CN102574376B - 用于制备低收缩率的柔性片材的方法 - Google Patents
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Abstract
本发明涉及一种用于制备低收缩率的柔性片材的方法,所述片材包含含有聚烯烃纤维的织物,所述方法包括下列步骤:a)将熔融的塑性体层沉积到所述纺织织物的至少一个表面上,以形成厚度约等于所述熔融塑性体层和所述织物的厚度之和的片材;并且b)通过在介于由DSC测定的所述塑性体的熔融温度和所述聚烯烃纤维的熔融温度之间的温度下将片材拉入两个压延辊之间的缝隙中,用至少一部分所述熔融的塑性体层浸渍所述织物,所述缝隙的宽度小于所述片材的厚度;其中选择所述缝隙的宽度,以使施加在所述片材上的浸渍压力为至少20bars。
Description
本发明涉及一种用于制备适用于多种应用的低收缩率的柔性片材的方法,例如货物和集装箱用的遮盖物、地面覆盖物、屋顶、帘、防水布和建筑物覆盖物,并且涉及所述片材的制备方法。
用于制备低收缩率的柔性片材的多种方法在文献中均有描述并且是实际已知的。由其制造的片材通常含有用于增强的织物,所述织物被包封在粘附于其上的热塑性材料的片材之间。由高强度和低收缩纤维(例如聚酯、尼龙、芳族聚酰胺或玻璃的纤维)制成的纺织或无纺织物被用于增强,而多种多样的聚合物被用于热塑性材料的片材。其中最常用的聚合物是弹性体,例如热塑性聚烯烃、乙烯-丙烯橡胶(EPM)、三元乙丙橡胶(EPDM)、热塑性氨基甲酸酯和聚氯乙烯聚合物。已知柔性片材的实施方式及其制备方法的例子为例如US5,773,373、US5,994,242、US6,864,195、US6,054,178、JP11138715、JP11291419和JP2000233477中公开的那些。
然而,观察到已知的方法在制备含有聚乙烯织物(即,由含聚乙烯纤维的纱线制成的编织物)的低收缩柔性片材中无效。
此外,本发明人注意到,柔性片材的制造者过去系统地避免使用聚乙烯织物用于增强。其原因是,试图构建含有这种聚乙烯织物的尺寸稳定的柔性片材时,所有的尝试均失败。长久以来便已知聚乙烯纤维具有低压缩屈服强度,并且这种纤维在使用期间可能受到所谓扭结带的形成的影响。不想束缚于任何解释,本发明人将扭结带的形成归因于纤维的收缩以及含有其的产品的收缩。因此,聚乙烯纤维的有利性能(例如轻质、耐化学性和高强度)在这种技术中不能最大程度地被利用。
尽管有上述缺点,仍存在使用聚乙烯织物用于增强的尝试,例如在US6,280,546中,其中通过将所述织物与低密度聚乙烯(LDPE)层或乙烯乙酸乙烯酯(EVA)层层压来制备柔性片材。然而,观察到这种柔性片材在使用期间仍表现出收缩增大,因此不适用于长期应用。
因此,本发明的一个目的是提供一种用于制备低收缩率的柔性片材的方法,所述片材包含含有聚烯烃纤维的织物。
本发明的方法包括下列步骤:
(a)将熔融的塑性体层沉积到纺织织物的至少一个表面上,以形成厚度约等于所述熔融塑性体层和所述织物的厚度之和的片材;并且
(b)通过在介于由DSC测定的塑性体的熔融温度和聚烯烃纤维的熔融温度之间的温度下将片材拉入压延辊之间的缝隙中,用至少一部分熔融的塑性体层浸渍所述织物,所述缝隙的宽度小于所述片材的厚度;
其中选择缝隙的宽度,以使施加在片材上的浸渍压力为至少20bars。
在步骤(a)中,塑性体在高于其熔融温度的温度下熔融,优选至多180℃,更优选至多165℃。优选地,塑性体在至少90℃,更优选至少95℃的温度下熔融。
优选地,在步骤(b)中选择缝隙的宽度,使施加在片材上的浸渍压力为至少30bars,更优选至少40bars,最优选至少50bars。
优选地,纺织织物所含的聚烯烃纤维是聚乙烯纤维,更优选高分子量聚乙烯纤维,最优选超高分子量聚乙烯(UHMWPE)纤维。
