CN110945062A - 发泡成型用树脂、发泡成型体、发泡成型体的制造方法 - Google Patents

发泡成型用树脂、发泡成型体、发泡成型体的制造方法 Download PDF

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CN110945062A
CN110945062A CN201880047788.8A CN201880047788A CN110945062A CN 110945062 A CN110945062 A CN 110945062A CN 201880047788 A CN201880047788 A CN 201880047788A CN 110945062 A CN110945062 A CN 110945062A
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resin
foam
foam molding
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density polyethylene
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CN110945062B (zh
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染谷孝明
佐野尊
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Kyoraku Co Ltd
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Abstract

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，上述低密度聚乙烯的应变硬化度为0.40以上。

Description

发泡成型用树脂、发泡成型体、发泡成型体的制造方法
【技術分野】
本发明涉及发泡成型用树脂、发泡成型体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，上述低密度聚乙烯的应变硬化度为0.40以上。
本发明人等进行了认真研究，发现LDPE的应变硬化度为0.40以上时，能够得到发泡倍率高的发泡成型体，从而完成了本发明。
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。
优选发泡成型用树脂进一步含有高密度聚乙烯。
优选上述低密度聚乙烯与上述高密度聚乙烯的质量比为2:8～8:2。
优选上述低密度聚乙烯的熔体张力为250mN以上。
优选上述低密度聚乙烯的剪切粘度为450Pa·s以上。
根据本发明的另一观点，提供一种发泡成型体，其是由上述发泡成型用树脂成型而得到的。
根据本发明的另一观点，提供一种发泡成型体的制造方法，具备以下工序:
将上述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上述发泡挤出机挤出来形成发泡型坯，将上诉发泡型坯进行成型而得到发泡成型体。
【附图说明】
图1表示本发明的λn的计算方法的图表。
图2表示本发明的应变硬化度的计算方法的图表。
图3表示本发明的一个实施方式的发泡挤出机1以及组合模具14的截面图。
图4表示图1中模头12的具体结构的截面图。
图5是关于实施例1、2以及比较例1～5的应变硬化度与发泡倍率的关系的图表。
图6是关于实施例1、2以及比较例1～5的MFR×MT与发泡倍率的关系的图表。
【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
本发明的一个实施方式的发泡成型用树脂为含有LDPE的发泡成型用树脂，上述LDPE的应变硬化度为0.40以上。
本实施方式注目了应变硬化度作为发泡成型性的有关粘度参数。本申请中，将通过下式(1)由单轴拉伸粘度(ηE)计算出λn(图1)，横轴为应变(ε)、纵轴为logλn时所得到的斜线定义为应变硬化度(图2)。
λn＝ηE(t、ε非线性)/ηE(t、ε线性)…式(1)
式(1)中，ηE(t、ε非线性)为应变硬化中的拉伸粘度的测定值，ηE(t、ε线性)为未应变硬化时的拉伸粘度的测定值。
在本说明书中，单轴拉伸粘度ηE(t、ε非线性)是指，使用ARES-G2(TA INSTRUMENTS制造)在应变速度1s-1、测定温度180℃测定得到的值，单轴拉伸粘度ηE(t、ε线性)是指，同样使用ARES-G2(TA INSTRUMENTS制造)在应变速度0.1s-1、测定温度180℃测定得到的值。
若含有的LDPE的应变硬化度过低，则出现在成型时树脂局部被急剧拉伸的现象，在该拉伸的部分产生小孔。本实施方式的发泡成型状树脂通过含有应变硬化度高的LDPE，可抑制上述现象，作为其结果可得到发泡倍率高的发泡成型体。
LDPE的应变硬化度为0.40以上，更优选为0.44以上，通常为1.0以下，例如为0.40、0.41、0.42、0.43、0.44、0.45、0.46、0.47、0.48、0.49、0.50、0.51、0.52、0.53、0.54、0.55、0.56、0.57、0.58、0.59、0.60、0.70、0.80、0.90、1.00等，也可以是任何这些数值之间的值。
LDPE的熔体张力(MT)没有特别限定，例如为100mN、130mN、150mN、180mN、200mN、210mN、220mN、230mN、240mN、250mN、260mN、270mN、280mN、290mN、300mN、350mN、400mN、450mN、500mN、550mN、600mN等，可以是任何这些数值之间的值。
