CN113677515A - 用于气囊应用的多层膜 - Google Patents
用于气囊应用的多层膜 Download PDFInfo
- Publication number
- CN113677515A CN113677515A CN202080027965.3A CN202080027965A CN113677515A CN 113677515 A CN113677515 A CN 113677515A CN 202080027965 A CN202080027965 A CN 202080027965A CN 113677515 A CN113677515 A CN 113677515A
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- Prior art keywords
- multilayer film
- mah
- adhesive layer
- layer
- multilayer
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Classifications
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Abstract
本发明涉及一种多层膜,其包括:阻隔层,和粘合剂层,所述粘合剂层包括马来酸酐(MAH)‑接枝聚烯烃;其中所述阻隔层的熔点高于所述粘合剂层的熔点,并且其中所述阻隔层的所述熔点高于165℃。本发明能够制造兼顾表现出高的耐剥离性与低的重量和/或厚度的气密性多层层叠体。在进一步的实施方案中,描述了一种多层层叠体和一种可充气气囊,所述可充气气囊包括粘附至所述多层膜的织物层,以及其制造方法。
Description
技术领域
本发明涉及用于织物的气密性涂层的多层膜,并且涉及包括所述多层膜的多层层叠体。另外,本发明涉及所述多层膜的制造方法和包括所述多层层叠体的可充气气囊。
背景技术
将气囊引入到车辆中以在碰撞事件期间为乘坐者提供柔软的缓冲和约束是已知的实践。
最广泛使用的变体,即正面气囊,被设计成在碰撞期间极其迅速地充气,然后迅速地放气。
然而,在最近几十年中,已经开发了数种类型的气囊,这些气囊需要长时间地保持充气状态。例如,设置在车门上方并且沿着车辆侧窗充气和展开的帘式气囊期望地在直到翻车时和翻车期间保持膨胀,从而约束乘坐者,并且防止乘坐者受伤,直到碰撞事件结束。还已知将气囊集成到背包中以制造所谓的雪崩气囊,其旨在保持充气状态以防止雪崩受害者下沉到雪覆盖层之下。
为了满足这些需求,气囊材料应当在主气囊表面上和通过将气囊的多个部分缝合在一起或粘附而形成的接缝处均表现出高的强度和合适的气密性。
同时,为了在放气状态下表现出小的体积并且避免对车辆、背包或其它包含气囊的制品造成不必要的重量增加,所述材料期望地是轻质和薄的。
通常,气囊表现出多层结构,该多层结构包括提供强度的基材层,例如针织或机织织物,在其上涂布有一个或多个能够实现气密性的聚合物系层。例如,EP 1 518 761 A1和US 2007/0065614 A1公开了示例性的多层材料。同时减少涂布织物的厚度和重量的简单方法为减少织物上涂布材料的量。然而,在实践中,由于在涂布过程期间或之后形成对多层结构的气密性有害的局部针孔(即,小的未涂布区域),涂层重量的减少受到高度限制。另外或选择性地,随着涂层重量的降低,涂布材料和织物之间的剥离强度趋于降低。EP 2 855 150A1公开了马来酸酐-接枝聚烯烃在包装膜的连接层中的用途。然而,没有公开对织物的粘合性和轻质气囊应用所需的厚度。WO 2018/230721 A1公开了通过经由热塑性聚酯弹性体层将多层膜粘附至布基材而制备的气囊。然而,其中公开的粘合剂层易于从不基于热塑性聚酯弹性体(如聚酰胺)的气密性阻隔层脱层。
