CN114369283A - 树脂多孔体的制造方法 - Google Patents
树脂多孔体的制造方法 Download PDFInfo
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- CN114369283A CN114369283A CN202111200853.6A CN202111200853A CN114369283A CN 114369283 A CN114369283 A CN 114369283A CN 202111200853 A CN202111200853 A CN 202111200853A CN 114369283 A CN114369283 A CN 114369283A
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Abstract
本发明提供一种能够使用非水溶性高分子以较少的工序数制造表皮层的形成得到抑制的树脂多孔体的方法。这里公开的树脂多孔体的制造方法包括:制备在含有非水溶性高分子的良溶剂和上述非水溶性高分子的不良溶剂的混合溶剂中溶解有上述非水溶性高分子的溶液的工序,以及将上述溶液干燥而去除上述混合溶剂的工序。上述不良溶剂的沸点高于上述良溶剂的沸点。使用过热水蒸气进行上述溶液的干燥。
Description
技术领域
本发明涉及树脂多孔体的制造方法。
背景技术
使用非水溶性高分子的树脂多孔体可表现出轻量性、缓冲性、绝热性、吸音性、分离性、吸附性等各种特性。因此,使用非水溶性高分子的树脂多孔体被用于捆包材料、建筑材料、吸音材料、打扫用品、化妆用品、分离膜、吸附材料、纯化用载体、催化剂载体、培养载体等多样化的用途。
从制造成本等观点出发,期望使用非水溶性高分子的树脂多孔体的制造方法简便。因此,作为能够简便地制造作为非水溶性高分子的聚偏二氟乙烯多孔体的方法,在专利文献1中公开了一种聚偏二氟乙烯的多孔体的制造方法,包括:在加热下使聚偏二氟乙烯溶解于其良溶剂与其不良溶剂的混合溶剂而制备溶液;冷却该溶液而得到成型体;使该成型体浸渍于其它溶剂而将上述混合溶剂置换为其它溶剂;以及干燥而去除该其它溶剂。
专利文献1:日本专利申请公开第2011-236292号公报
发明内容
然而,在上述现有技术的制造方法中,需要经过非水溶性高分子的溶液的制备、成型体的析出、溶剂的置换和干燥这样的许多工序。另外,根据本发明人等的研究发现,在树脂多孔体的制造中,在树脂多孔体的表面容易形成不具有孔隙的表皮层(皮层)。在树脂多孔体具有表皮层的情况下,存在无法透过流体、树脂多孔体的用途受到限制这样的不利情况。
因此,本发明的目的在于提供一种能够使用非水溶性高分子以较少的工序数制造表皮层的形成得到抑制的树脂多孔体的方法。
这里公开的树脂多孔体的制造方法包括:制备在含有非水溶性高分子的良溶剂和上述非水溶性高分子的不良溶剂的混合溶剂中溶解有上述非水溶性高分子的溶液的工序,以及将上述溶液干燥而去除上述混合溶剂的工序。上述不良溶剂的沸点高于上述良溶剂的沸点。使用过热水蒸气进行上述溶液的干燥。根据这样的构成,可提供一种能够使用非水溶性高分子以较少的工序数制造表皮层的形成得到抑制的树脂多孔体的方法。
这里公开的制造方法的优选的一个方案中,在制备上述溶液的工序之后且在将上述溶液干燥的工序之前,进一步包括在基材的表面上以薄膜状涂敷上述制备的非水溶性高分子的溶液的工序。根据这样的构成,可提供一种能够使用非水溶性高分子以较少的工序数制造表皮层的形成得到抑制的树脂多孔膜的方法。这里,在上述基材为二次电池的电极的情况下,能够制造二次电池的电极一体型隔离件。
从得到的树脂多孔体的用途和树脂多孔体的制造方法的有用性的观点出发,这里公开的制造方法的优选的一个方案中,上述非水溶性高分子为乙烯-乙烯醇共聚物或偏二氟乙烯-六氟丙烯共聚物。
附图说明
图1是用于比较过热水蒸气的焓和热风的焓的图表。
图2是本发明的制造方法中的干燥工序的实施方法的一个例子的说明图。
图3是比较例1中得到的多孔膜的表面的SEM照片。
图4是实施例1中得到的多孔膜的表面的SEM照片。
图5是实施例3中得到的多孔膜的表面的SEM照片。
符号说明
10 干燥炉
20 过热水蒸气导入管
30 第1阀门
40 热交换器
50 控制面板
60 水蒸气导入管
