CN111183019A - 芳纶织物、芳纶织物制备方法、芳纶织物预浸料、芳纶织物/热塑性聚氨酯基体树脂复合物 - Google Patents
芳纶织物、芳纶织物制备方法、芳纶织物预浸料、芳纶织物/热塑性聚氨酯基体树脂复合物 Download PDFInfo
- Publication number
- CN111183019A CN111183019A CN201880063229.6A CN201880063229A CN111183019A CN 111183019 A CN111183019 A CN 111183019A CN 201880063229 A CN201880063229 A CN 201880063229A CN 111183019 A CN111183019 A CN 111183019A
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- Prior art keywords
- aramid fabric
- aramid
- impregnated
- fabric
- attached
- 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.)
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- 239000011159 matrix material Substances 0.000 title claims abstract description 70
- 239000000805 composite resin Substances 0.000 title claims description 52
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- 238000002360 preparation method Methods 0.000 title description 5
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 82
- 229920005989 resin Polymers 0.000 claims abstract description 66
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 19
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- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
Images
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Abstract
通过包括以下步骤的方法来制备具有对聚氨酯基体树脂的优异的粘合性和优异的拉伸强度优异的芳纶织物:(i)使用芳纶纱线作为经纱和纬纱来编织方平结构的芳纶织物;然后(ii)将所编织的芳纶织物浸入由作为上浆剂的水性聚氨酯树脂和水组成的上浆剂溶液中,然后进行挤压和干燥。在本发明中,将上浆剂施加到所编织的芳纶织物,从而与在编织之前将上浆剂施加到芳纶纱线的方法相比,可以有效防止由于在编织过程中上浆剂的分离而导致的编织效率的降低。此外,在本发明中,将水性聚氨酯树脂附着或浸渍到芳纶织物的表面和内部中,因此改善了芳纶织物对聚氨酯基体树脂的粘合性,并且增加了芳纶织物中芳纶纱线的内聚力,从而增强了芳纶织物的拉伸强度。
Description
技术领域
本公开涉及一种具有对于聚氨酯基体树脂的优异的粘合性以及优异的拉伸强度的芳纶织物、该芳纶织物的制备方法、包括该芳纶织物的芳纶织物预浸料及包括该芳纶织物的芳纶织物/热塑性聚氨酯树脂复合物,更特别地,本公开涉及一种芳纶织物及该芳纶织物的制备方法,该芳纶织物可以增加构成芳纶织物的芳纶纱线的内聚力并因此增强芳纶织物的拉伸强度,该芳纶织物可以改善编织性能而不会在编织过程中引起上浆剂的脱落现象,并且可以增强对于聚氨酯基体树脂的粘合性。
本公开还涉及一种芳纶织物预浸料,其中芳纶织物用未固化或半固化的状态的聚氨酯基体树脂浸渍。
本公开还涉及由芳纶织物/热塑性聚氨酯基体树脂构成的复合物,该复合物通过包括芳纶织物而具有优异的抗冲击性、拉伸强度和拉伸弹性模量。
背景技术
作为电子部件材料或汽车部件材料,已经广泛使用聚氨酯基体树脂在增强纤维材料中被浸渍并固化的增强纤维材料/树脂复合物(以下称为“复合物”)。
玻璃纤维已经被用作增强纤维材料,但是玻璃纤维具有大比重,这使得难以减轻重量,并且存在对人体有害的问题。
在另一常规技术中,为了解决该问题,已使用碳纤维作为增强纤维材料,而不使用玻璃纤维,但是碳纤维具有非刚性较大的问题,因此可加工性和抗冲击性降低。
