CN104066781B - 聚烯烃微多孔膜的制造方法 - Google Patents
聚烯烃微多孔膜的制造方法 Download PDFInfo
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- CN104066781B CN104066781B CN201380004961.3A CN201380004961A CN104066781B CN 104066781 B CN104066781 B CN 104066781B CN 201380004961 A CN201380004961 A CN 201380004961A CN 104066781 B CN104066781 B CN 104066781B
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- film
- solvent
- dried
- plasticizer
- roller
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
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- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
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Classifications
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Abstract
聚烯烃微多孔膜的制造方法中,可抑制因提取溶剂的不均匀干燥引起的膜的不均匀化,且可实现高速干燥并可实现聚烯烃微多孔膜的高速连续生产。在将由聚烯烃树脂和增塑剂构成的组合物通过挤出成形制成膜状,拉伸后将增塑剂用溶剂提取除去,然后使其干燥的聚烯烃微多孔膜的制造方法中,在增塑剂提取后、干燥前,使膜紧贴在辊上或机械地限制膜的宽度,在维持紧贴在辊上或限制宽度的状态下,通过使溶剂的沸点以上的温度的液体(热介质)与膜接触而对膜进行加热干燥。
Description
技术领域
本发明涉及可优选用作例如过滤膜、各种电池、电容器的间隔物的聚烯烃微多孔膜的制造方法。更详细而言,涉及通过实现溶剂的高速干燥,能够实现高速连续生产,并且可获得优异的品质和优异的均匀性的聚烯烃微多孔膜的制造方法。
背景技术
微多孔膜一直以来被用作电池用间隔物或电解电容器用间隔物等的材料。近几年,特别是锂离子二次电池用途的需求增加,强烈希望间隔物的高速生产。
锂离子二次电池中因为使用电解液和正负极活性物质等的药剂,所以间隔物的材质考虑到耐化学品性,通常使用聚烯烃类聚合物,特别是使用低价的聚乙烯及聚丙烯。对于锂离子二次电池等的非水电解液类电池用途的间隔物,以往作为基本性能要求防止电极短路功能、高离子透过性、电池卷绕时的组装加工性、电池安全性和可靠性等。还有,近些年随着电池的大型化、高能量密度化、高输出功率化,对品质的均匀化的要求也变得强烈。
作为聚烯烃微多孔膜的制造方法,已知对由聚烯烃树脂和增塑剂构成的组合物进行熔融混炼,在从模具挤出成形为膜状、挤出成形后,对膜进行单轴或双轴拉伸,拉伸后,用溶剂从膜中提取上述增塑剂,使溶剂干燥,根据需要在干燥后进一步进行拉伸及热处理的方法(日本专利特开平5-156058号公报、日本专利特开平11-60789号公报、日本专利特开2010-235707号公报)。
此外,对于增塑剂提取后的溶剂的干燥,已知在干燥辊上、机械地限制膜的宽度的状态下,以干燥辊速度35~50m/分钟的条件进行干燥的方法(日本专利特开2011-42805号公报)。
