CN102227293B - 熔融混炼方法、挤出物及透明树脂材料 - Google Patents
熔融混炼方法、挤出物及透明树脂材料 Download PDFInfo
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- CN102227293B CN102227293B CN200980147178.6A CN200980147178A CN102227293B CN 102227293 B CN102227293 B CN 102227293B CN 200980147178 A CN200980147178 A CN 200980147178A CN 102227293 B CN102227293 B CN 102227293B
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Abstract
本发明的目的在于将非相容性高分子共混物熔融混炼、得到具有以一方的树脂作为基质、另一方的树脂的分散相尺寸控制在300nm以下、更优选100nm以下的微观的分散结构的光学透明的纳米分散高分子共混物挤出物及透明树脂材料。其不加入相容剂等的额外的添加物、使用搭载内部反馈型螺杆的高剪切成型装置、在螺杆的转速600rpm~3000rpm下将非相容性高分子共混物熔融混炼时,通过提高内部反馈型螺杆的转速、设定一定转速下的混炼时间等、调节高剪切成型条件,由此形成分散相尺寸控制在300nm以下、更优选100nm以下的结构。
Description
技术领域
本发明涉及熔融混炼方法及用该熔融混炼方法制造的纳米分散高分子共混物的挤出物,所述熔融混炼方法使用搭载内部反馈型螺杆的高剪切成型装置,对非相容性高分子共混物进行熔融混炼,由此制造以一方的高分子成分作为基质、另一方的高分子成分以将其分散相尺寸控制在数十纳米水平地分散在该基质中、具有微观的分散结构的纳米分散高分子共混物的挤出物(是通过高剪切成型装置混炼而挤出了的混炼物,包含膜、片状。)。
更详细而言,本发明涉及为在例如可见光区的波长区域(400nm~700nm)中具有80%以上的透射率的透明性优异、可在光学领域利用的材料、且机械特性优异的高分子共混物的挤出物、及其制造方法。
背景技术
以往,据报道,在使用通常的混炼挤出机(螺杆转速300rpm左右)进行非相容性高分子共混物体系的单纯机械上的混合的情况下,一方的高分子成分的分散相尺寸中的理论的·实验的界限为350纳米(nm)(参照非专利文献1)。
因此,为了使所期望的高分子共混物的性能、功能形成协同效果而呈现,以往,使用具有与共混物成分的一方或两方具有亲和性或粘接性的相容剂来进行混炼。
但是,本质上在分子水平互相不溶解,因此在将一方的高分子成分作为基质的情况下,只能得到另一方的高分子成分的分散相尺寸为数微米~亚微米水平的高分子共混物挤出物,不能将它们的性能、功能提高到极限。
另外,30年前发现的反应加工技术是存在于共混物成分间的官能团间发生反应、由此使表面张力降低、减小分散相尺寸的方法(参照非专利文献1),成功地将高分子共混物体系的分散相尺寸降低到亚微米~数十纳米水平,但在两成分间不存在反应性基团时不能实现,因此在技术上成为大的障碍。
因此,在以非相容性高分子共混物体系的性能、功能的系统效果的呈现为目标而谋求共混物化的情况下,需要以接近分子水平的尺寸控制分散相,在现有技术的延伸中,容易地制作纳米分散高分子共混物是困难的。
另外,由相容剂等添加物的混入、反应加工法而生成的反应生成物等,在需要连续且纯粹的微细结构的光学材料、电子·电气材料中成为结构上的“缺陷或杂质”,因此存在实用上成为大的障碍的缺点。
在这样的技术背景下,本发明人等成功地制作了可以进行1000rpm以上的螺杆旋转(最高输出功率3000rpm)的搭载内部反馈型螺杆的高剪切成型装置,并已经进行了专利申请(参照专利文献1)。
现有技术文献
专利文献
专利文献1:特开2005-313608号公报
非专利文献
非专利文献1:U.Sundararaj and C.W.Macosko,Macromolecules,28,2647,(1995)