作为又一常规技术,用平纹组织编织的芳纶织物已主要用作增强纤维材料,但是用平纹组织编织的芳纶织物对聚氨酯基体树脂的润湿性差,并且构成常规芳纶织物的芳纶纱线具有与聚氨酯基体树脂的相容性降低的问题,这导致芳纶织物与聚氨酯基体树脂之间的粘合性降低,进一步,存在构成芳纶织物的纱线之间的内聚力不足并因此芳纶织物的拉伸强度降低的问题。
发明内容
技术问题
本公开的目的是提供一种芳纶织物的制备方法,该芳纶织物对浸渍在芳纶织物中的聚氨酯基体树脂的润湿性优异,使得芳纶织物与聚氨酯基体树脂之间的粘合性优异,同时增加芳纶织物中纱线的内聚力,并且表现出优异的芳纶织物拉伸强度,并因此该芳纶织物可用作纤维增强复合材料。
本公开的另一个目的是提供一种芳纶织物及包括该芳纶织物的芳纶织物预浸料,该芳纶织物通过上述方法制备,并且具有对于聚氨酯基体树脂优异的粘合性以及优异的拉伸强度。
本公开的又一个目的是提供一种芳纶织物/热塑性聚氨酯基体树脂复合物,其具有优异的拉伸强度和拉伸弹性模量,并且在抗冲击性方面也特别优异,因此可用作要求优异的抗冲击性的汽车部件材料。
技术方案
为了实现上述目的,在本公开的一个方面中,通过包括以下步骤的方法来制备具有对于聚氨酯基体树脂优异的粘合性以及优异的拉伸强度的芳纶织物:(i)使用芳纶纱线作为经纱和纬纱来编织方平组织芳纶织物(basket weave aramid fabric);以及(ii)将所编织的芳纶织物浸入由作为上浆剂(sizing agent)的水性聚氨酯树脂和水构成的上浆剂溶液中,然后挤压和干燥,从而将上浆剂溶液附着并浸渍到芳纶织物,其中,基于附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的重量、以及在水性聚氨酯树脂附着于并浸渍之前的芳纶织物的重量的总和,将附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的含量调整为1重量%至8重量%。
在本公开的另一方面,通过使用表面和内部附着/浸渍有水性聚氨酯树脂的两个以上的方平组织芳纶织物作为构成芳纶织物/热塑性聚氨酯树脂复合物的增强纤维材料,并且使用热塑性聚氨酯树脂作为构成复合物的基体树脂来制备芳纶织物/热塑性聚氨酯基体树脂复合物。
有益效果
在本公开中,由于将上浆剂涂覆到所编织的芳纶织物,因此,与在编织之前将上浆剂涂覆到芳纶纱线的方法相比,可以有效地防止由于在编织过程中上浆剂(size agents)的脱落引起的编织效率的降低。
另外,在本公开中,由于水性聚氨酯树脂附着或浸渍到芳纶织物的表面和内部中,因此芳纶织物对聚氨酯基体树脂的粘合性得到改善,并且芳纶织物中芳纶纱线的内聚力提高,从而芳纶织物的拉伸强度增强。
此外,在本公开中,由于将芳纶织物编织成方平组织,因此芳纶织物的致密性降低并且芳纶织物对聚氨酯基体树脂的润湿性得到改善,其结果是,芳纶织物与聚氨酯基体树脂之间的粘合性增强。
因此,根据本公开制备的芳纶织物可用作增强纤维材料,以用于在电子部件材料等中使用的增强纤维材料/树脂复合物的制备。
此外,由于本公开的芳纶织物/热塑性聚氨酯树脂复合物是其的增强纤维材料的抗冲击性优异的芳纶织物,因此其可用作要求抗冲击性的汽车部件材料,例如汽车保险杠或电子部件材料。
附图说明
图1是根据本公开的芳纶织物的示例的结构图。
具体实施方式
在下文中,将参照附图详细描述本公开。
根据本公开的一种具有对聚氨酯基体树脂的优异的粘合性以及优异的拉伸强度的芳纶织物的制备方法包括:(i)编织步骤,使用芳纶纱线作为经纱和纬纱来编织方平组织芳纶织物;以及(ii)上浆处理步骤,将所编织的芳纶织物浸入由作为上浆剂的水性聚氨酯树脂以及水组成的上浆剂溶液中,然后挤压和干燥,从而将上浆剂溶液附着于并浸渍到芳纶织物,其中,基于附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的重量、以及在水性聚氨酯树脂附着并浸渍之前芳纶织物的重量的总和,将附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的含量调整为1重量%至8重量%。
具体地,根据本公开,通过(i)使用芳纶纱线作为经纱和纬纱来编织方平组织芳纶织物,然后(ii)将所编织的芳纶织物浸入由作为上浆剂的水性聚氨酯树脂以及水组成的上浆剂溶液中,然后挤压和干燥,来制备具有对于聚氨酯基体树脂优异的粘合性以及优异的拉伸强度的芳纶织物。
这时,如图1所示,方平组织为2×2的方平组织,这在降低芳纶织物的致密性以及改善对聚氨酯基体树脂的润湿性方面是优选的。