现有技术文献
专利文献
专利文献1:日本专利特开平5-156058号公报
专利文献2:日本专利特开平11-60789号公报
专利文献3:日本专利特开2010-235707号公报
专利文献4:日本专利特开2011-42805号公报
发明内容
发明所要解决的技术问题
现有技术中,在制膜速度慢的时代,增塑剂提取后的溶剂的干燥工序中的问题不怎么明显。因此,在观念上,作为干燥方法提出了采用热风的干燥、与加热辊接触的干燥、浸渍于加热介质的干燥等各种各样的方法(专利文献1),作为具体的方法,广泛采用干燥装置的结构简单、在加热辊上喷射热风的方法。
但是,如果制膜速度加快,自干燥开始到干燥结束为止的一个膜循环(日文:フィルムパス)变长,在干燥工序,干燥的部分和未干燥的部分的绝对长度分别增大。由于膜的稍微厚度不均,薄的部分在短时间内干燥,厚的部分的干燥耗费时间。此外,干燥的部分收缩,未干燥的部分保持长的状态,因此导致未干燥的部分浮在加热辊上,未干燥部分的干燥时间变得更长。
此外,微多孔膜在半干燥状态下,由于由拉普拉斯力产生的负压,空孔被挤破,所以干燥时间如果变长,则空孔率降低。因此,不均匀的干燥成为使空孔率和厚度的均匀性变差的主要因素。
另一方面,作为为了缩短自干燥开始到干燥结束为止的一个膜循环而欲缩短干燥时间的方法,如果将加热辊的温度设为远高于溶剂的沸点的温度,则溶剂在加热辊的表面迅速气化,导致膜自加热辊浮起来,加热效率下降。因此,通过提高加热辊的温度来缩短干燥时间也是困难的。
解决技术问题所采用的技术方案
鉴于上述问题进行认真研究的结果是:本发明人发现不采用加热辊及热风的干燥,而采用在维持使膜紧贴在低温的辊上的状态下、或维持机械地限制膜的宽度的状态下,通过使膜与液体的热介质接触,进行加热,使膜干燥,从而能够解决上述问题,并完成了本发明。
即、本发明的第一技术方案是一种聚烯烃微多孔膜的制造方法,其包括:(a)将至少含有聚烯烃树脂和增塑剂的组合物熔融混炼,从模具挤出成形为膜状的工序;(b)在所述挤出成形后,将所得的膜在至少单轴方向上拉伸的工序;(c)在所述拉伸后,用溶剂从膜中提取所述增塑剂而将所述增塑剂除去的工序;(d)在所述提取后,使膜干燥的工序;其中,在提取工序后、干燥工序前,使膜紧贴在低于溶剂的沸点的低温辊上,在维持膜紧贴在辊上的状态下,通过使溶剂的沸点以上的温度的液体与膜接触而对膜进行加热干燥,所述液体与聚烯烃相疏。
此外,本发明的第二技术方案是一种聚烯烃微多孔膜的制造方法,其包括:(a)将至少含有聚烯烃树脂和增塑剂的组合物熔融混炼,从模具挤出成形为膜状的工序;(b)在所述挤出成形后,将所得的膜在至少单轴方向上拉伸的工序;(c)在所述拉伸后,用溶剂从膜中提取所述增塑剂而将所述增塑剂除去的工序;(d)在所述提取后,使膜干燥的工序;其中,在提取工序后、干燥工序前,机械地限制膜的宽度,在维持机械地限制膜的宽度的状态下,通过使溶剂的沸点以上的温度的液体与膜接触而对膜进行加热干燥,所述液体与聚烯烃相疏。
本发明中,在提取工序后干燥工序前,通过使膜紧贴低温的辊或机械地限制膜的宽度,将其维持并进行干燥,防止由干燥引起的膜在宽度方向上的收缩。
使膜紧贴在辊上的情况下,需要将辊的温度设为低于溶剂的沸点的温度。如果将辊的温度设在溶剂的沸点以上,则溶剂在辊表面迅速气化,无法使膜紧贴在辊上,因而不理想。
作为机械地限制膜的宽度的手段,优选夹式的展辐机装置。此外,也可以是在使膜紧贴在辊上的状态下机械地限制两端部的方法。
