CN114929471A - 层状材料 - Google Patents
层状材料 Download PDFInfo
- Publication number
- CN114929471A CN114929471A CN202180008159.6A CN202180008159A CN114929471A CN 114929471 A CN114929471 A CN 114929471A CN 202180008159 A CN202180008159 A CN 202180008159A CN 114929471 A CN114929471 A CN 114929471A
- Authority
- CN
- China
- Prior art keywords
- layer
- layered material
- substrate
- film
- branched copolyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 83
- 229920001634 Copolyester Polymers 0.000 claims abstract description 58
- 239000000758 substrate Substances 0.000 claims abstract description 55
- 238000002844 melting Methods 0.000 claims abstract description 27
- 230000008018 melting Effects 0.000 claims abstract description 27
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- 238000000034 method Methods 0.000 claims description 41
- -1 polybutylene terephthalate Polymers 0.000 claims description 39
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 12
- 229920001451 polypropylene glycol Polymers 0.000 claims description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000000539 dimer Substances 0.000 claims description 6
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- 229920002647 polyamide Polymers 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 229920003232 aliphatic polyester Polymers 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
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- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
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- CUNPJFGIODEJLQ-UHFFFAOYSA-M potassium;2,2,2-trifluoroacetate Chemical compound [K+].[O-]C(=O)C(F)(F)F CUNPJFGIODEJLQ-UHFFFAOYSA-M 0.000 description 2
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- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 2
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- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- SFRDXVJWXWOTEW-UHFFFAOYSA-N 2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)CO SFRDXVJWXWOTEW-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
