CN107849283A - 物理交联的能发泡的粒子,由其制造原位发泡体和层合发泡体的方法 - Google Patents
物理交联的能发泡的粒子,由其制造原位发泡体和层合发泡体的方法 Download PDFInfo
- Publication number
- CN107849283A CN107849283A CN201680038831.5A CN201680038831A CN107849283A CN 107849283 A CN107849283 A CN 107849283A CN 201680038831 A CN201680038831 A CN 201680038831A CN 107849283 A CN107849283 A CN 107849283A
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- Prior art keywords
- particle
- foamed
- physical crosslinking
- foaming
- foam
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Abstract
物理交联的能发泡的粒子包括聚烯烃树脂和化学发泡剂,该能发泡的粒子具有至少约0.002mm3的体积。使用所述物理交联的能发泡的粒子通过如下制造原位发泡体:将所述物理交联的能发泡的粒子分散在模具的内部;加热到高于所述发泡剂的活化温度的温度,和使所述粒子在所述模具的内部发泡以制造与所述模具的形状相符的物理交联的发泡体。此外,将所制造的发泡体热结合到热塑性烯烃箔和热塑性烯烃基底的至少一个。
Description
背景技术
本申请要求2015年6月30日提交的美国临时申请No.62/187,128的权益。
本公开总体上涉及用于制造成型的热塑性聚烯烃和弹性体发泡体(泡沫体,foam)的方法和组合物,且更具体地涉及可用于例如制造原位(现场,in-situ)交联的发泡体芯材(core)的能发泡的粒子,该发泡体芯材可与用于汽车内部产品、船用产品或其它成型的发泡体组件的各种各样的模具形状相符(一致,comform)。
汽车仪表板(IP)市场分为三个主要的类别:1)硬质IP,2)聚烯烃(PO)真空成形的软质IP,和3)聚氨酯(PU)发泡体原地(in-place)软质IP。硬质IP涉及将固体塑料树脂向模具中注射成型。
PO真空成形的软质IP通过首先将发泡体片材与热塑性烯烃(TPO)片材或聚氯乙烯(PVC)箔层合而制成。将组合的层合体加热到~170℃,且然后放置到在真空下的模具中,以将可展延的层合体拉入所述模具中且使其呈现出模具的形状。在真空成型时,基底(substrate)可在或可不在模具中。PO真空成形的软质IP具有优势,例如具有低密度(例如大约4pcf)和低毒性,且是重量轻和可再循环的。
PO真空成形的IP的不足在于对设计的限制。因为箔加发泡体的双层合体被加热和真空成形为模具的形状,所以该双层合体是拉伸定形(shape)的。结果,无论哪里有深腔(型腔),所述材料都不得不进一步拉伸,导致所述材料变薄或者甚至在极端情况下的撕裂(tear)。因而,PO真空成形的软质IP设计经常不超过0.5的高度/直径(H/D)比率以避免过度拉伸。
PU发泡体原地软质IP通过将预成形的TPO或PVC箔放置在夹模(clam mold)的底半部上且将基底放置在顶夹模之下而完成。将所述模具闭合合拢,且然后将液体PU发泡体前体注入到由顶模和底模之间的间隙形成的腔中。所述前体在所述腔内发泡,且呈现出部件的形状,附着到所述箔和所述基底。
PU发泡体原地软质IP的优势是设计的自由性。因为将发泡体前体注入到由表皮(skin)和基底形成的腔中,因此它均一地填充该腔,从而在整个部件中提供均一的触感且保持精确的规格控制而没有任何由于极端的部件设计引起的撕裂的担忧。
然而,PU发泡体原地软质IP的缺点包括但不限于它的高密度(例如大约10pcf)、它的重量大、不能再循环以及各种健康和环境危害。PU的主要成分为异氰酸酯,并且暴露于它可导致皮肤和粘膜的刺激,胸闷(chest tightness),哮喘和其它肺问题,以及眼睛、鼻子、咽喉和皮肤的刺激。由发泡的部件所释放的挥发性有机化合物(VOC)可对人类造成相同的不利影响,当所述化学品未充分混合或仍然部分未反应时尤其如此。