本发明中,将与聚烯烃相疏的液体作为热介质,通过使在溶剂的沸点以上的温度的热介质与膜接触来对膜进行加热,蒸发除去溶剂使其干燥。通过用高温的液体直接对膜进行加热,可以在短时间内给予膜足够的热,能够缩短干燥时间。此外,因为用液体的热介质进行加热,所以即使未干燥部分浮在辊上,加热效率也不会下降,可实现高速干燥。还有,通过选择与聚烯烃相疏的液体作为热介质,即使在膜中不加入热介质、或者假如在膜中加入微量的热介质,由于与聚烯烃相疏,所以也不会产生由拉普拉斯力(日文:ラプラス力)引起的负压,不会将空孔破坏。
作为用作热介质的与聚烯烃相疏的液体,较好为比热大的水。
作为使上述热介质与膜接触的方法,可例举:使膜在热介质通过的方法、对膜喷射热介质的方法等。此外,为了抑制溶剂在辊表面气化而使得膜浮在输送辊上,在对膜喷射热介质的情况下,较好使液体的热介质从辊的相反侧与膜接触。
发明效果
根据本发明的聚烯烃微多孔膜的制造方法,能够实现高速连续生产,并且能够防止因膜的收缩引起的空孔率的下降,提高空孔率和膜压的均匀性。此外,可抑制干燥时的聚烯烃的取向的缓和,防止强度的降低。
附图说明
图1是本发明的实施例1中使用的干燥装置的简图。
图2是本发明的实施例2中使用的干燥装置的简图。
图3是由本发明的实施例1得到的微多孔膜的厚度和空孔率的分布的图。
图4是由本发明的实施例2得到的微多孔膜的厚度和空孔率的分布的图。
图5是由本发明的比较例1得到的微多孔膜的厚度和空孔率的分布的图。
图6是由本发明的比较例2得到的微多孔膜的厚度和空孔率的分布的图。
图7是由本发明的比较例3得到的微多孔膜的厚度和空孔率的分布的图。
具体实施方式
以下,对本发明的实施方式进行详细说明。作为本发明中使用的聚烯烃,可使用乙烯、丙烯、1-丁烯、4-甲基-1-戊烯、1-己烯、1-辛烯等的烯烃的单独聚合物或共聚物。其中,特别优选能够通过高拉伸而提高结晶化度、且价格低的高密度聚乙烯。
使用高密度聚乙烯时,重均分子量(由凝胶渗透色谱法测定)优选在1万以上,更优选在5万以上。如果分子量过于小,则有可能熔融成形的熔融张力小,成形性差,或者拉伸性差、强度变低,因而不优选。对于重均分子量的上限,只要是在能够熔融成形、且可获得均匀的树脂组合物的范围就没有特别限定,通常在100万以下,优选在70万以下。
作为本发明中使用的增塑剂,是在与聚烯烃树脂混合时,在聚烯烃树脂的熔点以上能形成均匀溶液的不挥发性溶剂。具体而言,可例示液体石蜡、石蜡等烃类,邻苯二甲酸二辛酯、邻苯二甲酸二丁酯等酯类,油醇、硬脂醇等高级醇。其中,特别优选容易获得且操作容易的液体石蜡、石蜡。
本发明中使用的聚烯烃树脂和增塑剂的比率只要是不使微相分离产生、在将增塑剂提取除去后形成微多孔膜所需的足够的比率即可。具体而言,聚烯烃树脂的含有比率为10~70重量%,特别优选20~50重量%。
聚烯烃树脂和增塑剂的熔融混炼通过使用多轴挤出机或单轴挤出机等、用通常的方法来进行。
在由聚烯烃树脂和增塑剂构成的组合物中,可以根据目的添加防氧化剂、晶核剂、防静电剂、阻燃剂、润滑剂、紫外线吸收剂等的添加剂。
经熔融混炼的树脂组合物通过挤出成形而成形为片状或膜状(以下统称为“膜状”)。挤出成形可以使用T型模(平模)挤出为膜状,也可以使用圆形模等挤出为筒状后加工成膜状。挤出成形得到的膜的厚度优选为1~500μm,特别优选5~100μm。如果膜厚过薄则容易强度不足,如果过厚则在用于电池间隔物等时有可能间隔物的占有体积过大。
由挤出成形所得的膜至少在单轴方向上进行拉伸。至少在单轴方向上拉伸是指机械方向单轴拉伸、宽度方向单轴拉伸、同时双轴拉伸、逐次双轴拉伸。此外,拉伸不限定于1段拉伸,也可以是多段或多次的拉伸。拉伸方法没有特别限定,可以是辊拉伸,也可以是使用展辐机的拉伸。此外,为了实现高强度,特别优选双轴拉伸。