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- UWJRJUDLJQOQSP-UHFFFAOYSA-N N=C=O.N=C=O.CC1=CC=CC(C)=C1C Chemical compound N=C=O.N=C=O.CC1=CC=CC(C)=C1C UWJRJUDLJQOQSP-UHFFFAOYSA-N 0.000 description 1
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- LNWBFIVSTXCJJG-UHFFFAOYSA-N [diisocyanato(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(N=C=O)(N=C=O)C1=CC=CC=C1 LNWBFIVSTXCJJG-UHFFFAOYSA-N 0.000 description 1
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- 239000002313 adhesive film Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
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- 229920001577 copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
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- 229920001112 grafted polyolefin Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
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- 238000009958 sewing Methods 0.000 description 1
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- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- RJIFVNWOLLIBJV-UHFFFAOYSA-N tributyl benzene-1,2,4-tricarboxylate Chemical compound CCCCOC(=O)C1=CC=C(C(=O)OCCCC)C(C(=O)OCCCC)=C1 RJIFVNWOLLIBJV-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
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Images
Classifications
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Abstract
本发明涉及一种层状材料,其包括基材和至少一个A层,其中所述至少一个A层包含至少50wt%的支化共聚酯,其中wt%是相对于A层的总重量,并且其中所述支化共聚酯的熔融温度为125℃至185℃,Mz/Mw为至少3.5,并且在190℃下用2.16kg测量的熔体流动指数(MFI)为最多10g/10min。本发明还涉及一种包含至少一个A层的膜。
Description
发明内容
本发明涉及层状材料、制备层状材料的方法、适用于层状材料中的膜以及层状材料的应用。
层状材料是已知的并且例如应用于车辆中的可充气保护垫,也称为安全气囊。保护垫可防止乘客正面或侧面撞击。这些保护垫必须符合许多要求。特别是对于横向应用,这些保护垫必须能够在特定的时间内承受一定的压力。在车辆翻车的情况下,保护垫中的气体必须在保护垫内停留更长的时间,从而防止乘客被弹出车辆和/或防止乘客受伤。
目前用于安全气囊的层状材料是通过将箔层压到织物层上来制备的,例如US6607797中所述。这种气囊材料的缺点是所使用的材料表现出不足的耐水解性和/或耐热性。另一种解决方案是使用共聚酯,例如在WO18230721中描述的。该解决方案的缺点是必须通过吹膜工艺制备箔,该工艺中使用支撑层或必须使用三层膜。该支撑层在生产后必须丢弃,这使得该工艺变得昂贵,或必须使用更浓稠的溶液,这导致更高的成本和需要更多的材料。
因此,本发明的一个目的是提供一种层状材料,该层状材料包含一个层,该层可以通过吹膜工艺制备而不需要支撑层和/或可以以较低的厚度存在。
该目的通过包含基材和至少一个A层的层状材料实现,其中所述至少一个A层包含至少50wt%的支化共聚酯,其中wt%是相对于A层的总重量,并且其中支化共聚酯的熔融温度为125℃至185℃,Mz/Mw为至少3.5,并且在190℃下用2.16kg测量的熔体流动指数(MeltFlow Index,MFI)为最多10g/10min。