优选地,在步骤(b)中所述温度介于80℃和160℃之间,更优选介于90℃和150℃之间;当使用包含含有UHMWPE纤维的纱线的纺织织物时,温度优选介于90℃和145℃之间,更优选介于100℃和130℃之间。
根据本发明的方法的步骤可以重复进行,以便在纺织织物的两个表面上沉积塑性体层,从而得到包封在塑性体中的纺织织物。
优选地,在其上沉积塑性体之前预加热纺织织物。观察到,对于这种经过预加热的织物来说,柔性片材的均匀性提高。优选地,纺织织物被预加热至50℃和130℃之间的温度,更优选至80℃和100℃之间的温度。纺织织物的预加热可以通过使用红外(IR)辐射或热空气流来进行。在一个优选的实施方式中,预加热是通过使纺织织物与经过加热的辊接触来进行。业已观察到,这种接触法与IR或热空气流相比,能更有效地预加热所述织物。
塑性体的熔融可以根据本领域已知的方法来进行,例如在挤出机中。优选地,塑性体在120℃和150℃之间的温度下熔融,更优选在130℃和145℃之间的温度下熔融。观察到,当使用所述温度使塑性体熔融时,得到对纺织织物更好的浸渍,并且所得到的柔性片材显示出降低的收缩率。还观察到在柔性片材中出现较少的空隙和/或气泡。
浸渍步骤之后,使柔性片材在冷却步骤中冷却(例如通过冷空气流或通过使所述片材与经过冷却的辊接触)至低于50℃的温度,更优选地冷却至10℃到30℃之间的温度。
在一个优选的实施方式中,制备低收缩率的柔性片材的方法包括在浸渍步骤之后的进一步的压缩步骤(c),优选地所述进一步的压缩步骤在所述冷却步骤之后。在所述进一步的压缩步骤期间,柔性片材被加热到由DSC测定的塑性体的熔融温度和聚烯烃纤维的熔融温度之间的加热温度下,更优选地加热到60-150℃。对于包含含有UHMWPE纤维的纱线的织物来说,加热温度优选地介于70℃和145℃之间,更优选地介于90℃和140℃之间,最优选地介于110℃和120℃之间。优选地,通过在与片材的横向尺寸所定义的平面(例如如果是矩形片材,平面包含片材的宽度和厚度尺寸;如果是圆形片材,平面包含片材的圆周)垂直的方向上施加压缩压力来压缩所述片材。优选地,压缩压力为至少30bars,更优选为至少40bars,最优选为至少45bars。优选地,通过在两个压延辊之间的缝隙中拉伸所述柔性片材来施加压缩压力。压缩压力可以通过如下来常规地设定:调整所述压延辊之间的所述缝隙的宽度,从而使所述宽度小于柔性片材进入缝隙被拉伸之前的厚度。优选地,压缩步骤之后,厚度减小至少2%,更优选至少4%,最优选至少6%。观察到,进一步的压缩步骤产生了具有收缩率甚至进一步降低且不易于分层的柔性片材。还观察到,柔性片材中所用的织物的经向和纬向上收缩率的差异进一步减小,因而得到更均匀的片材。
根据本发明所用的塑性体是属于热塑性材料类的塑性材料。优选地,所述塑性体是乙烯或丙烯与一种或更多种C2-C12的α-烯烃共聚单体的半结晶性共聚物,所述塑性体的密度为880-930kg/m3。观察到,通过其中使用这种塑性体的方法制备的柔性片材显示出良好的抗收缩性,特别是当所述塑性体是通过单点催化剂聚合法制备的时。优选地,所述塑性体是茂金属塑性体,即,通过茂金属单点催化剂制备的塑性体。乙烯是丙烯的共聚物中特别优选的共聚单体,而丁烯、己烯和辛烯是乙烯共聚物和丙烯共聚物中优选的α-烯烃共聚单体。
在一个优选的实施方式中,塑性体是乙烯或丙烯的热塑性共聚物并且包含一种或更多种具有2-12个碳原子的α-烯烃(特别是乙烯、异丁烯、1-丁烯、1-己烯、4-甲基-1-戊烯和1-辛烯)作为共聚单体。当使用乙烯和作为共聚单体的一种或更多种C3-C12的α-烯烃单体时,共聚物中共聚单体的量通常介于1-50wt.%之间,优选地介于5-35wt.%之间。如果是乙烯共聚物,优选的共聚单体为1-辛烯,所述共聚单体的量介于5wt%和25wt%之间,更优选介于15wt%和20wt%之间。如果是丙烯共聚物,共聚单体的量(特别是乙烯共聚单体的量)通常介于1-50wt.%之间,优选地介于2-35wt.%之间,更优选介于5-20wt.%之间。当塑性体的密度介于880-920kg/m3之间,更优选介于880-910kg/m3之间时,收缩方面将得到很好的结果。
