CN117222698A - 双轴拉伸聚酯膜及包括其的二次电池隔膜 - Google Patents
双轴拉伸聚酯膜及包括其的二次电池隔膜 Download PDFInfo
- Publication number
- CN117222698A CN117222698A CN202280031540.9A CN202280031540A CN117222698A CN 117222698 A CN117222698 A CN 117222698A CN 202280031540 A CN202280031540 A CN 202280031540A CN 117222698 A CN117222698 A CN 117222698A
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- China
- Prior art keywords
- polyester film
- biaxially stretched
- stretched polyester
- roll
- winding
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920006267 polyester film Polymers 0.000 title claims abstract description 96
- 238000004804 winding Methods 0.000 claims abstract description 69
- 239000010954 inorganic particle Substances 0.000 claims abstract description 40
- 229920001225 polyester resin Polymers 0.000 claims abstract description 12
- 239000004645 polyester resin Substances 0.000 claims abstract description 12
- 239000011229 interlayer Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000037303 wrinkles Effects 0.000 abstract description 47
- 230000000052 comparative effect Effects 0.000 description 31
- 239000010410 layer Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- -1 polyethylene terephthalate Polymers 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
本发明的双轴拉伸聚酯膜为包括无机颗粒和聚酯树脂的双轴拉伸聚酯膜,将卷绕有双轴拉伸聚酯膜的母卷进行分切后,以6.5kg/m至8.5kg/m的卷绕张力、35kg/m至50kg/m的卷绕面压及300m/min至350m/min的卷绕速度再卷绕的卷的硬度为90点至95点,其能够防止在卷绕成卷的状态下经时发生皱纹,因此在用作二次电池隔膜的夹层衬片时能够防止皱纹转移到隔膜上。
Description
技术领域
本发明涉及一种双轴拉伸聚酯膜,更具体地,涉及一种重新设计表面特性且优化卷绕条件,从而当用作二次电池隔膜的夹层衬片时能够防止经时发生的皱纹转移到二次电池隔膜上的双轴拉伸聚酯膜及包括其的二次电池隔膜。
背景技术
近年来,作为环保政策和二氧化碳减排政策的一部分,电动汽车正在取代以汽油或柴油为燃料的内燃机汽车,因此对电动汽车的需求逐渐扩大,普及率也在不断提高。如上所述,随着电动汽车普及率的提高,对电动汽车必不可少的二次电池的需求迅速增加,二次电池市场也在快速增长。