令人惊讶的是,本发明的层状材料易于生产、高吹塑比和稳定的吹塑膜性能,具有优异的熔体稳定性,同时可以获得对基材的足够粘合力。
“多层”在本文中被理解为包含至少两层,并且可能包含至少三层或甚至至少四层,并且甚至可以包含多于四层,这取决于层状材料的预期用途。多层中的最大层数取决于预期用途,并且可能高达10层。
“(共)聚酯”在本文中被理解为包含聚酯和共聚酯。
“(共)聚酰胺”在本文中被理解为包含聚酰胺和共聚酰胺。
根据ISO 11357-3:2011在氮气氛下使用差示扫描量热法(differentialscanning calorimetry,DSC)常规测定热塑性材料,特别是共聚酯的熔融温度(Tm)。熔融温度定义为峰值温度,因此是在第二次加热时使用10℃/min的加热速率确定的最高温度熔化峰的相关色谱图中的最大吸热高度。仪器应使用铟标准校准。铝盘用于盛放热塑性共聚酯弹性体的一小部分,优选为5-10mg。以10℃/min的恒定速率将样品加热至高于最高熔融温度至少20℃的温度,优选至至少240℃的温度。然后以10℃/min的速率将样品冷却至至多0℃的温度,更优选至至多-50℃的温度以消除任何可变的热历史。然后将样品以10℃/min的恒定速率再次加热到比最高熔融温度高至少20℃的温度,优选地加热到至少240℃的温度。
图1至图6示意性地表示了层状材料的几个实施方案。虚线表示可以部分或基本上完全嵌入的表面,如分别在图5和图6中进一步表示。
图1表示一种层状材料,包含基材和一个A层。
图2表示一种层状材料,其中在基材和A层之间存在另一个B层。
图3表示类似于图1的层状材料,其中另一个B层存在于基材的对面。
图4表示一种层状材料,其中基材与A层和另一个B层接触。
图5表示其中A层部分嵌入基材中的示意图,如果基材包含空隙,例如在织造或非织造的情况下,则尤其如此。基材以圆圈表示,箭头表示A层的最大厚度。
图6表示其中A层几乎完全嵌入基材中的示意图,如果基材包含空隙,例如在织物或非织物的情况下,尤其是这种情况。基材以圆圈表示,箭头表示A层的最大厚度。
图7提供了SEC色谱图的示例,其中积分限(垂直线)和基线(水平线)设置用于基于折射率(refractive index,RI)和差示粘度色谱图(differential viscositychromatograms,IV-DP)来确定摩尔质量矩(molar mass moment)和摩尔质量分布值。
基材
根据本发明的层状材料包含基材。
“基材”在本文中定义为在其上进行工艺以产生层状材料的材料,优选地,该工艺是粘附膜,更优选地层压膜以产生层状材料。
基材可以选自各种材料和形式并且取决于层状材料的预期用途。基材的形式可以例如为织物、非织物、膜、层压材料、布、板、片材、泡沫和这些的组合。如果例如应用于安全气囊,更优选应用于侧帘式安全气囊,则基材优选地是织物,例如纺织品。
基材可以包含各种材料,例如塑料,包含聚酰胺、聚酯、聚烯烃、聚氨酯,以及它们的共聚物和/或混合物。基材还可以包含其他材料,例如包含木材、棉花、亚麻、玻璃、金属,以及塑料和其他材料的组合。对于在安全气囊中的使用,基材优选地是织物,包含聚酰胺、共聚酰胺、聚酯或共聚酯,更优选聚酯或共聚酯,因为这有利于回收,更优选地,基材是包含(共)聚酯的一片式织物,更优选地基材基本上由(共)聚酯组成。
“一片式织物”(one piece woven,OPW)是一种采用特殊编织技术制成的产品,该技术可以绕过缝纫过程,因此被称为特殊编织技术。OPW能够制造出可以吹成单一编织结构的袋子。
优选地,基材的材料具有根据ISO 11357-3:2011通过DSC测量的熔融温度,该熔融温度高于A层中支化共聚酯的熔融温度,优选高出至少20℃,更优选至少高出30℃。这有利于将A层层压到基材上。如果基材包含各种材料,则基材的熔融温度优选地定义为各个材料的最高熔融温度。
例如如果形式是织物或非织物或泡沫或一片式织物,则基材可以包含空隙。如果将A层直接施加到基材上,则在这种情况下A层可以部分嵌入基材中,这在图5中示意性地表示。在这种情况下,A层的厚度定义为图5中箭头所示的最大厚度。如果将另一个B层直接施加到基材上,则该层也可以部分嵌入基材中。
A层
根据本发明的层状材料包含至少一个A层,也称为“A层”。A层包含支化共聚酯,所述支化共聚酯具有根据ISO 11357-3:2011通过DSC测量的125℃至185℃的熔融温度、至少3.5的Mz/Mw和在190℃下以2.16kg测量的最多10g/10min的MFI。
A层包含至少50wt%的支化共聚酯,更优选至少65wt%的支化共聚酯,甚至更优选至少80wt%的支化共聚酯,其中重量百分比是相对于A层的总重量。A层也可以基本上由支化共聚酯组成。