非专利文献2:F.Ide and A.Hasegawa,J.Appl.Polym.Sci.,18,963(1974)
发明内容
发明要解决的课题
本发明以解决上述以往产生的问题点为目的,其课题在于实现一种熔融混炼方法及该挤出物,所述熔融混炼方法中,对于非相容性高分子共混物体系,完全不加入相容剂等的额外的添加物,使用搭载内部反馈型螺杆的高剪切成型装置来熔融混炼,由此制造将一方的高分子成分作为基质、使另一方的高分子成分分散、具有将其分散相尺寸控制在300nm以下、更优选100nm以下的微观的分散结构的高分子共混物的挤出物(包含膜、片状)。
用于解决课题的手段
本发明为了解决上述课题,提供了一种熔融混炼方法,其特征在于,具备以下工序:将至少2种非相容性的共混了的树脂向具有滚筒、螺杆、材料投入部和加热部的熔融混炼部从该材料投入部投入的投入工序;和在上述螺杆的转速为600rpm~3000rpm、剪切速度为900~4500sec-1的条件下,进行上述非相容性的共混了的树脂的熔融混炼的熔融混炼工序。
本发明为了解决上述课题,提供了一种熔融混炼方法,其特征在于,具备以下工序:将至少2种非相容性的共混了的树脂向具有滚筒、螺杆、材料投入部和加热部的熔融混炼部从该材料投入部投入的投入工序;和在上述螺杆的转速为600rpm~3000rpm、剪切速度为900~4500sec-1的条件下,进行将上述熔融混炼了的上述树脂从螺杆的后端送到前端、封入上述螺杆的前端的间隙中、然后从该间隙返回到上述螺杆的后端的循环,进行上述非相容性的共混了的树脂的熔融混炼的熔融混炼工序。
本发明为了解决上述课题,提供了一种熔融混炼方法,其特征在于,具备以下工序:将至少2种非相容性的共混了的树脂向具有滚筒、螺杆、材料投入部、加热部和封口(seal)的熔融混炼部从该材料投入部投入的投入工序;和在上述螺杆的前端面和与该前端面相对的密封面的间隔为0~5mm、螺杆的孔内径为1mm~5mm、螺杆的转速为600rpm~3000rpm、剪切速度为900~4500sec-1、在非结晶性树脂的情况下加热至比玻璃化转变温度高的温度、在结晶性树脂的情况下加热至比其熔点高的温度,将上述熔融混炼了的上述树脂从螺杆的后端送到前端、封入上述螺杆的前端的间隙中、然后从该间隙返回到上述螺杆的后端的循环,进行上述非相容性的共混了的树脂的熔融混炼的熔融混炼工序。
上述非相容性的共混了的树脂优选聚碳酸酯为97~3重量%、及甲基丙烯酸系树脂为3~97重量%。
上述甲基丙烯酸系树脂优选为聚甲基丙烯酸甲酯、聚甲基丙烯酸乙酯或聚甲基丙烯酸丁酯。
也可以将熔融混炼了的树脂作为挤出物进行成型而挤出。
本发明为了解决上述课题,提供一种挤出物,其特征在于,通过以上的熔融混炼方法而制造的。
上述挤出物为棒、膜、片、纤维的任一种。
上述挤出物优选形成为以下构成:基质树脂中均匀地分散有具有300nm以下、优选100nm以下的尺寸的分散相。
上述挤出物优选在形成了厚度100μm的膜时,在可见部的波长区域即400nm~700nm中具有80%以上的透射率。
发明的效果
根据本发明,即使是以往在静置的情况下相互不溶合的非相容性共混物体系,也可以不加入相容剂等的额外的添加物、使用搭载内部反馈型螺杆的高剪切成型装置进行螺杆的转速为600rpm~3000rpm、数十秒~数分钟的熔融混炼,由此可容易地实现具有上述结构即300nm以下优选100nm以下的分散相的高分子共混物挤出物。
即,通过本发明,即使是非相容性共混物体系的材料,也可以制造具有以下结构等的高分子共混物挤出物(包含膜、片状):在将一方的高分子成分作为基质的情况下,另一方的高分子成分的分散相尺寸控制在直径300nm以下、优选100nm以下的微观的分散结构、或者两方的高分子成分在微观上相互连续连接的结构(共连续结构)。
在具有这样的结构的材料中,共混物成分的一方以直径300nm以下、优选100nm以下微观地混合到另一方中,因此,与以往进行相分离而分散相尺寸变大(数微米以上)海·岛结构(所谓“分散结构”)的材料相比,可以协同地发挥构成共混物的高分子本来的性质,因此可以创造出极高性能、高功能的附加价值高的材料。
另外,本发明涉及的制造方法,是使用搭载内部反馈型螺杆的高剪切成型装置而仅进行熔融混炼的简便的方法,根本不需要加入相容剂等的额外的添加物,因此,可以提供最适合于需要连续且纯粹的微细结构的光学材料、电子·电气材料的方法。
