CN116472317A - 涂布组合物、带涂膜的基材、隔板、二次电池、锂离子二次电池和电极材料 - Google Patents
涂布组合物、带涂膜的基材、隔板、二次电池、锂离子二次电池和电极材料 Download PDFInfo
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- CN116472317A CN116472317A CN202180069558.3A CN202180069558A CN116472317A CN 116472317 A CN116472317 A CN 116472317A CN 202180069558 A CN202180069558 A CN 202180069558A CN 116472317 A CN116472317 A CN 116472317A
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Abstract
本发明提供主要包含高分子的涂料、油墨、接合剂、锂离子电池的正极、负极、隔板等的涂布液中、可进行高速涂布性或表面平滑性优异的涂布的涂布组合物。一种包含填料、粘结剂、增稠剂和溶剂的涂布组合物,其特征在于,所述填料的长宽比为2以上,所述粘结剂包含选自二烯橡胶和(甲基)丙烯酸酯聚合物中的至少一种,以剪切速度0.01/s测定的涂布组合物的粘度为1.0×106Pa·s以下,下述触变指数TI为1.1×106以上。[触变指数(TI)]=[以剪切速度0.01/s测定的涂布组合物的粘度]/[以剪切速度10000/s测定的涂布组合物的粘度]。
Description
技术领域
本发明涉及包含填料、粘结剂和增稠剂的组合物,涉及主要包含高分子的涂布组合物中可形成高速涂布性或表面平滑性优异的涂布物的组合物。
背景技术
在工业领域,整体上从环境方面或安全方面的观点或效率性来看,使用组合物进行的涂布、印刷技术已经被广泛使用。这样的印刷技术中,期望能够高速且高精度排出必要最低限的组合物并涂布,而且具有所得的涂布面平滑的所谓高涂布性。
但是,涂布性优异的组合物的物性还没有被掌握。
例如,专利文献1中公开了,通过将以离子交换水稀释纤维状纤维素的悬浊液设定为特定的触变指数TI(Thixotropy·Index),而得到分散性与涂布容易性优异的电池用隔板涂液。
但是,并没有公开包含纤维状纤维素和离子交换水以外的组合物的状态的TI。并且,针对高速涂布性并无记载或暗示。
在专利文献2公开了,通过将在指定的剪切速度下的粘度比定为特定以上,可形成涂布性优异的均匀的涂膜的金属离子二次电池隔板用涂液。
然而,在专利文献2中,涂液中的水溶性成分的含量为5质量%以下时,为固体成分极多的状态的涂液,在一定为高速涂布性或表面平滑性的观点则完全无任何披露。
[现有技术文献]
[专利文献]
[专利文献1]国际公开第2018/070473号
[专利文献2]日本专利第5829557号公报
发明内容
[发明要解决的课题]
具有良好的涂布性的组合物虽多,但有助于高速涂布性或表面平滑性的特性并不清楚。
[用以解决课题的手段]
在该状况下,本发明者们进行努力研究的结果,发现通过使用在高剪切速度与低剪切速度的粘度比为特定范围的组合物,可形成涂布液的涂布性优异,表面平滑性优异的涂膜,可充分使用在上述的用途,而终于完成本发明。
也即,本发明的构成以下。
[1]一种涂布组合物,其是包含填料、与粘结剂、增稠剂、溶剂的涂布组合物,其特征在于,
前述填料的长宽比为2以上,
前述粘结剂包含选自二烯橡胶和(甲基)丙烯酸酯聚合物中的至少一种,
以剪切速度0.01/s测定的涂布组合物的粘度为1.0×106Pa·s以下,
