 2005-12-29 | 2006-12-20 | Multi-layer fluoropolymer films |
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| Publication Number | Publication Date |
|---|---|
| CN101351335A CN101351335A (zh) | 2009-01-21 |
| CN101351335B true CN101351335B (zh) | 2013-05-15 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800495281A Expired - Fee Related CN101351335B (zh) | 2005-12-29 | 2006-12-20 | 多层含氟聚合物膜 |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US9044923B2 (zh) |
| EP (1) | EP1971485B1 (zh) |
| JP (1) | JP5352238B2 (zh) |
| CN (1) | CN101351335B (zh) |
| WO (1) | WO2007078972A2 (zh) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008097641A2 (en) | 2007-02-08 | 2008-08-14 | Meissner Filtration Products, Inc. | Multilayer film, method of making the same and containers formed from the same |
| US9682526B2 (en) * | 2007-10-02 | 2017-06-20 | Meissner Filtration Products, Inc. | Radio frequency weldable multilayer tubing and method of making the same |
| FR2927016B1 (fr) † | 2008-02-06 | 2012-10-19 | Arkema France | Film tricouche pour cellule photovoltaique |
| EP2382090A4 (en) * | 2009-01-27 | 2012-05-30 | Arkema Inc | POLYVINYLIDE BARRIER LAYER FOR TANK ROOMS |
| EP2473345B1 (en) * | 2009-09-01 | 2017-03-22 | Dow Global Technologies LLC | Backsheet for rigid photovoltaic modules |
| US20120245238A1 (en) * | 2009-10-07 | 2012-09-27 | Arkema Inc. | Melt processable composition from recycled multi-layer articles containing a fluoropolymer layer |
| WO2011057005A2 (en) * | 2009-11-04 | 2011-05-12 | Klöckner Pentaplast Of America, Inc. | Configuration of multiple thermoformable film layers for rigid packaging requiring moisture and oxygen protection |
| US20110244241A1 (en) * | 2010-03-08 | 2011-10-06 | Aditya Ranade | Adhesion in ectfe/polyester co-extruded structures using tie layers |
| FR2958206A1 (fr) * | 2010-03-30 | 2011-10-07 | Arkema France | Films fluores multicouche |
| US9120912B2 (en) | 2011-05-25 | 2015-09-01 | Arkema Inc. | Irradiated fluoropolymer articles having low leachable fluoride ions |
| EP2751175A4 (en) * | 2011-09-02 | 2015-03-11 | Arkema Inc | MULTILAYER STRUCTURES OF POLYVINYLIDENE FILM |
| TW201331040A (zh) * | 2012-01-20 | 2013-08-01 | Entire Technology Co Ltd | 多層氟樹脂膜、其共押出方法及太陽能模組 |
| KR20140129062A (ko) | 2012-02-17 | 2014-11-06 | 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 | 중합체계 다층 가스 배리어 필름 |
| GB201214177D0 (en) * | 2012-08-08 | 2012-09-19 | Kritis Plastika | Multilayer plastic film with separable layers for covering of inflated freenhouse |
| US10562282B2 (en) * | 2013-03-15 | 2020-02-18 | Arkema France | Multilayer composite |
| EP3490799B1 (en) * | 2016-07-27 | 2021-06-30 | Honeywell International Inc. | Film layers and methods for forming the same |
| JP6971034B2 (ja) * | 2017-01-24 | 2021-11-24 | 東京応化工業株式会社 | 分析用器材 |
| DE102018112817A1 (de) | 2018-05-29 | 2019-12-05 | Klöckner Pentaplast Gmbh | Transparente Polymerfolie mit Verfärbungskompensation |
| JPWO2020203653A1 (zh) * | 2019-03-29 | 2020-10-08 | ||
| WO2021004594A1 (en) * | 2019-07-11 | 2021-01-14 | Danapak Flexibles A/S | Laminate methods and products |