在后述的实施例中,仅示出聚碳酸酯(PC)/聚甲基丙烯酸甲酯(PMMA)共混物的例子,作为甲基丙烯酸系树脂,除聚甲基丙烯酸甲酯外,使用聚甲基丙烯酸乙酯(PEMA)、聚甲基丙烯酸丁酯(PBMA)也可以得到同样的结果。
附图说明
图1是表示本发明涉及的制造方法中使用的搭载内部反馈型螺杆的高剪切成型装置中的材料混炼部的图。
图2是表示图1的主要部分(螺杆前端部)的图。
图3是图2的主要部分(螺杆前端部)的放大图。
图4的(a)、(b)、(c)是表示本发明的实施例1中得到的聚碳酸酯/聚甲基丙烯酸甲酯=80/20共混物所产生的挤出物的微观的分散结构的不同比例的TEM照片。
图5是本发明的实施例1中得到的聚碳酸酯/聚甲基丙烯酸甲酯=80/20共混物所产生的挤出物的可见波长区域中的透射率曲线。
图6是聚甲基丙烯酸甲酯(PMMA)、聚碳酸酯(PC)以及本发明的实施例1中得到的聚碳酸酯/聚甲基丙烯酸甲酯=80/20共混物所产生的挤出物的利用动态粘弹性测定的tanδ和温度的关系。
图7是聚甲基丙烯酸甲酯(PMMA)、聚碳酸酯(PC)及本发明的实施例1中得到的聚碳酸酯/聚甲基丙烯酸甲酯=80/20共混物所产生的挤出物的应力-应变曲线。图中,曲线1是PMMA单体,曲线2是PC单体。曲线3是低剪切下(螺杆转速300rpm、混炼时间2分钟)制作的PC/PMMA=80/20共混物,曲线4是高剪切下(螺杆转速1800rpm、混炼时间2分钟)制作的PC/PMMA=80/20共混物。
图8表示增塑部一体型高剪切成型装置的方块图。该装置具备:具备投入预干燥了的规定比例的试样的“试样投入部”(符号61)的“增塑部”(符号62),和用于通过“阀”(符号63)的开关供给一定量的保持在一定温度的熔融状态的试样、进行高剪切的“高剪切部”(符号65)。“高剪切部”和用于使内部反馈型螺杆以高速旋转的“驱动部”(符号64)连结。
图9的(a)、(b)是表示由本发明的实施例2中得到的聚碳酸酯/聚甲基丙烯酸甲酯=80/20共混物(a)以及20/80共混物(b)所产生的挤出物的微观的分散结构的TEM照片。
符号的说明
10 高剪切成型装置
12 熔融混炼部
14 成型部
16 材料投入部
18 滚筒
20 反馈型螺杆
22 轴承
24 轴
26 加热器
28 密封部件(密封面)
29 螺杆的最前端面
32 与螺杆的最前端面的间隔(缝隙)
35 挤出部加热器
36 T模头前端加热器
38 T模头后端加热器
40 排出口
42 热电偶
44 螺杆的孔
46 内部反馈型结构
48 螺杆后段
50 螺杆前段
61 试样投入部
62 增塑部
63 阀
具体实施方式
以下基于实施例、参照附图对用于实施本发明涉及的熔融混炼方法、挤出物及透明树脂材料的最佳方式进行说明。
本发明中,使用搭载内部反馈型螺杆的高剪切成型装置,以螺杆的转速600rpm~3000rpm使螺杆旋转,熔融混炼非相容性高分子共混物体系,由此制造将一方的高分子成分作为基质、另一方的高分子成分的分散相尺寸控制在300nm以下优选100nm以下的高分子共混物挤出物及透明树脂材料。予以说明的是,本发明中制造的“挤出物”,既可以是仅仅混炼了的状态的挤出物(称为“混炼物”),也可以是进行成型而形成为如片状的形状的挤出物(称为“成型物”)。
对通过作为非相容性高分子共混物的聚碳酸酯(PC)97~3重量%及甲基丙烯酸系树脂3-97重量%来制造高分子共混物挤出物及透明树脂材料的情况进行说明。
作为甲基丙烯酸系树脂,可使用聚甲基丙烯酸甲酯(PMMA)、聚甲基丙烯酸乙酯(PEMA)或者聚甲基丙烯酸丁酯(PBMA)等。
为了使聚碳酸酯和甲基丙烯酸系树脂的混合物混炼,可以使用利用使混合物以粒状物的状态混合的干共混的方法。干共混,将聚碳酸酯和甲基丙烯酸系树脂在真空中在80℃下干燥12小时后进行。
但是,聚碳酸酯和甲基丙烯酸系树脂为非相容性,为了得到它们的共混物,通常在200~240℃下使用双轴的熔融混炼机等将两者混合。
但是,它们的挤出物的内部结构形成以下的结构:在将一方的成分作为基质的情况下另一方的成分的分散相尺寸粗大至数微米~数十微米水平、即所谓的相分离了的结构,因此分散相的尺寸比可见趋于的波长大,形成不透明的材料。