在本公开中,基于附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的重量、以及在水性聚氨酯树脂附着并浸渍之前芳纶织物的重量的总和,将附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的含量调整为1重量%至8重量%,优选地2重量%至6重量%,从而改善了芳纶织物中纱线的内聚力,并且还改善了芳纶织物与聚氨酯基体树脂之间的粘合性。
水性聚氨酯树脂和水是构成上浆剂溶液的上浆剂,该水性聚氨酯树脂与水的重量比优选为1.8:1至2.2:1,这在赋予上浆剂以及提高可加工性方面是优选的。
当挤压在上浆剂溶液中进行浸渍处理后的芳纶织物时,优选使用轧布机等施加1kgf/cm2至2kgf/cm2的压力,然后将挤压后的芳纶织物在110℃至130℃的温度下干燥3分钟至5分钟。
本公开的芳纶织物具有以下的具体特征:作为芳纶纱线的经纱和纬纱被编织成方平组织,水性聚氨酯树脂附着于并浸渍到芳纶织物的表面和内部中,并且基于附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的重量、以及在水性聚氨酯树脂附着并浸渍之前芳纶织物的重量的总和,附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的含量为1重量%至8重量%。
这时,如图1所示,方平组织为2×2的方平组织,这在降低芳纶织物的致密性(compactness)以及改善对聚氨酯基体树脂的润湿性方面是优选的。
另外,构成芳纶织物的芳纶纱线具有1000旦尼尔至3000旦尼尔的纤度,并且经纱密度和纬纱密度为10至20根纱线/英寸,这在改善芳纶织物的拉伸强度方面是优选的。
如通过ASTM D 3039的方法所测得的,芳纶织物具有19,000至21,000N/5cm的优异的拉伸强度。
本公开的芳纶织物预浸料包括:(i)芳纶织物,所述芳纶织物具有作为芳纶纱线的经纱和纬纱被编织成方平组织的纹理,并且在所述芳纶织物中水性聚氨酯树脂附着于并浸渍到织物的表面和内部中;以及(ii)聚氨酯基体树脂,所述聚氨酯基体树脂浸渍在芳纶织物中并且处于未固化或半固化的状态,其中,基于附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的重量、以及在水性聚氨酯树脂附着并浸渍之前芳纶织物的重量的总和,附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的含量为1重量%至8重量%,优选地2重量%至6重量%。
基于附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的重量、以及在水性聚氨酯树脂附着并浸渍之前芳纶织物的重量的总和,附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的含量为1重量%至8重量%,优选地2重量%至6重量%,这在增加芳纶织物中纱线的内聚力和改善芳纶织物与聚氨酯基体树脂之间的粘合性方面是优选的。
根据本公开,由于将上浆剂涂覆到所编织的芳纶织物,因此,与在编织之前上浆剂涂覆到芳纶纱线的方法相比,可以有效地防止由于在编织过程中上浆剂的脱落引起的编织效率的降低。
另外,在本公开中,由于水性聚氨酯树脂附着于或浸渍到芳纶织物的表面和内部中,因此芳纶织物对聚氨酯基体树脂的粘合性得到改善,并且芳纶织物中芳纶纱线的内聚力增大,从而芳纶织物的拉伸强度增强。
此外,在本公开中,由于芳纶织物编织成方平组织,因此芳纶织物的致密性降低并且芳纶织物对聚氨酯基体树脂的润湿性得到改善,其结果是,芳纶织物与聚氨酯基体树脂之间的粘合性增强。
因此,根据本公开制备的芳纶织物可用作增强纤维材料,以用于在电子部件材料等中使用的增强纤维材料/树脂复合物的制备。
本公开的芳纶织物/热塑性聚氨酯树脂复合物包括:(i)两个以上芳纶织物,所述两个以上芳纶织物具有作为芳纶纱线的经纱和纬纱被编织成方平组织的纹理,并且在所述两个以上芳纶织物中水性聚氨酯树脂附着于并浸渍到织物的表面和内部中;以及(ii)聚氨酯基体树脂,所述聚氨酯基体树脂浸渍在芳纶织物中并且位于芳纶织物之间,其中,基于附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的重量、以及在水性聚氨酯树脂附着并浸渍之前芳纶织物的重量的总和,附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的含量为1重量%至8重量%,其中,通过ISO-6603的方法测得的峰值力为18,000N以上。
另外,本公开的复合物具有通过ASTM D 3039的方法测得的600MPa以上的拉伸强度和25GPa以上的拉伸弹性模量,并因此具有优异的拉伸强度和拉伸弹性模量。