当根据ASTMD3418测试,本发明所用的塑性体的DSC峰值熔点介于70℃和120℃之间,优选介于75℃和100℃之间,更优选介于80℃和95℃之间时,将得到更好的抗收缩性。
通过单点催化剂聚合法制备的塑性体(特别是茂金属塑性体)因其比重而区别于通过其他聚合技术(例如Ziegler-Natta催化)制备的乙烯共聚物和丙烯共聚物。所述塑性体还因较窄的分子量分布(Mw/Mn)和有限量的长链支化而使其区别于其他,其中分子量分布的值优选地为1.5-3。优选地,长支链的数量为每1000个碳原子至多3个。可用于本发明方法并且通过茂金属催化剂得到的合适的塑性体是商业规模生产的,例如以商标Exact、Tafmer、Exceed、Engage、Affinity、Vistamaxx和Versify由Exxon、Mitsui、DEX-Plastomers和DOW所提供的那些。塑性体(特别是茂金属塑性体)的说明以及其机械和物理性能的概述可以在例如HarutunG.Karian的″Handbookofpolypropyleneandpolypropylenecomposites″(ISBN0-8247-4064-5)的第7.2章中找到,更具体是在其子章节7.2.1、7.2.2和7.2.5到7.2.7中,它们均通过引用结合于此。
塑性体还可以包含添加到其中的各种填料和添加剂。填料的例子包括增强型和非增强型材料,例如炭黑、碳酸钙、粘土、硅石、云母、滑石和玻璃。添加剂包括稳定剂(例如UV稳定剂)、颜料、抗氧化剂、阻燃剂等。优选的阻燃剂包括三水合铝、脱水镁和磷酸铵。优选地,阻燃剂的量占柔性片材中塑性体量的1-60重量%、更优选1-10重量%。最优选的阻燃剂是磷酸铵(例如Exolit)。
选择塑性体的量以产生面密度(AD)比其中所用的纺织织物的AD高至少20%、更优选高至少50%的柔性片材时,将得到良好的抗收缩性。优选地,柔性片材的面密度(AD)比其中所用的纺织织物的AD高至多500%、更优选高至多400%,最优选高至多300%。当塑性体包封住纺织织物并且按上面所指出地选择塑性体的量时,得到最好的结果。AD用kg/m2表示,是通过称量一定面积(0.01m2)的重量,将所得重量除以该样品的面积而得到。
本文中“纤维”被理解为连续的细长体,它们的长度尺寸远远大于纤维的横向尺寸(例如宽度和厚度)。术语“纤维”也包括各种实施方式,例如丝线、丝带、条、宽带、带以及其它具有规则或不规则横截面的物体。本发明目的中的纱线是含有多根纤维的细长体。
如上所述,优选的聚烯烃纤维是聚乙烯纤维,更优选地所述聚烯烃纤维是高分子量聚乙烯(HMWPE)纤维,最优选地所述聚烯烃纤维是超高分子量聚乙烯(UHMWPE)纤维。可以通过本领域已知的任何技术来制备聚烯烃(特别是聚乙烯)纤维,优选地通过熔融纺丝或凝胶纺丝工艺。最优选的纤维是凝胶纺丝的UHMWPE纤维,例如由DSMDyneema以商品名Dyneema出售的那些。如果使用熔融纺丝工艺,用于制备纤维的聚烯烃(特别是聚乙烯)原料的重均分子量优选地介于20000和600000g/mol之间,更优选地介于60000和200000g/mol之间。在EP1,350,868(通过引用结合于此)中公开了熔融纺丝工艺的实例。如果使用凝胶纺丝工艺来制备所述纤维,优选使用特性粘度(IV)优选为至少3dl/g、更优选为至少4dl/g、最优选为至少5dl/g的UHMWPE。优选地,所述IV为至多40dl/g,更优选至多25dl/g,更优选至多15dl/g。优选地,UHMWPE每100个C原子具有小于1个侧链,更优选每300个C原子具有小于1个侧链。优选地,所述UHMWPE纤维根据多个出版物中描述的凝胶纺丝工艺来制备,所述出版物包括EP0205960A、EP0213208A1、US4413110、GP2042414A、GB-A-2051667、EP0200547B1、EP0472114B1、WO01/73173A1、EP1699954和“AdvancedFibreSpinningTechnology”,Ed.T.Nakajima,WoodheadPubl.Ltd(1994),ISBN1-855-73182-7。