A层包含支化共聚酯,所述支化共聚酯的融化温度优选在130℃至175℃、更优选在140℃至165℃、甚至更优选在145℃至160℃。支化共聚酯的熔融温度可以通过硬链段和/或软链段的量,以及硬链段和/或软链段的类型来调节。优选地,支化共聚酯包含PBT和PBI作为硬链段,与仅包含PBT作为硬链段的支化共聚酯相比,包含PBT和PBI作为硬链段的支化共聚酯降低了支化共聚酯的熔融温度。
A层可以含有其他添加剂,例如热稳定剂、着色剂、成核剂、UV稳定剂、润滑剂、增塑剂。通常这些另外的添加剂以相对于A层的总重量至多10wt%,优选至多5wt%的量存在于A层中。
A层可以如图1所示的与基材接触,但也可以由如图2所示的被另一个B层隔开。如果基材是编物,则A层也可以部分嵌入基材中。图5示意性地表示了这种特殊情况。A层也可能几乎完全嵌入基材中,如图6示意性地表示的。
A层可以通过各种方法制备,包含例如通过挤出涂布、流延膜工艺、吹膜工艺。优选地,A层通过吹膜工艺制备。令人惊讶的是,A层包含至少50wt%的支化共聚酯,其中wt%是相对于A层的总重量,支化共聚酯具有125℃至185℃的熔融温度,并且具有在190℃下用2.16kg测量的最多10g/10min的MFI,至少3.5的Mz/Mw,允许通过简单的吹膜工艺进行生产。通过吹膜工艺制备的A层的优点是可以省略支撑层,在生产A层时可以使用更高的加工速度,可以获得更低的厚度,和/或可以获得更高的吹胀比,这可以导致更高的膜宽度。A层可以制备为单层,但A层也可以制备为多层,从而包含至少一个另外的B层。
支化共聚酯
A层包含熔融温度为125℃至185℃、Mz/Mw为至少3.5和至多10g/10min的在190℃下以2.16kg测量的MFI的支化共聚酯。
“共聚酯”在本文中被理解为包含聚酯的硬链段和软链段的聚合物。聚酯的硬链段可以例如是聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丙二醇酯(PPT)、聚对苯二甲酸丁二醇酯(PBT)、聚间苯二甲酸丁二醇酯(PBI)、聚间苯二甲酸乙二醇酯(PEI)、聚萘二甲酸乙二醇酯、聚萘二甲酸丁二醇酯和聚萘二甲酸丙二醇酯及其组合。优选地,硬链段是PBT和PBI的组合,因为这很容易获得并且允许共聚酯的较低熔融温度。
软链段可选自多种聚合物,包含例如聚四亚甲基氧化物(polytetramethyleneoxide,PTMO)、聚环氧乙烷(PEO)、聚环氧丙烷(PPO)、聚(环氧乙烷)和聚(环氧丙烷)的嵌段共聚物、线性脂肪族聚碳酸酯、聚己二酸丁二醇酯(PBA)和二聚脂肪酸或二聚脂肪酸二醇的衍生物、线性脂肪族聚酯及其组合。优选地,软链段包含聚四亚甲基氧化物(PTMO),因为这提供了足够的水解稳定性。
支化共聚酯的Mz/Mw为至少3.5,优选至少3.7,更优选至少3.9。支化共聚酯优选的Mw/Mn为至少2.1、更优选至少2.2、甚至更优选至少2.3和最优选至少2.4。Mz/Mw值越高表明支化程度越高,这有利于将支化共聚酯加工成膜。
数均分子量(Mn)、重均分子量(Mw)和Z均分子量(Mz)可以通过如下所述的尺寸排阻(SEC)法测定。用于测定摩尔质量的SEC方法通常在ASTM:D5296–11(2011)中进行了描述。此外,ASTM规范D5226-98(2010)定义了可用于聚合物分析的溶剂。对于热塑性共聚酯弹性体,使用含有0.1wt%三氟乙酸钾的六氟异丙醇溶剂。所有尺寸排阻色谱测量均在配备TDA305三重检测器阵列的Viscotek GPCMax VE2001溶剂/样品模块系统上进行。对于色谱分离,使用了来自PSS Polymer Standards Service GmbH的3个PFG线性XL色谱柱。检测器和色谱柱在35℃下运行。先前的尺寸排阻色谱法,聚合物以1.0至1.5mg/ml的浓度溶解在含有0.1wt%三氟乙酸钾的六氟异丙醇中,该溶液也用作SEC分析中的洗脱液,流速为0.8ml/min。摩尔质量和摩尔质量分布采用三重检测法,使用折射率、差示粘度和直角光散射信号确定。对于分子量平均值和摩尔质量分布的计算,使用范围为0.22至0.24ml/g的折射率(dn/dc)。使用OmniSEC软件4.7版计算摩尔质量矩和摩尔质量分布。折射率由整个折射率色谱图的积分确定。摩尔质量矩和摩尔质量分布计算的积分极限是通过考虑为感兴趣的样品记录的差示粘度色谱图的开始和结束来设置的。图7提供了积分极限设置的示例。有关这些计算的更多详细信息,请参见Niehaus,D.E.,Jackson,C.“Size excludechromatographyof step-growthpolymers with cyclic species:theory model and data analysismethods”,Polymer 41(2000),259-268。
如果A层中存在多种支化共聚酯,则支化共聚酯的总量应为相对于A层的至少50wt%,并且Mz/Mw、Mw/Mn、熔融温度和MFI值应相对于支化共聚酯的总量测量。