因此,本发明的目的为提供多层膜和层叠体,其克服了上述问题,并且能够提供薄且轻重量的气囊,该气囊不易崩解并且表现出充分的强度和不透气性,以有效地用于需要气囊长时间处于完全展开状态的应用(例如,帘式气囊和类似应用)。
另外,本发明的目的为提供多层膜和层叠体,其可以廉价地制造并且允许宽范围的加工条件(例如,在层叠期间的温度和/或压力)。
发明内容
本发明通过本文限定的权利要求的主题解决了这些目的。本发明的其它优点将在下面的部分中进一步详细解释。
通常,本发明涉及一种多层膜,其包括:阻隔层,和粘合剂层,所述粘合剂层包括马来酸酐(MAH)-接枝聚烯烃;其中所述阻隔层的熔点高于所述粘合剂层的熔点,并且其中所述阻隔层的所述熔点高于165℃。该多层膜可以用作合成织物的涂层,该涂层对织物基材具有优异的剥离强度,并且该多层膜可以以低的厚度和/或涂层重量涂布,而不易于形成针孔。
在另一方面,本发明提供一种多层层叠体,其包括经由所述粘合剂层粘附至上述多层膜的织物层。
本发明的其它方面涉及一种可充气气囊,其包括上述多层层叠体,以及涉及上述多层膜用于机织或针织织物的气密性涂层的用途。
在以下说明书和权利要求书中描述了本发明的优选的实施方案以及其它方面。
附图说明
图1A示出根据本发明的一个实施方案的两层多层膜。
图1B示出根据本发明的一个实施方案的多层层叠体。
图1C示出用根据本发明的多层膜在一片式织物的两侧涂布的示例性方法。
具体实施方式
为了更完整地理解本发明,现在参考其示例性实施方案的以下描述:
多层膜
在第一实施方案中,本发明通常涉及一种多层膜,其包括阻隔层,和粘合剂层,所述粘合剂层包括马来酸酐(MAH)-接枝聚烯烃;其中所述阻隔层的熔点高于所述粘合剂层的熔点,并且其中所述阻隔层的所述熔点高于165℃。
MAH-接枝聚烯烃通常可以在宽的温度范围内表现出熔点。然而,层叠工艺对MAH-接枝聚烯烃与阻隔层材料的相容性施加了限制,因为可能存在窄的加工窗口(例如,就温度或层叠压力而言),在该窗口内可以获得高品质的层叠体。通过选择阻隔层,使得其熔融温度高于165℃,层叠加工窗口可以变宽并且可以将宽范围的MAH-接枝聚烯烃用于粘合剂层,而不会损害层叠体的品质。
如图1所示,根据本实施方案的多层膜(100)具有至少两层结构,所述两层结构包括阻隔层(10)和粘合剂层(20)。因此,通过使用多层膜作为织物或网状基材的涂层,与单层涂层相比,对基材的粘合性和气密性可以得到改善,因为不需要平衡阻气性和粘合性。阻隔层(10)一般特征在于其防止气体流入和流出该层。粘合剂层(20)为对织物或网状基材显示出粘合性的层。通常,该粘合性通过在预定条件下,例如在升高的温度和/或压力的条件下软化或熔融而表现出来。
本发明中使用的粘合剂层主要包括至少一种马来酸酐(MAH)-接枝聚烯烃。如本文所用的术语“马来酸酐(MAH)-接枝聚烯烃”和“MAH-接枝聚烯烃”表示用马来酸酐接枝的烯烃系均聚物或共聚物。MAH-接枝聚烯烃可以通过本领域技术人员已知的方法来合成,所述方法例如包括自由基聚合。
虽然不限于此,MAH-接枝聚烯烃优选基于C2-C20烯烃的聚合物或共聚物。在进一步优选的实施方案中,MAH-接枝聚烯烃选自MAH-接枝聚乙烯、MAH-接枝聚丙烯、或其共聚物。