下述触变指数(TI)为1.1×106以上;
[触变指数(TI)]=[以剪切速度0.01/s测定的涂布组合物的粘度]/[以剪切速度10000/s测定的涂布组合物的粘度]。
[2]如[1]的涂布组合物,其中,前述填料与前述增稠剂之比以质量比(填料/增稠剂)为0.1~500。
[3]如[1]或[2]的涂布组合物,其中,前述增稠剂为聚N-乙烯基羧酸酰胺。
[4]如[1]~[3]的涂布组合物,其中,前述增稠剂为聚N-乙烯基乙酰胺。
[5]如[1]或[2]的涂布组合物,其中,前述增稠剂为聚乙烯基吡咯烷酮。
[6]如[1]~[5]的涂布组合物,其包含水作为溶剂。
[7]如[1]~[6]的涂布组合物,其中,前述触变指数(TI)的值为1.1×107以下。
[8]如[1]~[7]的涂布组合物,其中,前述填料的长宽比为100以下。
[9]一种带涂膜的基材,其包含由[1]~[8]的涂布组合物所形成的涂膜和基材。
[10]一种隔板,其由[9]的带涂膜的基材所形成。
[11]一种二次电池,其使用了[10]的隔板。
[12]一种锂离子二次电池,其使用[10]的隔板。
[13]一种电极材料,其于基材表面具备由[1]~[8]的涂布组合物所形成的涂膜。
[发明效果]
本发明的涂布组合物以高速且高精度涂布组合物时,可得到涂布面的表面平滑的涂膜。这样的技术如果被采用在二次电池、尤其是锂离子二次电池等的电极或隔板等的形成,就能够提升二次电池的生产效率。
具体实施方式
以下,针对实施本发明的形态进行说明。
[涂布组合物]
本发明的涂布组合物包含填料、与粘结剂、增稠剂、溶剂,前述填料的长宽比为2以上,前述粘结剂包含选自二烯橡胶和(甲基)丙烯酸酯聚合物中的至少一种,以剪切速度0.01/s测定的涂布组合物的粘度为1.0×106Pa·s以下。
下述触变指数(TI)为1.1×106以上,优选为3.0×106以上,更优选为1.0×107以上。此外,触变指数(TI)优选为1.1×108以下,更优选为5.0×107以下。这样的指定的触变指数(TI)可通过前述组成调整。
[触变指数(TI)]=[以剪切速度0.01/s测定的涂布组合物的粘度]/[以剪切速度10000/s测定的涂布组合物的粘度]。
本发明的触变指数(TI)是高剪切速度下的粘度、与低剪切速度下的粘度的比率,通过此比率为指定的范围,即使在以高速进行高精度的涂布的情况,在表面也不会产生条纹或流动等,可得到极为平滑的涂膜。
[填料]
填料使用由无机物构成的。作为填料,优选为氧化铝、勃姆石、滑石、高岭土碳酸钙、磷酸钙、非晶性二氧化硅、结晶性的玻璃填料、二氧化钛、二氧化硅-氧化铝复合氧化物粒子、硫酸钡、氟化钙、氟化锂、沸石、硫化钼、云母等。其中,更优选为氧化铝、勃姆石。
填料的形状只要是长宽比为2以上,就无特别限制,除了椭球状、多面体状、板状、鳞片状、柱状、管状以外,也可为纤维状。
填料的长宽比为2以上,更优选为5以上,再更优选为10以上。如果填料的长宽比为2以上,能够达成前述触变指数(TI),即使以高速进行高精度的涂布的情况,在表面也不会产生条纹或流动等,可得到极为平滑的涂膜。此外,例如,在使用于隔板时发挥以下效果:即使锂枝晶成长的情况,由于结晶的通道变长,有难以到达隔板原膜的优点。再者,填料的长宽比优选为100以下。
填料的长径期望为0.1~1000μm,优选为1~500μm的范围。
填料的短径期望为0.01~100μm,优选为0.1~10μm的范围。
[增稠剂]
增稠剂由有机高分子构成。后述的粘结剂不包含在增稠剂中。优选的增稠剂可列举聚N-乙烯基羧酸酰胺、聚N-乙烯基吡咯烷酮、羧甲基纤维素的钠盐、聚丙烯酰胺、聚乙烯醇、角叉菜胶、黄原胶、瓜尔豆胶、果胶等的多醣类、羧甲基纤维素、羟基甲基纤维素、羟基乙基纤维素、甲基乙基羟基纤维素、甲基纤维素、羟基丙基纤维素等的纤维素聚合物,以及这些纤维素聚合物的铵盐和碱金属盐。