如在190℃下用2.16kg测量的,支化共聚酯的MFI为最多10g/10min。MFI可以根据ISO 1133-1程序B进行测量。测量是使用具有约2mm直径开口的标准模具进行的,熔融时间为300秒。称重样品的量在4.5和5.0克之间。在称重之前,将材料在150℃下干燥2小时。优选地,如在190℃下用2.16kg测量的,支化共聚酯具有至多7g/10min的MFI,甚至更优选MFI为至多5g/10min,最优选至多3g/10min,因为这使得更容易处理,特别是当通过吹膜工艺制备时。如果在190℃下用2.16kg测量的MFI非常低,则熔体流动稳定性不足以在此重量下测量,因此必须使用10kg的更高重量。在这种情况下,如在190℃下用10kg测量的,MFI优选为至多25g/10min,更优选至多20g/10min。
支化共聚酯可以通过本身已知的方法制备,包含熔融聚合,通常随后进行熔融整理以获得所需的MFI。其他制备技术包含例如熔融聚合,然后使用具有两个或更多个反应性基团的化合物(例如具有环氧基、碳二亚胺或异氰酸酯基团的化合物)对共聚酯进行反应性挤出。异氰酸酯化合物包含例如亚甲基二苯基二异氰酸酯(MDI)、液化的亚甲基二苯基二异氰酸酯(l-MDI)、聚合MDI、三甲苯二异氰酸酯、联茴香胺二异氰酸酯(dianisidediisocyanate)、二苯醚二异氰酸酯、萘二异氰酸酯、三苯基甲烷三异氰酸酯、三异氰酸酯苯硫代磷酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、赖氨酸二异氰酸酯甲酯、亚甲基二异氰酸酯、2,2,4-三甲基六亚甲基二异氰酸酯、二异氰酸酯二酸酯、异亚丙基双(4-环己基异氰酸酯)、二环己基甲烷二异氰酸酯、甲基环己烷二异氰酸酯等。也可以使用两种或更多种异氰酸酯。这些可以以例如相对于支化共聚酯0.01wt%至2.00wt%的量使用。
通过在制备支化共聚酯的方法中使用支化剂来获得支化。
“支化剂”本身是已知的并且在本文中被理解为具有至少三个能够与单体、低聚物或聚合物反应以在聚合物中引入支化的官能团的分子。支化剂包含例如三羟甲基丙烷(trimethylol propane,TMP)、二(三羟甲基丙烷)、季戊四醇、二季戊四醇、三季戊四醇、偏苯三酸三甲酯、偏苯三酸三丁酯、2-羟甲基-1,3-丙二醇、偏苯三酸三辛酯(Trioctyltrimellitate,TOTM)、偏苯三酸三己酯(trihexyl trimellitate,THTM)。支化剂可以采用相对于支化共聚酯0.01wt%至2.00wt%的量并且取决于所需的支化度。
层状材料
层状材料可以任选地包含一个或多个另外的B层。一个或多个另外的B层可以位于基材与A层之间(图2),但是在A层与基材彼此接触的情况下,一个或多个另外的B层位于A层的相对面(图3)或基材的相对面(图4)。层状材料还可以包含多个另外的B层,例如位于A层两侧相对的位置和/或基材两侧相对的位置。多个另外的B层可以是相同的材料,但也可以包含不同的材料。
B层可以与A层一起制备,因此作为包含至少两个层的膜。B层也可以单独制备,随后在制备层状材料时添加。
B层可以包含各种材料,例如聚酯、共聚酯、聚酰胺、共聚酰胺、热塑性聚氨酯、聚烯烃、接枝聚烯烃以及它们的组合,并且可以是单层的,但也可以是多层的。优选地,B层包含支化共聚酯,因为这具有在吹膜工艺过程中进一步稳定熔体稳定性的优点。甚至更优选地,B层包含熔融温度TmB高于用于A层中的支化共聚酯的Tm的材料,因为这具有以下优点:在层压到基材上时,A层将熔化并部分或可能完全流入基材的开放结构,如图5和图6所示,而B层没有变形并保持其强度。
B层可以包含另外的添加剂,例如热稳定剂、着色剂、成核剂、UV稳定剂、润滑剂、增塑剂。通常这些另外的添加剂以相对于B层的总重量至多10wt%,优选至多5wt%的量存在于B层中。
B层可以通过与上述A层类似的方法制备。优选地,A层和B通过吹膜工艺通过多层膜工艺一起制备。
根据本发明的层状材料可以通过本身已知的方法制备,例如将A层层压到基材上或通过使用粘合剂将A层施加到基材上。
“层压”在本文中被理解为包含加热和施加压力的步骤,其中基材或A层被熔化。优选地,A层和/或B层被熔化并且基材保持基本上固体。最优选地,A层被熔化并且基材保持基本上固体。
包含A层的膜
本发明还涉及一种适用于包含基材的层状材料的膜,该膜包含至少一个A层或由至少一个A层组成,所述A层包含支化共聚酯,所述支化共聚酯的熔融温度为125℃至185℃,Mz/Mw为至少3.5,在190℃下用2.16kg测量的MFI为最多10g/10min。上面明确公开的所有优选和实施方式也涉及该膜,特别是与支化共聚酯有关的优选和实施方式。
优选地,膜的厚度为1*10-5至100*10-3mm,更优选为1*10-5mm至60*10-3mm,甚至更优选为1*10-5mm至50*10-3mm,最优选为1*10-5mm至40*10-3mm。
优选地,该膜通过吹膜工艺制备,因为这使得生产容易。在一个实施方案中,该膜由A层组成。在另一个实施方案中,该膜包含至少一个A层,还包含另一个层,在下文中称为B层。以上提及B层的实施方案也涉及根据本发明包含至少一个A层并且进一步包含B层的膜。
