CN107849282A - 发泡成型用树脂、发泡成型体的制造方法 - Google Patents

发泡成型用树脂、发泡成型体的制造方法 Download PDF

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CN107849282A
CN107849282A CN201680039842.5A CN201680039842A CN107849282A CN 107849282 A CN107849282 A CN 107849282A CN 201680039842 A CN201680039842 A CN 201680039842A CN 107849282 A CN107849282 A CN 107849282A
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resin
foaming
ldpe
expanded moldings
density polyethylene
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CN107849282B (zh
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染谷孝明
佐野尊
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Kyoraku Co Ltd
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Abstract

提供一种含有可提高发泡倍率LDPE的发泡成型用树脂。根据本发明，提供一种发泡成型用树脂，其含有低密度聚乙烯，所述低密度聚乙烯的熔体张力为100～250mN，且剪切粘度为350～450PA·s。

Description

发泡成型用树脂、发泡成型体的制造方法
【技术领域】
本发明涉及发泡成型用树脂、以及发泡成型体的制造方法。
【背景技术】
例如，汽车等空调装置中，使用用于通风的管状的空调用管道。
作为空调用管道，使用了藉由发泡剂将热塑性树脂发泡的发泡树脂的发泡成型体被熟知。发泡成型体是因为其可同时实现高绝热性和轻量化，因此需求在增大。
作为这样的发泡成型体的制造方法，用组合模具将熔融状态的发泡树脂闭模，在内部吹入空气使其膨胀的吹塑成型方法被广泛知晓。
专利文献1中公开了，为了提高发泡成型中发泡成型体的发泡倍率，使熔体张力(MT)为规定值以上，且使MT×熔体质量流动速率(MFR)为规定值以上的技术。
【现有技术文献】
【专利文献】
【专利文献1】日本专利特开2012－067256号公报
【发明内容】
【发明要解决的问题】
在专利文献1中公开的基准是可适用于各种原料树脂的，但是关于用于发泡成型用的原料树脂的低密度聚乙烯(LDPE)，研究了MT以及MT×MFR和所得到的发泡成型体的发泡倍率的关系，发现尽管MT和MT×MFR都显示较高的值，但有时候发泡倍率也会变低。
本发明是鉴于这样的情况而完成的，提供一种含有能够提高发泡倍率的LDPE的发泡成型用树脂。
【解决问题的手段】
根据本发明，提供一种含有低密度聚乙烯的发泡成型用树脂，所述低密度聚乙烯的熔体张力为100～250mN，且剪切粘度为350～450PA·s。
本发明人等进行了认真研究，发现LDPE的MT在规定的范围内，且LDPE的剪切粘度在规定的范围内时，能够得到发泡倍率高的发泡成型体，从而完成了本发明。
本发明中，作为关于发泡成型性的粘度的参数，着眼于剪切粘度。与从模头压出后的发泡型坯的成型性相关的MFR不同，剪切粘度是与在发泡挤出机内的气体被树脂吸收的举动相关的粘度参数。并且，剪切粘度在规定范围时，通过提高气体在树脂中的溶解和分散，发泡成型性也变得优异。