虽然不限于此,MAH接枝聚乙烯的合适的基础聚合物及其共聚物包括高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)、极低密度聚乙烯(VDLPE)、超低密度聚乙烯(ULDPE)、线性乙烯/α-烯烃互聚物、基本线性乙烯/α-烯烃互聚物或烯烃多嵌段互聚物。特别优选的基础聚合物包括LDPE、LLDPE、VDLPE(具有密度在0.89~0.914g/cm3之间)和ULDPE(具有密度小于0.89g/cm3)。如本文所用的术语“互聚物”包括具有多于一种聚合单体的任意聚合物,其包括共聚物和三元共聚物。虽然不限于此,优选的与乙烯聚合的共聚单体包括C3-C20α-烯烃,更优选C3-C10α-烯烃,并且特别优选聚丙烯、1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯、1-庚烯和1-辛烯。进一步优选的共聚单体包括丙烯、1-丁烯、1-己烯和1-辛烯。合适的乙烯系互聚物的市售实例包括均可从The Dow Chemical Company获得的ENGAGETM、ATTANETM、AFFINITYTM、DOWLEXTM、ELITETM;可从Exxon Chemical Company获得的EXCEEDTM和EXACTTM;以及可从Arkema,S.A.获得的来自OREVACTM系列的MAH-接枝PE,可从Mitsui Chemical Company获得的ADMERTM聚合物。
马来酸酐(MAH)-接枝聚烯烃的合适的基础聚合物还包括聚丙烯均聚物和丙烯共聚物,以及其它烯烃系聚合物,如由一种或多种C4-C20α-烯烃形成的那些。MAH-接枝聚丙烯的市售实例包括可从Arkema,S.A.获得的来自OREVACTM系列的MAH-接枝PP。烯烃系聚合物可以任选地包含可共聚的共轭二烯、非共轭二烯和/或乙烯基单体。在本发明的优选的实施方案中,丙烯系互聚物用作接枝反应中的基础聚合物。优选的共聚单体包括但不限于乙烯、异丁烯、1-丁烯、1-戊烯、1-己烯、3-甲基-1-戊烯、4-甲基-1-戊烯、1-辛烯、非共轭二烯烃、多烯、丁二烯、异戊二烯、戊二烯和己二烯(例如1,4-己二烯)、辛二烯、苯乙烯、卤素取代的苯乙烯、烷基取代的苯乙烯、四氟乙烯、乙烯基苯并环丁烯、环烷烃、环烯烃(例如环戊烯、环己烯、环辛烯)及其混合物。优选地,共聚单体为乙烯或C4-C20α-烯烃。进一步优选的共聚单体包括乙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯和1-辛烯,并且更优选包括乙烯、1-丁烯、1-己烯和1-辛烯。
在进一步优选的实施方案中,本发明中使用的粘合剂层包括MAH-接枝聚烯烃和非MAH-改性聚烯烃的共混物。在该情况下,MAH-接枝聚烯烃优选选自MAH-接枝聚乙烯、MAH-接枝聚丙烯、或其共聚物;并且非MAH-改性聚烯烃优选选自聚乙烯或聚丙烯。虽然不限于此,合适的非MAH改性聚烯烃包括高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)、极低密度聚乙烯(VDLPE)、超低密度聚乙烯(ULDPE)、线性乙烯/α-烯烃互聚物、基本线性乙烯/α-烯烃互聚物或烯烃多嵌段互聚物。特别优选的基础聚合物包括LDPE、LLDPE、VDLPE(具有密度在0.89~0.914g/cm3之间)和ULDPE(具有密度小于0.89g/cm3)。相应的PE共混物的市售实例包括可从LyondellBasell,Inc.获得的PLEXARTM PX3227和可从TheDow Chemical Company获得的来自AMPLIFYTM系列的MAH-改性聚烯烃。
虽然不限于此,相对于马来酸酐(MAH)-接枝聚烯烃的总重量,马来酸酐(MAH)-接枝聚烯烃优选包括0.1~2.0wt.-%MAH,进一步优选在0.25~1.5wt.-%之间的MAH。