| EP4247881A1 (en) | 2020-11-18 | 2023-09-27 | Klöckner Pentaplast of America, Inc. | Thermoformed packaging and methods of forming the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1529726A (zh) * | 2001-05-21 | 2004-09-15 | 3M | 含氟聚合物粘合 |
| CN1648507A (zh) * | 2004-01-29 | 2005-08-03 | Ti汽车传动股份有限公司 | 多层塑料管 |
Family Cites Families (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3178399A (en) | 1961-08-10 | 1965-04-13 | Minnesota Mining & Mfg | Fluorine-containing polymers and preparation thereof |
| FR2545040B1 (fr) * | 1983-04-27 | 1985-07-19 | Solvay | Structures thermoplastiques a couches multiples comprenant une couche en polymere du fluorure de vinylidene liee a une couche en polymere d'alpha-olefine |
| FR2563156B1 (fr) * | 1984-04-19 | 1987-01-30 | Solvay | Structures a couches polymeriques multiples comprenant une couche en polymere du fluorure de vinyle ou de vinylidene liee a une couche en polymere polaire |
| JPH0671785B2 (ja) * | 1984-06-23 | 1994-09-14 | 電気化学工業株式会社 | フッ化ビニリデン樹脂系複合フイルムの製造方法 |
| BE1001335A3 (fr) * | 1988-01-08 | 1989-10-03 | Solvay | Structures a couches polymeriques multiples comprenant une couche en polymere du fluorure de vinylidene liee a une couche en polymere plastifie du chlorure de vinyle et utilisation de ces structures pour la fabrication d'emballages souples. |
| US5198505A (en) * | 1991-04-11 | 1993-03-30 | Pall Corporation | Uniform polyvinylidene difluoride membranes |
| FR2687619B1 (fr) * | 1992-02-25 | 1994-04-08 | Elf Atochem Sa | Tube pour transport d'essence. |
| JP3218440B2 (ja) * | 1992-03-05 | 2001-10-15 | ニッタ・ムアー株式会社 | 燃料移送用チューブ |
| US5454795A (en) * | 1994-06-27 | 1995-10-03 | Target Therapeutics, Inc. | Kink-free spiral-wound catheter |
| US5496294A (en) * | 1994-07-08 | 1996-03-05 | Target Therapeutics, Inc. | Catheter with kink-resistant distal tip |
| JPH08142151A (ja) | 1994-11-22 | 1996-06-04 | Hakko:Kk | 積層チューブ |
| FR2731943B1 (fr) * | 1995-03-24 | 1997-07-18 | Atochem Elf Sa | Materiau complexe a proprietes ameliorees constitue de polyfluorure de vinylidene et d'un thermoplastique non compatible |
| JPH08281884A (ja) * | 1995-04-19 | 1996-10-29 | Mitsubishi Chem Corp | 積層体 |
| EP0754535B1 (fr) | 1995-07-17 | 2000-04-12 | Elf Atochem S.A. | Procédé pour la coextrusion de deux matières à des températures différentes |
| JPH09157616A (ja) * | 1995-12-08 | 1997-06-17 | Daikin Ind Ltd | 含フッ素接着剤ならびにそれを用いた接着性フィルムおよび積層体 |
| JPH1024537A (ja) * | 1996-07-09 | 1998-01-27 | Toray Ind Inc | 多層フッ素フィルム、膜材およびその製造方法ならびにその膜材を用いた成型物 |
| US6165166A (en) * | 1997-04-25 | 2000-12-26 | Schneider (Usa) Inc. | Trilayer, extruded medical tubing and medical devices incorporating such tubing |
| DE29822036U1 (de) * | 1998-12-10 | 1999-02-11 | Ifk Isofluor Kunststoffverarbe | Dualschrumpfschlauch |
| JP2001193872A (ja) | 2000-01-12 | 2001-07-17 | Sanyo Electric Co Ltd | 飲料用チューブ |
| FR2813235B1 (fr) * | 2000-08-30 | 2002-10-25 | Commissariat Energie Atomique | Structure et reservoir thermoplastique |
| EP2305446B1 (en) * | 2001-06-18 | 2018-08-01 | Becton, Dickinson and Company | Process for forming multilayer containers |
