CN105873736B - 透明树脂组合物的制造方法 - Google Patents

透明树脂组合物的制造方法 Download PDF

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CN105873736B
CN105873736B CN201480070667.7A CN201480070667A CN105873736B CN 105873736 B CN105873736 B CN 105873736B CN 201480070667 A CN201480070667 A CN 201480070667A CN 105873736 B CN105873736 B CN 105873736B
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resin
screw rod
melting mixing
resin composition
treatment portion
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CN105873736A (zh
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小林昭美
藤井重行
鲛岛孝文
清水博
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Shibaura Machine Co Ltd
HSP Technologies Inc
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Abstract

透明树脂组合物的制造方法，包括：通过将聚碳酸酯树脂和丙烯酸树脂向双轴挤出机连续供给以生成熔融混合树脂，将该熔融混合树脂向具有设置有剪切处理部的螺杆的单轴挤出机供给。进一步通过利用以500rpm以上、4000rpm以下的转速旋转的所述剪切处理部对所述熔融混合树脂进行混炼，来连续生成透明树脂组合物。

Description

透明树脂组合物的制造方法
技术领域
本发明涉及含有聚碳酸酯树脂和丙烯酸树脂的透明树脂组合物的制造方法。
背景技术
聚碳酸酯树脂在透明性、尺寸稳定性和耐冲击性等性能上优异，以往多用于汽车、电器设备和住宅等各种领域中。另一方面，虽然聚碳酸酯具有如上所述的优异特性，但由于其表面硬度或耐UV性差，因此正在进行关于其与丙烯酸树脂的掺合物的研发。
专利文献1中公开了利用具有内反馈型(日文：内部帰還型)螺杆的高剪切成形装置对由聚碳酸酯树脂与丙烯酸系树脂掺合而成的原料进行混炼而得到透明树脂材料的技术。
在该现有技术中，使由聚碳酸酯树脂与丙烯酸系树脂掺合而成的原料在200～240℃的熔点附近熔融并混炼。籍此，使直径在300nm以下、优选在100nm以下的甲基丙烯酸系树脂分散相在聚碳酸酯基质相中均匀且致密地纳米分散化，混炼得到的树脂材料变得透明。
现有技术中还记载，利用双轴的熔融混炼机等对原料进行混合的场合，分散相的尺寸变得比可见区域的波长还要大，混炼后的树脂材料不透明而呈白浊状。
现有技术文献
专利文献
专利文献1：WO2010/061872号文本
发明内容
发明所要解决的技术问题
专利文献1中所公开的具有内反馈型螺杆的高剪切成形装置是批处理式的成形装置，无法连续取出混炼后的树脂材料。而且，混炼2～5g原料却需要2分钟。因此，其与挤出机那样的以往的连续式制造装置相比，生产效率差，现实中难以适用于用来连续制造树脂制品的生产线。