70 第2阀门
80 锅炉
具体实施方式
本发明的树脂多孔体的制造方法包括:制备在含有非水溶性高分子的良溶剂和该非水溶性高分子的不良溶剂的混合溶剂中溶解有该非水溶性高分子的溶液的工序(以下也称为“溶液制备工序”),以及将该溶液干燥而去除该混合溶剂的工序(以下也称为“干燥工序”)。这里,该不良溶剂的沸点高于该良溶剂的沸点。使用过热水蒸气进行该溶液的干燥。
首先,对溶液制备工序进行说明。在本发明中,“非水溶性高分子的良溶剂”是指在25℃下对非水溶性高分子显示1质量%以上的溶解性的溶剂。良溶剂在25℃下对非水溶性高分子优选显示2.5质量%以上的溶解性,更优选显示5质量%以上的溶解性,进一步优选显示7.5质量%以上的溶解性,最优选显示10质量%以上的溶解性。应予说明,本发明中使用的良溶剂的种类可根据非水溶性高分子的种类而适当地选择。良溶剂可以是单独的溶剂,也可以是混合有2种以上的溶剂的混合溶剂。
在本发明中,“非水溶性高分子的不良溶剂”是指在25℃下对非水溶性高分子显示小于1质量%的溶解性的溶剂。不良溶剂在25℃下对非水溶性高分子优选显示0.5质量%以下的溶解性,更优选显示0.2质量%以下的溶解性,进一步优选显示0.1质量%以下的溶解性,最优选显示0.05质量%以下的溶解性。本发明中使用的不良溶剂的种类可根据非水溶性高分子的种类而适当地选择。不良溶剂可以是单独的溶剂,也可以是混合有2种以上的溶剂的混合溶剂。
在判断特定的溶剂对特定的高分子化合物是良溶剂还是不良溶剂时,可以利用汉森溶解度参数(HSP)。例如,在将该高分子化合物的HSP的分散项、极化项和氢键项分别设为δD1、δP1、δH1,将该溶剂的HSP的分散项、极化项和氢键项分别设为δD2、δP2、δH2时,有如下趋势:下述式表示的高分子化合物与溶剂的HSP的距离Ra(MPa1/2)的值越小,高分子化合物的溶解度越高。
Ra2=4(δD1-δD2)2+(δP1-δP2)2+(δH1-δH2)2
另外,在将上述特定的高分子化合物的相互作用半径设为R0时,如果Ra/R0的比小于1,则可预测为可溶,如果Ra/R0的比为1,则可预测为部分可溶,以及如果Ra/R0的比超过1,则可预测为不溶。
或者,能够通过在样品瓶等中进行混合特定的高分子化合物和特定的溶剂的试验而容易地判别该溶剂对该高分子化合物是良溶剂还是不良溶剂。
将上述良溶剂和上述不良溶剂混合而以均相的溶剂的形式使用。因此,上述良溶剂和上述不良溶剂相互具有相溶性。在本发明中,所使用的不良溶剂的沸点高于所使用的良溶剂的沸点。从容易得到孔隙率较高且均匀的多孔体的方面出发,不良溶剂的沸点优选比良溶剂的沸点高10℃以上,更优选高90℃以上。从干燥速度的观点出发,不良溶剂的沸点优选小于300℃。
在本发明中,“非水溶性高分子”是指在25℃下在水中的溶解度小于1质量%的高分子。非水溶性高分子在25℃下在水中的溶解度优选为0.5质量%以下,更优选为0.2质量%以下,进一步优选为0.1质量%以下。
溶液制备工序中使用的“非水溶性高分子”是与构成多孔成型体的非水溶性高分子相同的高分子。作为非水溶性高分子,可使用存在良溶剂和不良溶剂的高分子。所使用的非水溶性高分子的种类只要存在良溶剂和不良溶剂就没有特别限制。作为非水溶性高分子的例子,可举出聚乙烯、聚丙烯等烯烃系树脂;聚氟乙烯、聚偏二氟乙烯、偏二氟乙烯-六氟丙烯共聚物等氟系树脂;聚(甲基)丙烯酸甲酯、聚(甲基)丙烯酸乙酯等(甲基)丙烯酸系树脂;聚苯乙烯、苯乙烯-丙烯腈共聚物、丙烯腈-丁二烯-苯乙烯共聚物等苯乙烯系树脂;乙基纤维素、乙酸纤维素、丙酸纤维素等非水溶性纤维素衍生物;聚氯乙烯、乙烯-氯乙烯共聚物等氯乙烯系树脂;乙烯-乙烯醇共聚物等。也可以使用将水溶性高分子修饰而非水溶化的聚合物等。其中,从非水溶性高分子的多孔体的有用性和其制造方法的有用性的观点出发,非水溶性高分子优选为脂肪族高分子化合物(即不具有芳香环的高分子化合物)。从容易得到孔隙率较高且均匀的多孔体的方面出发,非水溶性高分子优选为加聚型高分子化合物(即通过具有烯键式不饱和双键的单体的该烯键式不饱和双键的聚合而生成的高分子化合物;例如乙烯基系聚合物、亚乙烯基系聚合物)。从具有三维网状的多孔结构的多孔体的有用性和其制造方法的有用性的观点出发,非水溶性高分子优选为乙烯-乙烯醇共聚物或偏二氟乙烯-六氟丙烯共聚物。