为了解决这样的问题,本发明人等进行了深刻的研究开发,结果,发现了如下的划时代的见解:代替通常的双轴螺杆型混炼机而使用搭载内部反馈型螺杆的高剪切成型装置,将包含聚碳酸酯和甲基丙烯酸系树脂的共混物在熔点附近的200~240℃下熔融混炼两者,由此可以得到具有直径300nm以下、优选100nm以下的分散相(甲基丙烯酸系树脂)均匀并且紧密地分散在聚碳酸酯基质相中的纳米分散结构的共混物挤出物及透明树脂材料。另外,在甲基丙烯酸系树脂基质相中形成聚碳酸酯分散相的共混物的情况下也可以得到完全相同的结果。
将通过本发明人等而制造的搭载内部反馈型螺杆的高剪切成型装置示于图1。该高剪切成型装置自身和上述的专利文献1中介绍的高剪切成型装置大体相同,因此在此简单地进行说明,使用这样的高剪切成型装置,按照如下的顺序进行调整后使用。
图1中,高剪切成型装置10具备熔融混炼部12和成型部14。成型部14具有挤出成型部或者注射成型部。熔融混炼部12具备材料投入部16、滚筒18、安装在滚筒18内的反馈型螺杆20、介有轴承22连接于滚筒18上的轴24。滚筒18具备用于使滚筒18内的树脂熔融的加热器26。
滚筒18在滚筒18的轴24的相对端具备用于密封与成型部14的之间的密封部件28。滚筒18,如图2及图3所示,在螺杆后部侧具备用于调整螺杆20的最前端面29和与该最前端面29相对的密封部件28的密封面(以下,称为“密封面28”。)的间隔(缝隙)32的调整装置。该间隔32调整在约0.5~约5mm的范围内。
作为成型部14的挤出成型部具备挤出部加热器35和膜制作用T模头34。T模头34具备T模头前端加热器36和T模头后端加热器38。挤出的膜通过两端的加热器36、38之间的排出口40。在挤出成型部以及T模头前端加热器36中安装有热电偶42,进行温度测定。将测定结果送到控制装置(无图示)来调整上述熔融混炼部12的温度及T模头的温度。
螺杆20具有内径约1mm~约5mm、优选约2mm~约3mm的孔44,螺杆的转速为600rpm~3000rpm,剪切速度为900~4500sec-1。滚筒18内的温度根据被熔融混炼树脂而不同,在非结晶性树脂的情况下设定为比玻璃化转变温度高的温度,在结晶性树脂的情况下设定为比其熔点高的温度。在本发明的情况下优选在230~240℃加热熔融。
螺杆20具备在螺杆20内部将至少2种非相容性的共混了的树脂充分熔融混炼的结构。
图3表示反馈型螺杆20中的树脂的内部反馈型结构46。内部反馈型结构46将从螺杆后段48投入的混合树脂通过螺杆20一边送至螺杆前段50一边充分进行混炼,将混炼了的树脂封入在螺杆20的最前端面29和与该前端面相对的密封面28的间隔32中,进而将混炼了的树脂送至在螺杆20的大致中心部在长度方向设置的孔44内,然后再返回螺杆20的后段。
内部反馈型结构46中的混炼时间,可以根据在内部反馈型结构46中的循环时间任意变化。混炼的程度可以通过改变螺杆20的前端面和与该前端面相对的密封面28的间隔32及螺杆20的孔44的内径进行调整。
这样,间隔32越窄、及螺杆20的孔44的内径越小,混炼的程度变得越高,考虑树脂的粘度等,需要将间隔32和螺杆20的孔44的内径最优化。滚筒18内的树脂的混合时间为5秒钟~10分钟。
这样,根据本发明,可对非相容性的共混物树脂不添加相容剂等的添加物地进行熔融混炼。而且,通过熔融混炼,可作成在以一方的高分子成分作为基质的情况下、另一方的高分子成分的分散相尺寸控制在直径300nm以下优选100nm以下的尺寸的高分子共混物挤出物及透明树脂材料。
为了降低上述螺杆20的高速转动所引起的剪切发热的效果,高剪切成型装置10具备将滚筒18冷却的冷却装置(没有图示,例如为围绕滚筒18的周围使冷却水流动的结构等。参照专利文献1的说明书的段落0038、图5等)。
在使用上述搭载内部反馈型螺杆的高剪切成型装置的情况下,作为成型加工条件,不仅上述的特定温度的设定(230~240℃),该成型装置中的螺杆转速和混炼时间的设定也是重要的。
本发明中,作为螺杆转速可以设定为600~3000rpm,作为混炼时间可设定为5秒钟~60分种之间,作为转速以及混炼时间分别设定为1200~2500rpm、5秒钟~4分种,由此可以得到最佳的结果。