本发明的目的在于，得到能够连续高效地生成由聚碳酸酯树脂与丙烯酸树脂掺合而成的透明树脂组合物的制造方法。
解决技术问题所采用的技术方案
为了达到上述目的，本发明的透明树脂组合物的制造方法的特征在于：将每单位时间供给量设定为95～60重量％的聚碳酸酯树脂和每单位时间供给量设定为5～40重量％的丙烯酸树脂向双轴挤出机连续供给，所述双轴挤出机的互相啮合的两根第一螺杆以600rpm以下的转速向着相同方向旋转，
通过使所述聚碳酸酯树脂和所述丙烯酸树脂在所述双轴挤出机中熔融并混合来生成熔融混合树脂，同时将所述熔融混合树脂从所述双轴挤出机连续排出，
将从所述双轴挤出机中排出的所述熔融混合树脂向单轴挤出机连续供给，所述单轴挤出机具有第二螺杆和收纳该第二螺杆的筒体，所述第二螺杆从基端部向前端部形成有输送螺纹、且在中间部设置有剪切处理部，
利用与所述第二螺杆一起以500rpm以上、4000rpm以下的转速旋转的所述剪切处理部对所述熔融混合树脂进行混炼以生成透明树脂组合物，同时将所述透明树脂组合物从所述单轴挤出机连续排出。
发明的效果
利用本发明，能够连续高效地生产由聚碳酸酯树脂与丙烯酸树脂掺合而成的透明树脂组合物。因此，能够适用于连续制造树脂制品的生产线。
附图的简要说明
[图1]图1是概略地显示本发明的制造方法中所使用的制造装置的剖面图。
[图2]图2是概略地显示本发明的制造方法中所使用的单轴挤出机的剖面图。
[图3]图3是概略地显示本发明的制造方法中所使用的单轴挤出机的其它形态的剖面图。
具体实施方式
下面，参照图1～图3对本发明的第一实施方式进行说明。
图1概略地展示了实施本发明的透明树脂组合物的制造方法时所使用的制造装置10。制造装置10具有第一原料供给装置11、第二原料供给装置12、双轴挤出机13、单管14和单轴挤出机15。
第一原料供给装置11是连续供给聚碳酸酯树脂A的构件，在本实施方式中，将聚碳酸酯树脂A每单位时间的供给量设定在95～60重量％的范围内。第二原料供给装置12是连续供给丙烯酸树脂B的构件，在本实施方式中，将丙烯酸树脂B每单位时间的供给量设定在5～40重量％的范围内。双轴挤出机13是通过使从第一原料供给装置11供给的聚碳酸酯树脂A和从第二原料供给装置12供给的丙烯酸树脂B连续熔融并混合来生成熔融混合树脂C的构件，将生成的熔融混合树脂C从双轴挤出机13连续排出。单管14以使从双轴挤出机13排出的熔融混合树脂C流过的方式构成。单轴挤出机15是通过对从单管14供给的熔融混合树脂C进行连续混炼来生成透明树脂组合物D的构件，生成的透明树脂组合物D从单轴挤出机15连续排出。
如图1所示，双轴挤出机13具有机筒20、和插入机筒20内部的筒体21中的两根第一螺杆22(图中仅示出一根)。第一螺杆22在筒体21内一边相互啮合一边向相同方向旋转。沿着机筒20的长边方向在一端设置有原料供给口23。原料供给口23在与第一螺杆22的基端部侧对应的位置处与筒体21连通。
聚碳酸酯树脂A从第一原料供给装置11通过原料供给口23向筒体21连续供给。同样地，丙烯酸树脂B从第二原料供给装置12通过原料供给口23向筒体21连续供给。
机筒20在第一螺杆22前端部侧的位置处具有另一端。单管14与机筒20的另一端连接。另外，在机筒20的外周部安装有对机筒20进行加热的加热器24。
第一螺杆22受到来自未图示的驱动马达的力矩而旋转。从原料供给口23向筒体21供给的聚碳酸酯树脂A和丙烯酸树脂B随着第一螺杆22的旋转而从第一螺杆22的基端部向前端部连续输送。