可与含有聚烯烃纤维的纱线组合使用以构建纺织织物的其他纤维的纱线包括但不限于由聚酰胺和聚芳酰胺制成的纤维,诸如聚(对苯二甲酰对苯二胺)(亦称为Kevlar);聚(四氟乙烯)(PTFE);聚{2,6-二咪唑并-[4,5b-4’,5’e]吡啶-1,4(2,5-二羟基)苯撑}(亦称为M5);聚(对-苯撑-2,6-苯并二噁唑)(PBO)(亦称为Zylon);聚己二酰己二胺(亦称为尼龙6,6)、聚(4-氨基丁酸)(亦称为尼龙6);聚酯,例如聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸1,4-亚环己基二亚甲基酯;聚乙烯醇;热致液晶聚合物(LCP),如从例如US4,384,016中已知的;还有除已经使用过一次之外的其他类型的聚烯烃,诸如聚乙烯或聚丙烯的均聚物和共聚物。并且,由上述聚合物制成的纤维的组合也可以用于制备本发明的柔性片材中所含的纺织织物。优选的其他纱线是含有聚酰胺纤维和/或LCP纤维的那些。
优选地,本发明所用纤维的旦尼尔在0.5-20dpf的范围内,更优选在0.7-10dpf的范围内,最优选在1-5dpf的范围内。优选地,含有所述纤维的纱线的旦尼尔在100-3000dtex的范围内,更优选在200-2500dtex的范围内,最优选在400-1000dtex的范围内。
优选地,根据ASTMD2256测试时,聚烯烃(特别是本发明所用的聚乙烯)纤维的拉伸强度为至少1.2GPa,更优选为至少2.5GPa,最优选为至少3.5GPa。使用由这种强度的纤维制成的织物的柔性片材与具有相同结构但使用由例如聚酯、尼龙、芳族聚酰胺或玻璃纤维制成的织物的任何其他柔性片材相比,重量较轻且强度较高。优选地,根据ASTMD2256测试时,聚烯烃(特别是聚乙烯)纤维的拉伸模量为至少30GPa,更优选为至少50GPa,最优选为至少60GPa。
适用于本发明方法的纺织织物的优选的实施方式包括平织(平纹)织物、方平网眼织物、破斜纹(crowfeet)织物和缎织织物,但是也可以使用更复杂的织物,例如三维织物。更优选地,纺织织物是平织织物;最优选地,纺织织物是方平网眼织物。优选地,用于制备纺织织物的纤维由具有近似圆形横截面的纤维组成,所述横截面的纵横比为至多4∶1,更优选地为至多2∶1。
借助于下列非限制性实施例进一步说明本发明。
测试方法
特性粘度(IV):根据方法PTC-179(HerculesInc.Rev.Apr.29,1982)来测定UHMWPE的特性粘度,测试条件为:在135℃下,十氢化萘中,溶解时间为16小时,采用用量为2g/l溶液的DBPC作为抗氧剂,将在不同浓度下测量的粘度外推得到零浓度下的粘度。
Dtex:通过称重100米的纤维来测定纤维的纤度(dtex)。将重量(以毫克计)除以10来计算纤维的dtex;
空隙总体积V 空隙 (以%计):根据下式计算柔性片材所含的空隙总体积:
其中T片材为柔性片材的厚度;AD织物和AD涂层分别为柔性片材和涂层的面密度;而ρ纤维和ρ涂层分别为聚乙烯纤维和涂层的密度。根据ASTMD1505-03来测定纤维的密度ρ纤维。
厚度:通过10次在不同位置测量其表面之间的距离并使结果平均来确定纺织织物或柔性片材的厚度。要注意,测量期间不能使样品变形。