在本发明的多层膜中,相对于粘合剂层的总重量,粘合剂层中的马来酸酐(MAH)-接枝聚烯烃的含量(或MAH-接枝聚烯烃和非MAH-改性聚烯烃的总含量,如果存在后者)优选为10~100wt.-%。
在优选的实施方案中,从增加粘合剂层对织物或网状基材的剥离强度的观点,除了MAH-接枝聚烯烃以外,粘合剂层还包括α-烯烃共聚物,优选为包含C3-C12烯烃的弹性体α-烯烃共聚物。虽然不限于此,所述α-烯烃共聚物优选不用MAH接枝。由α-烯烃共聚物建立的支化聚合物链的存在促进了侧链之间的缠结和与基材材料的范德华相互作用,改善了粘合剂层对基材的粘性,并且因此增加了剥离强度,并且为多层膜提供了柔软性和类似橡胶的性质。α-烯烃共聚物的优选的实例包括但不限于乙烯和直链或支链C3-C12α-烯烃例如丙烯、1-丁烯、异丁烯、1-戊烯和1-辛烯的共聚物。
在α-烯烃共聚物的存在下,相对于粘合剂层的总重量,粘合剂层中的马来酸酐(MAH)-接枝聚烯烃的含量(或MAH-接枝聚烯烃和非MAH-改性聚烯烃的总含量,如果存在后者)优选为10~99wt-%,进一步优选25~80wt.-%,并且α-烯烃共聚物的含量优选为1~90wt.-%,优选20~75wt.-%,以提供优异的挠性和弹性,同时保持充分的机械强度。
在优选的实施方案中,粘合剂层进一步包括根据ISO 868的邵氏D硬度小于80如30~80或35~75的聚合物。虽然不限于此,这种聚合物可以选自例如聚烯烃或热塑性弹性体。合适的聚烯烃的实例包括但不限于聚乙烯和聚丙烯。合适的热塑性弹性体(TPE)包括但不限于例如烯烃系TPE(例如,PP/EPDM)、苯乙烯嵌段共聚物(包括,但不限于,苯乙烯-丁二烯-苯乙烯(SBS)、苯乙烯-异戊二烯-苯乙烯(SIS)、苯乙烯-异戊二烯/丁二烯/苯乙烯(SIBS)、苯乙烯-乙烯/丁烯-苯乙烯(SEBS)、苯乙烯-乙烯/丙烯(SEP)和苯乙烯-乙烯/丙烯-苯乙烯(SEPS))、共聚酯系热塑性弹性体(TPC)、聚氨酯系热塑性弹性体(TPU)或聚酰胺系热塑性弹性体(TPA)。在优选的实施方案中,相对于粘合剂层的总重量,具有上述确定范围内的邵氏D硬度的聚合物以0.5~40wt.-%的含量包括,进一步优选以1~30wt.-%的含量包括。
在优选的实施方案中,粘合剂层的厚度在2~45μm的范围内,进一步优选在2~20μm的范围内,并且特别优选在2~15μm的范围内。
粘合剂层的表面密度优选在5~50g/m2的范围内,更优选15~45g/m2,特别优选20~35g/m2。
如上所述,阻隔层具有防止气体流入和流出该层的功能。
根据本发明,阻隔层的熔点高于粘合剂层的熔点并且高于165℃。因此,当通过在低于阻隔层的熔点的温度下加热而将多层膜接合至粘合剂层侧上的基层时,粘合剂层适用于接合至织物基材或网状基材,同时抑制构成阻隔层的材料的软化。由此,确保了粘合剂层的可靠的粘合功能。进一步优选的是,阻隔层的熔点和马来酸酐(MAH)-接枝聚烯烃的熔点之间的差为至少35℃,因此可以有效地防止在作为薄层层叠到织物或网状基材上时,针孔的生成。因此,即使在使用少量的涂布量时,也可以同时实现所得多层层叠体中的高的剥离强度和阻气性的保持。另外,当长时间使用或储存时,或在高温和高湿环境中使用或储存时,可以保持高的挠性和抗脱层性。
如上文所陈述,阻隔层的熔点高于165℃,优选为至少168℃。在进一步优选的实施方案中,阻隔层的熔点为170℃以上,更优选180℃以上,特别优选在190℃~300℃之间,如195℃~270℃。阻隔层的熔点的上限优选为300℃,更优选270℃,特别优选230℃。在另一优选的实施方案中,阻隔层的熔点和粘合剂层的熔点之间的差优选在10~100℃的范围内,进一步优选在20~80℃的范围内。通常,熔点或温度可以通过本领域已知的方法来确定,如根据ISO11357-1/-3来确定。当通过将熔点和熔点之间的差设定为上述范围而通过加热和按压将多层膜接合至织物或网状基材时,有利于在接合期间的层叠温度的控制。