本发明涉及的制造方法的特征在于,在上述的特定的温度条件下,使螺杆转速和混炼时间为最佳数值条件来进行高剪切成型。这样,组合特定的条件才可得到良好的结果。如果温度设定或上述螺杆转速等的设定条件的一方不符合上述条件,则不能得到满意的结果。
在使用上述搭载内部反馈型螺杆的高剪切成型装置10的情况下,通过改变填充有共混物的滚筒18中的螺杆20的前端面29和与该前端面相对的密封面的间隔32及螺杆20的孔44的内径,可以调整剪切流场的强度或混炼的程度。
通常,间隔32可以在1毫米(ミリ)~5毫米之间以0.5毫米间隔设定任意值,螺杆20的孔44的内径也同样可以在1φ至5φ之间以0.5φ间隔设定任意值,通过将间隔32及螺杆20的孔44的内径分别设定为1~2毫米、2.5φ,可以得到最佳的结果。
本发明的特征在于,在上述的特定的温度下,使螺杆的前端面和与该前端面相对的密封面的间隔(缝隙)及螺杆的孔的内径为最佳数值来进行高剪切成型,组合特定的条件才可得到良好的结果,如果温度设定或上述缝隙等的设定条件中的一方不符合上述条件,则不能得到满意的结果。
实施例
(实施例1)
对于本发明,对作为非相容性高分子共混物,由聚碳酸酯及甲基丙烯酸系树脂制造高分子共混物挤出物及透明树脂材料的实施例进行说明。该实施例中,原料的聚碳酸酯使用帝人化成(株)社制造的パンライトL-1225L、L-1225Y或L-1250Y(均为商品名)。
另外,作为聚甲基丙烯酸甲酯(PMMA),使用台湾奇美实业社制造的CM-205或CM-207(均为商品名)、或住友化学(株)社制造的スミペツクスLG21(商品名)。
将两者在真空下在温度80℃下干燥12小时后,在室温下以聚碳酸酯97~3重量%和聚甲基丙烯酸甲酯的3~97重量%的比例进行干共混。进而,将该干混物的2~5g投入图1~图3所述的高剪切成型装置,将缝隙(图3中的间隔32)以及内部反馈螺杆的孔的内径(图3中的孔44的内径)分别设定为1~2毫米、2.5φ,加热至230~240℃熔融,使螺杆转速为1800rpm而混炼2分钟,从T模头挤出。另外,为了比较,作为低剪切下试样,制作使螺杆转速为300rpm而混炼了2分钟的试样。
此时,为了降低剪切发热,使用将滚筒冷却的冷却手段,进行温度控制为使得树脂温度不超过250℃。通过这样的工艺,可以得到表面状态良好的挤出物。
图4(a)、(b)以及(c)为表示该实施例中得到的挤出物的微观的分散结构的照片。该实施例中,微观的分散结构使用透射型电子显微镜(TEM)(日立制H7600)、在加速电压100kV下进行测定。该TEM观察中的照片用CCD照相机形成数码图像来进行拍摄。
在结构观察时,用四氧化钌(RuO4)对共混物试样染色30秒后,通过超微切片机(ライカ制ウルトラカツトUCT)制作超薄切片(120nm),展开在贴有火棉胶的网上。
图4的照片(a)、(b)中,观察到聚碳酸酯基质中混入尺寸为200nm左右的PMMA微区的结构。即,图4中,背景的黑色部分为聚碳酸酯基质相,在其中分散的白色部分(小圆)为PMMA微区。
这里,可知尺寸为200nm左右的聚甲基丙烯酸甲酯微区均匀且紧密地存在于聚碳酸酯基质相中。这样的纳米分散结构在聚碳酸酯/聚甲基丙烯酸甲酯=97/3~3/97共混物这样的宽范围的共混物组成中,即,即使基质相相互变化也可以观察到。
另一方面,为了比较而表示的图4(c)为作为低剪切下试样在使螺杆转速为300rpm而混炼2分钟来制作的试样的透射型电子显微镜(TEM)照片。该条件相当于以往技术,在用以往技术制作的试样中如图所示,在黑地的聚碳酸酯基质相中分散有1.5~2μm的聚甲基丙烯酸甲酯相(白地),明显地得知形成比可见波长区域(400~700nm)的波长大的尺寸。由该尺寸也可以明确,利用以往技术的条件、即在低剪切下制作的共混物试样不成为透明、发生白浊。
另外,试样的光学透射率如下测定:在将各试样形成为厚度100μm的膜状态下,使用市售的JASCO V-550(商品名)UV/VIS分光光度计(Spectrophotometer),在紫外·可见波长区域进行测定。
图5表示在上述实施例中制备的聚碳酸酯/聚甲基丙烯酸甲酯=80/20共混物试样中、测定可见波长区域中的透射率所得的结果即相对于波长的透射率曲线。