非水溶性高分子的平均聚合度没有特别限定,优选为70~500000,更优选为100~200000。应予说明,非水溶性高分子的平均聚合度可以通过公知方法(例如NMR测定等)来求出。
以下,例举特定的非水溶性高分子对优选的良溶剂和优选的不良溶剂具体进行说明。通过对以下的非水溶性高分子使用以下说明的良溶剂和不良溶剂,能够有利地实施本发明的制造方法。应予说明,以下举出的良溶剂可以单独使用1种或组合使用2种以上。以下举出的不良溶剂可以单独使用1种或组合使用2种以上。
1.非水溶性高分子为乙烯-乙烯醇共聚物的情况
乙烯-乙烯醇共聚物(EVOH)是含有乙烯单元和乙烯醇单元作为单体单元的共聚物。EVOH中的乙烯单元的含量没有特别限制,优选为10摩尔%以上,更优选为15摩尔%以上,进一步优选为20摩尔%以上,特别优选为25摩尔%以上。另外,EVOH中的乙烯单元的含量优选为60摩尔%以下,更优选为50摩尔%以下,进一步优选为45摩尔%以下。EVOH的皂化度没有特别限制,优选为80摩尔%以上,更优选为90摩尔%以上,进一步优选为95摩尔%以上。皂化度的上限由与皂化相关的技术限制决定,例如为99.99摩尔%。应予说明,EVOH的乙烯单元的含量和皂化度可以通过公知方法(例如1H-NMR测定等)来求出。
另外,EVOH通常使用碱催化剂等将乙烯与乙烯酯的共聚物皂化来制造。因此,EVOH可含有乙烯酯单元。该单元的乙烯酯典型地为乙酸乙烯酯,也可以为甲酸乙烯酯、丙酸乙烯酯、戊酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯等。在不显著损害本发明效果的范围内,EVOH也可以含有除乙烯单元、乙烯醇单元和乙烯酯单元以外的其它单体单元。
作为EVOH的优选的良溶剂,可举出水与醇的混合溶剂、二甲基亚砜(DMSO)等。作为混合溶剂中使用的醇,优选为丙醇。丙醇可以为正丙醇和异丙醇中的任一者。因此,特别优选的良溶剂为水与丙醇的混合溶剂、或者DMSO。
作为EVOH的优选的不良溶剂,可举出水;醇;γ-丁内酯等环状酯类;碳酸亚丙酯等环状碳酸酯类;环丁砜等环状砜类;丙二醇单甲醚、丙二醇单乙醚、二乙二醇单甲醚、二乙二醇单乙醚、2-乙氧基乙醇等含醚基的一元醇类;1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇等二醇类等。其中,优选为环状酯类、环状碳酸酯类、环状砜类或含醚基的一元醇类,更优选为γ-丁内酯、碳酸亚丙酯、环丁砜或含醚基的一元醇类,进一步优选γ-丁内酯或环丁砜。优选不良溶剂的溶解参数(希尔德布兰德(Hildebrand)的SP值)δ比EVOH的溶解参数δ大1.6MPa1/2以上。
应予说明,对于EVOH,水和醇是EVOH的不良溶剂,但水与醇(特别是丙醇)的混合溶剂是良溶剂。这里,水与醇的混合溶剂可以看作是减量水而得的良溶剂的水与醇的混合溶剂、与沸点比该混合溶剂高的不良溶剂的水的混合溶剂,因此可以在EVOH的溶液的制备中单独使用水与醇的混合溶剂。因此,在本发明中,在对特定的非水溶性高分子混合2种以上的不良溶剂而得的溶剂成为良溶剂的情况下,作为含有用于溶液制备的非水溶性高分子的良溶剂和非水溶性高分子的不良溶剂的混合溶剂,可以单独使用该2种以上的不良溶剂的混合溶剂。
2.非水溶性高分子为乙酸纤维素的情况
作为乙酸纤维素的优选的良溶剂,可举出N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮等含氮极性溶剂(特别是含氮非质子极性溶剂);甲酸甲酯、乙酸甲酯等酯类;丙酮、环己酮等酮类;四氢呋喃、二烷、二氧戊环等环状醚类;甲基乙二醇、甲基乙二醇乙酸酯等乙二醇衍生物;二氯甲烷、氯仿、四氯乙烷等卤代烃;碳酸亚丙酯等环状碳酸酯类;DMSO等含硫极性溶剂(特别是含硫非质子极性溶剂)等。其中,优选含硫非质子极性溶剂,更优选DMSO。
作为乙酸纤维素的优选的不良溶剂,可举出水;1-己醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇等醇类。作为醇类,优选碳原子数4~6的1元或2元的醇类。
3.非水溶性高分子为聚偏二氟乙烯的情况