收缩率:将长度为0.4m且宽度为0.4m的正方形样品放置在洗衣机的滚筒内,在不存在水的情况下、在约23℃的温度和约65%的湿度下,以60转/分钟的转速与5个粘土球一起转动72小时。各粘土球的质量为0.22Kg,直径为约50mm,通过将球放入刚好仅能容纳该球的棉布袋而使各球的表面被棉织物覆盖。测量处理之前和之后样品的尺寸,认为其差值(用%表示)代表样品的收缩率。
实施例和对比实验
实施例1
从线轴中连续地抽出AD为0.193kg/m2、长度连续的、厚度为约0.6mm、宽度为约1.72m且含有880dtex的聚乙烯纱线(被称为DyneemaSK65)的方平网眼织物,通过使其与转速为15m/min的经加热的辊的表面接触而预加热至约90℃的温度。
塑性体在挤出机中在约145℃的温度下熔融,并排入以约15m/min的表面速度转动的第一和第二压延辊之间的缝隙中。缝隙的宽度为约0.2m。第一压延辊的表面保持为约130℃的温度,而第二压延辊的表面保持为约137℃。熔融的塑性体粘附在第二辊的表面,并拉伸通过缝隙,从而在对面侧作为粘附在第二辊表面上的一个层出现。
所用的塑性体是来自DexPlastomer的Exact0203塑性体,其为含约18%的辛烯的基于乙烯的辛烯塑性体,密度为902kg/m3,DSC峰值熔点为95℃。预热的织物被引入由第二压延辊和随所述第二辊转动的第三压延辊所限定的约0.5mm宽的缝隙中,所述第三辊保持约20℃的温度。第三辊以约15m/min的表面速度转动。织物的一个表面与第三辊的表面抵靠,而另一个表面与熔融的塑性体层接触,从而形成含有粘附在织物表面上的塑性体熔融层的片材。该片材在缝隙的对面形成,随后在室温(约20℃)下冷却。
重复进行上述过程,使纺织织物的两个表面均用塑性体层涂布,从而将织物包封在塑性体中。在该包封过程中,第二压延辊和第三辊之间的缝隙为0.7mm。
所得到的片材是柔性的,厚度为约0.8mm,AD为0.550kg/m2,空隙率小于40%。该片材的AD比纺织织物的AD大280%。塑性体层被分为:
●覆盖一个表面的AD为约0.175kg/m2的第一部分;
●浸入织物的纱线和纤维之间的第二部分;
●覆盖另一个表面的AD为约0.175kg/m2的第三部分;
结果如表1所示。
实施例2
重复实施例1,但不同之处在于,在最后一个冷却步骤之后进行进一步的压缩步骤。所述进一步的压缩步骤包括在温度为120℃和压力为45bars的两个压延辊之间进行的后压延过程。在进一步的压缩步骤中厚度减小为6%。
对比实验A-C
通过浸涂法分别用对比实验(A)的氯丁橡胶和另一个对比实验(B)的聚氨酯(来自BarrdayInc,加拿大)来浸渍实施例1的织物。随后使橡胶固化。
在第三个实验(C)中,根据US6,280,546的实施例2中所述的方法用EVA覆盖聚乙烯织物。
样品 | 经向收缩率(%) | 纬向收缩率(%) | 总收缩率(%) |
实施例1 | 0.96 | 0.42 | 0.69 |
实施例2 | 0.58 | 0.50 | 0.54 |
对比实验A | 3.10 | 1.30 | 2.20 |
对比实验B | 5.00 | 3.95 | 4.47 |
对比实验C | 1.60 | 2.25 | 1.92 |
未经涂布的聚乙烯织物 | 21.00 | 34.00 | 27.5 |
从上面的实施例和对比实验中可以看出,用本发明方法制备的柔性片材与已知织物或根据各种出版物所公开的方法制成的织物相比,具有降低的收缩率。
Claims (12)
1.一种用于制备低收缩率的柔性片材的方法,所述片材包含含有高分子量聚乙烯(HMWPE)纤维或超高分子量聚乙烯(UHMWPE)纤维的纺织织物,所述方法包括下列步骤:
(a)将熔融的塑性体层沉积到所述纺织织物的至少一个表面上,以形成厚度约等于所述熔融塑性体层和所述织物的厚度之和的片材;并且