包含化学交联剂的能发泡的粒子记载于美国专利公布No.20070249743A1中,其公开了一种熔融共混的组合物,可将该组合物挤出并切割成粒料(pellet)或者以其它方式成形为粒子,可将该粒子倾倒或放置到腔中且使其膨胀。然而,化学交联在发泡产品中产生不期望的气味,且不保证产品密度的稳定再现性,因为交联水平取决于包括加热的温度、时间和速率在内的很多变量,且进而该交联水平影响发泡体的膨胀性。例如,交联程度过高将导致坚硬的发泡体且抑制膨胀,从而导致比想要的高的密度。
发明内容
本公开涉及物理交联的能发泡的粒子的组合物和使用该能发泡的粒子制造物理交联的发泡体的方法。
在一个方面中,物理交联的能发泡的粒子包括聚烯烃树脂和发泡剂,且具有至少约0.002mm3的粒子体积。
在另一方面中,将所述物理交联的能发泡的粒子分散到模具中,且将其在高于所述发泡剂的活化温度的温度下加热以制造与模具的形状相符的物理交联的发泡体。
附图说明
图1A为模具的简化横截面,其显示片状发泡体前体对于不规则形状的模腔的原位发泡(包括潜在的基底和箔层合)。
图1B为模具的简化横截面,其显示能发泡的粒子对于不规则形状的模腔的原位发泡(包括潜在的基底和箔层合)。
图2为显示对于一种样品配方,由不同的物理交联的能发泡的粒子体积得到的发泡体密度的线图。
图3为显示对于另外的样品配方,由不同的物理交联的能发泡的粒子体积得到的发泡体密度的线图。
图4为显示对于实现甚至更低的发泡体密度的另外的样品配方,由不同的物理交联的能发泡的粒子体积得到的发泡体密度的线图。
图5为显示由具有不同凝胶含量的物理交联的能发泡的粒子得到的发泡体密度的线图。
图6为显示由具有变化的发泡剂载量的物理交联的能发泡的粒子得到的发泡体密度的线图。
图7为显示由不同的物理交联的能发泡的粒子体积发泡得到的通过墨转印透光率测试测量的发泡体表面品质的条形图。
图8为显示由物理交联的能发泡的粒子产生的原位发泡体vs.传统的片状发泡体的发泡体密度和肖氏00(Shore00)硬度值之间的关系的线图。
图9为显示由物理交联的能发泡的粒子vs.含化学交联剂的粒子制成的发泡体的热稳定性的对比的条形图。
具体实施方式
本文中公开了使用物理交联的能发泡的粒子来制造物理交联的原位发泡体芯材的组合物和方法,且其容许适用于范围广泛的应用的具有期望范围的密度、硬度、表面特性和凝胶含量的成型发泡体的灵活制作。例如,由于所发明的组合物和方法,例如对于汽车仪表板或其它最终用途应用,可实现具有复杂设计的质量轻、低毒性、无味的成型发泡体部件,其包括具有期望的表面特性、层合和柔软性的发泡体。
原位发泡体芯材的化学交联容许固体能发泡的粒子彼此均匀地熔融和熔合(fuse)。然而,对于物理交联的能发泡的粒子,聚合物的形状原地锁定,因此固体粒子一般并不均匀地熔融和熔合。相反,所述粒子在膨胀的同时保留它们的形状,从而在膨胀的粒子之间可能留下未填充的间隙。粒度越小,则与各发泡的粒子相较,所述间隙的尺寸变得越小,且因此设想只要发泡体前体全部以能发泡的粒子存在,则在原位发泡时越小的粒子将越高效地填充。然而,发现当所述能发泡的粒子的尺寸太小时,尽管所述前体以所述粒子存在,发泡效率仍然降至其中以重量计相同量的前体不会填充相同尺寸的腔的点。换言之,发现发泡效率下降。
在一个实施方式中,提供具有至少约.002mm3粒子体积的物理交联的能发泡的粒子。发现,对于具有至少约.002mm3粒子体积的物理交联的能发泡的粒子,该粒子可实现与化学交联的能发泡的粒子相同的发泡效率。当超过约1.10mm3的粒子体积时,对所得的发泡体密度的影响变得平稳,且在某点之后,对粒子体积存在实用限制,因为将热量均一地传递遍及模具内部的能发泡材料的每个粒子变得更困难,因此产生发泡体耗费更久,以及在所述粒子之间形成较大的间隙且对粒子熔合具有不利的影响。
在另一实施方式中,所述能发泡的粒子在发泡之前处于物理交联的状态。交联键一旦建立就不会改变,而不管随后的加热和发泡过程如何。因此,可严格地控制交联程度,且导致所得发泡体中与含用于原位交联的化学交联剂的能发泡的粒子或组合物相比时更好的产品密度的再现性。对于例如其中需要较严格控制的具有低密度例如约2.5pcf-约6pcf的发泡体而言,这是尤为重要的。