图5中,曲线1为聚甲基丙烯酸甲酯单体的透射率曲线,曲线3为聚碳酸酯单体的透射率曲线。可知两者为单体时在400nm以上的波长区域其透射率为80%以上,为透明性非常高的材料。
但是,在低剪切下(在300rpm的螺杆转速下、混炼2分钟)制作的聚碳酸酯/聚甲基丙烯酸甲酯=80/20共混物挤出物的透射率曲线为曲线4所示,在整个可见波长区域其透射率为0%,因此成为不透明(白浊)试样。
相对于此,在高剪切下(在1800rpm的转速下、混炼2分钟)制作的共混物挤出物的透射率曲线为曲线2所示的透射率曲线,在可见波长区域示出80%以上的透射率,可知成为透明试样。
进而,为了评价这些一系列的试样的力学性能,进行动态粘弹性测定(DMA)及应力-应变测定。动态粘弹性测定使用RheovibronDDV-25FP-S(Orientec Co.制)以拉伸模式进行。测定在-150℃~240℃的范围、升温速度3℃/min、频率1Hz下进行。应力-应变测定如下进行:制作哑铃型试样,用基于ASTM D412-80试验法的方法进行拉伸,使用试验机Tensilon UMT-300(Orientec Co.制),在十字头速度10mm/min、温度25℃、湿度50%下进行。
图6表示动态粘弹性测定所产生的tanδ和温度的关系。此处的tanδ的峰值温度相当于玻璃化转变温度(Tg)。如图所示,PMMA的Tg为115℃,PC的为162.5℃。在PC/PMMA=80/20共混物中,其Tg成为152.5℃,可知Tg升高了37℃。即,可知在共混物试样中,耐热性显著提高。
图7表示应力-应变曲线。图中,可知,曲线1为PMMA单体,在几乎还未伸长中就断裂。另一方面,曲线2为PC单体,在伸长近120%时断裂。曲线3为在低剪切下(螺杆转速300rpm、混炼时间2分钟)下制作的PC/PMMA=80/20共混物,其断裂伸长率为42%。相对于此,曲线4为在高剪切下(螺杆转速1800rpm、混炼时间2分钟)制作的PC/PMMA=80/20共混物,其断裂伸长率显著得到改善,达到90%。如此可知,通过减小分散相尺寸,断裂伸长率也显著提高。
(实施例2)
对于本发明,对作为非相容性高分子共混物,由聚碳酸酯及甲基丙烯酸系树脂制造高分子共混物挤出物及透明树脂材料的实施例进行说明。该实施例中,原料的聚碳酸酯使用帝人化成(株)社制造的パンライトL-1225L、L-1225Y或L-1250Y(均为商品名)。
另外,作为聚甲基丙烯酸甲酯(PMMA),使用台湾奇美实业社制造的CM-205或CM-207(均为商品名)、或住友化学(株)社制造的スミペツクスLG21(商品名)。
图8表示增塑部一体型高剪切成型装置((株)ニイガタマシンテクノ制造NHSS2-28)的方块图。该装置具备:具备投入预先干燥了的规定比例的试样的“试样投入部”(符号61)的“增塑部”(符号62)、和用于通过“阀”(符号63)的开闭供给一定量的保持在一定温度的熔融状态的试样进行高剪切的“高剪切部”(符号65)。“高剪切部”与用于使内部反馈螺杆以高速旋转的“驱动部”(符号64)连结。该增塑部一体型高剪切成型装置不仅连结增塑部,且装置各部受到自动控制,因此也可以无人下的连续运转,与实施例1中使用的装置不同。
将两者在真空下在温度80℃下干燥12小时后,在室温下以聚碳酸酯97~3重量%和聚甲基丙烯酸甲酯的3~97重量%的比例进行干共混。进而,将在增塑部熔融了该干混物3.5g投入高剪切部(图3),将缝隙(图3中的间隔32)以及内部反馈型螺杆的孔的内径(图3中的孔44的内径)分别设定为2毫米、2.5φ,加热至230~240℃熔融,使螺杆转速为2250rpm而混炼20秒钟,从T模头挤出。另外,为了比较,作为低剪切下试样,制作使螺杆转速为300rpm而混炼20秒钟所得的试样。
此时,为了降低剪切发热,使用将滚筒冷却的冷却装置,进行温度控制以使得树脂温度不超过250℃。通过这样的工艺,可以得到表面状态良好的挤出物。
图9(a)、(b)为表示该实施例中得到的挤出物及透明树脂材料的微观的分散结构的照片。该实施例中,微观的分散结构,使用透射型电子显微镜(TEM)(日本电子制JEM1230)、在加速电压120kV下进行测定。该TEM观察中的照片用CCD照相机形成数码图像来进行拍摄。(a)、(b)分别对应共混物组成为PC/PMMA=80/20、20/80。