作为聚偏二氟乙烯的优选的良溶剂,可举出N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮等含氮极性溶剂(特别是含氮非质子极性溶剂);DMSO等含硫极性溶剂(特别是含硫非质子极性溶剂)等。其中,优选含氮非质子极性溶剂,更优选N,N-二甲基甲酰胺。
作为聚偏二氟乙烯的优选的不良溶剂,可举出水;1-己醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、甘油等醇类;四氢呋喃、二烷、二氧戊环等环状醚类等。其中,优选醇类,更优选碳原子数3~6的2元或3元的醇类。
4.非水溶性高分子为偏二氟乙烯-六氟丙烯共聚物的情况
偏二氟乙烯-六氟丙烯共聚物(P(VDF-HFP))是含有偏二氟乙烯单元和六氟丙烯单元作为单体单元的共聚物。这些单元的共聚比例没有特别限制,只要根据隔离件的特性而适当地决定即可。偏二氟乙烯-六氟丙烯共聚物可以根据公知方法进行合成而获得,也可以作为市售品(例如ARKEMA制Kynar FLEX 2850-00、2800-00、2800-20、2750-01、2500-20、3120-50、2851-00、2801-00、2821-00、2751-00、2501-00等)获得。
作为P(VDF-HFP)的优选的良溶剂,可举出丙酮、甲基乙基酮等酮类;四氢呋喃等环状醚类;N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮等含氮极性溶剂(特别是含氮非质子极性溶剂);DMSO等含硫极性溶剂(特别是含硫非质子极性溶剂)等。从容易通过气化而去除的方面出发,作为良溶剂,优选丙酮、甲基乙基酮或四氢呋喃,更优选丙酮或甲基乙基酮。
作为P(VDF-HFP)的优选的不良溶剂,可举出水;1-己醇、1,2-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、甘油等醇类等。从对环境的负荷低、容易获得、容易处理等观点出发,作为不良溶剂,优选水或者碳原子数3~6的2元或3元的醇类。
非水溶性高分子、良溶剂和不良溶剂的使用量可以根据所使用的它们的种类而适当地选择。相对于良溶剂100质量份,非水溶性高分子的混合量优选为1质量份以上,更优选为5质量份以上,进一步优选为10质量份以上。另外,相对于良溶剂100质量份,非水溶性高分子的混合量优选为40质量份以下,更优选为上35质量份以下,进一步优选为30质量份以下。相对于良溶剂100质量份,不良溶剂的混合量优选为10质量份以上,更优选为20质量份以上,进一步优选为30质量份以上。另外,相对于良溶剂100质量份,不良溶剂的混合量优选为400质量份以下,更优选为200质量份以下,进一步优选为100质量份以下。通过改变它们的量,能够控制所得到的多孔体的孔的状态(例如孔隙率、孔径等)。
在不显著损害本发明效果的范围内,非水溶性高分子的溶液可以进一步含有除非水溶性高分子和混合溶剂以外的成分。
非水溶性高分子的溶液的制备方法没有特别限制。可以使非水溶性高分子溶解于良溶剂后向其中添加不良溶剂并均匀混合,也可以将非水溶性高分子添加于良溶剂与不良溶剂的混合溶剂而使非水溶性高分子溶解。溶液的制备可以使用公知的搅拌装置、混合装置等。在制备非水溶性高分子的溶液时,可以进行超声波照射、加热等。作为加热温度,例如为40℃~100℃。可以在通过加热而制备非水溶性高分子的溶液后,在良溶剂与不良溶剂不分离的范围进行冷却。另外,该冷却优选在非水溶性高分子不析出的范围进行。这是因为析出的非水溶性高分子会成为杂质。
接下来,对干燥工序进行说明。在该干燥工序中,将上述制备的非水溶性高分子的溶液干燥,去除混合溶剂。而且,使用过热水蒸气进行该溶液的干燥。在该干燥工序中,形成非水溶性高分子的多孔状的骨架。在该干燥工序中,通过去除混合溶剂的操作,具体而言通过不良溶剂的气化,形成孔隙,得到树脂多孔体。
典型而言,例如通过使非水溶性高分子与不良溶剂高浓度化的混合溶剂相分离而形成孔隙。具体而言,由于不良溶剂的沸点比良溶剂高,因此在该工序中,与不良溶剂相比,良溶剂优先气化。如果良溶剂减少,则混合溶剂中的不良溶剂的浓度增加。由于非水溶性高分子对不良溶剂的溶解度小于对良溶剂的溶解度,因此非水溶性高分子与不良溶剂高浓度化的混合溶剂相分离而形成非水溶性高分子的多孔状的骨架。该相分离可以为斯皮诺达分解。最终,去除良溶剂而非水溶性高分子析出,通过气化去除高沸点的不良溶剂而生成孔隙。以这样的方式生成非水溶性高分子的多孔体。应予说明,为了使非水溶性高分子与不良溶剂高浓度化的混合溶剂相分离,可以适当地选择良溶剂的种类和使用量以及不良溶剂的种类和使用量。