换言之，聚碳酸酯树脂A和丙烯酸树脂B从筒体21的一端向另一端通过筒体21的内部。此时，聚碳酸酯树脂A和丙烯酸树脂B在被旋转的第一螺杆22搅拌的同时，受到来自加热器24的热量而被加热。结果是，聚碳酸酯树脂A和丙烯酸树脂B熔融并混合，形成熔融混合树脂C。
从双轴挤出机13连续排出的熔融混合树脂C流过单管14内的通路30，供给至单轴挤出机15。单管14的外周安装有加热器31。加热器31以使熔融混合树脂C维持熔融状态的方式对单管14进行加热。
如图1所示，单轴挤出机15具有机筒40、和插入机筒40内部的筒体41中的第二螺杆42。沿着机筒40的长边方向在一端设置有树脂供给口44。树脂供给口44在与第二螺杆42的基端部侧对应的位置处与筒体41连通。单管14的通路30的下游端与机筒40的树脂供给口44连接。因此，流过单管14的通路30的熔融混合树脂C从树脂供给口44连续供给至筒体41。
另外，机筒40在第二螺杆42前端部侧的位置处具有另一端。在机筒40的另一端设置有模头45。在机筒40的外周安装有对筒体41进行加热的加热器46。
图2概略地显示了单轴挤出机15的第二螺杆42。第二螺杆42受到来自未图示的驱动马达的力矩而旋转。如图2所示，第二螺杆42在沿着其长边方向的中间部处具有剪切处理部43。在从第二螺杆42的基端部至剪切处理部43之间、以及从剪切处理部43至第二螺杆42的前端部之间，分别形成有输送螺纹47。输送螺纹47中包括牙尖在内的外径和根径(日文：谷径)设定在恒定值。
剪切处理部43具有反向输送螺纹48。反向输送螺纹48向着输送螺纹47的扭转方向相反的方向扭转，且在第二螺杆42的轴向上连续形成。反向输送螺纹48中的牙数例如在2牙以上、5牙以下，从反向输送螺纹48的一端至另一端之间不存在沟或凹槽。因此，反向输送螺纹48连续地形成为相同的形状。
根据第一实施方式，从单管14通过机筒40的树脂供给口44连续供给至筒体41的熔融混合树脂C随着第二螺杆42的旋转从第二螺杆42的基端部向剪切处理部43输送。到达剪切处理部43的熔融混合树脂C通过筒体41的内周壁与反向输送螺纹48的外周部之间。此时，熔融混合树脂C受到剪切作用而混炼，丙烯酸树脂B在聚碳酸酯树脂A中均匀且致密地分散。结果生成含有聚碳酸酯树脂A和丙烯酸树脂B的透明树脂组合物D。
生成的透明树脂组合物D从剪切处理部43向第二螺杆42的前端部输送，并在与机筒40的另一端连接的模头45处排出。模头45通过对透明树脂组合物D实施赋形加工来使透明树脂组合物D成形成规定的形状。成形后的透明树脂组合物D被从模头45挤出而成为制品。
图3概略地显示了第二实施方式中单轴挤出机15的第二螺杆42。第二螺杆42中关于剪切处理部43的形态的事项与第一实施方式不同。除此以外的第二螺杆42的构成与第一实施方式相同。
如图3所示，剪切处理部43具有圆环状的突出部49。突出部49在第二螺杆42的径向上同轴状突出，且在第二螺杆42的周向上连续形成。具体而言，突出部49作为其外周面上没有沟或凹槽等的连续的一体构造物形成在第二螺杆42上。
根据第二实施方式，从单管14通过机筒40的树脂供给口44连续供给至筒体41的熔融混合树脂C随着第二螺杆42的旋转从第二螺杆42的基端部向剪切处理部43输送。到达剪切处理部43的熔融混合树脂C通过筒体41的内周壁与突出部49的外周部之间。此时，熔融混合树脂C受到剪切作用而混炼，丙烯酸树脂B在聚碳酸酯树脂A中均匀且致密地分散。结果生成含有聚碳酸酯树脂A和丙烯酸树脂B的透明树脂组合物D。