在本公开的一个实施例中,当复合物的厚度为2.0mm至2.2mm,并且热塑性聚氨酯基体树脂的含量为30重量%至45重量%时,(i)峰值力约为18845N,这在抗冲击性方面是优异的,(ii)通过ASTM D 3039的方法测得的拉伸强度约为635MPa,并且(iii)通过ASTM D3039的方法测得的拉伸弹性模量约为31GPa,这在拉伸强度和拉伸弹性模量方面是优异的,并且在抗冲击性方面也特别优异。
如图1所示,方平组织为2×2的方平组织,这在降低芳纶织物的致密性以及改善对聚氨酯基体树脂的润湿性方面是优选的。
另外,构成芳纶织物的芳纶纱线具有1000旦尼尔至3000旦尼尔的纤度,并且经纱密度和纬纱密度为10至20根纱线/英寸,这在改善芳纶织物的拉伸强度方面是优选的。
基于附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的重量、以及在水性聚氨酯树脂附着并浸渍之前芳纶织物的重量的总和,附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的含量为1重量%至8重量%,优选地2重量%至6重量%,这在改善芳纶织物中纱线的内聚力以及改善芳纶织物与聚氨酯基体树脂之间的粘合性方面是优选的。
接下来,将描述本公开的复合物的制备方法的示例。
用于根据本公开的芳纶织物/热塑性聚氨酯复合物的制备方法包括:(i)使用芳纶纱线作为经纱和纬纱来编织方平组织芳纶织物的步骤;(ii)上浆处理步骤,将所编织的芳纶织物浸入由作为上浆剂的水性聚氨酯树脂以及水组成的上浆剂溶液中,然后挤压和干燥,从而将上浆剂溶液附着于并浸渍到芳纶织物,其中,基于附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的重量、以及在水性聚氨酯树脂附着并浸渍之前芳纶织物的重量的总和,将附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的含量调整为1重量%至8重量%;(iii)将热塑性聚氨酯基体树脂浸渍到上浆剂附着并浸渍于的芳纶织物中以制备芳纶织物预浸料的步骤;以及(iv)层叠两个以上的芳纶织物预浸料,然后对其进行加热和按压以制备芳纶织物/热塑性聚氨酯树脂复合物的步骤。
具体地,在本公开中,首先使用芳纶纱线作为经纱和纬纱来编织方平组织芳纶织物。
这时,如图1所示,方平组织为2×2的方平组织,这在降低芳纶织物的致密性以及改善对聚氨酯基体树脂的润湿性方面是优选的。
芳纶纱线的纤度为1000旦尼尔至7000旦尼尔,优选地1000旦尼尔至4000旦尼尔,并且芳纶织物的经纱密度和纬纱密度为10至20根纱线/英寸,这在改善芳纶织物的拉伸强度等方面是优选的。
接下来,将所编织的芳纶织物浸入由作为上浆剂的水性聚氨酯树脂以及水组成的上浆剂溶液中,然后挤压和干燥,从而将上浆剂溶液附着于并浸渍到芳纶织物。
此时,基于附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的重量、以及在水性聚氨酯树脂附着并浸渍之前芳纶织物的重量的总和,附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的含量为1重量%至8重量%,优选地2重量%至6重量%,这在提高芳纶织物中纱线的内聚力以及改善芳纶织物与聚氨酯基体树脂之间的粘合性方面是优选的。
水性聚氨酯树脂和水是构成上浆剂溶液的上浆剂,水性聚氨酯树脂与水的重量比优选为1.8:1至2.2:1,这在赋予上浆剂以及提高可加工性方面是优选的。
当挤压在上浆剂溶液中进行浸渍处理后的芳纶织物时,优选使用轧布机等施加1kgf/cm2至2kgf/cm2的压力,然后将挤压后的芳纶织物在110℃至130℃的温度下干燥3分钟至5分钟。
接下来,通过将热塑性聚氨酯基体树脂浸渍到上浆剂附着并浸渍于的芳纶织物中来制备芳纶织物预浸料。
此时,由于使用热塑性聚氨酯树脂作为基体树脂,而不使用热固性聚氨酯树脂,因此可以大幅提高复合物的拉伸强度、拉伸弹性模量和抗冲击性。
接下来,将两个以上的芳纶织物预浸料层叠,然后加热并按压以制备芳纶织物/热塑性聚氨酯树脂复合物。
此时,所层叠的芳纶预浸料的数量为2至8,这在提高轻量(lightness)和抗冲击性方面是优选的,但是所层叠的芳纶预浸料的数量可以根据复合物的用途进行调整。
由于本公开使用抗冲击性优异的芳纶织物作为增强纤维材料,因此复合物的抗冲击性进一步得到改善。
另外,在本公开中,由于作为上浆剂的水性聚氨酯树脂附着于或浸渍到芳纶织物的表面和内部中,因此与热塑性聚氨酯基体树脂的粘合性得到改善并且芳纶织物中芳纶纱线的内聚力提高,从而芳纶织物的拉伸强度和拉伸弹性模量增强。
此外,在本公开中,由于芳纶织物编织成方平组织,因此芳纶织物的致密性降低并且芳纶织物对聚氨酯基体树脂的润湿性得到改善,其结果是,芳纶织物与聚氨酯基体树脂之间的粘合性增强。