这里,在通过加热或减压而进行非水溶性高分子溶液的干燥的情况下,露出到气氛的非水溶性高分子的溶液的表面成为干燥界面。在溶液的表面和其附近(即表层部),与溶液内部相比,混合溶剂的气化速度变大,由此,在溶液的表层部与内部在组成上产生偏差。其结果,在溶液的表层部不会发生多孔化,在得到的树脂多孔体的表层部形成表皮层。
与此相对,在本发明中,利用过热水蒸气进行干燥。因此,干燥伴有过热水蒸气与非水溶性高分子的溶液的接触。因此,在过热水蒸气的存在下,特别是过热水蒸气气氛下进行干燥。通过利用过热水蒸气进行干燥,能够抑制树脂多孔体的表层部的表皮层的形成。认为其理由如下。
过热水蒸气是加热到100℃以上的水蒸气。如图1所示,过热水蒸气具有远大于热风的焓,传热方法为对流、辐射、冷凝的复合传热。因此,根据过热水蒸气,与热风等加热方法相比,能够进行急速的加热。
如果在过热水蒸气的存在下放置非水溶性高分子的溶液,则在非水溶性高分子的溶液的表面发生过热水蒸气的冷凝,在非水溶性高分子的溶液的表面上形成水层。通过从该水层进行热传递,非水溶性高分子的溶液中包含的溶剂和水层中的水气化,进行非水溶性高分子的溶液的干燥。这里,水是非水溶性高分子的不良溶剂,因此在非水溶性高分子的溶液的表层部因水而发生相分离,由于该相分离而在表层部形成多孔骨架和孔隙。因此,通过利用过热水蒸气进行干燥,能够在非水溶性高分子溶液的表层部积极地发生多孔化,能够抑制所得到的树脂多孔体的表层部的表皮层的形成。
利用过热水蒸气的非水溶性高分子的溶液的干燥例如可以通过在干燥炉、干燥室等中导入通过公知方法生成的过热水蒸气并在干燥炉、干燥室等中放置非水溶性高分子的溶液来进行。由于过热水蒸气为100℃以上的水蒸气,因此,干燥温度为100℃以上,优选为140℃以上,更优选为150℃~200℃。以下对干燥工序的实施方法的具体例子进行说明。
准备能够导入过热水蒸气的干燥炉。将该干燥炉的构成例示于图2。在图2所示的例子中,干燥炉10介由过热水蒸气导入管20连接作为加热装置的热交换器40。干燥炉10可以为分批式,也可以为具备带式输送机等的连续式。过热水蒸气导入管20具有第1阀门30。热交换器40与控制面板50电连接。热交换器40在内部具有成为热介质的流道的管(未图示)。热交换器40介由水蒸气导入管60与作为水蒸气产生装置的锅炉80连接。水蒸气导入管60具有第2阀门70。
在关闭第1阀门30和第2阀门70的状态下,在锅炉80内产生水蒸气。打开第2阀门70,介由水蒸气导入管60将水蒸气导入到热交换器40。在热交换器40内的管中流通热介质,介由管加热水蒸气。此时,通过控制面板50来控制热介质的温度和流速。热介质的温度可根据干燥炉10内的温度而从超过100℃的温度中适当地选择。通过该加热,使水蒸气变成过热水蒸气。应予说明,过热水蒸气也可以使用公知的过热水蒸气产生装置来生成。
打开第1阀门30,介由过热水蒸气导入管20在干燥炉10内导入过热水蒸气。此时,以过热水蒸气在干燥炉10内不会冷凝的方式将干燥炉10内预先加热到100℃以上。干燥炉内的温度优选为140℃以上,更优选为150℃~200℃。应予说明,在干燥过程中,在混合溶剂气化时从非水溶性高分子的溶液夺取热而冷却该溶液,因此非水溶性高分子的溶液的温度通常低于干燥炉内的温度。因此,干燥炉内的温度可以为非水溶性高分子的熔点以上。
在导入有过热水蒸气的干燥炉10内放置非水溶性高分子的溶液。过热水蒸气与非水溶性高分子的溶液接触,通过过热水蒸气所具有的热而溶液中的混合溶剂气化,进行干燥。干燥中,优选将过热水蒸气持续导入到干燥炉10内。
在得到期望形状的多孔体的情况下,可以优选使用在与该期望形状对应的形状的模具中放入非水溶性高分子的溶液并使用过热水蒸气将其干燥的方法。在得到膜状的多孔体的情况下,可以优选使用在基材的表面上以薄膜状涂敷非水溶性高分子的溶液并使用过热水蒸气将其干燥的方法。
从有益的用途多的方面出发,在本发明中优选得到膜状的多孔体。因此,本发明的制造方法优选在溶液制备工序之后且干燥工序之前包括在基材的表面上以薄膜状涂敷所制备的非水溶性高分子的溶液的工序(以下也称为“涂敷工序”)。