在一个优选的实施方案中,根据本发明的膜包含至少一个A层和B层,并且通过吹膜工艺制备。更优选地,根据本发明的膜包含如上文所公开的至少一个A层和B层,其中B层包含熔融温度TmB高于用于A层中的支化共聚酯的Tm的材料。这具有以下优点:在将包含A层和B层的膜层压到基材上时,A层将熔化并部分或可能完全流入基材的开放结构中,分别如图5和6所示,而B层不会变形并保持其强度。最优选地,B层是(共)聚酯,因为这有利于膜的再循环。
根据本发明的膜可以有利地用于例如需要防护气体和/或液体,或例如防止机械影响的应用中,并且更优选在气囊生产中,最优选在侧帘式气囊的生产中。
优选地,根据本发明的膜包含支化共聚酯或由支化共聚酯组成,其中支化共聚酯包含硬链段和软链段,所述硬链段为聚对苯二甲酸丁二醇酯(PBT)和聚间苯二甲酸丁二醇酯(PBI),所述软链段为聚四亚甲基氧化物(PTMO)、聚环氧乙烷(PEO)、聚环氧丙烷(PPO)、聚(环氧乙烷)和聚(环氧丙烷)的嵌段共聚物、线性脂肪族聚碳酸酯、聚己二酸丁二醇酯(PBA)和二聚脂肪酸或二聚脂肪酸二醇的衍生物、线性脂肪族聚酯及它们的组合。更优选地,软链段是聚四亚甲基氧化物(PTMO)。
层状材料适用于广泛的应用,包含例如安全气囊(特别是侧帘式安全气囊)、屋顶、房屋包裹应用、保护膜和医疗应用(例如消毒被单)。
实施例
对比材料A是4056;可从杜邦获得。4056是一种热塑性共聚醚酯,基于PBT/PBI硬链段和聚四亚甲基氧化物(PTMO)软链段,分子量为1000。4056的熔融温度为150℃,MFI为5g/10min(2.16kg,190℃,ISO 1133-1,程序B)。
对比材料B是具有PBT/PBI硬链段和分子量为1000的聚四亚甲基氧化物(PTMO)作为软链段的共聚酯。对比材料B具有162℃的熔融温度和4.5的MFI(2.16kg,190℃,ISO1133-1,程序B)。对比材料B以两步法制成。首先,使用本领域技术人员已知的熔融聚合工艺以相对低的粘度生产基础聚合物。在第二步中,使用不同量的液态二苯基亚甲基二异氰酸酯(l-MDI)进行反应性挤出以增加粘度以实现表1中指定的所需MFI。反应性挤出过程在ZSK40MC+挤出机上进行,操作温度为200rpm,通量为54kg/hr,机筒温度为250℃。对比材料B具有0.56wt%的l-MDI含量。
材料1-4是通过在反应挤出装置的进料喉处将支化剂添加到对比材料B中并增加1-MDI的量来制备的。
材料1含有0.4m/m%三羟甲基作为支化剂、1.3至1.5m/m%l-MDI和100–0.4–[l-MDI-材料1]+[l-MDI-对比B]m/m%对比材料B。
材料2、3和4含有0.3m/m%季戊四醇作为支化剂,1.2至1.6m/m%l-MDI和100-0.3-[l-MDI-材料]+[l-MDI-对比B]m/m%对比材料B。
材料2具有1.55wt%的l-MDI,材料4具有1.25wt%的l-MDI,材料1和3均具有1.45wt%的l-MDI,其中wt%是相对于材料的总量。
测试材料的熔体强度通常根据ISO 16790:2005使用Rheotens测试来确定。Rheotens测试展示了熔融聚合物的可拉伸性,这对于许多工业过程(例如挤出、纤维纺丝、吹膜、吹塑等)很重要。高熔体强度表明在吹膜工艺过程中具有良好的气泡稳定性和/或较高的吹胀比。
用于测量熔体强度的实验装置构成为毛细管挤出流变仪、Rheograph 75和Rheotens设备,Rheotens 71.97,制造商:作为卷取装置(take up device)。Rheotens 71.97的测力范围为0–2.0N,分辨率为1mN。此处呈现的熔体强度结果遵循以下测量方案。首先,将样品在80℃下真空干燥至少14小时。然后将颗粒送入(填充时间<1分钟)到毛细管流变仪的预热流变仪烘箱(T=190℃,直径=12mm)中,然后等待5分钟,使颗粒熔化。毛细管模头用于所有L/D=30/2mm和平坦入口角(180°)的材料,从而将熔体挤出成细丝。流变仪的活塞速度设置为Vpiston=0.049mm/s,这导致细丝速度(filament velocity)为1.8mm/s。模具出口和卷取轮(take-up wheel)之间的下拉距离设置为10cm以允许等温条件。轮间隙设置为0.2mm,并在轮子上喷洒硅油以防止挤出线材粘连。实验室温度和湿度分别控制在22±2℃、45±5rH。在实验开始时,Rheotens轮的卷取速度设置为细丝的出口速度,导致张力为零。卷取轮的加速度设置为1.2mm/s2,因此速度开始缓慢增加,直到聚合物细丝断裂。分析了产生的张力与牵伸速度的关系,并报告了相应的熔体强度值。对于每个样品,熔体强度测量被重复至少3次,熔体强度值的平均值和标准偏差报告在表1中。还研究了熔体强度与温度的相关性,并注意到在流变仪烘箱中,随着温度的升高,熔体强度预计会下降。