从在上述范围内的熔点、良好的低温冲击强度、耐擦洗性、提高的挠性和柔软性的观点,阻隔层包括热塑性聚酯弹性体或聚酰胺共聚物。
在各自具有由尼龙-6、尼龙-6,6、尼龙-11、尼龙-12、尼龙-6,6,12或这些的混合物构成的聚合物嵌段与由聚乙二醇、聚丙二醇、聚四氢呋喃、聚醚或这些的混合物构成的聚合物嵌段的组合的情况下,进一步优选的是共聚酯弹性体材料、共聚酰胺弹性体材料或聚酰胺弹性体材料。
共聚酯的市售实例包括可从DowDuPont,Inc.获得的来自HYTRELTM系列的热塑性聚酯弹性体、可从Mitsubishi Chemical Co.获得的来自MODICTM系列的热塑性聚酯弹性体、和可从DSM Engineering Plastics B.V.获得的来自系列的热塑性聚酯弹性体。聚酰胺和共聚酰胺的市售实例包括可从Ube Industries,Ltd.获得的UBE Nylon系列、可从Evonik AG获得的系列、和来自Arkema,S.A.的系列。
在优选的实施方案中,阻隔层的厚度在2~30μm的范围内,进一步优选在2~20μm的范围内,并且特别优选在2~15μm的范围内。
阻隔层的表面密度优选在2~20g/m2的范围内,更优选5~15g/m2。
阻隔层和粘合剂层可以独立地进一步包括本领域已知的常规添加剂,例如抗氧化剂、着色剂、阻燃剂、润滑剂、稳定剂或防粘连剂(例如,二氧化硅系防粘连剂)。这样的添加剂优选以基于每层的总重量为至多10wt.-%的总含量添加,优选在0.1~8wt.-%之间,以改善层材料的可加工性、稳定性或其它性能。
理解的是,根据本发明的多层膜除了粘合剂层和阻隔层以外还可以包括一个或多个其它层,例如阻隔层和粘合剂层之间的连接层或回收层。另外,粘合剂层和阻隔层各自可以由多个子层构成。例如,可以优选将粘合剂层构造为包括三层构造或由三层构造组成,其中中间层设置在两个粘合剂子层之间,所述粘合剂子层包括马来酸酐(MAH)-接枝聚烯烃并且具有相同或不同的组成。中间层的材料没有特别限制,并且可以包括非接枝聚烯烃(如PE或PP等)或其它相容性聚合物。有利地,这样的构造可以增加粘合剂层的有效厚度,并且从而改善经纱和纬纱区域中对机织织物的粘合力,而基本上没有增加制造中的材料成本。然而,在一些实施方案中,多层膜可以由上述阻隔层和粘合剂层的多个单个膜组成。
通常,优选的是,多层膜的总厚度在5~80μm的范围内,特别优选在10~75μm的范围内。
多层层叠体
在第二实施方案中,如图1B所示,本发明涉及一种多层层叠体(200),其包括经由粘合剂层(20)粘附至根据上述第一实施方案的多层膜的织物层(30)。因此,粘合剂层(20)可以直接层叠至织物层(30)以形成多层层叠体(200)。
除非另有定义,如本文所用的术语“织物层”表示由机织或针织的合成纤维、天然纤维、再生纤维、半合成纤维、无机纤维及其组合(包括混纺纱线和混合织物)制成的网或织物的层。其中,当旨在更高的机械强度时,可以优选机织织物。
在优选的实施方案中,织物层由合成纤维制成,其中包括基于聚酰胺(例如,尼龙、芳族聚酰胺)、聚酯(例如,聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸乙二醇酯(PET))、聚砜、聚醚酮(例如,PEEK)和/或聚烯烃(例如,聚乙烯、聚丙烯)的(共)聚合物的那些为进一步优选的。由于与包含在粘合剂层中的MAH-接枝聚烯烃中存在的马来酸酐基团形成牢固的极性键,因此通过从包含杂原子基团的聚合物中选择纤维层材料,获得了多层膜和织物层之间的特别改善的粘合性。其优选的实例包括但不限于聚酰胺、聚酯、人造丝、聚醚酮、聚砜及其衍生物。聚酰胺和聚酯为特别优选的。