拉伸温度只要是常规方法中使用的温度即可。例如,在聚烯烃树脂组合物的熔点(Tm)以下、(Tm-50)℃以上的范围内进行拉伸。
拉伸倍率没有特别限定,单轴拉伸的情况下,通常是2~20倍,特别优选4~10倍。双轴拉伸的情况下,以面积倍率计通常为2~400倍,特别优选4~200倍。
拉伸后,将增塑剂从膜中提取、除去。提取增塑剂的方法通过向装满了提取溶剂的槽中连续地送入微多孔膜,以除去增塑剂所需的足够的时间将膜浸渍在槽中,然后将附着的溶剂干燥来进行。此时,如果采用向将槽内部分割成多段而使其带有浓度差的各槽中依次送入微多孔膜的多段法,或从微多孔膜的前进方向的反方向供给提取溶剂以用于形成浓度梯度的逆流法等公知的方法,可以提高提取效率,因而优选。重要的是将增塑剂从微多孔膜中实质上除去。此外,如果将提取溶剂的温度在低于溶剂的沸点的范围内进行加温,则能够促进增塑剂和溶剂的扩散,因此能够提高提取效率,从而更加优选。
本发明中使用的提取溶剂只要是相对于聚烯烃为不良溶剂、而相对于增塑剂为良溶剂、沸点比聚烯烃树脂的熔点低的溶剂即可。溶剂的沸点更优选低于100℃。作为这样的溶剂的具体例,在增塑剂是液体石蜡或石蜡的情况下,可例举正己烷、环己烷等烃类,二氯甲烷、1,1,1-三氯乙烷等卤代烃类,乙醇、异丙醇等醇类,四氢呋喃、***等醚类,丙酮、甲基乙基酮等酮类。其中,从获得和操作的容易度考虑,特别优选二氯甲烷或环己烷。
将增塑剂提取后,在干燥工序前使膜紧贴冷却辊、或者机械地限制膜的宽度。
在使膜紧贴冷却辊的情况下,冷却辊的表面温度设为溶剂的沸点以下且溶剂的凝结或结露不剧烈的温度。具体而言,溶剂是二氯甲烷的情况下,优选0~40℃,更优选35℃前后。
在机械地限制膜的宽度的情况下,作为机械地限定的方法,优选将膜的两端部用多个夹子抓住,随着膜的移动使该夹子移动的采用展辐机装置的方法。此外,在使膜紧贴在辊上的状态下,通过用带状的物件将膜的两端部压住的方法也能机械地限制膜的宽度。
在紧贴在冷却辊上或者机械地限制膜的宽度后,在维持紧贴在冷却辊上或维持限制膜的宽度的状态下,通过使液体状的热介质与膜接触而对膜进行加热,进行溶剂的干燥。热介质所用的液体必须与聚烯烃相疏。因为热介质所用的液体与聚烯烃相疏,所以热介质的液体不会进入到聚烯烃微多孔膜中。热介质所用的液体,具体而言优选水。
热介质的液体的沸点在提取溶剂的沸点以上。
作为使热介质的液体与膜接触的方法,可例举将膜浸渍在热介质中的方法、使膜通过填充有热介质的液体的槽中的方法、对膜喷射热介质的方法等。
在将热介质喷射到膜上的情况下,优选从输送辊侧的相反面侧对膜进行喷射。如果从辊侧喷射热介质,则溶剂在辊表面迅速气化,膜有可能从辊上浮起。
实施例
以下,通过实施例对本发明的实施方式进行更详细的说明,但本发明并不局限于这些实施例。
[实施例1]
将30重量份的聚烯烃树脂材料(在100重量份的高密度聚乙烯(重均分子量30万、重均分子量/数均分子量7、密度0.956)中干混合0.3重量份的2,6-二叔丁基对甲酚而得的物质)和70重量份的液体石蜡(37.78℃时的动态粘度75.9cSt)用双轴挤出机进行熔融混炼,将树脂混合物从平模(衣架模(日文:ハンガーコートダイ))挤出到表面温度控制在40℃的冷却辊上,得到厚度1.1mm的片状的微多孔膜前体。
接着,用展辐机式双轴拉伸机将所得的片状的微多孔膜前体在119℃下拉伸5×5倍,得到宽度1000mm、厚度40μm且均匀的膜状微多孔膜前体。
使所得的膜状微多孔膜前体与二氯甲烷(溶剂)逆流接触约2分钟,提取除去液体石蜡(增塑剂)。
提取除去液体石蜡后,使用图1的干燥装置,以制膜速度70m/分钟进行了加热干燥。具体而言,使提取除去液体石蜡后的聚乙烯微多孔膜1在点2处紧贴在温度控制在35℃的冷却辊3上,在维持紧贴的状态下从喷嘴4喷射温度65℃的温水,将二氯甲烷加热除去。