其中,优选聚N-乙烯基羧酸酰胺或聚N-乙烯基吡咯烷酮,更优选聚N-乙烯基羧酸酰胺,再更优选聚N-乙烯基乙酰胺。使用这样的增稠剂时,可将触变指数(TI)调整在指定的范围,可得到涂布表面外观优异的涂布物。
作为构成聚N-乙烯基羧酸酰胺的单体,作为具体例可列举N-乙烯基甲酰胺、N-乙烯基乙酰胺、N-乙烯基丙酰胺、N-乙烯基苯甲酰胺、N-乙烯基-N-甲基甲酰胺、N-乙烯基-N-乙基甲酰胺、N-乙烯基-N-甲基乙酰胺、N-乙烯基-N-乙基乙酰胺等。
这些可为单独的均聚物,也可为共聚物。共聚合时,也可共聚合衣康酸、马来酸、巴豆酸、(甲基)丙烯酸等的盐,并无特别限定。
源自聚N-乙烯基羧酸酰胺中的N-乙烯基乙酰胺的成分,优选为60摩尔%以上。
增稠剂的粘度以原有粘度(不调整溶液浓度)计,优选为30mPa·s以上10,000mPa·s以下。如果为此范围,容易进行涂布所以优选。
[粘结剂]
粘结剂优选为选自二烯橡胶和(甲基)丙烯酸酯聚合物中的至少一种,更优选为仅由选自二烯橡胶和(甲基)丙烯酸酯聚合物中的至少一种构成。作为二烯橡胶,可列举苯乙烯丁二烯橡胶、丁基橡胶、丁二烯橡胶、异戊二烯橡胶、丙烯腈·丁二烯橡胶、乙烯丙烯二烯橡胶或是它们的改性物。(甲基)丙烯酸酯聚合物是指包含丙烯酸酯、甲基丙烯酸酯中的至少一种的聚合物。(甲基)丙烯酸酯聚合物可进行了共聚合,包含50mol%以上丙烯酸酯和甲基丙烯酸酯。
(甲基)丙烯酸酯聚合物所包含的其他单体,只要是能够与(甲基)丙烯酸酯共聚合,就无特别限定。
其中,优选为交联型的丙烯酸酯乳液。丙烯酸酯乳液可为单独的均聚物,也可为共聚物,任一者都可。此外,可直接使用乳液,也可使其固化后使用。
此外,聚乙烯基醇、聚(甲基)丙烯酸、高级醇环氧乙烷加成物、聚丙二醇环氧乙烷加成物等也可作为粘结剂使用,为聚(甲基)丙烯酸时,作为盐,虽并无特别限定,但优选为不包含金属的铵盐作为盐,例如可使用聚丙烯酸铵等。
[溶剂]
溶剂只要为分散上述各成分或使其溶解,且不反应,就无特别限制,但鉴于干燥性,使用具有挥发性的溶剂。具体而言,使用水或与水有相溶性的极性溶剂,但优选为包含50质量%以上水的溶剂,更优选为单独的水。水特优选为离子交换水。作为水以外的溶剂,可列举甲醇、乙醇、异丙醇等的醇。
[分散剂]
本发明的涂布组合物如有必要可包含分散剂。分散剂只要能够使填料分散,就无特别限定,但优选为十二烷基苯磺酸、山梨糖醇和山梨醇酐的脂肪酸酯。作为盐,虽并无特别限定,但优选以不包含金属的铵盐作为盐。
[涂布组合物的组成和调制方法]
涂布组合物中的填料与增稠剂之比以质量比(填料/增稠剂)优选为0.1~500,更优选为50~200。为此比率时,涂布容易进行,且干燥性也良好,涂布层也得到充分的强度所以优选。
涂布组合物中的填料的质量优选为10~80质量%,更优选为20~50质量%的范围。将涂布组合物中的固体成分作为基准,填料的质量优选为50~99质量%,更优选为70~98质量%的范围。粘结剂以相对于填料的质量优选为0.1~20质量%,更优选为1~5质量%的范围而包含。
涂布组合物中的粘结剂(固体成分)的质量优选为0.1~20质量%,更优选为1.0~5.0质量%的范围。将涂布组合物中的固体成分作为基准,粘结剂(固体成分)的质量优选为0.2~10质量%,更优选为0.5~5.0质量%的范围。
涂布组合物中的增稠剂的质量优选为0.01~20质量%,更优选为1.0~5.0质量%的范围。将涂布组合物中的固体成分作为基准,增稠剂的质量优选为0.2~10质量%,更优选为0.5~5质量%的范围。