织物层的厚度没有特别限制,并且可以由本领域技术人员根据所得多层层叠体的用途和所选择的织物材料适当地选择。例如,对于气囊应用,织物层的典型厚度在0.05mm~0.50mm之间的范围内,如0.1~0.40mm。
气囊
在第三实施方案中,本发明涉及一种可充气气囊,其包括根据第二实施方案的多层层叠体。
虽然不限于此,气囊可以是正面气囊、侧面气囊、膝部气囊、帘式气囊、座垫气囊、中心气囊、外部气囊、安全带气囊、行人气囊、摩托车气囊(其可以集成到背心或摩托车中)、自行车气囊(例如,领型气囊)、雪崩气囊(例如,背包集成)等。虽然在多层层叠体中使用的多层膜的重量轻且薄,但所得气囊耐崩解并且表现出充分的强度和不透气性,以有效地用作常规车辆气囊以降低放气状态下的重量和体积,或用作需要长时间完全展开的气囊(例如帘式气囊、雪崩气囊、摩托车或自行车气囊)。
因此,气囊的几何形状、接缝的类型和密封工艺没有限制,并且可以从本领域已知的那些中适当地选择。例如,可充气气囊可以制造为无接缝的一体式编织气囊(OPW)(例如,根据DE 102 24 771 A1),或者通过将多层层叠体的多个切割成适当尺寸的片接合来制造,该多层层叠体在接合之前可以任选地适当折叠(例如,根据US 2010/0320736 A1或US2014/0014253 A1)。通常,用于帘式气囊的OPW展现出其中形成多个空间的复杂的曲面,并且在充气状态下会具有不均匀的结构,这特别容易在织物层和多层膜之间剥离。然而,通过使用根据第一实施方案的多层膜,即使在这样的不规则表面上也可以牢固地粘附多层膜,并且可以有效地防止脱层。
气囊可以结合到本领域已知的被动约束系统和安全气囊组件中,其通常包括安全气囊控制单元(ACU),该安全气囊控制单元监测一个或多个相关的传感器(例如,包括加速计、冲击传感器、侧(门)压力传感器、轮速传感器、陀螺仪、制动压力传感器和座位占用传感器),并且当传感器测量的值达到或超过预定阈值时触发气体发生器单元。
制造方法和用途
在第四实施方案中,本发明涉及一种气囊用多层层叠体的制造方法,其包括以下步骤:设置根据第一实施方案的多层膜,并且将该多层膜接合至织物层。
根据第一实施方案的多层膜可以使用本领域技术人员已知的技术来形成。例如,对于那些可以共挤出的层,可使用本领域技术人员已知的技术在单个挤出步骤中将这些层共挤出为吹塑膜或流延膜。选择性地,多层膜可以通过例如挤出将粘合剂层和阻隔层预先形成为单独的片或膜,然后将片或膜彼此接合和一体化来制造。例如,可以将各片或膜叠加并且通过热压机或热辊来熔融压制。
然后将由此制造的多层膜接合至织物层,如上文在第二实施方案的上下文中所述的织物层。接合可以通过层叠步骤实现,其中将多层膜设置在织物层上并且加热至低于阻隔层的熔点的温度(例如,在设置在织物层上期间或之后)。
通过将多层膜和织物层层叠而获得的所得多层层叠体表现出片状结构,除了平面形状以外,其还可以包括圆柱状、袋状和气球状。
在图1C所示的示例性实施方案中,根据本发明的第一实施方案的两个相同或不同的多层膜可以同时接合至圆柱状、袋状或气球状织物层(30)的相对的表面,使得粘合剂层(20a)和(20b)在接缝处彼此接触和粘附(如图1C中的箭头所示)。
虽然不限于此,但是例如,在WO 2018/230721 A1、US 2007/0065614 A1和EP 1967 422 A1中公开了用于将多层膜接合至织物层的合适的技术和设备。