在另一实施方式中,将所述能发泡的粒子物理交联至约15%-约85%的程度,优选地至约25%-约60%、和更优选地约30%-约40%的程度,其中在约35%的程度下实现最佳效率。交联程度也可称为发泡体的“凝胶含量”。在化学交联方法中,发泡效率随凝胶含量的增大而提高,然而发现,在所述能发泡的粒子的物理交联的情况下,发泡效率随凝胶含量的增大而降低。另外,发现,所述能发泡的粒子的物理交联的结构提供在所得发泡产品中与化学交联的发泡体可比的热稳定性。适合的物理交联方法包括用例如电子束照射。
在另一实施方式中,物理交联的能发泡的粒子的粒子体积、凝胶含量和组成在最佳的预定范围内变更以使得能够准确且灵活地控制适用于各特定的最终用途应用的所得发泡体密度。例如,发现,所述能发泡的粒子的体积越大,则将要得到的发泡体的密度越低。如上所述,为了确保足够的发泡效率,能发泡的粒子的合适体积为至少约.002mm3,且可超过约1.10mm3,尽管在该粒子体积下对发泡体密度的影响开始变得平稳。
此外,所述能发泡的粒子的凝胶含量越低,则所得发泡体的密度越小,但是该标准可相对于对足够的发泡效率的需要取平衡,发泡效率在约30%-约40%下、更优选地在约35%下是最强的。
另外,与所述能发泡的粒子的体积和凝胶含量相平衡,可增大所使用的发泡剂的量以降低所得发泡体的密度。对于本发明的能发泡的粒子,发泡剂的合适量为约1-约60phr、优选为约1-约35phr、和更优选为约5-约30phr。合适的发泡剂可包括但不限于偶氮二甲酰胺(ADCA)、碳酸氢钠和碳酸钙。
因此,通过在所限定的最佳范围内为粒子体积、凝胶含量和发泡剂的量的各变量选择适当的值,可实现在约1.2pcf-约40pcf范围内的发泡体密度,其包括严格控制密度为约2.5pcf-约23pcf。发泡体密度的进一步增大还可通过过度装填所述模具和约束在所述模具内部的发泡过程而实现。此外,产生期望的发泡体密度所需的发泡剂的量可通过如下而最小化:选择适当的物理交联的能发泡的粒子的体积和凝胶含量以弥补发泡效率的降低。这在例如其中所述发泡剂为ADCA以及出于环境或其它原因所得的发泡体产品中的ADCA残留物的量受到管制的情况下可能是合乎需要的。
在另一实施方式中,可对物理交联的能发泡的粒子的粒子体积进行选择以产生所得发泡体的期望的表面特性,其中较小的粒子体积导致较平滑的表面特性,且较大的粒子体积导致较粗糙的表面特性。对所述发泡体的表面特性的控制对于某些应用而言是合乎需要的,例如,用于汽车仪表板的发泡体一般需要较平滑的表面使得TPO层合体在它随时间与发泡体表面相符时不反映该表面的不规则性。
在另一实施方式中,物理交联的能发泡的粒子在模腔中原位发泡以产生与所述模具的形状相符的发泡体。和其中将液体发泡体前体注入到模腔中且使其发泡的PU原位发泡方法不同,本发明的方法包括(在关闭模具之前或之后)将能发泡的粒子分散到所述模腔中。将所述模具内的所述能发泡的粒子加热到高于化学发泡剂的活化温度和树脂软化时的温度。然后,所述粒子发泡,从而填充所述腔以呈现出复杂的成型部件的形状。参考图1A,可认识到,将能发泡的片材放入模具内不会均一地填充具有不同尺寸和几何形状的各种间隙、特别是具有倒凹的不规则形状区域。所得的发泡体芯材将具有未填充的空间,且在它确实被填充的情况下,所述发泡体的触感将是不均一的。然而,参考图1B,可认识到,用适当量的物理交联的能发泡的粒子填充所述腔将导致在原位发泡时不规则形状的模腔被均一地填充,从而产生具有均一触感的发泡体芯材。
适于在物理交联的能发泡的粒子中使用的聚烯烃树脂包括但不限于低密度聚乙烯(LDPE),线型低密度聚乙烯(LLDPE);乙烯乙酸乙烯酯(EVA);聚丙烯(PP);乙烯丙烯二烯烃单体(EPDM),热塑性烯烃(TPO),热塑性弹性体(TPE),和橡胶。对于所述粒子的能发泡的组合物,可选择单一树脂以及两种或更多种树脂的共混物。
在另一实施方式中,物理交联的能发泡的粒子可在模具内原位发泡,且热结合到在所得发泡体一侧上的箔,和/或热结合到在所述发泡体另一侧上的聚丙烯(PP)或聚乙烯(PE)基底,从而容许一步原位层合和基底结合而不需要胶粘剂。例如,参考图1B,如果将TPO箔加入到所述模具在物理交联的能发泡的粒子的下面,并且将基底设置在所述能发泡的粒子的上面且其也为聚烯烃,则所述发泡体将直接地且以热的方式结合到所述箔而不是简单地附着,从而赋予成型的发泡体部件更好的结构完整性。