分散剂的量,以优选为0.01~10质量%,更优选为0.1~5质量%的范围包含于涂布组合物中。以此范围包含时,可提高填料的分散性。
通常相对于水等的溶剂100质量份,填料优选为0.1~1000质量份,更优选为1~200质量份。为此范围时,得到涂布组合物的良好的流动性,可得到以剪切速度0.01/s测定的粘度为1.0×106Pa·s以下的涂布组合物。
涂布组合物的各成分的混合方法虽并无特别限定,但为了成为更均匀的混合状态,优选为使粘结剂、增稠剂等溶解或分散在溶剂中后,添加、混合填料。此外,更优选为一边对于使粘结剂、增稠剂等溶解或分散的溶液进行持续搅拌,一边依次地添加填料并搅拌混合,进行均匀化。通过这样,变成可取得理想的混合形态。
[用途]
实施形态的涂布组合物可按照要掺合的填料的种类,用于涂料、油墨、接合剂、锂离子电池的正极、负极、隔板等的各种涂布液。
涂布组合物虽可直接作为涂布液使用,但如有必要可适当以溶剂等调整浓度或粘度,作为涂布液使用。
例如,通过将前述涂布组合物涂布在基材表面,并干燥,制造涂膜。此外,也可于基材表面具备(称为带涂膜的基材)由涂布组合物所构成的涂膜,而成为电极材料。
本实施形态的涂布组合物由于包含填料、与粘结剂、增稠剂、溶剂、分散剂,前述填料的长宽比为2以上,具有指定的粘度和TI,即使以高速且高精度涂布涂布组合物,也可得到涂布面的表面平滑的涂膜。
对涂布组合物的基材的涂布方法虽并无特别限制,除了喷涂、辊涂、棒涂、凹版涂布、缝模涂布、刀涂、喷墨涂布或毛刷涂布、浸渍涂布等以外,也可使用辊对辊(Roll toRoll)图案涂布装置连续式进行涂布。
进而,可在涂布组合物中包含上述以外的能够在涂料中添加的公知材料,例如可包含表面调整剂、消泡剂、流平剂、颜料、染料等。
作为基材,可不特别限制使用薄膜、不织布、多孔体、板状体等。
作为构成基材的材料,可列举乙烯的单独聚合物或是与其他α-烯烃的共聚物、均聚丙烯、丙烯与其他烯烃的共聚物、聚对苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚酰胺醚酮、聚酰亚胺、聚酰胺、聚苯砜、聚苯醚、聚乙烯、聚醚砜、聚醚醚酮、聚苯并咪唑、聚醚酰亚胺、聚酰胺酰亚胺、聚(对苯基-2,6-苯并双噁唑)、氟树脂、环氧树脂等的有机树脂材料、铝、铜、银、铁等的金属材料、玻璃(氧化硅)、氧化铝、氧化镁、氮化铝、碳化铝、氮化硅、钛酸钡等的无机材料。基材可1种单独使用,也可组合2种以上使用。其中,作为基材,优选为聚烯烃,更优选为选自聚乙烯、聚丙烯中的至少一种,最优选为聚丙烯/聚乙烯/聚丙烯依次层合的3层层合体。使用由这样的材料构成的多孔质基材时,可作为二次电池用隔板等使用。
多孔质基材为聚烯烃制薄膜时,可为以湿式法制造的,也可为以干式法制造的,并无特别限定。此外,由3层的层合体所构成的多孔质基材时,优选为3层都为以干式法制造。通过具有这样的构成,无卷曲,耐热性、机械性强度等良好。
再者,所谓干式法,是于薄膜的制造时未使用溶剂的干式工艺,例如可列举将熔融的树脂通过T型模的熔融成型或注塑成型等。此外,外层和内层可为干式法,也可为湿式法,湿式法是通过使用添加·混合添加物的树脂,制膜薄膜后,用溶剂萃取添加物,而形成孔隙的方法。
基材全体的厚度可从按照目的的机械性强度、性能、小型化等的方面适当选择,优选为7.0μm以上,上限优选为50μm以下。为此范围的厚度时,可提高强度。
此外,为多孔质基材时,依照该JIS P 8117:2009所测定的透气度优选为80秒/100ml以上,上限优选为700秒/100ml以下。具有此范围的透气度时,难以短路且离子的移动度也高。