在第五实施方案中,本发明涉及根据第一实施方案的多层膜用于机织或针织织物或网的气密性涂层的用途。在该方面,多层膜是薄的、轻质的并且基本上不透气,并且因此可以优选用作宽范围的织物的涂层,用于制造气囊、帆和服装。
应当理解的是,第一实施方案至第五实施方案的优选特征可以以任何组合彼此自由组合,除了其中至少一些特征相互排斥的组合以外。
实施例
根据US 2007/0065614 A1中公开的方法,使用表1中所示的组合物,使用吹塑膜挤出分别制造每单位面积重量为10g/cm2的阻隔层膜和每单位面积重量为30g/cm2(参考实施例1、2、4、7-10和13-16)或25g/cm2(参考实施例3、5、6、11、12、17和18;以及比较例1~4)的粘合剂层膜。
表1中使用的试剂及其缩写解释如下:
聚合物B:UBE尼龙(熔融温度为188℃的尼龙6,6,12三元共聚物,可从UbeIndustries,Ltd.商购)
聚合物C:AdstifTM聚丙烯(熔融温度为165℃的高结晶度聚丙烯,可从LyondellBasell商购)。
MAH-聚烯烃1:PlexarTM连接层树脂(熔融温度为124℃的马来酸酐改性线性低密度聚乙烯塑性体,可从LyondellBasell商购)。
MAH-聚烯烃2:AdmerTM粘合树脂(熔融温度为147℃的马来酸酐接枝的共聚丙烯,可从Mitsui Chemicals,Inc.商购)
α-烯烃共聚物1:QueoTM塑性体(熔融温度为73℃的乙烯系辛烯-1塑性体,可从Borealis商购)
α-烯烃共聚物2:TafmerTM弹性体(熔点为160℃的丙烯系α-烯烃共聚物,可从Mitsui Chemicals,Inc.商购)
邵氏D<80的聚合物:SeptonTM弹性体(邵氏A硬度为36的苯乙烯-乙烯-丙烯-苯乙烯(SEPS)热塑性弹性体,可从Kuraray Co.,Ltd.商购)。
使用175℃的层叠温度、设定为0mm的层厚、水平(上压辊的高度调节)为0mm、18N/cm2的施加压力和1m/分钟的层叠速度,在Meyer双带平面层叠系统(Meyer Twin-Belt FlatLamination System)(KFK-S 400 700)中,将各个膜层叠在一起,以提供2层膜。
在Meyer双带层叠系统上,将所得2层膜层叠至由高强度纱线(OPW,Berger SafetyTextiles)构成的聚对苯二甲酸乙二醇酯(PET)织物(实施例1-6和13-17以及比较例1和2)或聚酰胺织物(实施例7-12和18以及比较例3和4)。
将多层膜层叠至织物的工艺条件包括将层叠温度设定为比各粘合剂层的熔点高20℃,层厚度设定为0mm,水平(上压辊的高度调节)为0mm,所施加的压力为18N/cm2,以及层叠速度为1.6m/分钟。
在制造后,对样品进行剥离强度测量。出于该目的,将背衬层设置在多层膜上,以便防止剥离期间的膜伸长,并且将每对层叠体夹持在拉伸试验机中,并且在室温下以100mm/分钟测量各实施例的多层膜和PET或PA织物层之间的剥离力。另外,用显微镜检查阻隔层表面的针孔。这些测量的结果示于表1。
实施例1-20以及比较例2和4之间的比较表明,其中阻隔层的熔点高于165℃的根据本发明的多层层叠体特别抗针孔形成。另一方面,其粘合剂层不包括马来酸酐(MAH)-接枝聚烯烃的比较例1和3的多层层叠体表现出低的剥离强度。特别有利的耐剥离性通过实施例1~18而实现,其粘合剂层包括MAH-接枝聚烯烃与α-烯烃共聚物的组合。
因此,本发明可以提供多层层叠体,其抗局部针孔的形成,并且即使在使用小的涂层重量和/或非常薄的涂膜时,也确保多层结构的高的气密性和涂布材料与织物之间充分的剥离强度二者。
一旦给出上述公开,许多其它特征、修改和改进对于本领域技术人员将变得显而易见。