因此,本公开的芳纶织物/热塑性聚氨酯树脂复合物可用作要求抗冲击性的汽车部件材料,例如汽车保险杠或电子部件材料。
在下文中,将参照实施例和比较例更详细地描述本公开。
以下实施例是本公开的优选实施例,并且本公开的范围不仅限于这些实施例。
实施例1
使用3000旦尼尔的芳纶纱线作为经纱和纬纱来编织2×2的方平组织芳纶织物。
此时,经纱密度和纬纱密度分别设定为17根纱线/英寸。
接下来,将上述编织的芳纶织物浸入由100重量份的水性聚氨酯树脂(上浆剂)和50重量份的水组成的上浆剂溶液中,然后使用轧布机在1.5kgf/cm2的压力下对其进行按压,并在120℃下干燥4分钟,以制备上浆剂处理后的芳纶织物。
此时,基于附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的重量、以及在水性聚氨酯树脂附着并浸渍之前芳纶织物的重量的总和,将附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的含量调整为3wt%。
接下来,在将上述的上浆剂处理后的芳纶织物用35wt%的聚氨酯树脂(基体树脂)浸渍以制备芳纶织物预浸料之后,层叠五个芳纶织物预浸料,然后加热/加压而成型以制备增强纤维材料/树脂复合物。
测量所制备的芳纶织物的拉伸强度和增强纤维材料/树脂复合物的弹性模量,结果示于下表1中。
比较例1
使用3000旦尼尔的芳纶纱线作为经纱和纬纱来编织平纹组织芳纶织物。
此时,经纱密度和纬纱密度分别设定为17根纱线/英寸。
接下来,将如上所述编织的芳纶织物浸入由100重量份的水性聚氨酯树脂(上浆剂)和50重量份的水组成的上浆剂溶液中,然后使用轧布机在1.5kgf/cm2的压力下对其进行按压,并在120℃下干燥4分钟,以制备上浆剂处理后的芳纶织物。
此时,基于附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的重量、以及在水性聚氨酯树脂附着并浸渍之前芳纶织物的重量的总和,将附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的含量调整为3wt%。
接下来,在将如上所述的上浆剂处理后的芳纶织物用35wt%的聚氨酯树脂(基体树脂)浸渍以制备芳纶织物预浸料后,层叠五个芳纶织物预浸料,然后加热/加压而成型以制备增强纤维材料/树脂复合物。
测量所制备的芳纶织物的拉伸强度和增强纤维材料/树脂复合物的弹性模量,结果示于下表1中。
比较例2
使用3000旦尼尔的芳纶纱线作为经纱和纬纱来编织斜纹组织芳纶织物。
此时,经纱密度和纬纱密度分别设定为17根纱线/英寸。
接下来,将如上所述编织的芳纶织物浸渍在由100重量份的水性聚氨酯树脂(上浆剂)和50重量份的水组成的上浆剂溶液中,然后使用轧布机在1.5kgf/cm2的压力下对其进行按压,并在120℃下干燥4分钟,以制备上浆剂处理后的芳纶织物。
此时,基于附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的重量、以及在水性聚氨酯树脂附着并浸渍之前芳纶织物的重量的总和,将附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的含量调整为3wt%。
接下来,在将上述的上浆剂处理后的芳纶织物用35wt%的聚氨酯树脂(基体树脂)浸渍以制备芳纶织物预浸料之后,层叠五个芳纶织物预浸料,然后加热/加压而成型,以制备增强纤维材料/树脂复合物。
测量所制备的芳纶织物的拉伸强度和增强纤维材料/树脂复合物的弹性模量,结果示于下表1中。
比较例3
使用3000旦尼尔的芳纶纱线作为经纱和纬纱来编织2×2的方平组织芳纶织物。
此时,经纱密度和纬纱密度分别设定为17根纱线/英寸。
接下来,将如上编织的芳纶织物(未用上浆剂处理)用35重量份的聚氨酯树脂(基体树脂)浸渍以制备芳纶织物预浸料,然后层叠五个芳纶织物预浸料,然后加热/加压而成型以制备增强纤维材料/树脂复合物。
测量所制备的芳纶织物的拉伸强度和增强纤维材料/树脂复合物的弹性模量,结果示于下表1中。
[表1]
通过ASTM D 3039的方法测量表1中记载的芳纶织物的拉伸强度和增强纤维材料/树脂复合物的弹性模量。
实施例1中制备的芳纶织物的拉伸强度优异,但是比较例1至比较例3中制备的芳纶织物的拉伸强度与实施例1相比较差。
另外,实施例1中制备的复合物的弹性模量优异,但是比较例1至比较例3中制备的复合物的弹性模量与实施例1相比较差。
实施例2
使用3000旦尼尔的芳纶纱线作为经纱和纬纱来编织2×2的方平组织芳纶织物。
此时,经纱密度和纬纱密度分别设定为17根纱线/英寸。
接下来,将如上述编织的芳纶织物浸入由100重量份的水性聚氨酯树脂(上浆剂)和50重量份的水组成的上浆剂溶液中,然后使用轧布机在1.5kgf/cm2的压力下按压,并在120℃下干燥4分钟,以制备上浆剂处理后的芳纶织物。