在另一实施方式中,可使用物理交联的能发泡的粒子实现在相同的密度下比传统的片状发泡体软的发泡体。典型地,较软的发泡体是通过使用经常包含高的VOC含量的树脂实现的。因此,例如对于其中VOC排放受到管制的汽车内部装饰应用,通过利用所述物理交联的能发泡的粒子,可以在选择具有较低的VOC含量的树脂方面上更大的灵活性实现软发泡体的制造。
实验方法
将各测试样品的发泡体配方共混,并通过单或双螺杆挤出机和片材模头在高于所述聚合物的熔融温度且低于所述发泡剂的活化温度的温度下挤出,从而制造能发泡的片材。
将挤出的片材用电子束物理照射至期望的交联水平。聚烯烃发泡体的交联水平通过如下测定:制备在内部具有3个均一的狭缝的12mm宽的样品,从而得到四个3mm宽的条带,然后在使得所述样品的重量在0.047g和0.053g之间的适当长度处进行切割。然后,将经称重的交联的聚烯烃发泡体(A,以克计)在120℃下在25mL二甲苯中浸渍24小时。在24小时之后,将内容物通过200目的丝网过滤且将其在通风橱内静置最少12小时。随后,将所述样品与所述丝网一起放置在设定在15inHG的100℃真空烘箱中4小时以真空-干燥所述丝网上的不溶物。测量所述不溶物的干重(B,以克计),且根据以下方程式计算交联水平:交联水平(重量%)=100×(B/A)。
然后,使物理交联的片材经受不同的研磨技术以制造物理交联的粒子,包括具有大致球形vs.立方形或角形几何形状的那些。尽管使用挤出的片材,但是能发泡的配混固体对于制造物理交联的能发泡的粒子也是合适的。此外,可利用用于制造粒子的任何合适的方法,其包括但不限于,研磨、撕碎、磨碎、切碎、切块、低温研磨、切割、冲切、成粒和成微粒。此外,所述粒子还可直接交联而不是由预先交联的挤出的能发泡的片材或能发泡的配混固体制成。
为了产生期望的粒子体积,将能发泡的粒子根据ASTM D6913通过使用各种尺寸的分子筛(特别地筛NO12(1700μm)、NO20(850μm)、NO30(600μm)、NO50(300μm)、NO80(180μm)和NO100(150μm))分离。粒子体积由计算的平均粒度(测量的直径)和粒子的几何形状(例如球形vs.立方形或角形)得到。对于所分析的每个样品,将来自所述样品的约0.7克-约6.2克的能发泡的粒子均一地装填在2x 2x 0.25英寸周界的模具中,并且使其在高于所述发泡剂的活化温度的温度下原位发泡直至所述粒子完全发泡。在所述发泡完成之后,将所述模具在一桶水中骤冷1分钟。
在冷却之后,测量所得发泡体的密度。密度通过称量所得发泡体的重量且将其除以模腔的体积而测量,所述模腔的体积为1in3或0.0005787ft3。
实施例1–粒子体积vs.发泡体密度
根据上述的实验方法,由下表1中所示的包括低密度聚烯烃(LDPE)作为树脂的三个样品发泡体配方制备能发泡的粒子。硬脂酸锌用作发泡催化剂(kicker)(其起到降低发泡剂的分解温度的作用),也用作润滑剂。还使用氧化锌作为另外的发泡催化剂,同时使用硬脂酸作为润滑剂。然而,合适的发泡催化剂还可包括但不限于尿素、OBSH、硬脂酸铝、硬脂酸钡、硬脂酸钙、氧化钙、二氧化钛和炭黑。合适的润滑剂还可包括但不限于聚乙烯蜡、聚乙二醇和脂肪酸。合适的抗氧化剂包括酚类、亚磷酸酯和基于硫的化合物。
表1
由样品1配方制成具有大致球形vs.立方形或角形几何形状的物理交联的能发泡的粒子且使其交联至约40%的凝胶含量。然后,将对于各目标密度适当质量的能发泡的粒子在模具中发泡,且对于使用的各相应的粒子体积,测量所述发泡体的所得密度,如下表2中所示。如从球形vs.立方形的粒子几何形状的平均中值粒度(即粒径)vs.粒子体积的数据可认识到,由于球体的较高的体积对表面的比率,球形粒子的粒子体积比立方形的高。
表2
所得发泡体密度和能发泡的粒子体积之间的关系图示于描绘表2数据的图2的线图中,其表明在较小的粒子体积下,所得的发泡体密度高(即较低的发泡效率),而随着粒子体积的增大,发泡体密度下降(即较高的发泡效率)。可看出,粒子体积对所得的发泡体密度的影响从大约1.1mm3开始起变得平稳。此外,发现,所得的发泡体密度和粒子体积之间的这种关系与粒子的几何形状无关,且因此与线性度量例如基于粒径的平均中值粒度对比,粒子体积被确定为能发泡的粒子的预期发泡效率的更好的指标。