以下例示本发明的各种实施方式。以下示出的实施方式可以相互结合。
优选所述发泡成型用树脂为进一步含有高密度聚乙烯。
优选所述低密度聚乙烯与所述高密度聚乙烯的质量比为2：8～8：2。
根据本发明的另一观点，提供一种发泡成型体的制造方法，其具备将上述的发泡成型用树脂和发泡剂在发泡挤出机内进行熔融混练而成的熔融混练树脂从所述发泡挤出机挤出来形成发泡型坯，将所述发泡型坯进行成型而得到发泡成型体的工序。
【附图说明】
图1表示本发明的一个实施方式的发泡挤出机1和组合模具14的截面图。
图2表示图1中的模头12的具体结构的截面图。
图3是关于本发明的实验例1的样品A～L，描绘MT与MT×MFR的关系的图表。
图4是关于本发明的实验例1的样品A～L，描绘MT与剪切粘度的关系的图表。
【具体实施方式】
以下说明本发明的实施方式。以下示出的实施方式中的各种特征事项可以互相组合。并且，各特征事项可独立地使发明成立。
1.发泡成型用树脂
本发明的一种实施方式的发泡成型用树脂为含有LDPE的发泡成型用树脂，所述LDPE的MT为100～250mN且剪切粘度为350～450PA·s。
如后述的实验例·比较例所示，通过使用含有MT和剪切粘度在上述范围内的LDPE的原料树脂进行发泡成型，可以提高发泡成型体的发泡倍率。原料树脂含有LDPE以外的树脂的情况下，LDPE的物性也特别重要。这是由于，如LDPE具有长链分支的树脂的分子链之间交织，具有保持气泡之间的单元结构的作用，对具有长链分支的LDPE的物性会对发泡成型性的好坏具有强大的影响。
本实施方式中，LDPE的MT为100～250mN。当LDPE的MT小于100mN时，因树脂强度过弱，破泡而发生小孔，因此发泡倍率变低。另一方面，当LDPE的MT超过250mN时，因树脂强度过高，气泡的成长被阻碍，因此发泡倍率变低。MT优选为100～200mN。此时，发泡倍率更容易变高。在本说明书中，「熔体张力(MT)」是指，利用熔体张力测试仪(株式会社东洋精机制作所制造)，以试验温度190℃、挤出速度10mm/分，从直径2.095mm、长度8mm的口中将线束(Strand)挤出，将该线束以卷取速度16rPm卷取到直径80mm的辊时的张力。
本实施方式中，LDPE的剪切粘度为350～450PA·s。当LDPE的剪切粘度小于350PA·s时，由于在将发泡成型用树脂和发泡剂混练的发泡挤出机内的树脂压过低，无法将发泡用的气体充分溶解于发泡成型用树脂中，因而发泡倍率变低。另一方面，当LDPE的剪切粘度超过450PA·s时，由于在将发泡成型用树脂和发泡剂混练的发泡挤出机内的树脂压与气体注入压力的差变小，树脂难以融合到气体，因此气体的分散性变低，发泡倍率变低。剪切粘度优选为350～400PA·s。此时，发泡倍率更容易变高。本说明书中，「剪切粘度」是指，依据JIS K－7199，以试验温度190℃、表观的剪切速度600/秒进行测定而得到的值。
本实施方式的LDPE的MFR没有特别限定，例如优选0.2～2.5g/10分，更优选0.8～2.0g/10分。此时，因为发泡倍率特别容易变高。本说明书中，「熔体质量流动速率(MFR)」是指，依据JIS K－7210，以试验温度190℃、试验荷载2.16kg进行测定而得到的值。
本实施方式的发泡成型用树脂可以仅由LDPE构成，也可以含有别的树脂。作为LDPE以外的树脂，可列举高密度聚乙烯(HDPE)。这是由于藉由在发泡成型用树脂中含有HDPE，可提高所得到的发泡成型体的刚性。LDPE与HDPE的质量比没有特别限定，优选2：8～8：2，更有选3：7～7：3。这是由于若HDPE的比例过小，则发泡成型体的刚性容易变低，若HDPE的比例过大，则发泡倍率容易变低。藉由使用以上述比例将LDPE与HDPE进行混合的树脂，可得到刚性和发泡倍率高的发泡成型体。