此时,基于附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的重量、以及在水性聚氨酯树脂附着并浸渍之前芳纶织物的重量的总和,将附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的含量调整为3wt%。
接下来,在将上述的上浆剂处理后的芳纶织物用35wt%的聚氨酯树脂(基体树脂)浸渍以制备芳纶织物预浸料之后,层叠四个芳纶织物预浸料,然后加热/加压而成型以制备厚度为2.1mm的增强纤维材料/树脂复合物。
测量所制备的芳纶织物/热塑性聚氨酯树脂复合物的拉伸强度、拉伸弹性模量和峰值力,结果示于下表2中。
比较例4
使用3000旦尼尔的芳纶纱线作为经纱和纬纱来编织1×1的平纹组织芳纶织物。
此时,经纱密度和纬纱密度分别设定为17根纱线/英寸。
接下来,将如上述编织的芳纶织物浸入由100重量份的水性聚氨酯树脂(上浆剂)和50重量份的水组成的上浆剂溶液中,然后使用轧布机在1.5kgf/cm2的压力下对其进行按压,并在120℃下干燥4分钟,以制备上浆剂处理后的芳纶织物。
此时,基于附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的重量、以及在水性聚氨酯树脂附着并浸渍之前芳纶织物的重量的总和,将附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的含量调整为3wt%。
接下来,在将上述的上浆剂处理后的芳纶织物用35wt%的聚氨酯树脂(基体树脂)浸渍以制备芳纶织物预浸料后,层叠四个芳纶织物预浸料,然后加热/加压而成型,以制备厚度为2.1mm的增强纤维材料/树脂复合物。
测量所制备的芳纶织物/热塑性聚氨酯树脂复合物的拉伸强度、拉伸弹性模量和峰值力,结果示于下表2中。
比较例5
使用3000旦尼尔的芳纶纱线作为经纱和纬纱来编织斜纹组织碳纤维织物。
此时,经纱密度和纬纱密度分别设定为17根纱线/英寸。
接下来,将如上述编织的碳纤维织物浸入由100重量份的水性聚氨酯树脂(上浆剂)和50重量份的水组成的上浆剂溶液中,然后使用轧布机在1.5kgf/cm2的压力下对其进行按压,并在120℃下干燥4分钟,以制备上浆剂处理后的芳纶织物。
此时,基于附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的重量、以及在水性聚氨酯树脂附着并浸渍之前碳纤维织物的重量的总和,将附着于并浸渍到碳纤维织物的表面和内部的水性聚氨酯树脂的含量调整为3wt%。
接下来,在将上述的上浆剂处理后的碳纤维织物用35wt%的聚氨酯树脂(基体树脂)浸渍以制备碳纤维织物预浸料之后,层叠四个碳纤维织物预浸料,然后加热/加压而成型,以制备厚度为2.1mm的增强纤维材料/树脂复合物。
测量所制备的芳纶织物/热塑性聚氨酯树脂复合物的拉伸强度、拉伸弹性模量和峰值力,结果示于下表2中。
比较例6
使用3000旦尼尔的芳纶纱线作为经纱和纬纱来编织斜纹组织芳纶织物。
此时,经纱密度和纬纱密度分别设定为17根纱线/英寸。
接下来,将如上述编织的碳纤维织物浸入由100重量份的水性聚氨酯树脂(上浆剂)和50重量份的水组成的上浆剂溶液中,然后使用轧布机在1.5kgf/cm2的压力下对其进行按压,并在120℃下干燥4分钟,以制备上浆剂处理后的芳纶织物。
此时,基于附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的重量、以及在水性聚氨酯树脂附着并浸渍之前碳纤维织物的重量的总和,将附着于并浸渍到碳纤维织物的表面和内部中的水性聚氨酯树脂的含量调整为3wt%。
接下来,在将上述的上浆剂处理后的碳纤维织物用35wt%的聚氨酯树脂(基体树脂)浸渍以制备碳纤维织物预浸料之后,层叠九个碳纤维织物预浸料,然后加热/加压而成型,以制备厚度为2.0mm的增强纤维材料/树脂复合物。
测量所制备的碳纤维织物/热塑性聚氨酯树脂复合物的拉伸强度、拉伸弹性模量和峰值力,结果示于下表2中。
比较例7
使用3000旦尼尔的芳纶纱线作为经纱和纬纱来编织2×2的方平组织芳纶织物。
此时,经纱密度和纬纱密度分别设定为17根纱线/英寸。
接下来,将如上编织的芳纶织物(未用上浆剂处理)用35重量份的聚氨酯树脂(基体树脂)浸渍以制备芳纶织物预浸料,然后层叠四个芳纶织物预浸料,然后加热/加压而成型,以制备厚度为2.1mm的芳纶织物/热塑性聚氨酯树脂复合物。
测量所制备的芳纶织物/热塑性聚氨酯树脂复合物的拉伸强度、拉伸弹性模量和峰值力,结果示于下表2中。
[表2]复合物的物理性能
通过ASTM D 3039的方法测量拉伸强度和拉伸弹性模量,并且通过ISO-6603的方法测量峰值力。