多孔质基材的孔隙率优选为30%以上,上限优选为70%以下。如果为此范围的孔隙率,则机械性强度高,且不会产生短路,离子的移动度也可提高。
多孔质基材的极大孔径优选为0.05μm以上,上限优选为2μm以下,为此范围时,成为隔板时,离子的移动性高,且电阻也大幅降低。
涂膜的厚度并无特别限制,为0.5~20μm的厚度的涂膜即可,并无特别限制。
涂膜的干燥方法并无特别限制,可列举旋转干燥、真空干燥、热风干燥、红外线干燥等。干燥时间也并无特别限制。
构建隔板时,可通过将前述涂布组合物涂布在前述基材表面的方法等构成。
构建电极时,可通过将前述涂布组合物与正极活性物质或负极活性物质混合,并涂布在前述基材表面或集电体表面的方法,或将混合了正极活性物质或负极活性物质或其双方的涂布在电极箔,或是使涂布组合物薄膜化,插入正极或是负极或其双方的集电体表面,来构成电池电极。
作为构成锂离子二次电池的构件,可大致分成正极电极、负极电极、隔板、电解液。正极电极和负极电极分别含有进行送出并接受电子的氧化/还原反应的活性物质。正极电极与负极电极,可以介由电池用隔板层合的层合构造的电极群,或进而以将此缠绕的缠绕构造的电极群的形态使用。
作为正极,只要使用过去就知道的锂离子二次电池的正极,就无特别限制。正极含有可吸藏释出Li+离子的活性物质。
作为负极,只要使用以往所知悉的锂离子二次电池的负极,就无特别限制。负极含有可吸藏释出Li+离子的活性物质。
正极与负极,可以以介由隔板层合的层合构造的电极群,或进而将此缠绕的缠绕构造的电极群的形态使用。作为电解液,使用将锂盐溶解在有机溶剂的溶液。作为锂盐,只要是于溶剂中解离,形成Li+离子,并于作为电池使用的电压范围不会引起分解等的副反应的,就无特别限制。作为有机溶剂,只要是溶解锂盐,并于作为电池使用的电压范围不会引起分解等的副反应的,就无特别限定。
使用本实施形态的涂布组合物制作的各构件,可适当使用在前述电池的各构件。
锂离子电池除了手机、笔记本电脑等的移动设备、电动车、油电混合式汽车、电动机车、电动辅助自行车、电动工具、刮胡刀等的各种机器的电源用途等,也可使用在过去就知道的各种用途。
[实施例]
以下,通过实施例说明本发明,但本发明并不受限于这些的实施例。
[使用的材料]
·填料
鳞片状勃姆石:Cerasur(河合石灰工业(株)制)长宽比:20~40、长径10μm、短径0.3μm(各平均值)
鳞片状氧化铝:Cerasurα(河合石灰工业(株)制)长宽比:20~40、长径13μm、短径0.4μm(各平均值)
·粘结剂
丙烯酸酯乳液:Polysol(注册商标)LB-350(昭和电工(株)制)
SBR(苯乙烯丁二烯橡胶水分散液):BM400B(日本ZEON(株)制)
聚丙烯酸铵:ARON(注册商标)A-30SL(东亚合成(株)制)
·增稠剂
聚N-乙烯基乙酰胺PNVA(注册商标)-1:GE191-043(昭和电工(株)制)、原有粘度5000mPa·s、固体成分4质量%
聚N-乙烯基乙酰胺PNVA(注册商标)-2:GE191-104(昭和电工(株)制)、原有粘度18000mPa·s、固体成分10质量%
聚N-乙烯基乙酰胺PNVA(注册商标)-3:GE191-107(昭和电工(株)制)、原有粘度50mPa·s、固体成分10质量%
羧甲基纤维素CMC-Na:MAC350HC(日本制纸(株)制)
聚乙烯基吡咯烷酮:PVP K-90(东京化成工业(株)制)
·分散剂
十二烷基苯磺酸钠水分散液:NEOPELEX(注册商标)G-65(花王(株)制)
[实施例1~7、比较例1~6]