HDPE的物性没有特别限定，优选的MFR、剪切粘度、密度、MT分别如下。当并用具有以下物性的HDPE与LDPE时，容易得到刚性和发泡倍率高的发泡成型体。
MFR：0.2～0.4g/10分
剪切粘度：550～650PA·s
密度：0.94～0.96g/cm3
MT：70～200mN
形成于发泡成型体的气泡的厚度方向的长度优选为50～100μm。50μm时，由于气泡的成长不充分而发泡倍率容易变低，当超过100μm时，由于引发破泡而容易产生小孔。
2.发泡成型体的制造方法
本发明的一个实施方式的发泡成型体的制造方法中，具备如下工序，即，在发泡挤出机内将上述发泡成型用树脂和发泡剂进行熔融混练而成的熔融混练树脂从所述发泡挤出机挤出来形成发泡型坯，将所述发泡型坯进行成型得到发泡成型体。
该方法的一个例子中，可使用如图1所示的发泡挤出机1和组合模具14来实施。发泡挤出机1具备气缸3、树脂投入口5、螺旋7、发泡剂注入口P、温度控制部9、树脂挤出口11以及模头12。
以下详细说明各个构成要素。
＜树脂投入口5＞
树脂投入口5是所谓的料斗，由此投入原料树脂。原料树脂的形态没有特别限定，通常为颗粒状。原料树脂为上述的本发明的一个实施方式的发泡成型用树脂。将原料树脂从树脂投入口5投入到气缸3中之后，通过在气缸3中加热而被熔融成为熔融树脂。并且，通过配置于气缸3中的螺旋7的旋转，朝向设置于气缸3的一端的树脂挤出口11搬运。
＜螺旋7＞
螺旋7配置于气缸3中，通过其旋转来将熔融树脂进行混练的同时朝向树脂挤出口11搬运。螺旋7的一端设有齿轮装置15，螺旋7通过齿轮装置15被旋转驱动。配置在气缸3中的螺旋7的个数可以为1个，也可以为2个以上。
＜发泡剂注入口P＞
气缸3设有用于在气缸3中注入发泡剂的发泡剂注入口P。设置发泡剂注入口P的位置没有特别限定，将气缸3的树脂投入口5侧的端部的位置为0、树脂挤出口11侧的端部的位置为L时，发泡剂注入口P优选设置于0.3L～0.7L(优选0.4～0.6L)的位置。若发泡剂注入口P设置于比0.3L更靠近树脂投入口5侧，则在熔融树脂的混练不充分的状态下发泡剂被注入而有时候发泡剂的分散变得不充分。并且，由于熔融树脂的温度通常以朝向树脂挤出口11慢慢降低的方式控制，因此若设置于比发泡剂注入口P0.7L更靠近树脂挤出口11侧，则有时候在注入发泡剂的部位的熔融树脂的温度过低而发泡剂的注入量减少。
从发泡剂注入口P注入的发泡剂可列举物理发泡剂、化学发泡剂、以及其混合物，优选物理发泡剂。作为物理发泡剂，可使用空气、二氧化碳、氮气、水等无机类物理发泡剂、以及丁烷、戊烷、己烷、二氯甲烷、二氯乙烷等有机类物理发泡剂、还有这些的超临界流体。作为超临界流体，优选利用二氧化碳、氮等来制备，若为氮则可通过设临界温度为－149.1℃、临界压力为3.4MPA以上来得到，若为二氧化碳则可通过设临界温度为31℃、临界压力为7.4MPA以上来得到。作为化学发泡剂，可列举通过酸(例：柠檬酸或其盐)与碱(例：碳酸氢钠)的化学反应来产生二氧化碳气体的化学发泡剂。化学发泡剂可以从发泡剂注入口P投入，但也可以从树脂投入口5投入。
＜温度控制部9＞
温度控制部9以分别控制沿着气缸3设置的多个调温单元来控制气缸3的各部分的温度的方式构成。并且，温度控制部9也可以控制用于形成型坯的模头12的温度、以及气缸3与模头12之间的连接部10的温度。
＜树脂挤出口11·模头12＞
将原料树脂和发泡剂进行熔融混练而成的熔融混练树脂从树脂挤出口11被挤出，通过连接部10注入到模头12中。如图2所示，模头12具备圆筒状的塑模外筒41、容纳于其内部的模芯43，在其之间的空间47储存从气缸3挤出的熔融混练树脂。此外，在空间47储存规定量的熔融混练树脂之后，朝向垂直方向向下推动环状活塞45，从而从塑模缝隙49挤出熔融混练树脂而形成圆筒状的发泡型坯13。应予说明，在此，表示用于形成圆筒状的发泡型坯13的模头12，但模头12也可以为用于形成片状的发泡型坯的模头。
＜组合模具14＞