生成的透明树脂组合物D从剪切处理部43向第二螺杆42的前端部输送，并在与机筒40的另一端连接的模头45处排出。模头45通过对透明树脂组合物D实施赋形加工来使透明树脂组合物D成形成规定的形状。成形后的透明树脂组合物D被从模头45挤出而成为制品。
在第一和第二实施方式中，单轴挤出机15的第二螺杆42的外径比双轴挤出机13的第一螺杆22的外径大。另外，剪切处理部43不限于设置在第二螺杆42中间部的一处，也可以例如根据混炼的情况而在第二螺杆42的轴向上排列配置多个剪切处理部43。
下面，对制造透明树脂组合物D的方法进行说明。
向制造装置10的第一原料供给装置11中投入作为原料的聚碳酸酯树脂A。同样地，向制造装置10的第二原料供给装置12中投入作为原料的丙烯酸树脂B。第一原料供给装置11以每单位时间的聚碳酸酯树脂A的供给量达到95～60重量％的范围的条件对聚碳酸酯树脂A进行称量，将该聚碳酸酯树脂A连续供给至双轴挤出机13的筒体21。同样地，第二原料供给装置12以每单位时间的丙烯酸树脂B的供给量达到5～40重量％的范围的条件对丙烯酸树脂B进行称量，将该丙烯酸树脂B连续供给至双轴挤出机13的筒体21。
供给至筒体21的聚碳酸酯树脂A和丙烯酸树脂B通过一边相互啮合一边旋转的第一螺杆22从筒体21的一端向另一端输送。在该输送的过程中，聚碳酸酯树脂A和丙烯酸树脂B熔融并混合。将输送聚碳酸酯树脂A和丙烯酸树脂B时的机筒20的温度设定在240～300℃，将第一螺杆22的转速设定在50～600rpm。
双轴挤出机13由固相的聚碳酸酯树脂A和固相的丙烯酸树脂B连续生成液相的熔融混合树脂C。此时，丙烯酸树脂B相对于聚碳酸酯树脂A尚未均匀且致密地分散，熔融混合树脂C呈现白浊状。
从双轴挤出机13排出的熔融混合树脂C不与大气接触地通过单管14内的通路30供给至单轴挤出机15。以使熔融混合树脂C维持熔融状态的方式利用加热器31对单管14进行加热。利用加热器31对单管14进行加热的加热温度设定在220～280℃。
从单管14连续供给至单轴挤出机15的筒体41的熔融混合树脂C通过旋转的第二螺杆42从第二螺杆42的基端部向剪切处理部43输送。此时，将筒体41的温度设定在220～280℃，将第二螺杆42的转速设定在500～4000rpm。
根据本实施方式，将具有比双轴挤出机13的第一螺杆22大的外径的单轴挤出机15的第二螺杆42的转速设定在500～4000rpm。因此，从树脂供给口44连续供给至筒体41的熔融混合树脂C以不在第二螺杆42的输送螺纹47之间充满的方式向剪切处理部43输送。另外，由于输送螺纹47的外径和根径规定成恒定值，因此供给至筒体41的熔融混合树脂C能够在稳定的状态下输送入剪切处理部43。
到达剪切处理部43的熔融混合树脂C通过剪切处理部43的外周部与筒体41的内周壁之间。此时，使剪切处理部43以比常规挤出成形中所使用的单轴挤出机的螺杆转速高的500～4000rpm的转速旋转。因此，通过剪切处理部43的外周部与筒体41的内周壁之间的熔融混合树脂C在短时间内一边受到强力的剪切作用一边混炼。
结果是，丙烯酸树脂B在聚碳酸酯树脂A中均匀且致密地分散，生成了含有聚碳酸酯树脂A和丙烯酸树脂B的透明树脂组合物D。
生成的透明树脂组合物D通过外径和根径恒定的输送螺纹47稳定地输送至第二螺杆42的前端部，并通过模头45对其实施赋形加工。籍此，能够不削减透明树脂组合物D地得到所需形状的制品。制品从模头45中挤出。
根据本发明的制造方法，制造装置10前段的双轴挤出机13负责使聚碳酸酯树脂A和丙烯酸树脂B熔融并混合的工序，后段的单轴挤出机15负责一边对聚碳酸酯树脂A和丙烯酸树脂B施加剪切作用一边进行混炼的工序。因此，可以对包括熔融和混合时第一螺杆22的转速在内的制造条件、以及包括在短时间内施加强力剪切作用的第二螺杆42的转速在内的制造条件进行相互关联同时又个别地设定。因此，能够稳定连续地生产含有聚碳酸酯树脂A和丙烯酸树脂B的透明树脂组合物D。