干燥后的微多孔膜的厚度和空孔率在宽度方向上的分布用下述方法测定,将测定的结果示于表1及图3。
[厚度的测定]
使用三丰株式会社制的LITEMATIC VL-50A-B(测头型号:120060),以微多孔膜的宽度的中心作为基准,在宽度方向上以10mm间距测定厚度。
[空孔率的测定]
以微多孔膜的宽度的中心作为基准,在宽度方向上每隔20mm切出20mm×20mm的样品,测定微多孔膜的重量(μg)。接着,根据上述20mm×20mm的样品的重量及由与其对应的3点算出的平均厚度(对中心厚度Tc赋以2倍的权重而得的加和平均),按照下式算出空孔率。
[数学式1]
另外,上述式中,使用结晶化度85~90%的聚乙烯的密度(0.995g/cm3)进行了计算。
[实施例2]
除了使用图2的装置进行干燥,以制膜速度120m/分钟进行以外,与实施例1同样。具体而言,使聚乙烯微多孔膜11在水12中通过,在用展辐机13限制宽度方向的状态下,在约60℃的温水14中加热。另外,用展辐机开始限制宽度方向的位置的水15控制在约25℃。所得的微多孔膜的厚度和空孔率在宽度方向上的分布示于表1及图4。
[比较例1]
对于干燥,在制膜速度10m/分钟、40℃的加热辊上喷射50℃的热风进行干燥处理,除此以外,与实施例1同样。制得的微多孔膜的厚度和空孔率在宽度方向上的分布示于表1及图5。
[比较例2]
除了将制膜速度设为20m/分钟以外,与比较例1同样。制得的微多孔膜的厚度和空孔率在宽度方向上的分布示于表1及图6。
[比较例3]
除了将制膜速度设为20m/分钟、没有进行以展辐机13在宽度方向上的机械限制以外,与实施例2同样。制得的微多孔膜的厚度和空孔率在宽度方向上的分布示于表1及图6。
[表1]
厚度和空孔率通过除以两端部40mm而算出
从实施例1、2可知,本发明的方法中,制膜速度即使是70m/分钟或120m/分钟的高速,也能够得到厚度和空孔率均匀的微多孔膜。与此相对,在加热辊上喷射热风进行干燥的情况下,如果是制膜速度10m/分钟的低速则可获得厚度和空孔率均匀的微多孔膜(比较例1),但是如果是制膜速度20m/分钟,则厚度和空孔率的不均匀变大,严重损害了品质的均匀性和稳定性(比较例2)。此外,即使是浸渍在温水中的方法,在没有进行宽度方向上的机械限制的情况下,宽度方向的收缩增大,或厚度和空孔率的不均匀增大。
工业上利用的可能性
本发明可用于高速生产过滤膜、各种电池、电容器的间隔物等中所使用的聚烯烃微多孔膜。
符号的说明
1:微多孔膜、
2:膜紧贴在冷却辊上的位置、
3:冷却辊(控制在约35℃)、
4:喷嘴(约65℃的温水)。
5:泵
6:加热器
11:微多孔膜、
12:水、
13:展辐机装置、
14:温水(约60℃)、
15:水(约25℃)、
16:隔热材料
17:加热器、
18:冷却器、
19:泵。
Claims (3)
1.一种聚烯烃微多孔膜的制造方法,其包括:
(a)将至少含有聚烯烃树脂和增塑剂的组合物熔融混炼,从模具挤出成形为膜状的工序;
(b)在所述挤出成形后,将所得的膜在至少单轴方向上拉伸的工序;
(c)在所述拉伸后,用溶剂从膜中提取所述增塑剂而将所述增塑剂除去的工序;
(d)在所述提取后,使膜干燥的工序;其特征在于,
在所述(c)的提取工序后、所述(d)的干燥工序前,使膜紧贴在低于溶剂的沸点的低温辊上,在维持膜紧贴在辊上的状态下,通过使溶剂的沸点以上的温度的液体与膜接触并加热而进行所述(d)的使膜干燥的工序,所述液体与聚烯烃相疏。
2.如权利要求1所述的聚烯烃微多孔膜的制造方法,其特征在于,与聚烯烃相疏的液体是水。