根据本实施方式的发泡成型用树脂，由于LDPE的MT例如为250mN以上、300mN以上等，被预测为以现有技术难以提高发泡倍率的树脂强度高的LDPE中也可选择合适的LDPE从而制造发泡倍率高的成型体。
在本说明书中，熔体张力(MT)是指，使用熔体张力测试仪(株式会社东洋精机制作所制造)在试验温度190℃、挤压速度10mm/分，从直径2.095mm、长度8mm的空口挤压股线，将该的股线以16rpm的卷绕速度在卷绕在直径为80mm的辊上时测定的张力。
本实施方式中LDPE的剪切粘度没有特别限定，可以是200Pa·s、250Pa·s、300Pa·s、350Pa·s、400Pa·s、450Pa·s、500Pa·s等，也可以是任何这些数值之间的值。
以往，剪切粘度为例如300Pa·s以下、350Pa·s以下等的LDPE，由于其在发泡挤出机内的树脂压过低，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。而且，剪切粘度为例如400Pa·s以上、450Pa·s以上等的LDPE，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。
然而，根据本实施方式的发泡成型用树脂，由于LDPE的应变硬化度为0.40以上，被预测为以现有技术难以提高发泡倍率的LDPE中也可选择合适的LDPE从而制造发泡倍率高的成型体。
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的熔体张力(MFR)没有特别限定，例如优选0.2～2.5g/10分、更优选0.3～2.0g/10分、最优选0.5～1.6g/10分。此时，因为发泡倍率特别容易变高。
本说明书中，熔体张力(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上述发泡挤出机挤出来形成发泡型坯，将上述发泡型坯进行成型得到发泡成型体。
得到的发泡成型体可使用于例如车辆用空调风管等。
该方法的一个例子中，可使用如图3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，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:重曹)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4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3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中一起显示MFR、MT、MFR×MT、应变硬化度、以及剪切粘度的値。MT、MFR、应变硬化度以及剪切粘度以在实施方式中说明的方法进行测定。
【表1】
Figure BDA0002371608500000091
表示实施例1、2以及比较例1～5的应变硬化度与发泡倍率的关系的图表示于图5，将表示MFR×MT与发泡倍率的关系的图表示于图6。
比较实施例1、2以及比较例可知，在使用应变硬化度为0.40以上的LDPE的实施例1、2中，示出2.5倍以上的优良的发泡倍率。而且，比较实施例2与比较例1可知，尽管MFR×MT的值几乎相同，实施例2示出了格外优良的发泡倍率的值。
<实验例2>
实验例2中，使用了实施例2的LDPE(标号:1005FY20、Reliance制造)，制作了将LDPE和HDPE的质量比改为7:3的实施例3、将LDPE和HDPE的质量比改为3:7的实施例4，测定了可成型的发泡倍率。结果，可成型的发泡倍率，实施例3为3.5倍、实施例4为2.4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，通过使用应变硬化度为0.40以上的LDPE，也可以提高发泡成型体的发泡倍率。
【符号说明】
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、43:芯棒、45:环状活塞、47:空间、49:塑模缝隙。

Claims (7)

1.一种含有低密度聚乙烯的发泡成型用树脂，其特征在于，
所述低密度聚乙烯的应变硬化度为0.40以上。
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.根据权利要求1～权利要求3中任一项所述的发泡成型用树脂，其中，
所述低密度聚乙烯的熔体张力为250mN以上。
5.根据权利要求1～权利要求4中任一项所述的发泡成型用树脂，其中，
所述低密度聚乙烯的剪切粘度为450Pa·s以上。
6.一种发泡成型体，其特征在于，是由权利要求1～权利要求5中任一项所述的发泡成型用树脂成型而得到的。
7.一种发泡成型体的制造方法，其特征在于，具备以下工序:
将权利要求1～权利要求5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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CN110945062B (zh) 2022-06-24
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JP6963171B2 (ja) 2021-11-05
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