当测量峰值力时,冲击速度为4.4m/s,总重量为60kg,下落高度为987.085mm。
在实施例2中制备的芳纶织物/热塑性聚氨酯复合物中,拉伸强度和拉伸弹性模量与在比较例4和比较例7中制备的芳纶织物/热塑性聚氨酯树脂复合物相比显著提高,并且表现抗冲击性的峰值力与在比较例5中制备的碳纤维织物/热塑性聚氨酯树脂复合物以及在比较例6中制备的碳纤维织物/热固性聚氨酯树脂复合物相比显著提高。
在比较例4中制备的芳纶织物/热塑性聚氨酯树脂复合物中,由于该芳纶织物是平纹组织而不是方平组织,因此拉伸强度和拉伸弹性模量比在实施例2中制备的芳纶织物/热塑性聚氨酯树脂复合物的拉伸强度和拉伸弹性模量显著更低。
在比较例7中制备的芳纶织物/热塑性聚氨酯树脂复合物中,由于芳纶织物未使用作为水性聚氨酯树脂的上浆剂进行处理,因此拉伸强度和拉伸弹性模量比在实施例2中制备的芳纶织物/热塑性聚氨酯树脂复合物的拉伸强度和拉伸弹性模量显著更低。
在比较例5中制备的碳纤维织物/热塑性聚氨酯树脂中,表示抗冲击性的峰值力比在实施例2中制备的芳纶织物/热塑性聚氨酯树脂复合物的峰值力显著更低。
在比较例6中制备的碳纤维织物/热固性环氧树脂复合物中,表示抗冲击性的峰值力比在实施例2中制备的芳纶纤维/热塑性聚氨酯树脂复合物的峰值力显著更低,并且,由于热固性环氧树脂的使用,使得表现抗冲击性的峰值力比在比较例2中制备的碳纤维织物/热塑性聚氨酯树脂复合物的峰值力差。
在本公开中,通过以下方法测量附着于并浸渍在芳纶织物中的水性聚氨酯树脂的含量(wt%)。
首先,制备2.5g的芳纶织物(以下称为“样品”),在该2.5g的芳纶织物中,上浆剂组成中的有机溶剂和水挥发并且仅水性聚氨酯树脂附着于并浸渍在织物的表面和内部中。接下来,将样品放置在注射器形状的圆柱形管中,然后添加约8ml的甲醇以使样品充分地湿润,并且对管反复地施加压力直到溶剂不再释放。
接下来,在将约8ml的甲醇再次添加到管中并对管反复地施加压力直到溶剂不再释放的步骤被重复两次之后,将样品从管中取出,在110℃下干燥,并且测量聚氨酯树脂未附着于或浸渍到其表面上或内部中的芳纶织物的重量(W0)。
接下来,将仅是上浆剂组成中的水性聚氨酯树脂附着于并浸渍到织物的表面和内部中的芳纶织物的重量(W1:样品重量)、以及水性聚氨酯树脂未附着于并浸渍到织物的表面和内部中的芳纶织物(WO)的重量代入下式中以确定附着于并浸渍到芳纶织物的表面和内部中的水性聚氨酯树脂的含量(W)。
[式]
工业适用性
本公开的芳纶织物具有优异的抗冲击性并且对热塑性聚氨酯树脂的粘合性优异,因此可用作制备芳纶织物/热塑性聚氨酯树脂复合物的材料。
本公开的芳纶织物/热塑性聚氨酯树脂复合物可用作要求抗冲击性的汽车部件材料,例如汽车保险杠或电子部件材料。
Claims (22)
1.一种具有对聚氨酯基体树脂的优异的粘合性以及优异的拉伸强度的芳纶织物的制备方法,所述方法包括:
(i)编织步骤,使用芳纶纱线作为经纱和纬纱来编织方平组织芳纶织物;以及
(ii)上浆处理步骤,将编织的所述芳纶织物浸入由作为上浆剂的水性聚氨酯树脂和水组成的上浆剂溶液中,然后进行挤压和干燥,从而将所述上浆剂溶液附着并浸渍到所述芳纶织物,其中,基于附着于并浸渍到所述芳纶织物的表面和内部中的所述水性聚氨酯树脂的重量、以及在所述水性聚氨酯树脂附着并浸渍之前所述芳纶织物的重量的总和,将附着于并浸渍到所述芳纶织物的所述表面和所述内部中的所述水性聚氨酯树脂的含量调整为1重量%至8重量%。
2.根据权利要求1所述的具有对聚氨酯基体树脂的优异的粘合性以及优异的拉伸强度的芳纶织物的制备方法,其中,将所述芳纶织物编织成2×2的方平组织。
3.根据权利要求1所述的具有对聚氨酯基体树脂的优异的粘合性以及优异的拉伸强度的芳纶织物的制备方法,其中,基于附着于并浸渍到所述芳纶织物的所述表面和所述内部中的所述水性聚氨酯树脂的重量、以及在所述水性聚氨酯树脂附着并浸渍之前所述芳纶织物的所述重量的总和,将附着于并浸渍到所述芳纶织物的所述表面和所述内部中的所述水性聚氨酯树脂的所述含量调整为2重量%至6重量%。
4.根据权利要求1所述的具有对聚氨酯基体树脂的优异的粘合性以及优异的拉伸强度的芳纶织物的制备方法,其中,作为构成所述上浆剂溶液的上浆剂的所述水性聚氨酯树脂与构成所述上浆剂溶液的上浆剂的水之间的重量比为1.8:1至2.2:1。
5.根据权利要求1所述的具有对聚氨酯基体树脂的优异的粘合性以及优异的拉伸强度的芳纶织物的制备方法,其中,将在所述上浆处理步骤中在所述上浆剂溶液中浸渍处理后的所述芳纶织物在1kgf/cm2至2kgf/cm2的压力下挤压。
6.根据权利要求1所述的具有对聚氨酯基体树脂的优异的粘合性以及优异的拉伸强度的芳纶织物的制备方法,其中,将在所述上浆处理步骤中挤压后的所述芳纶织物在110℃至130℃的温度下干燥3分钟至5分钟。