对得到膜状的树脂多孔体时的涂敷工序详细地进行说明。使用的基材只要能够作为基材发挥功能就没有特别限定。基材可以最终从多孔体剥离而使用,也可以不剥离而使用。基材的形状没有特别限定,优选具有平面。作为形状的例子,可举出片状、膜状、箔状、板状等。作为基材的构成材料,可举出树脂、玻璃、金属等。
作为上述树脂的例子,可举出聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)、聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯、聚氯乙烯、聚(甲基)丙烯酸酯、聚碳酸酯、聚酰亚胺、聚酰胺、聚酰胺酰亚胺等。
作为上述金属的例子,可举出铝、铜、镍、不锈钢等。另外,可以使用采用玻璃纤维强化环氧树脂等纤维强化树脂等多种材料而得的材料作为基材。
另外,基材可以具有多层结构。例如,基材可以具有包含氟树脂的剥离层。例如,基材可以为具有树脂层的纸等。
在不剥离而使用基材的情况下,可以具有作为所得到的树脂多孔体的功能层的作用。例如,基材可以具有加强材料、支承材料等功能。另外,基材可以为二次电池的电极(特别是二次电池的电极的活性物质层)。此时,可以将树脂多孔体的制造方法作为二次电池的电极一体型隔离件的制造方法。
非水溶性高分子的溶液的涂敷方法没有特别限制,只要根据基材的种类而适当地选择即可。作为涂敷方法的例子,可举出模涂法、凹版涂布法、辊涂法、旋涂法、浸涂法、棒涂法、刮板涂布法、喷涂法、流延法等。涂敷厚度没有特别限制,只要根据多孔体的用途而适当地设定即可,例如为1μm~500μm,优选为10μm~300μm。
通过将如上得到的基材上所涂敷的非水溶性高分子的溶液供于干燥工序,能够得到膜状的树脂多孔体(即树脂多孔膜)。
如上能够得到包含膜状在内的各种形状的树脂多孔体。树脂多孔体由于表皮层的形成得到抑制,因此具有孔从一个主面连通到与其对置的主面的三维网状的多孔结构。根据本发明的制造方法,能够得到平均孔径例如为0.5μm以上(特别是0.9μm以上、进一步为1.4μm以上)且5μm以下(特别是4.2μm以下、进一步为3.8μm以下)的多孔体。应予说明,平均孔径可以拍摄多孔体的截面电子显微镜照片,作为100个以上的孔的直径的平均值而求出。在孔的截面为非球状的情况下,可以将孔的最大径与最小径的平均值作为孔径。另外,根据本发明的制造方法,能够得到孔隙率例如为15%以上(特别是42%以上、进一步为51.5%以上、再进一步为61.5%以上)且小于80%(特别是小于75%)的多孔体。应予说明,孔隙率可以根据公知方法使用真密度和表观密度来算出。
根据本发明,不需要进行冷却使成型体析出的操作和置换溶剂的操作,通过制备非水溶性高分子的溶液以及利用干燥去除良溶剂和不良溶剂的工序,能够制造树脂多孔体。即,根据本发明,能够以较少的工序数制造树脂多孔体。另外,在本发明中抑制了树脂多孔体的表层部的表皮层的形成。因此,树脂多孔体能够用于广泛的用途。
作为树脂多孔体的用途的例子,可举出捆包材料、建筑材料、吸音材料、打扫用品、化妆用品、分离膜、吸附材料、纯化用载体、催化剂载体、培养载体等。另外,可以利用由于没有表皮层而能够透过电解液的性质,将树脂多孔体用作二次电池用的隔离件。在将树脂多孔体应用于隔离件用途的情况下,能够在活性物质层上直接形成隔离件,因此在隔离件的制造方面有利。
因此,上述的制造方法可以用作二次电池的电极一体型隔离件的制造方法,包括:制备在含有非水溶性高分子的良溶剂和该非水溶性高分子的不良溶剂的混合溶剂中溶解有该非水溶性高分子的溶液的工序;将该制备的溶液涂敷在电极的活性物质层上的工序;以及将该涂敷的溶液干燥而去除该混合溶剂的工序,该不良溶剂的沸点高于该良溶剂的沸点,使用过热水蒸气进行该涂敷的溶液的干燥。
在电极为正极的情况下,活性物质层(即正极活性物质层)可包含正极活性物质。作为正极活性物质,例如可举出锂过渡金属氧化物(例如LiNi1/3Co1/3Mn1/3O2、LiNiO2、LiCoO2、LiFeO2、LiMn2O4、LiNi0.5Mn1.5O4等)、锂过渡金属磷酸化合物(例如LiFePO4等)等。正极活性物质层可包含除活性物质以外的成分,例如导电材料、粘合剂、磷酸锂等。作为导电材料,例如可优选使用乙炔黑(AB)等炭黑、其它(例如石墨等)碳材料。作为粘合剂,例如可以使用聚偏二氟乙烯(PVDF)等。