另外,由样品2和3的配方制成物理交联的能发泡的粒子,且其具有约40%的凝胶含量。然后,使对于各目标密度适当质量的能发泡的粒子在模具中发泡,且对于使用的各相应的粒子体积,测量所得的发泡体密度,如表3中所示的。
表3
如描绘表3数据的图3线图中所示的,所得的发泡体密度和能发泡的粒子体积之间的关系与图2是一致的,但是通过加入更多的发泡剂,样品2和3的配方能够实现甚至更低的发泡体密度,且对于样品3,通过如下实现甚至更大的发泡效率:使用更多的发泡催化剂和抗氧化剂来分别加速发泡剂分解反应和提高对通过热暴露而降解的耐受性。
另外,由样品2和3的配方制成物理交联的能发泡的粒子,但是这次对于样品2而言,具有约38%的凝胶含量,且对于样品3而言,34%。然后,使对于各目标密度适当质量的能发泡的粒子在模具中发泡,且对于所使用的各相应的粒子体积,测量所得的发泡体密度,如表4中所示的。
表4
样品2 | 样品3 | |
粒子体积(mm3) | 发泡体密度(pcf) | 发泡体密度(pcf) |
0.946 | 2.7 | 2.5 |
0.399 | 2.9 | 3.1 |
0.073 | 3.4 | 3.6 |
如描绘表4数据的图4线图中所示的,所得的发泡体密度和能发泡的粒子体积之间的关系与图2和3是一致的,但是实现了甚至更低的发泡体密度,其部分地是因为样品2和3较低的凝胶含量,发现该较低的凝胶含量具有改善发泡效率的效果,这还参考以下的实施例2进行描述。
根据之前描述的实验方法,还对由下表5中所示的另外的聚烯烃树脂配方制成的物理交联的能发泡的粒子进行测试。具体地,使用如下制成能发泡的配方:乙烯乙酸乙烯酯(EVA);线型低密度聚乙烯(LLDPE);聚丙烯(PP);乙烯丙烯二烯烃单体(EPDM),热塑性烯烃(TPO)和热塑性弹性体(TPE)。
表5
使样品4物理交联至具有约35%的凝胶含量,样品5约25%,样品6约45%,样品7约60%,且样品8约50%。使由样品4-8各自获得的能发泡的粒子在模具中使用适当质量的所述粒子发泡以实现各目标密度,且对于选择的0.946mm3粒子体积,测量所得的各发泡体密度,如下表6中所示的。
表6
如从表6可认识到的,各树脂成功地形成具有基于物理交联的能发泡的粒子体积可预测的密度的发泡体,其中对于各配方,任何微小的差异归因于不同的熔体指数值和凝胶含量。
实施例2–凝胶含量vs.发泡体密度
根据之前描述的实验方法,由上表1中所示的样品2和3各自的配方制成能发泡的挤出片材,且用电子束以变化的剂量对其进行物理照射以产生下表7中所示范围的凝胶含量。然后,由所述片材制备具有0.946mm3粒子体积的物理交联的能发泡的粒子,且使其在模具中发泡,其中对于各能发泡的粒子的凝胶含量,测量所得的发泡体密度,如表7中所示的。
表7
物理交联的能发泡的粒子的凝胶含量和所得的发泡体密度之间的关系图示于描绘表7数据的图5线图中,且表明发泡体密度随着所述粒子的凝胶含量的增大而增大。因此,为了实现高的发泡效率和低的发泡体密度,约35%的能发泡的粒子的凝胶含量是合适的,且可预期其在到达太低以致不能使发泡发生的水平之前,例如将继续使发泡体密度降低到低至约1.2pcf。基于由所述样品的结果所查明的趋势,还可通过如下实现1.2pcf的发泡体密度:在使用35%凝胶和大的球形粒子几何形状(以使体积对表面的比率最大)的同时使所述能发泡的粒子中发泡剂的载量最大化。如由所述结果可认识到的,一旦凝胶含量变成低于约30%,则发泡效率变差且密度开始升高,例如由参考表5和6描述的样品5和6所证明的。例如,虽然具有25%的凝胶含量的样品5包含比具有45%的凝胶含量的样品6多的发泡剂,但是样品5导致5.8pcf的较高的发泡体密度,而样品6实现4.5pcf的较低的发泡体密度。因此,发现,低的凝胶含量比高的凝胶含量对发泡效率是更有害的。
实施例3–发泡剂vs.发泡体密度
根据之前描述的实验方法由下表8中所示的配方制成物理交联的能发泡的粒子。所选择的粒子体积为0.946mm3且凝胶含量为约40%。
表8
样品A(phr) | 样品B(phr) | 样品C(phr) | 样品D(phr) | 样品E(phr) | |
LDPE | 100 | 100 | 100 | 100 | 100 |
ADCA | 7.1 | 10.5 | 15.3 | 22.8 | 28.8 |