下面，对实施例1、实施例2以及比较例进行说明。
[实施例1]
首先，在实施本发明的制造方法时，准备第一螺杆22的外径的公称直径规定为18mm的东芝机械株式会社(東芝機械株式会社)制造的双轴挤出机、型号TEM-18SS作为负责制造装置10前段工序的双轴挤出机13。准备第二螺杆42的外径的公称直径规定为36mm的东芝机械株式会社制造的单轴挤出机、型号SE-36SP作为负责制造装置10后段工序的单轴挤出机。另外，将型号TEM-18SS的双轴挤出机与型号SE-36SP的单轴挤出机通过单管14连接。
双轴挤出机13的第一螺杆22中，相对于第一螺杆22外径的第一螺杆22的长度(有效长度)为48。单轴挤出机15的第二螺杆42中，相对于第二螺杆42外径的第二螺杆42的长度(有效长度)为8。另外，在第二螺杆42的长边方向上隔开的两处设置反向输送螺纹48，以作为剪切处理部43。将筒体41的内周壁与反向输送螺纹48的外周部之间的间隙设定为0.3mm。除此以外，将双轴挤出机13的机筒20的温度、单轴挤出机15的机筒40的温度以及单管14的温度分别设定为260℃。
使用帝人株式会社(帝人株式会社)制造的Panlite L-1250Y作为供给至双轴挤出机13的聚碳酸酯树脂A。使用三菱丽阳株式会社(三菱レイヨン株式会社)制造的AcrypetVH001作为供给至双轴挤出机13的丙烯酸树脂B。将聚碳酸酯树脂A以每小时8kg从第一原料供给装置11供给至双轴挤出机13的筒体21中，同时将丙烯酸树脂B以每小时2kg从第二原料供给装置12供给至双轴挤出机13的筒体21中。在该状态下，使第一螺杆22的转速为200rpm而使聚碳酸酯树脂A和丙烯酸树脂B熔融并混合，生成熔融混合树脂C。
再使单轴挤出机15的第二螺杆42的转速为2800rpm而对熔融混合树脂C进行混炼，利用模头45以每小时10kg(每分钟约167g)得到含有聚碳酸酯树脂A和丙烯酸树脂B的树脂组合物。通过目视对得到的树脂组合物进行评价，未发现白浊，该树脂组合物呈透明状。
[实施例2]
在实施例2中，使用具有剪切处理部43的形态不同的第二螺杆42的单轴挤出机15对熔融混合树脂C进行混炼。剪切处理部43在第二螺杆42的长边方向上隔开的两处具有圆环状的突出部49。制造装置10的构成除了单轴挤出机15以外与实施例相同。
在实施例2中，将聚碳酸酯树脂A以每小时8kg从第一原料供给装置11供给至双轴挤出机13的筒体21中，同时将丙烯酸树脂B以每小时2kg从第二原料供给装置12供给至双轴挤出机13的筒体21中。在该状态下，使第一螺杆22的转速为200rpm而使聚碳酸酯树脂A和丙烯酸树脂B熔融并混合，生成熔融混合树脂C。
再使单轴挤出机15的第二螺杆42的转速为2800rpm而对熔融混合树脂C进行混炼，利用模头45以每小时10kg(每分钟约167g)得到含有聚碳酸酯树脂A和丙烯酸树脂B的树脂组合物。通过目视对得到的树脂组合物进行评价，未发现白浊，该树脂组合物呈透明状。
[比较例1]
在比较例中，准备螺杆外径的公称直径规定为18mm的东芝机械株式会社制造的双轴挤出机、型号TEM-18SS，在该双轴挤出机的互相啮合的两根螺杆中分别配置了捏合盘。
使螺杆的转速在300rpm～1200rpm之间变化，对从双轴挤出机挤出的含有聚碳酸酯树脂和丙烯酸树脂的熔融混合树脂进行了观察。结果是，从双轴挤出机挤出的熔融混合树脂总是呈白浊状，无法变得透明。