在200ml树脂容器中按照表1记载的规定量将离子交换水、分散剂、粘结剂、增稠剂、无机填料依次计量,并投入自转公转型捏合机(THINKY公司制ARE-250)。盖紧盖子,以混合(MIXING)60秒和脱泡(DEFORMING)60秒的条件混合,而得到均匀的涂布组合物。
表1
针对所得的涂布组合物进行以下评价。
<涂布试验方法>
在涂布机的涂布台上固定聚丙烯薄片(厚度1mm),将所得的涂布组合物3.5g使用棒涂机(YOSHIMITSU精机株式会社制,宽度50mm×厚度5μm),以自动涂布机(TESTER产业株式会社制Pi-1210)200mm/秒的速度涂布成宽度15cm、长度30cm。
然后,将形成涂布物的聚丙烯薄片在热风干燥器中以40℃的温度干燥1小时而得到涂布薄片。
<耐热性试验方法>
从涂布薄片,剥离涂布物的厚度(6~7μm)为等同的部位的涂布物,取长方形(5cm×4cm),测定四边的长度。接着,将该试验片于金属制拍上空出与四边无干扰的距离而静置。
将该金属制拍放入内温150℃的风炉并静置15分钟,取出并测定四边的尺寸。
将测定结束的试验片再度放入调整至200℃的风炉,静置15分钟后取出,测定四边的尺寸。
[测定方法]
<旋转粘度>
使用Brookfield公司制DV2T型粘度计Spindle SC4-28带水套的少量样品适配器,并在样品架上放上涂布组合物20g,测定在0.3rpm、100rpm的旋转速度下的旋转粘度(η0.3和η100),并求出比率。
再者,实施例3、比较例3和5的斜线部分的项目无法算出。Over表示是测定极限以上。
<溶液粘度>
将涂布组合物在B型粘度计(Brookfield公司制DV2T型粘度计SpindleSC4-28附水套的少量样品适配器),以23℃、50rpm的条件评价。
再者,实施例3~7、比较例6的空栏处没有进行数据的测定。
<剪切粘度、TI>
TI(触变指数,Thixotropy·Index)通过以下的式算出。
TI=在0.01/s的剪切速度下的粘度(Pa·s)÷在10000/s的剪切速度下的粘度(Pa·s)
剪切粘度使用Anton Parr制旋转式粘度计测定。具体而言,将23℃的涂布组合物的粘度从剪切速度0.01sec-1至10,000sec-1,历时400秒一边提升速度一边测定,连续从10000sec-1至0.01sec-1历时400秒一边降低速度一边测定。将一边降低剪切速度一边测定时的测定值定为在各剪切速度下的粘度。
<涂膜厚>
使用TECLOCK公司制定压厚度测定器PF-11J,依照JIS K6400-1-2004,测定涂布干燥了的薄膜的中心和从中心上下偏离10cm的2点、合计3点,取平均。
<涂布表面外观>
将涂布薄片的表面外观用以下的基准实施评价。
〇:于涂布表面未确认到空隙
△:于涂布表面确认到10个以内的空隙
×:于涂布表面确认到超过10个的空隙
<表面粗糙度>
使用Surtronic Duo表面粗糙度计(TAYLOR HOBSON公司制),依照JIS B0601-2013,对于涂布薄片(15cm×30cm)测定中心和从中心上下偏离10cm的2点,合计3点的算术平均粗糙度(Ra),取平均。将Ra除以涂膜厚者定为表面粗糙度比。
<剥离评价>
在涂布薄片的涂布面通过NICHIBAN制15mm宽度玻璃纸胶带进行玻璃纸胶带剥离试验,将涂布物与聚丙烯薄片之间的密着性用以下的3阶段评价。
○:涂布部分并无剥离。
△:涂布部分虽有些微剥离但可实用。
×:涂布部分剥离,实用上不允许。
<耐热评价>
从涂布薄片的厚度等同(6~7μm)部位取长方形,测定四边的长度。接着,将该试验片于金属制拍上空出四边无干扰的距离而静置。
将该金属制拍放入内温150℃的风炉并静置15分钟,取出并测定四边的尺寸。将测定结束的试验片再度放入调整至200℃的风炉,静置15分钟后取出,测定四边的尺寸。用以下的项目评价。