成功测量了这些材料的拉伸特性,即熔体强度,但无法报告拉伸比,因为所有细丝都开始以高速粘在轮子上。在所有实验中都获得了稳定的张力,因此可以报告绝对熔体强度值。没有观察到细丝断裂,因此未报告任何材料的牵伸比。
表1材料
材料1至4可以适合用于吹膜工艺,而不需要支撑层和/或可以以较低厚度存在以获得根据本发明的膜。令人惊奇的是,可以通过吹膜工艺制备膜而不需要支撑层,或者可以制备具有较低厚度的膜。可以将这些膜层压到基材上,从而获得根据本发明的层状材料。
令人惊讶的是,与对比材料A和B相比,材料1和2的熔体强度要高得多。当材料用于吹膜工艺时,熔体强度是预期的吹胀比和气泡稳定性的指标。
Claims (15)
1.一种层状材料,其包含基材和至少一个A层,其中所述至少一个A层包含至少50wt%的支化共聚酯,其中wt%是相对于A层的总重量,所述支化共聚酯的熔融温度为125℃至185℃,Mz/Mw为至少3.5,并且在190℃下用2.16kg测量的熔体流动指数(MFI)为最多10g/10min。
2.根据权利要求1所述的层状材料,其中,A层粘附到所述基材上。
3.根据权利要求1所述的层状材料,其中,所述至少一个A层的最大厚度为1*10-5mm至100*10-3mm。
4.根据权利要求1所述的层状材料,所述层状材料还包含B层,所述B层包含聚酯、共聚酯、聚酰胺、共聚酰胺、热塑性聚氨酯、聚烯烃以及它们的组合。
5.根据权利要求4所述的层状材料,其中B层粘附到A层上。
6.根据权利要求5所述的层状材料,其中A层粘附到基材上。
7.根据前述权利要求中任一项所述的层状材料,其中A层包含至少80wt%的支化共聚酯,其中wt%是相对于A层的总重量。
8.根据前述权利要求中任一项所述的层状材料,其中A层包含支化共聚酯,所述支化共聚酯包含硬链段和软链段,所述硬链段为聚对苯二甲酸丁二醇酯(PBT)和聚间苯二甲酸丁二醇酯(PBI),所述软链段为聚四亚甲基氧化物(PTMO)、聚环氧乙烷(PEO)、聚环氧丙烷(PPO)、聚(环氧乙烷)和聚(环氧丙烷)的嵌段共聚物、线性脂肪族聚碳酸酯、聚己二酸丁二醇酯(PBA)和二聚脂肪酸或二聚脂肪酸二醇的衍生物、线性脂肪族聚酯以及它们的组合。
9.一种制备根据前述权利要求中任一项所述的层状材料的方法,所述方法包含将包含A层的膜层压到基材上的步骤。
10.根据权利要求9所述的方法,其中所述包含A层的膜通过吹膜工艺制备。
11.一种膜,其包含至少一个A层或由至少一个A层组成,所述A层包含至少50wt%的支化共聚酯,其中wt%是相对于所述层的总重量,其中所述支化共聚酯的熔融温度为125℃至185℃,Mz/Mw为至少3.5,并且在190℃下用2.16kg测量的熔体流动指数(MFI)为最多10g/10min。
12.根据权利要求11所述的膜,其中所述至少一个A层包含至少80wt%的支化共聚酯,其中wt%是相对于所述层的总重量。
13.根据权利要求11或12所述的膜,其中所述支化共聚酯的熔融温度为140℃至160℃,并且在190℃下用2.16kg测量的熔体流动指数(MFI)为最多5g/10min。
14.根据权利要求11至13中任一项所述的膜,其中所述支化共聚酯包含硬链段和软链段,所述硬链段为聚对苯二甲酸丁二醇酯(PBT)和聚间苯二甲酸丁二醇酯(PBI),所述软链段为聚四亚甲基氧化物(PTMO)、聚环氧乙烷(PEO)、聚环氧丙烷(PPO)的软链段、聚(环氧乙烷)和聚(环氧丙烷)的嵌段共聚物、线性脂肪族聚碳酸酯,聚己二酸丁二醇酯(PBA)和二聚脂肪酸或二聚脂肪酸二醇的衍生物、线性脂肪族聚酯以及它们的组合。
15.根据权利要求14所述的膜,其中所述软链段包含聚四亚甲基氧化物(PTMO)或由聚四亚甲基氧化物(PTMO)组成。
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CN101868486A (zh) * | 2007-11-21 | 2010-10-20 | 帝斯曼知识产权资产管理有限公司 | E级区段的缆线和管件 |
CN101868351A (zh) * | 2007-11-21 | 2010-10-20 | 帝斯曼知识产权资产管理有限公司 | 多层结构 |
CN101981081A (zh) * | 2008-03-26 | 2011-02-23 | 诺瓦蒙特股份公司 | 可生物降解聚酯,其制备方法及包含所述聚酯的产品 |
WO2018230722A1 (ja) * | 2017-06-16 | 2018-12-20 | 日東電工株式会社 | 多層フィルム、積層体、エアバッグ、及び積層体の製造方法 |
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DE29906538U1 (de) | 1999-04-13 | 1999-09-30 | Trw Repa Gmbh | Textiles Gassack-Material |