上述二次电池是由一个或多个可充电和放电的电化学电池组成的电池,通过再充电可以多次使用,因此使用方便,并且因不产生电池废物而环保。一般来说,二次电池由决定电池容量和电压并使电流流动的阳极和阴极、作为帮助离子顺利移动的介质的电解质以及阻止阳极和阴极之间接触的隔膜组成。
此外,作为二次电池制备过程的一部分,二次电池所使用的隔膜(PE材料,软质)上会涂敷用于增强安全性的涂层(Safety Reinforced Separator,SRS),在涂敷后再卷绕的过程中,在隔膜之间会出现粘连现象,因此在隔膜之间插入聚酯膜作为夹层衬片并进行贴合,以防止在复卷时隔膜相互粘连的现象。
然而,若用作夹层衬片的聚酯膜具有严重的皱纹,则皱纹会转移到作为软质材料的隔膜上,导致隔膜的质量劣化。尤其,现有的聚酯膜在刚生产出来的卷状状态下没有皱纹,但其经时性较差,因此膜内部的空气没有充分释放而被困在内部,从而产生皱纹,上述聚酯膜的皱纹被转移到隔膜,极大地影响隔膜的质量。
因此,迫切需要通过改善用于二次电池隔膜的夹层衬片的聚酯膜经时发生皱纹的问题来防止其转移到隔膜上。
现有技术文献
专利文献
(专利文献001)韩国公开专利公报10-2018-0077585号
发明内容
技术问题
本发明是为了解决上述问题而研制的,本发明的目的在于提供能够防止在生产聚酯膜后在卷绕成卷的状态下经时发生皱纹的双轴拉伸聚酯膜及包括其的二次电池隔膜。
本发明的上述和其他目的和优点将通过以下优选实施例的的说明会更为明确。
解决问题的方案
上述目的通过一种双轴拉伸聚酯膜实现,上述双轴拉伸聚酯膜为包括无机颗粒和聚酯树脂的双轴拉伸聚酯膜,将卷绕有双轴拉伸聚酯膜的母卷进行分切后,以6.5kg/m至8.5kg/m的卷绕张力、35kg/m至50kg/m的卷绕面压及300m/min至350m/min的卷绕速度再卷绕的卷的硬度为90点至95点。
优选地,无机颗粒的平均粒径可以为3.0μm至5.0μm。
优选地,无机颗粒的含量可以为0.0008重量%至0.0015重量%。
优选地,双轴拉伸聚酯膜的中心线平均粗糙度SRa可以为40nm至80nm,十点平均粗糙度SRz可以为800nm至1300nm。
优选地,双轴拉伸聚酯膜的最大粗糙度SRmax可以为1100nm至1800nm。
优选地,双轴拉伸聚酯膜的雾度可以为4%以上。
优选地,双轴拉伸聚酯膜在表面的峰值计数SPC中在0.1mm2面积内的高度为0.15μm以上的突起数可以为100个以上。
优选地,无机颗粒可以为二氧化硅颗粒。
优选地,双轴拉伸聚酯膜的厚度可以为10μm至16μm。
另外,上述目的通过用作二次电池隔膜的夹层衬片的上述双轴拉伸聚酯膜来实现。
另外,上述目的通过包含上述双轴拉伸聚酯膜的二次电池隔膜以及包含其的二次电池来实现。
发明的效果
根据本发明的一实施例的双轴拉伸聚酯膜通过重新设计聚酯膜的表面特性并优化卷绕条件来使卷绕的膜卷内部的空气顺利逸出,从而在生产膜后不会经时发生皱纹,且在卷绕时不出现由于内部空气引起的皱纹。
另外,根据本发明,由于不经时发生皱纹,因此当用作二次电池隔膜的夹层衬片时,皱纹不会转移到隔膜上,从而防止在隔膜贴合加工时由于皱纹引起的质量问题,以提高二次电池隔膜的质量,能够稳定供给产品。
另外,根据本发明,当用作二次电池隔膜的夹层衬片时,皱纹不会转移至隔膜,因此可以提供包括高效二次电池隔膜的二次电池等。
然而,本发明的效果并不限定于以上所述的效果,通过下面的记载,本领域所属技术人员可以明确地理解到未提及的其他效果。
附图说明
图1为根据本发明的一实施例的双轴拉伸聚酯膜的示意性截面图。
具体实施方式
参照附图来对本发明的实施例进行详细说明,以使本发明所属技术领域的普通技术人员轻松实现本发明。然而,本发明可通过多种不同的实施方式实现,并不限定于在本说明书中所说明的实施例。