硬脂酸锌 | 2 | 2 | 2 | 2 | 2 |
抗氧化剂 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
硬脂酸 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
氧化锌 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
使具有不同的发泡剂(ADCA)水平的样品A-E各自的物理交联的能发泡的粒子在模具内发泡,且测量密度,如表9中所示的。
表9
样品A | 样品B | 样品C | 样品D | 样品E | |
发泡剂(phr) | 7.1 | 10.5 | 15.3 | 22.8 | 28.8 |
密度(pcf) | 9.4 | 6.4 | 5.3 | 4.8 | 4.2 |
如描绘表9数据的图6线图中所示的,对于物理交联的能发泡的粒子,在较低的发泡剂载量水平下,所得的发泡体密度较高(且发泡效率较低),并且随着发泡剂载量的增大,所述密度下降(且发泡效率提高)。
实施例4–能发泡的粒子的体积vs.表面平滑度
根据之前描述的实验方法,由表1中所示的样品2的配方制成具有约40%的凝胶含量和变化的粒子体积的物理交联的能发泡的粒子。对于各粒子体积的样品,在所述模具内制造具有10pcf的密度的发泡体以量化通过以下的墨转印透光率测试方法测量的平滑vs.粗糙的表面特性。
将各2x 2x 0.25英寸的发泡体样品用胶带粘到尺寸为2x 2x 3.5英寸且重量为4lbs的金属块的底部上。此外,将一层Pacon Art 1st半透明轻质平滑描图纸(Semi-Transparent Lightweight Smooth Tracing Paper)放置在由0.8mm厚EVA发泡体组成的衬里发泡体之上,其按照ASTM-3575方法的25%压缩变形值为约6.5psi。将其上粘有重物的各发泡体样品放置在Ranger的Archival Ink Jet Black印台上,且使其旋转完整的三圈以将墨转印到所述发泡体表面且除了施加1psi压力的金属块之外不向所述样品外部地传递任何压缩力。然后,将各样品从所述印台立即移除,且在5秒内将其以墨侧向下轻轻地放置在描图纸之上。在30秒之后,移除所述金属块和样品。然后,根据以下方法对各样品测量通过各经压印的描图纸的透光率。将Extech407026光度计附着到具有3英寸内径且涂覆有Krylon Colormaster Paint+Primer Black Flat的光约束管的一个开放端。在所述光约束管的另一端上,将具有Sylvania F15T8/DSGN50荧光灯泡的Porta Trace 1417光源放置成与所述管接触,且在所述光度计设定为荧光模式的情况下,记录全亮度以验证所述光源的输出规格和所述光度计(300流明)的校准。然后,将一块未经压印的描图纸放置在所述光源之上且与光约束管的开放端(与光度计相对)接触,且通过光度计记录亮度作为对照数据点。为了测量通过各样品的透光率,将具有各压印印痕的描图纸接连地放置在光源上且与光约束管的开放端接触,与光度计相对,距离5.5英寸,确保管的周界不阻挡任意压印印痕,且记录各自的亮度。为了计算百分比透光率,将各压印印痕的测量亮度除以未经压印的纸的对照数据。所述样品越平滑,则越多的墨转印到所述纸,因此妨碍了光的透射。因此,透光率越低,则发泡体的表面越平滑,且透射率越高,则发泡体表面越粗糙。
在表10中总结了所述测试的结果,其显示了使用不同的物理交联的能发泡的粒子体积制造的发泡体的%透光率(且由此的平滑vs.粗糙的表面特性)。
表10
图7为描绘表10数据的条形图,其表明对于物理交联的能发泡的粒子,粒子体积越小,则所得发泡体的表面特性越平滑,且粒子体积越大,则所得发泡体的表面特性越粗糙。因此,对于变化的各应用的需求,以原位制造的发泡体的不同的表面特性为目标,可选择最佳的粒子体积。基于表10的样品结果的外推,使用1.5mm3粒子体积可实现高至60%的透光率值。
实施例5–层合