附图标记说明
10、10a:阻隔层
20、20a:粘合剂层
30:织物层
100:多层膜
200:多层层叠体
Claims (15)
1.一种多层膜,其包括:
阻隔层,和
粘合剂层,所述粘合剂层包括马来酸酐(MAH)-接枝聚烯烃;
其中所述阻隔层的熔点高于所述粘合剂层的熔点,并且其中所述阻隔层的所述熔点高于165℃。
2.根据权利要求1所述的多层膜,其中所述马来酸酐(MAH)-接枝聚烯烃选自MAH-接枝聚乙烯、MAH-接枝聚丙烯、或其共聚物。
3.根据权利要求1或2所述的多层膜,其中相对于所述马来酸酐(MAH)-接枝聚烯烃的总重量,所述马来酸酐(MAH)-接枝聚烯烃包括0.1~2.0wt.-%MAH。
4.根据权利要求1至3中任一项所述的多层膜,其中所述粘合剂层进一步包括α-烯烃共聚物,优选为包括C3-C12烯烃的α-烯烃共聚物。
5.根据权利要求4所述的多层膜,其中在所述粘合剂层中,相对于所述粘合剂层的总重量,所述马来酸酐(MAH)-接枝聚烯烃的含量为10~99wt.-%,并且所述α-烯烃共聚物的含量为1~90wt.-%。
6.根据权利要求1至5中任一项所述的多层膜,其中所述粘合剂层进一步包括根据ISO868的邵氏D硬度小于80的聚合物。
7.根据权利要求6所述的多层膜,其中所述聚合物选自聚烯烃或热塑性弹性体,优选选自聚乙烯、聚丙烯或苯乙烯嵌段共聚物中的任一种。
8.根据权利要求1至7中任一项所述的多层膜,其中所述阻隔层包括热塑性聚酯弹性体或聚酰胺共聚物。
9.根据权利要求1至8中任一项所述的多层膜,其中所述粘合剂层的厚度在2~45μm的范围内,其中所述阻隔层的厚度在2~30μm的范围内;和/或其中所述多层膜的总厚度在10~75μm的范围内。
10.根据权利要求1至9中任一项所述的多层膜,其中所述粘合剂层的表面密度在5~50g/m2的范围内,优选15~45g/m2,并且所述阻隔层的表面密度在2~20g/m2的范围内,优选5~15g/m2。
11.一种多层层叠体,其包括经由粘合剂层粘附至根据权利要求1至10中任一项所述的多层膜的织物层。
12.根据权利要求11所述的多层层叠体,其中所述织物层包括聚酰胺、聚酯和/或聚烯烃。
13.一种可充气气囊,其包括根据权利要求11或12所述的多层层叠体。
14.一种气囊用多层层叠体的制造方法,其包括以下步骤:
设置根据权利要求1至10中任一项所述的多层膜,并且
将所述多层膜接合至织物层。
15.根据权利要求1至10中任一项所述的多层膜用于机织或针织织物的气密性涂层的用途。
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PCT/EP2020/060226 WO2020208172A1 (en) | 2019-04-12 | 2020-04-09 | Multilayer films for airbag applications |
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CN114133887A (zh) * | 2021-12-11 | 2022-03-04 | 江阴市格瑞包装材料有限公司 | 一种车内织物用贴合膜及复合织物的生产工艺 |
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EP3980262A1 (en) | 2022-04-13 |
WO2020207919A1 (en) | 2020-10-15 |
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