| US20060068674A1 (en) * | 2002-02-13 | 2006-03-30 | Dixit Ajit S | Novel laminates for producing high strength porous sterilizable packaging |
| EP1362870A1 (fr) * | 2002-05-16 | 2003-11-19 | Atofina | Structure multicouche comprenant un liant à base de polyoléfine greffée par un monomère acrylique |
| US8337968B2 (en) * | 2002-09-11 | 2012-12-25 | Boston Scientific Scimed, Inc. | Radiation sterilized medical devices comprising radiation sensitive polymers |
| US20050050854A1 (en) * | 2003-09-09 | 2005-03-10 | Jean-Pascal Zambaux | Sterile, pyrogen-free, polymeric film-based heating bag |
| US8129024B2 (en) * | 2004-05-20 | 2012-03-06 | Arkema Inc. | Multi-layer rotational moulding |
| US7233788B2 (en) * | 2004-07-20 | 2007-06-19 | San Disk Il Ltd. | Recovering from a disconnected phone call |
| EP1798253B8 (en) * | 2004-08-11 | 2014-06-18 | Kaneka Corporation | Method for producing a vinylidene fluoride-based resin multilayered film |
| DE102004048776A1 (de) * | 2004-10-07 | 2006-04-13 | Degussa Ag | Mehrschichtverbund mit EVOH-Schicht und Schutzschicht |
| FR2879281B1 (fr) * | 2004-12-13 | 2007-02-16 | Nobel Plastiques Soc Par Actio | Tube fluoropolymere/evoh/pa modifie |
| US20060246008A1 (en) * | 2005-04-29 | 2006-11-02 | Jenkins Lauri L | Process for the formulation of therapeutic protein |
| US20060246244A1 (en) * | 2005-04-29 | 2006-11-02 | Jenkins Lauri L | Disposable vessel for the containment of biological materials and corrosive reagents |
| US20060243666A1 (en) * | 2005-04-29 | 2006-11-02 | Jenkins Lauri L | Process for the preparation of protein separation solution |
| US20060246537A1 (en) * | 2005-04-29 | 2006-11-02 | Jenkins Lauri L | Multi-step process for the manufacture of therapeutic protein |
| FR2892172B1 (fr) * | 2005-10-13 | 2007-12-14 | Arkema Sa | Tube multicouche a base de polymere fluore modifie |
| FR2892171B1 (fr) * | 2005-10-13 | 2008-04-18 | Arkema Sa | Tube multicouche a base de polymere fluore modifie |
| US20070128393A1 (en) * | 2005-12-06 | 2007-06-07 | Moulton Jeffrey D | Heat sealable PCTFE film and tubing using high VF2 containing copolymers of CTFE/VF2 |
| CN101494316A (zh) | 2008-01-21 | 2009-07-29 | 何珊珊 | 无线射频天线及其制法 |
-
2006
- 2006-12-20 EP EP06847868.4A patent/EP1971485B1/en active Active
- 2006-12-20 WO PCT/US2006/048694 patent/WO2007078972A2/en active Application Filing
- 2006-12-20 JP JP2008548618A patent/JP5352238B2/ja not_active Expired - Fee Related
- 2006-12-20 US US11/817,054 patent/US9044923B2/en active Active
- 2006-12-20 CN CN2006800495281A patent/CN101351335B/zh not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1529726A (zh) * | 2001-05-21 | 2004-09-15 | 3M | 含氟聚合物粘合 |
| CN1648507A (zh) * | 2004-01-29 | 2005-08-03 | Ti汽车传动股份有限公司 | 多层塑料管 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5352238B2 (ja) | 2013-11-27 |
| WO2007078972A3 (en) | 2008-04-10 |
| EP1971485B1 (en) | 2018-04-11 |
| WO2007078972A2 (en) | 2007-07-12 |
| CN101351335A (zh) | 2009-01-21 |
| JP2009522134A (ja) | 2009-06-11 |
| US9044923B2 (en) | 2015-06-02 |
| US20080261050A1 (en) | 2008-10-23 |
| EP1971485A4 (en) | 2012-05-30 |
| EP1971485A2 (en) | 2008-09-24 |
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