7.根据权利要求1所述的具有对聚氨酯基体树脂的优异的粘合性以及优异的拉伸强度的芳纶织物的制备方法,其中,用作经纱和纬纱的所述芳纶纱线具有1000旦尼尔至3000旦尼尔的纤度。
8.根据权利要求1所述的具有对聚氨酯基体树脂的优异的粘合性以及优异的拉伸强度的芳纶织物的制备方法,其中,所述芳纶织物的所述经纱的密度和所述纬纱的密度分别为10至20根纱线/英寸。
9.一种具有对聚氨酯基体树脂的优异的粘合性以及优异的拉伸强度的芳纶织物,其特征在于,
所述芳纶织物具有作为芳纶纱线的经纱和纬纱被编织成方平组织的纹理,
水性聚氨酯树脂附着于并浸渍到所述芳纶织物的表面和内部中,并且
基于附着于并浸渍到所述芳纶织物的所述表面和所述内部中的所述水性聚氨酯树脂的重量、以及在所述水性聚氨酯树脂附着并浸渍之前所述芳纶织物的重量的总和,附着于并浸渍到所述芳纶织物的所述表面和所述内部中的所述水性聚氨酯树脂的含量为1重量%至8重量%。
10.根据权利要求9所述的具有对聚氨酯基体树脂的优异的粘合性以及优异的拉伸强度的芳纶织物,其中,所述芳纶织物被编织成2×2的方平组织。
11.根据权利要求9所述的具有对聚氨酯基体树脂的优异的粘合性以及优异的拉伸强度的芳纶织物,其中,作为经纱和纬纱的所述芳纶纱线具有1000旦尼尔至3000旦尼尔的纤度。
12.根据权利要求9所述的具有对聚氨酯基体树脂的优异的粘合性以及优异的拉伸强度的芳纶织物,其中,所述芳纶织物的所述经纱的密度和所述纬纱的密度分别为10至20根纱线/英寸。
13.根据权利要求9所述的具有对聚氨酯基体树脂的优异的粘合性以及优异的拉伸强度的芳纶织物,其中,通过ASTM D 3039的方法测得的拉伸强度为19,000至21,000N/5cm。
14.根据权利要求9所述的具有对聚氨酯基体树脂的优异的粘合性以及优异的拉伸强度的芳纶织物,其中,基于附着于并浸渍到所述芳纶织物的所述表面和所述内部中的所述水性聚氨酯树脂的重量、以及在所述水性聚氨酯树脂附着并浸渍之前所述芳纶织物的重量的总和,附着于并浸渍到所述芳纶织物的所述表面和所述内部中的所述水性聚氨酯树脂的所述含量为2重量%至6重量%。
15.一种芳纶织物预浸料,包括:
(i)芳纶织物,所述芳纶织物具有作为芳纶纱线的经纱和纬纱被编织成方平组织的纹理,在所述芳纶织物中,作为上浆剂的水性聚氨酯树脂附着于并浸渍到所述织物的表面和内部中;以及
(ii)聚氨酯基体树脂,所述聚氨酯基体树脂浸渍在所述芳纶织物中并且处于未固化或半固化的状态,
其中,基于附着于并浸渍到所述芳纶织物的所述表面和所述内部中的所述水性聚氨酯树脂的重量、以及在所述水性聚氨酯树脂附着并浸渍之前所述芳纶织物的重量的总和,附着于并浸渍到所述芳纶织物的所述表面和所述内部中的所述水性聚氨酯树脂的含量为1重量%至8重量%。
16.一种芳纶织物/热塑性聚氨酯树脂复合物,包括:
(i)两个以上的芳纶织物,所述两个以上的芳纶织物具有作为芳纶纱线的经纱和纬纱被编织成方平组织的结构,在所述两个以上的芳纶织物中水性聚氨酯树脂附着于并浸渍到所述织物的表面和内部中;以及
(ii)聚氨酯基体树脂,所述聚氨酯基体树脂浸渍在所述芳纶织物内并且位于所述芳纶织物之间,
其中,基于附着于并浸渍到所述芳纶织物的所述表面和所述内部中的所述水性聚氨酯树脂的重量、以及在所述水性聚氨酯树脂附着并浸渍之前所述芳纶织物的重量的总和,附着于并浸渍到所述芳纶织物的所述表面和所述内部中的所述水性聚氨酯树脂的含量为1重量%至8重量%,并且
其中,通过ISO-6603的方法测得的峰值力为18.000N以上。
17.根据权利要求16所述的芳纶织物/热塑性聚氨酯树脂复合物,其中,所述复合物具有通过ASTM D 3039的方法测得的600MPa以上的拉伸强度和25GPa以上的拉伸弹性模量。
18.根据权利要求16所述的芳纶织物/热塑性聚氨酯树脂复合物,其中,所述复合物具有2.0mm至2.2mm的厚度,并且所述热塑性聚氨酯基体树脂的含量为30重量%至45重量%。
19.根据权利要求16所述的芳纶织物/热塑性聚氨酯树脂复合物,其中,所述芳纶织物被编织成2×2的方平组织。
20.根据权利要求16所述的芳纶织物/热塑性聚氨酯树脂复合物,其中,作为经纱和纬纱的所述芳纶纱线具有1000旦尼尔至7000旦尼尔的纤度。
21.根据权利要求16所述的芳纶织物/热塑性聚氨酯树脂复合物,其中,所述芳纶织物的所述经纱的密度和所述纬纱的密度分别为10至20根纱线/英寸。
22.根据权利要求16所述的芳纶织物/热塑性聚氨酯树脂复合物,其中,基于附着于并浸渍到所述芳纶织物的所述表面和所述内部中的所述水性聚氨酯树脂的重量、以及在所述水性聚氨酯树脂附着并浸渍之前所述芳纶织物的重量的总和,附着于并浸渍到所述芳纶织物的所述表面和所述内部中的所述水性聚氨酯树脂的所述含量为2重量%至6重量%。
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