根据之前描述的实验方法,由表1中所示的样品2的配方制成具有约40%的凝胶含量和约0.073mm3的粒子体积的物理交联的能发泡的粒子。将1.1克所述能发泡的粒子加入到模具,该模具具有放置在模具下面的3英寸x3英寸x 35密耳的TPO箔。将4英寸x 4英寸的PVC网放置在TPO箔的下面以形成浮雕图案并且为在TPO和底板之间捕获的空气提供逃逸路径。在发泡和冷却之后,取出的发泡体样品具有约4.0pcf的密度且具有热结合到其的浮雕TPO箔,从而证实使用物理交联的能发泡的粒子可在模具内以一步完成TPO层合到发泡体。
另外,实施以上相同的实验,其中在所述模具的不同于TPO箔的另一侧上有1.95英寸x 1.95英寸x 48密耳的聚丙烯(PP)片材,该片材落在物理交联的能发泡的粒子之上。再次,在发泡和冷却之后,取出的发泡体样品为约4.0pcf,且具有热结合到一面上的浮雕TPO箔和热结合到另一面的PP基底,从而证实使用物理交联的能发泡的粒子可在模具内以一步完成TPO层合到原位发泡体及基底结合。还可使用聚乙烯(PE)片材作为发泡体基底进行热结合。
另外,按照之前描述的实验方法,将包含100份低密度聚乙烯(LDPE)的发泡体配方与16.1phr化学发泡剂(ADCA)、0.2份氧化锌、2.0份硬脂酸锌、0.2份润滑剂和0.2份抗氧化剂混合,将其用于制造能发泡的片材,且将其交联至40%的水平。然后,制备具有约0.946mm3粒子体积的能发泡的粒子且使其在模具内发泡,其中之前描述的TPO箔放置在该模具的下面。在发泡和冷却之后,取出的发泡体样品具有5.1pcf的密度且具有热结合到其的浮雕TPO箔。
另外,还使来自以上的相同粒子在包含1.95英寸x 1.95英寸x 48密耳的聚丙烯(PP)或聚乙烯(PE)片材的模具内发泡,所述片材从物理交联的能发泡的粒子上方落入模具中。在发泡和冷却之后,取出的发泡体样品具有5.1pcf的密度,其中浮雕TPO箔热结合到一面上且固体PP或PE基底热结合到另一面。
尽管在以上实施例中使用TPO箔,但是例如其它合适的基于聚烯烃的箔也可使用物理交联的能发泡的粒子热结合,例如TPE。替代地,对于基于非聚烯烃的箔例如PVC和天然或合成皮革,可使用胶粘剂建立与发泡体的结合。
实施例6–肖氏00硬度
根据之前描述的实验方法,由表1中所示的样品2配方制成具有约40%的凝胶含量和约0.946mm3的粒子体积的物理交联的能发泡的粒子,以制造下表12中所示的四个原位发泡体样品,且测量各样品的密度和肖氏00值。为了对比,还根据表11中所示的配方制备传统的片状发泡体配方的四个样品,且测量密度和肖氏00值,也在表12中示出。
表11
表12
图8为描绘表11数据的线图,其表明由物理交联的能发泡的粒子制成的发泡体的肖氏00曲线比具有相同密度的传统片状发泡体的低(因此更软)。较软的发泡体通常需要使用具有高的挥发性有机化合物(VOC)排放的树脂,其可导致不满足各种环境和工业规章(例如,对于汽车内部装饰市场)的发泡体。因此,通过使用所述物理交联的能发泡的粒子,可在相同密度下实现比传统的片状发泡体软的发泡体,从而容许在发泡体配方中选择具有较低的VOC排放的树脂方面上的更大的灵活性。
实施例7–热稳定性
根据之前描述的实验方法,由表1中所示的样品2配方制成具有约40%的凝胶含量和约0.946mm3的粒子体积的物理交联的能发泡的粒子,且使其在模具内发泡。为了对比,使用化学交联剂配制具有相同粒子体积的能发泡的粒子(配方包括100phr LDPE、22.8phrADCA、1.3phr抗氧化剂、1.8phr氧化锌、4.0phr硬脂酸锌、0.2phr硬脂酸和3phr过氧化物),且使其在模具内发泡以制造具有约65%凝胶含量的化学交联的发泡体样品。将两个样品暴露于60℃、80℃或100℃的温度24小时。在热循环之前和之后测量所述样品的长度、宽度和厚度,且对尺度变化进行比较,如表13中所示的。
表13
60℃ | 80℃ | 100℃ | |
化学交联的 | 2.3% | 2.9% | 5.4% |
物理交联的 | 2.6% | 3.0% | 6.3% |
如描绘表13数据的图9条形图中所示的,由物理交联的能发泡的粒子制造的发泡体呈现出与由包含化学交联剂的能发泡的粒子制成的发泡体可比的良好的热稳定性。
尽管已经参考示例性实施方式对本发明进行了描述,但是本领域技术人员将理解,可做出多种多样的变化且可用等同物对其要素进行替代而不偏离本发明的范围。另外,可做出很多改变以使特定的情形或材料适用于本发明的教导而不偏离其实质范围。因此,希望,本发明不受到所公开的具体实施方式的限制,而是本发明将包括落在所附权利要求的范围内的所有实施方式。