EP3689606B1 (en) | 2017-06-16 | 2022-08-10 | ZF Automotive Germany GmbH | Multilayer film, laminate, airbag, and method of manufacturing laminate |
-
2021
- 2021-01-26 EP EP21702013.0A patent/EP4096916B1/en active Active
- 2021-01-26 CN CN202180008159.6A patent/CN114929471B/zh active Active
- 2021-01-26 JP JP2022541893A patent/JP2023510762A/ja active Pending
- 2021-01-26 US US17/795,134 patent/US20230052428A1/en active Pending
- 2021-01-26 KR KR1020227029069A patent/KR20220133236A/ko unknown
- 2021-01-26 WO PCT/EP2021/051760 patent/WO2021151892A1/en unknown
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JPH1019126A (ja) * | 1996-07-04 | 1998-01-23 | Naberu:Kk | 蛇 腹 |
EP1518761A1 (de) * | 2003-09-16 | 2005-03-30 | Collano Xiro AG | Verbundschichtmaterial insbesondere für einen Airbag, und Verfahren zu dessen Herstellung, Airbag, Passivrückhaltesysteme mit Airbag, sowie gasdichter Polyamidpolymerfilm |
EP1731302A1 (en) * | 2005-06-06 | 2006-12-13 | DSM IP Assets B.V. | Process for making a layered structure |
EP1764212A1 (de) * | 2005-09-17 | 2007-03-21 | Epurex Films GmbH & Co. KG | Thermoplastischer Materialverbund, Verfahren zu seiner Herstellung sowie seine Verwendung |
CN101868486A (zh) * | 2007-11-21 | 2010-10-20 | 帝斯曼知识产权资产管理有限公司 | E级区段的缆线和管件 |
CN101868351A (zh) * | 2007-11-21 | 2010-10-20 | 帝斯曼知识产权资产管理有限公司 | 多层结构 |
CN101981081A (zh) * | 2008-03-26 | 2011-02-23 | 诺瓦蒙特股份公司 | 可生物降解聚酯,其制备方法及包含所述聚酯的产品 |
CN104448281A (zh) * | 2008-03-26 | 2015-03-25 | 诺瓦蒙特股份公司 | 可生物降解聚酯,其制备方法及包含所述聚酯的产品 |
DE102008038375A1 (de) * | 2008-08-19 | 2010-02-25 | Epurex Films Gmbh & Co. Kg | Thermoplastische Mehrschichtfolie zur Gewebekaschierung und ein Verfahren zu ihrer Herstellung |
WO2018230722A1 (ja) * | 2017-06-16 | 2018-12-20 | 日東電工株式会社 | 多層フィルム、積層体、エアバッグ、及び積層体の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
US20230052428A1 (en) | 2023-02-16 |
WO2021151892A1 (en) | 2021-08-05 |
EP4096916B1 (en) | 2023-11-08 |
KR20220133236A (ko) | 2022-10-04 |
CN114929471B (zh) | 2024-02-20 |
EP4096916A1 (en) | 2022-12-07 |
JP2023510762A (ja) | 2023-03-15 |
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