3.如权利要求1或2所述的聚烯烃微多孔膜的制造方法,其特征在于,所述(d)的干燥工序是通过使溶剂的沸点以上的温度的与聚烯烃相疏的液体从膜的输送辊的相反侧接触而对膜进行加热。
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PCT/JP2013/050027 WO2013105526A1 (ja) | 2012-01-10 | 2013-01-07 | ポリオレフィン微多孔膜の製造方法 |
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KR20170066686A (ko) | 2014-08-29 | 2017-06-14 | 스미또모 가가꾸 가부시키가이샤 | 다공질층, 다공질층을 적층하여 이루어지는 세퍼레이터, 및 다공질층 또는 세퍼레이터를 포함하는 비수 전해액 이차 전지 |
WO2016080200A1 (ja) * | 2014-11-18 | 2016-05-26 | 東レバッテリーセパレータフィルム株式会社 | ポリオレフィン微多孔膜、電池用セパレータおよびその製造方法 |
JP5914789B1 (ja) * | 2014-11-18 | 2016-05-11 | 東レバッテリーセパレータフィルム株式会社 | ポリオレフィン微多孔膜、電池用セパレータおよびその製造方法 |
JP5914790B1 (ja) * | 2014-12-11 | 2016-05-11 | 東レバッテリーセパレータフィルム株式会社 | ポリオレフィン微多孔膜、電池用セパレータおよびそれらの製造方法 |
KR102166652B1 (ko) * | 2014-12-11 | 2020-10-16 | 도레이 카부시키가이샤 | 폴리올레핀 미다공막, 전지용 세퍼레이터 및 그들의 제조 방법 |
KR20170131401A (ko) * | 2015-03-27 | 2017-11-29 | 데이진 가부시키가이샤 | 복합막의 제조 방법 |
JP6027214B1 (ja) * | 2015-06-11 | 2016-11-16 | 住友化学株式会社 | フィルム製造方法 |
CN107851766B (zh) * | 2015-07-29 | 2021-02-26 | 东丽株式会社 | 电池用隔膜及其制造方法 |
CN105131327B (zh) * | 2015-09-07 | 2019-07-02 | 广东工业大学 | 一种可控孔径的多孔薄膜的制造方法 |
US10770707B2 (en) | 2015-12-04 | 2020-09-08 | Toray Industries, Inc. | Battery separator and method of manufacturing same |
KR102101688B1 (ko) * | 2015-12-24 | 2020-04-17 | 도레이 카부시키가이샤 | 폴리올레핀 미다공막, 전지용 세퍼레이터 및 그것들의 제조 방법 |
EP3471171A4 (en) * | 2016-06-08 | 2019-05-15 | Nissan Motor Co., Ltd. | NONAQUEOUS ELECTROLYTE SECONDARY BATTERY |
TWI716496B (zh) * | 2016-11-21 | 2021-01-21 | 日商東麗股份有限公司 | 電池用隔膜及其製造方法以及電池用隔膜之捲繞體 |
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