在电极为负极的情况下,活性物质层(即负极活性物质层)可包含负极活性物质。作为负极活性物质,例如可举出石墨、硬碳、软碳等碳材料等。负极活性物质层可包含除活性物质以外的成分,例如粘合剂、增稠剂等。作为粘合剂,例如可使用苯乙烯丁二烯橡胶(SBR)等。作为增稠剂,例如可使用羧甲基纤维素(CMC)等。
活性物质层典型地形成在集电体上。作为集电体的例子,可举出铝箔、铜箔等。
各工序的操作如上所述。该二次电池用的电极一体型隔离件的制造方法在能够以较少的工序数制造二次电池的电极一体型隔离件的方面非常优异。
如上制造的隔离件一体型电极能够根据公知方法而用于各种二次电池。作为二次电池,优选为锂二次电池,该锂二次电池能够适用于个人计算机、移动终端等的便携式电源、电动汽车(EV)、混合动力汽车(HV)、插电式混合动力汽车(PHV)等的车辆驱动用电源等。
实施例
以下,对本发明所涉及的实施例进行说明,但并不打算将本发明限定于该实施例所示的内容。
实施例1
在样品瓶中称量乙酸纤维素(Aldrich公司制、平均分子量50000)2.1质量份。在该样品瓶中添加作为良溶剂的丙酮10质量份。将样品瓶加热到40℃~50℃,使乙酸纤维素完全溶解于丙酮。然后,在样品瓶中添加作为不良溶剂的水1.5质量份,进行搅拌。以这样的方式得到使溶剂为丙酮/水的混合溶剂的乙酸纤维素溶液。
通过流延将乙酸纤维素溶液涂布在作为基材的铝箔上。此时,涂布厚度为200μm。
准备在上游连接有热交换器并进一步在其上游连接有锅炉的带式输送机式干燥炉。利用锅炉产生水蒸气,将水蒸气送入热交换器,进行加热而变成过热水蒸气。将干燥炉内的温度设定为150℃,以100kg/hr的流量将该过热水蒸气送入干燥炉内,待机直到干燥炉内的温度稳定在150℃。然后,将涂布有乙酸纤维素溶液的铝箔放入干燥炉内,进行60秒干燥,去除丙酮/水的混合溶剂。以这样的方式在铝箔上得到乙酸纤维素的多孔膜。
实施例2
将干燥炉内的温度变更为200℃,除此之外,与实施例1同样地制作乙酸纤维素的多孔膜。
比较例1
通过流延将实施例1中制作的乙酸纤维素溶液涂布在作为基材的铝箔上。此时,涂布厚度为200μm。将涂布有乙酸纤维素溶液的铝箔放入设定为30℃的热风干燥机内,进行60秒干燥,去除丙酮/水的混合溶剂。以这样的方式在铝箔上得到乙酸纤维素的多孔膜。
比较例2
通过流延将实施例1中制作的乙酸纤维素溶液涂布在作为基材的铝箔上。此时,涂布厚度为200μm。将涂布有乙酸纤维素溶液的铝箔放入设定为60℃的热风干燥机内,进行60秒干燥,去除丙酮/水的混合溶剂。以这样的方式在铝箔上得到乙酸纤维素的多孔膜。
比较例3
通过流延将实施例1中制作的乙酸纤维素溶液涂布于作为基材的铝箔上。此时,涂布厚度为200μm。将涂布有乙酸纤维素溶液的铝箔放置在设定为表面温度50℃的加热板上,进行60秒干燥,去除丙酮/水的混合溶剂。以这样的方式在铝箔上得到乙酸纤维素的多孔膜。
实施例3
在样品瓶中称量偏二氟乙烯-六氟丙烯共聚物(ARKEMA K.K.制“Kynar-FLEX2821-00”,等级:粉末型,以下记为“P(VDF-HFP)”)1.0质量份。在该样品瓶中添加作为良溶剂的甲基乙基酮(MEK)3.2质量份。将样品瓶加热到40℃~50℃,使P(VDF-HFP)完全溶解于MEK。然后,在样品瓶中添加作为不良溶剂的1,2-丙二醇0.4质量份,进行搅拌。这样,得到将溶剂制成MEK/丙二醇的混合溶剂的P(VDF-HFP)溶液。
通过流延将P(VDF-HFP)溶液涂布在作为基材的铝箔上。此时,涂布厚度为200μm。
准备在上游连接有热交换器并进一步在其上游连接有锅炉的带式输送机式干燥炉。利用锅炉产生水蒸气,将水蒸气送入热交换器,进行加热而变成过热水蒸气。将干燥炉内的温度设定为170℃,以100kg/hr的流量将该过热水蒸气送入干燥炉内,待机直到干燥炉内的温度稳定在170℃。然后,将涂布有P(VDF-HFP)溶液的铝箔导入到干燥炉内,进行60秒干燥,去除MEK/丙二醇的混合溶剂。以这样的方式在铝箔上得到P(VDF-HFP)的多孔膜。
实施例4
将干燥炉内的温度设定为200℃,除此之外,与实施例3同样地在铝箔上得到P(VDF-HFP)的多孔膜。