结构观察时,用四氧化钌(RuO4)对共混物试样染色30秒钟后,通过超微切片机(ライカ制ウルトラカツトUCT),制作超薄切片(120nm),展开在贴有火棉胶的网上。
图9(a)的照片中,被染色为黑色的是聚碳酸酯(PC)基质,在PC中观察到尺寸为10nm左右的非常微细的聚甲基丙烯酸甲酯(PMMA)微区(白色圆的部分)。图9(b)的照片中,在白色的PMMA基质中,观察到尺寸为30~40nm水平的染黑了的PC微区。
在此,可知,分别均匀地存在有尺寸10nm左右或尺寸30~40nm左右的聚甲基丙烯酸甲酯微区或者聚碳酸酯微区。这样的纳米分散结构在聚碳酸酯/聚甲基丙烯酸甲酯=97/3~3/97共混物这样的宽范围的共混物组成中,即,即使基质相相互变化也可以观察到。
这样,可知在实施例2中形成比实施例1小一位数的微细的微区结构。这由以下效果产生的:与实施例1在1800rpm下进行2分钟高剪切混炼相比,在实施例2中,由于使用增塑部一体型的装置,因此将事先在增塑部中熔融了的试样投入高剪切部,由此在2250rpm下实施20秒钟这样的短时间的高剪切混炼。通常,在共混物由不同折射率的聚合物构成的情况下,分散相尺寸变大时散射的效果变得显著,透明性受损。但是,如通过本发明制作的共混物这样,分散相尺寸为100nm以下,因此显著确保了透明性。
另外,使用(株)アタゴ社制的阿贝折射仪DR-M2,在波长589nm、室温下测定实施例2中制作的PC/PMMA共混物挤出物及透明树脂材料的膜(厚度为0.5毫米)的折射率。
折射率的结果汇总示于以下。
这样,可以通过PC/PMMA透明共混物制作具有PC单体的折射率1.585和PMMA的1.492之间的折射率的透明树脂材料,为PC/PMMA=80/20共混物时为1.573,为PC/PMMA=20/80共混物时为1.511。
另一方面,使用实施例2中制作的试样来测定试样的透明性、力学性能等,结果可认为与实施例1中制备的试样的结果几乎没有差异。
以上,基于实施例对用于实施本发明涉及的熔融混炼方法、用该熔融混炼方法制造的挤出物及透明树脂材料的最佳方式进行了说明,但本发明不限定于这些实施例,不用说,在权利要求的范围记载的技术事项的范围内有各种各样的实施例。
产业上的可利用性
如仅使用以往的成型加工机(螺杆转速300rpm左右)熔融混炼非相容性高分子共混物,则共混物挤出物的内部结构为相分离结构、即在以一方的高分子成分作为基质的情况下另一方的高分子成分的分散相尺寸为数十微米水平,共混物所产生的协同效果受损,不能发挥所期望的性能·功能。特别是即使用以往技术将本发明涉及的透明树脂的聚碳酸酯和甲基丙烯酸系树脂共混,也得不到透明的共混物,只得到发生白浊了的物质。
另外,如果添加相容剂等的额外的添加物,也为即使实现亚微米水平的分散相尺寸、但由于杂质混入而在需要连续且纯粹的微细结构的光学材料、电子·电气材料中在实用上形成大的障碍的方法。
相对于此,本发明如上所述,即使是非相容性共混物体系的材料,也可以得到具有在以一方的高分子成分作为基质的情况下、另一方的高分子成分的分散相以直径为300nm以下、更微细的为100nm以下的尺寸均匀地分散的微观的分散结构、或两方的高分子成分微观地相互连续地连接的结构等的高分子共混物挤出物及透明树脂材料。
因此,本发明,与以往的形成相分离而分散相尺寸大的(数微米以上)海·岛结构的材料相比,可以协同地发挥构成共混物的高分子本来的性质,因此,可以创造出极其高的性能、高功能的付加价值高的材料,作为需要连续且纯粹的微细结构的各种用途的需要透明性的材料或者光学材料、电子·电气材料是极其有用的。
例如,在应该来临的光通信时代到来时,光纤将起主要的作用。在此,期待将透明树脂即甲基丙烯酸系树脂作为光纤用材料使用。但是,甲基丙烯酸系树脂在耐热性不足的情况下,通过将耐热性优异的聚碳酸酯共混而保持透明性,可以提供高品质的耐热性光纤。所期望的耐热性通过本发明的纳米共混物化根据聚碳酸酯的添加量来进行最优化。