〇:在150℃、200℃下全部的边收缩率为20%以下。
△:在150℃、200℃试验中任一边收缩率超过20%且为30%以下,且全部边的收缩率为30%以下。
×:在150℃、200℃试验中任一边收缩率超过30%。
<长宽比>
依照JISR1670-2006,在显微镜照片,分别测定100粒子的长径、短边并平均,通过平均长径÷平均短边求出。
表2
由表2可以知道,TI为特定范围的实施例形成了涂布表面无紊乱,表面平滑性高,而且剥离性或耐热性都优异的涂膜。
Claims (13)
1.一种涂布组合物,其是包含填料、粘结剂、增稠剂和溶剂的涂布组合物,其特征在于,
所述填料的长宽比为2以上,
所述粘结剂包含选自二烯橡胶和(甲基)丙烯酸酯聚合物中的至少一种,
以剪切速度0.01/s测定的涂布组合物的粘度为1.0×106Pa·s以下,
下述触变指数TI为1.1×106以上,
触变指数TI=以剪切速度0.01/s测定的涂布组合物的粘度/以剪切速度10000/s测定的涂布组合物的粘度。
2.如权利要求1所述的涂布组合物,所述填料与所述增稠剂之比以质量比计为:
填料/增稠剂为0.1~500。
3.如权利要求1或2所述的涂布组合物,所述增稠剂为聚N-乙烯基羧酸酰胺。
4.如权利要求1~3中任一项所述的涂布组合物,所述增稠剂为聚N-乙烯基乙酰胺。
5.如权利要求1或2所述的涂布组合物,所述增稠剂为聚乙烯基吡咯烷酮。
6.如权利要求1~5中任一项所述的涂布组合物,包含水作为溶剂。
7.如权利要求1~6中任一项所述的涂布组合物,所述触变指数TI的值为1.1×108以下。
8.如权利要求1~7中任一项所述的涂布组合物,所述填料的长宽比为100以下。
9.一种带涂膜的基材,其包含由权利要求1~8中任一项所述的涂布组合物形成的涂膜、和基材。
10.一种隔板,其由权利要求9所述的带涂膜的基材形成。
11.一种二次电池,使用了权利要求10所述的隔板。
12.一种锂离子二次电池,使用了权利要求10所述的隔板。
13.一种电极材料,在基材表面具备由权利要求1~8中任一项所述的涂布组合物形成的涂膜。
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US8771859B2 (en) * | 2009-03-13 | 2014-07-08 | Hitachi Maxell, Ltd. | Separator for battery and nonaqueous electrolyte battery using same |
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JP2013196780A (ja) * | 2012-03-15 | 2013-09-30 | Mitsubishi Paper Mills Ltd | 金属イオン二次電池セパレータ用塗液及び金属イオン二次電池セパレータ |
JP6390815B2 (ja) * | 2016-10-14 | 2018-09-19 | 王子ホールディングス株式会社 | 電池用セパレータ塗液用増粘剤、電池用セパレータ塗液及び電池用セパレータ |
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CN109233577A (zh) * | 2017-05-12 | 2019-01-18 | 住友化学株式会社 | 非水电解液二次电池用涂料 |
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