比较例4
通过流延将实施例3中制作的P(VDF-HFP)溶液涂布于作为基材的铝箔上。此时,涂布厚度为200μm。将涂布有P(VDF-HFP)溶液的铝箔导入到设定为100℃的热风干燥机内,进行60秒干燥,去除MEK/丙二醇的混合溶剂。以这样的方式在铝箔上得到P(VDF-HFP)的多孔膜。
比较例5
通过流延将实施例3中制作的P(VDF-HFP)溶液涂布于作为基材的铝箔上。此时,涂布厚度为200μm。将涂布有P(VDF-HFP)溶液的铝箔放置在设定为表面温度80℃的加热板上,进行60秒干燥,去除MEK/丙二醇的混合溶剂。以这样的方式在铝箔上得到P(VDF-HFP)的多孔膜。
〔液渗透评价〕
在各实施例和各比较例中得到的多孔膜的表面滴加乙醇,目视评价乙醇是否渗透到多孔膜的背面。将结果示于表1。在乙醇渗透到多孔膜的背面的情况下,可以判断为没有表皮层且整体被多孔化。另一方面,在乙醇不渗透的情况下,可以判断为在多孔膜的表层部形成有表皮层。
〔基于SEM观察的评价〕
利用扫描式电子显微镜(SEM)观察比较例1和实施例1、3中得到的多孔膜的表面。将比较例1和实施例1、3中得到的多孔膜的表面的SEM照片分别示于图3~5。
[表1]
树脂种类 | 干燥方法 | 干燥温度 | 表皮层 | |
实施例1 | 乙酸纤维素 | 过热水蒸气 | 150℃(炉内温度) | 无 |
实施例2 | 乙酸纤维素 | 过热水蒸气 | 200℃(炉内温度) | 无 |
比较例1 | 乙酸纤维素 | 热风 | 30℃(炉内温度) | 有 |
比较例2 | 乙酸纤维素 | 热风 | 60℃(炉内温度) | 有 |
比较例3 | 乙酸纤维素 | 加热板 | 50℃(表面温度) | 有 |
实施例3 | P(VDF-HFP) | 过热水蒸气 | 170℃(炉内温度) | 无 |
实施例4 | P(VDF-HFP) | 过热水蒸气 | 200℃(炉内温度) | 无 |
比较例4 | P(VDF-HFP) | 热风 | 100℃(炉内温度) | 有 |
比较例5 | P(VDF-HFP) | 加热板 | 80℃(表面温度) | 有 |
如表1的结果所示,在用热风进行了干燥的比较例1中,乙醇未渗透到多孔膜的背面。进而,如SEM图像(图3)所示,在比较例1中得到的多孔膜的表面无法确认到孔。由此可知,在比较例1中在多孔膜表面形成有表皮层。此外,可知即使在提高了热风温度的比较例2和将加热方法变更为加热板的比较例3中,乙醇也没有渗透到多孔膜的背面,形成有表皮层。
另一方面,在使用过热水蒸气进行了干燥的实施例1和2中,乙醇渗透到多孔膜的背面。进而如SEM图像(图4)所示,能够确认到在实施例1和2中得到的多孔膜的表面形成有许多孔。由此可知,实施例1和2中得到的多孔膜没有形成表皮层而被多孔化。应予说明,在实施例1和实施例2中,在得到的多孔膜的多孔结构中没有发现差异。
另外,根据实施例3和4以及比较例4和5的结果、以及图5可知,即使在改变树脂种类的情况下,通过使用过热水蒸气进行干燥,也没有形成表皮层而被多孔化。由此可知,对水成为不良溶剂的树脂(即非水溶性高分子)发挥通过使用过热水蒸气进行干燥而产生的表皮层的形成抑制效果。
在上述实施例中,制造树脂多孔体所需的工序是制备非水溶性高分子的溶液和通过干燥去除混合溶剂。因此,综上可知,根据本发明,能够使用非水溶性高分子以较少的工序数制造表皮层的形成得到抑制的树脂多孔体。
Claims (4)
1.一种树脂多孔体的制造方法,包括:
制备在含有非水溶性高分子的良溶剂和所述非水溶性高分子的不良溶剂的混合溶剂中溶解有所述非水溶性高分子的溶液的工序,以及
将所述溶液干燥而去除所述混合溶剂的工序;
所述不良溶剂的沸点高于所述良溶剂的沸点,
使用过热水蒸气进行所述溶液的干燥。
2.根据权利要求1所述的制造方法,其中,在制备所述溶液的工序之后且在将所述溶液干燥的工序之前,进一步包括在基材的表面上以薄膜状涂敷所述制备的非水溶性高分子的溶液的工序。
3.根据权利要求2所述的制造方法,其中,所述基材为二次电池的电极。
4.根据权利要求1~3中任一项所述的制造方法,其中,所述非水溶性高分子为乙烯-乙烯醇共聚物或偏二氟乙烯-六氟丙烯共聚物。
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