由图7的结果可明确,甲基丙烯酸系树脂(PMMA)的弹性模量高,刚性优良,但断裂伸长率差,延展性不足。另外,聚碳酸酯(PC)与甲基丙烯酸系树脂相比,刚性差,但延展性优异。因此,可以通过制作以纳米水平混合、分散了的结构的PC/PMMA共混物来互补两者的缺点,提供力学上取得了平衡的材料、即取得了刚性和延展性的平衡的最佳材料。
这些材料的力学性质也表现为表面硬度,PMMA的铅笔硬度为3H左右这样硬度,难以形成损伤,由于PC的铅笔硬度为2B左右这样软,因此容易形成损伤。即,PC与PMMA相比,虽然耐热性等优异但表面硬度低,因此不适合将PC作为在表面或者外侧使用的材料。因此,根据本发明通过制作以纳米水平混合、分散了的结构的PC/PMMA共混物,可以提供即使在表面硬度中也取得了平衡的材料即材料表面的铅笔硬度在3H~2B之间具有通过共混物组成而最优化了的铅笔硬度的透明材料。
进而,甲基丙烯酸系树脂(PMMA)和聚碳酸酯的折射率分别为1.492和1.585,因此在提供需要在其之间的数值的折射率的光学材料时,可以提供具有通过制作本发明的透明树脂共混物而最优化了的折射率的材料。
Claims (10)
1.一种用于制造分散相结构的共混树脂的熔融混炼方法,其特征在于,具备以下工序:
将至少2种非相容性的共混了的树脂向具备滚筒、螺杆、材料投入部和加热部的熔融混炼部从该材料投入部投入的投入工序;和
在上述螺杆的转速为600rpm~3000rpm、剪切速度为900~4500sec-1的条件下,进行上述非相容性的共混了的树脂的熔融混炼的熔融混炼工序,
上述至少2种非相容性的共混了的树脂是聚碳酸酯为97~3重量%及甲基丙烯酸系树脂为3~97重量%,没有添加额外的添加物。
2.一种用于制造分散相结构的共混树脂的熔融混炼方法,其特征在于,具备以下工序:
将至少2种非相容性的共混了的树脂向具备滚筒、螺杆、材料投入部和加热部的熔融混炼部从该材料投入部投入的投入工序;和
在上述螺杆的转速为600rpm~3000rpm、剪切速度为900~4500sec-1的条件下,进行将上述熔融混炼了的树脂从螺杆的后端送到前端、封入上述螺杆的前端的间隙中、然后从该间隙返回到上述螺杆的后端的循环,进行上述非相容性的共混了的树脂的熔融混炼的熔融混炼工序,
上述至少2种非相容性的共混了的树脂是聚碳酸酯为97~3重量%及甲基丙烯酸系树脂为3~97重量%,没有添加额外的添加物。
3.一种用于制造分散相结构的共混树脂的熔融混炼方法,其特征在于,具备以下工序:
将至少2种非相容性的共混了的树脂向具备滚筒、螺杆、材料投入部、加热部和封口的熔融混炼部从该材料投入部投入的投入工序;和
在上述螺杆的前端面和与该前端面相对的密封面的间隔为0~5mm、螺杆的孔内径为1mm~5mm、螺杆的转速为600rpm~3000rpm、剪切速度为900~4500sec-1、在非结晶性树脂的情况下加热至比玻璃化转变温度高的温度、在结晶性树脂的情况下加热至比其熔点高的温度,进行将上述树脂从螺杆的后端送到前端、封入上述螺杆的前端的间隙中、然后从该间隙返回到上述螺杆的后端的循环,进行上述非相容性的共混了的树脂的熔融混炼的熔融混炼工序,
上述至少2种非相容性的共混了的树脂是聚碳酸酯为97~3重量%及甲基丙烯酸系树脂为3~97重量%,没有添加额外的添加物。
4.一种透明树脂材料,其为由聚碳酸酯97~3重量%及甲基丙烯酸系树脂3~97重量%构成的没有添加额外的添加物的透明树脂材料,且具有300nm以下的尺寸的分散相(甲基丙烯酸系树脂或聚碳酸酯)均匀地分散在基质树脂(聚碳酸酯或甲基丙烯酸系树脂)中,在形成厚度100μm的膜时,在可见部的波长区域即400nm~700nm中具有80%以上的透射率。
5.如权利要求4所述的透明树脂材料,其特征在于,上述甲基丙烯酸系树脂为聚甲基丙烯酸甲酯、聚甲基丙烯酸乙酯或聚甲基丙烯酸丁酯。
6.一种挤出物,其特征在于,其是通过权利要求1~3中的任一项所述的熔融混炼方法而制造的。
7.如权利要求6所述的挤出物,其特征在于,所述挤出物为棒、膜、片、纤维的任一种。
8.一种光学材料,其含有权利要求4所述的透明树脂材料。
9.一种光纤,其由权利要求8所述的光学材料形成。
10.一种电子·电气材料,其含有权利要求4所述的透明树脂材料。
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