根据该比较例，当螺杆的转速达到1200rpm时，双轴挤出机发出异响和振动。对该原因进行查明，结果发现是由于聚碳酸酯树脂和丙烯酸树脂到达处于预热不足状态下的螺杆的捏合盘所致。而且，由于通过双轴挤出机生成的熔融混合树脂的粘度极低，使双轴挤出机在超过1200rpm的转速下的运行中止。
比较实施例1、实施例2和比较例1则可明了，通过本发明的制造方法连续制造的含有聚碳酸酯树脂和丙烯酸树脂的树脂组合物不会发生白浊而是透明的，丙烯酸树脂在聚碳酸酯树脂中均匀且致密地分散。
符号说明
10：制造装置、13：双轴挤出机、15：单轴挤出机、22：第一螺杆、41：筒体、42：第二螺杆、43：剪切处理部、47：螺纹、A：聚碳酸酯树脂、B：丙烯酸树脂、C：熔融混合树脂、D：透明树脂组合物。

Claims (7)

1.一种透明树脂组合物的制造方法，该方法是含有聚碳酸酯树脂和丙烯酸树脂的透明树脂组合物的制造方法，该方法包括：
将每单位时间供给量设定为95～60重量％的所述聚碳酸酯树脂和每单位时间供给量设定为5～40重量％的所述丙烯酸树脂向双轴挤出机连续供给，所述双轴挤出机的互相啮合的两根第一螺杆以600rpm以下的转速向着相同方向旋转，
通过使所述聚碳酸酯树脂和所述丙烯酸树脂在所述双轴挤出机中熔融并混合来生成熔融混合树脂，同时将所述熔融混合树脂从所述双轴挤出机连续排出，
将从所述双轴挤出机中排出的所述熔融混合树脂向单轴挤出机连续供给，所述单轴挤出机具有第二螺杆和收纳该第二螺杆的筒体，所述第二螺杆从基端部向前端部形成有输送螺纹、且在中间部设置有剪切处理部，
利用与所述第二螺杆一起以500rpm以上、4000rpm以下的转速旋转的所述剪切处理部对所述熔融混合树脂进行混炼以生成透明树脂组合物，同时将生成的所述透明树脂组合物从所述单轴挤出机连续排出。
2.如权利要求1所述的透明树脂组合物的制造方法，其特征在于，所述剪切处理部具有朝着与所述输送螺纹的扭转方向相反的方向扭转的反向输送螺纹，利用所述第二螺杆输送的所述熔融混合树脂在通过所述筒体的内周壁与所述反向输送螺纹的外周部之间的间隙时被混炼。
3.如权利要求2所述的透明树脂组合物的制造方法，其特征在于，当所述熔融混合树脂通过所述筒体的内周壁与所述反向输送螺纹的外周部之间的间隙时，向所述熔融混合树脂施加剪切作用。
4.如权利要求1所述的透明树脂组合物的制造方法，其特征在于，所述剪切处理部具有在所述第二螺杆的径向上同轴状突出、且在所述第二螺杆的周向上连续形成的圆环状突出部，由所述第二螺杆输送的所述熔融混合树脂在通过所述筒体的内周壁与所述突出部的外周部之间的间隙时被混炼。
5.如权利要求4所述的透明树脂组合物的制造方法，其特征在于，当所述熔融混合树脂通过所述筒体的内周壁与所述突出部的外周部之间的间隙时，向所述熔融混合树脂施加剪切作用。
6.如权利要求1～5中任一项所述的透明树脂组合物的制造方法，其特征在于，所述单轴挤出机的所述输送螺纹的外径和根径设定在恒定值，将从所述双轴挤出机供给的所述熔融混合树脂从所述第二螺杆的基端部输送至所述剪切处理部，将在所述剪切处理部生成的所述透明树脂组合物从所述剪切处理部输送至所述第二螺杆的前端部。
7.如权利要求6所述的透明树脂组合物的制造方法，其特征在于，所述第二螺杆的外径比所述第一螺杆的外径大，由所述第二螺杆输送的所述熔融混合树脂以不在所述第二螺杆的所述输送螺纹之间充满的方式向所述剪切处理部输送。
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