发泡型坯13被引导于一对组合模具14之间。通过利用组合模具14来进行发泡型坯13的成型，从而得到发泡成型体。利用组合模具14的成型方法没有特别限定，可以为在组合模具14的型腔内吹入空气而进行成型的吹塑成型，也可以为从组合模具14的型腔的内面对型腔内进行減压而进行发泡型坯13的成型的真空成型，也可以为其组合。
【实施例】
＜实验例1＞
利用如图1所示的发泡挤出机1和组合模具14，制作发泡成型品，进行发泡成型性的评价。发泡挤出机1的气缸3的内径为50mm，L/D＝34。原料树脂使用如表1所示的将LDPE和HDPE(标号：B470，旭化成化学制造)以质量比1：1进行混合的原料树脂。进行温度控制部9的设定使发泡型坯13的温度为190～200℃。使螺旋7的旋转次数为60rmm，挤出量为20kg/hr。发泡剂使用N2气体，从设置于0.5L的位置的发泡剂注入口P进行注入。通过改变注入气体量来调整发泡倍率。
利用以以上的条件形成的发泡型坯进行吹塑成型，制作了φ50mm、高度100mm且厚度5mm的圆筒状的发泡成型体。
关于各原料树脂，制作了注入气体量不同的多种发泡成型体，将不产生因小孔以及破泡引起的表面粗糙的最大发泡倍率判断为可成型的发泡倍率。应予说明，在以下的说明中，可成型的发泡倍率简单记为发泡倍率。
将得到的结果示于表1。表1中的样品A～D为本发明的实施例，样品E～L为比较例。表1中一起显示MT、MFR、MT×MFR、以及剪切粘度的值。MT、MFR、以及剪切粘度以在施方式中说明的方法进行测定。
【表1】
关于表1中的样品A～L，图3表示描绘MT与MT×MFT的关系的图表，图4表示描绘MT与剪切粘度的关系的图表。图3～图4中，以黑圈「●」表示发泡倍率为2倍以上的，以内部为白色的钻石形状「◇」表示小于2倍的。在各描绘点的相邻位置所记载的数值表示发泡倍率。
从图3中的样品A，C，H的比较可知，即使在MT×MFR高的情况下，发泡倍率不一定变高。另一方面，如图4所示，可知发泡倍率为2倍以上的样品集中在图4中的被粗线围成的四方形区域。可知，由于被粗线围成的四方形区域，MT为100～250mN且剪切粘度为350～450PA·s，通过将含有MT和剪切粘度在这样的范围内的LDPE的树脂作为原料树脂使用，可以提高发泡倍率。另外，当剪切粘度が350～400PA·s时，发泡倍率会进一步变高。
＜实验例2＞
实施例2中，使用与样品D相同的LDPE，制作了将LDPE与HDPE的质量比改为7：3的样品D1和将LDPE与HDPE的质量比改为3：7的样品D2，对于各样品，测定了可成型的发泡倍率。结果，可成型的发泡倍率，样品D1为4倍、样品D2为2.3倍。此结果表示即使在LDPE与HDPE的质量比为1：1以外的情况下，通过使用MT为100～250mN且剪切粘度为350～450PA·s的LDPE，也可以提高发泡成型体的发泡倍率。
【符号的说明】
1：发泡挤出机、3：气缸、5：树脂投入口、7：螺旋、9：温度控制部、11：树脂挤出口、12：模头、13：发泡型坯、14：组合模具、P：发泡剂注入口。

Claims (4)

1.一种含有低密度聚乙烯的发泡成型用树脂，其中，
所述低密度聚乙烯的熔体张力为100～250mN，且剪切粘度为350～450Pa·s。
2.根据权利要求1所述的发泡成型用树脂，其中，
所述发泡成型用树脂进一步含有高密度聚乙烯。
3.根据权利要求2所述的发泡成型用树脂，其中，
所述低密度聚乙烯与所述高密度聚乙烯的质量比为2：8～8：2。
4.一种发泡成型体的制造方法，具备以下工序：
将权利要求1～权利要求3中任一项所述的发泡成型用树脂和发泡剂在发泡挤出机内进行熔融混练而成的熔融混练树脂从所述发泡挤出机挤出来形成发泡型坯，将所述发泡型坯进行成型而得到发泡成型体。
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