Claims (15)
1.物理交联的能发泡的粒子,其包括聚烯烃树脂和发泡剂,所述能发泡的粒子具有至少约0.002mm3的粒子体积。
2.如权利要求1所述的物理交联的能发泡的粒子,其中所述能发泡的粒子具有约15%-约85%的凝胶含量。
3.如权利要求1所述的物理交联的能发泡的粒子,其中所述聚烯烃树脂包括选自LDPE、LLDPE、EVA、PP、EPDM、TPO、TPE和橡胶的至少一种。
4.如权利要求1所述的物理交联的能发泡的粒子,其进一步包括约1phr-约60phr的所述发泡剂。
5.如权利要求1所述的物理交联的能发泡的粒子,其中所述发泡剂包括选自偶氮二甲酰胺、碳酸氢钠和碳酸钙的至少一种。
6.如权利要求1所述的物理交联的能发泡的粒子,其中由所述能发泡的粒子制造的发泡体具有约1.2pcf-约40pcf的密度。
7.如权利要求1所述的物理交联的能发泡的粒子,其中由所述能发泡的粒子制造的发泡体具有约40%-约60%的基于墨转印透光率测试方法的表面平滑度。
8.如权利要求1所述的物理交联的能发泡的粒子,其中由所述能发泡的粒子制造的发泡体具有比相同密度的片状发泡体的平均肖氏00硬度低的平均肖氏00硬度。
9.如权利要求1所述的物理交联的能发泡的粒子,其中由所述能发泡的粒子制造的发泡体具有约55-约75的肖氏00硬度。
10.使用如权利要求1所述的物理交联的能发泡的粒子制造的发泡体,其中所述发泡体热结合到热塑性烯烃箔和热塑性烯烃基底的至少一个。
11.如权利要求10所述的发泡体,其中所述热塑性烯烃基底为聚丙烯或聚乙烯片材。
12.如权利要求1所述的物理交联的能发泡的粒子,其中所述粒子是由能发泡的配混固体制造的。
13.如权利要求12所述的物理交联的能发泡的粒子,其中所述能发泡的配混固体是物理交联的。
14.如权利要求12所述的物理交联的能发泡的粒子,其中所述能发泡的配混固体是以挤出片材的形式。
15.使用如权利要求1所述的物理交联的能发泡的粒子制造原位发泡体的方法,其包括:
将所述物理交联的能发泡的粒子分散在模具的内部;
将所述物理交联的能发泡的粒子加热到高于所述发泡剂的活化温度的温度;和
使所述粒子在所述模具的内部发泡,从而制造与所述模具的形状相符的物理交联的发泡体。
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CN109580702A (zh) * | 2018-11-26 | 2019-04-05 | 中国石油大学(北京) | 一种流体包裹体的均一温度和冰点温度的测定方法 |
CN111019183A (zh) * | 2019-12-23 | 2020-04-17 | 安踏(中国)有限公司 | 一种微交联弹性体发泡材料、其制备方法和应用 |
CN114765983A (zh) * | 2019-11-28 | 2022-07-19 | 积水化学工业株式会社 | 具有大芯孔的交联聚烯烃发泡体 |
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US11225047B2 (en) * | 2017-03-15 | 2022-01-18 | International Automotive Components Group North America, Inc. | Skin-foam-substrate structure via induction heating |
DE102018126646A1 (de) * | 2018-10-25 | 2020-04-30 | Leoni Kabel Gmbh | Biobasiertes Kunstleder |
JP7474704B2 (ja) * | 2019-07-31 | 2024-04-25 | 積水化学工業株式会社 | ポリオレフィン系樹脂発泡体シート及びそれを用いた粘着テープ |
KR20210073790A (ko) * | 2019-12-11 | 2021-06-21 | 한화솔루션 주식회사 | 발포용 프레스를 사용하는 물리발포 공정 |
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