(b)通过在介于由DSC测定的所述塑性体的熔融温度和所述聚乙烯纤维的熔融温度之间的温度下将片材拉入两个压延辊之间的缝隙中,用至少一部分所述熔融的塑性体层浸渍所述织物,所述缝隙的宽度小于所述片材的厚度;
其中选择所述缝隙的所述宽度,以使施加在所述片材上的浸渍压力为至少20bars,并且所述塑性体是乙烯或丙烯与一种或更多种C2-C12的α-烯烃共聚单体的半结晶性共聚物,所述塑性体的密度为880-930kg/m3,并且其中,选择所述塑性体的量,以便产生面密度(AD)比其所使用的所述纺织织物的AD高至少20%的柔性片材。
2.如权利要求1所述的方法,其中,在步骤(a)中,所述塑性体在高于其熔融温度的温度下熔融。
3.如权利要求2所述的方法,其中所述塑性体在介于120℃和150℃之间的温度下熔融。
4.如前面任何一个权利要求所述的方法,其中,在步骤(b)中,选择所述缝隙的所述宽度,以使施加的浸渍压力为至少30bars。
5.如权利要求1至3中任意一项所述的方法,其中,在步骤(b)中,所述温度介于80℃和160℃之间。
6.如权利要求1至3中任意一项所述的方法,其中,在沉积所述塑性体之前预加热所述纺织织物。
7.如权利要求6所述的方法,其中,所述纺织织物被预加热至50℃和130℃之间的温度。
8.如权利要求1至3中任意一项所述的方法,其中在所述浸渍步骤(b)之后,实施进一步的压缩步骤(c),其中所述柔性片材被加热至介于由DSC测定的所述塑性体的熔融温度和所述聚乙烯纤维的熔融温度之间的加热温度下。
9.如权利要求1至3中任意一项所述的方法,其中在所述浸渍步骤(b)之后,实施进一步的压缩步骤(c),其中所述柔性片材被加热至由DSC测定的所述塑性体的熔融温度和所述聚乙烯纤维的熔融温度之间的加热温度下,其中所施加的压缩压力为至少30bars。
10.如权利要求9所述的方法,其中,在所述压缩步骤之后,所述片材的厚度减小至少2%。
11.如权利要求1至3中任意一项所述的方法,其中,所述塑性体是乙烯或丙烯的热塑性共聚物并且包含一种或更多种具有2-12个碳原子的α-烯烃作为共聚单体。
12.如权利要求1至3中任意一项所述的方法,其中所述纺织织物选自由平织织物、方平网眼织物、破斜纹织物、缎织织物和三维织物组成的组。
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EP09172806 | 2009-10-12 | ||
EP09172806.3 | 2009-10-12 | ||
PCT/EP2010/065291 WO2011045325A1 (en) | 2009-10-12 | 2010-10-12 | Method for the manufacturing of a low shrinkage flexible sheet |
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CN102574376B true CN102574376B (zh) | 2016-02-24 |
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CN201080046232.0A Expired - Fee Related CN102574377B (zh) | 2009-10-12 | 2010-10-12 | 柔性片材、所述片材的制备方法及其应用 |
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EP (2) | EP2488363B1 (zh) |
KR (2) | KR101796803B1 (zh) |
CN (2) | CN102574376B (zh) |
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