在附图中,为了更清楚地表现各个层和区域,附图中所示的每个部件厚度被放大。在说明书全文中,对于相同或相似的组件赋予相同的附图标记。如层、膜、区域或板等的元件放置在另一元件“上”或“上方”的表达不仅表示元件“直接”放置在上述另一元件“上”或放置在上述另一元件“正上方”的情况,而且还表示另外的元件置于上述元件与上述另一元件之间的情况。相反,当某一元件放置在另一元件“正上方”时,意味着其中间没有其他元件。
除非另有定义,本说明书中所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。若发生矛盾,则以包括定义的本说明书为准。尽管与本文所述的那些方法和材料的类似者或等同者均可用于本发明实施例的实践或测试,但合适的方法和材料如下文所述。
根据本发明的一实施例的双轴拉伸聚酯膜旨在提供通过调节制备膜时使用的无机颗粒的尺寸且改变卷绕工艺条件来改善经时发生的皱纹的膜。在下文中,将更详细地描述本发明。
图1为根据本发明的一实施例的双轴拉伸聚酯膜的示意性截面图。
参照图1,根据本发明的一实施例的双轴拉伸聚酯膜包括无机颗粒100和聚酯树脂200,以具有在聚酯树脂200中分散无机颗粒100的结构。
本发明中使用的无机颗粒100优选含有二氧化硅(SiO2)、硼硅酸盐、硅铝酸盐及氧化铝,更优选含有二氧化硅颗粒。
在一实施例中,无机颗粒100的平均粒径优选为3.0μm至5.0μm。当使用平均粒径小于3.0μm的无机颗粒100时,卷绕时皱纹变得更严重,并且在卷成卷状的状态下空气难以逸出,导致经时发生皱纹。相反,若无机颗粒100的平均粒径超过5.0μm,则在膜层之间被大颗粒按压,从而在制备膜时过滤器(Filter)中的压力在短时间内增加,导致生产损失(Loss)增加。
在一实施例中,相对于100重量%的整个双轴拉伸聚酯膜,无机颗粒100的含量优选为0.0008重量%至0.0015重量%。若无机颗粒100的含量小于0.0008重量%,则膜层之间的空气层变得不足,导致膜的特定部分出现表面突起,这些表面突起累积,使得卷绕的卷上的突起变得严重,导致加工不良,还降低卷绕性,因此卷绕时MD方向的皱纹增多。相反,若无机颗粒100的含量超过0.0015重量%,则由于颗粒的聚集导致异物增加而出现缺陷,从而在拉伸膜时由于颗粒而出现膜破裂。
在一实施例中,构成双轴拉伸聚酯膜的聚酯树脂100可以通过聚合二羧酸和二醇形成,并且可以包括聚对苯二甲酸乙二醇酯(PET)。
其中,二羧酸可以包括如对苯二甲酸、萘二甲酸、间苯二甲酸、二苯基羧酸、二苯砜二羧酸、二苯氧基乙烷二羧酸、5-钠砜二羧酸及邻苯二甲酸等的芳香族二羧酸;或如草酸、琥珀酸、己二酸、癸二酸、二聚酸、马来酸及富马酸等的脂肪族二羧酸;及如环己烷二甲酸等的脂环族二羧酸;以及如对羟基苯甲酸等氧化羧酸等。并且,作为二醇,可以使用如乙二醇、丙二醇、丁二醇、戊二醇、己二醇、新戊二醇等的脂肪族二醇;如二甘醇、聚乙二醇、聚丙二醇等的聚氧化烯二醇;如环己烷二甲醇等的脂环二醇;以及如双酚A和双酚S等的芳香族二醇等。
在一实施例中,根据本发明的一实施例的双轴拉伸聚酯膜的中心线平均粗糙度SRa优选为40nm至80nm。此时,若中心线平均粗糙度SRa小于40nm,则在堆叠膜时每层之间空气逸出的空间较小,发生经时皱纹,若中心线平均粗糙度SRa大于80nm,则因投入过多颗粒而在生产时过滤器压力增加,生产率降低。
在一实施例中,双轴拉伸聚酯膜的十点平均粗糙度SRz优选为800nm至1300nm。此时,若十点平均粗糙度SRz小于800nm,则在堆叠膜时每层之间空气逸出的空间较小,发生经时皱纹,若十点平均粗糙度SRz大于1300nm,则因投入过多颗粒而在生产时过滤器压力增加,生产率降低。
在一实施例中,双轴拉伸聚酯膜的最大粗糙度SRmax优选为1100nm至1800nm。此时,若最大粗糙度SRmax小于1100nm,则在堆叠膜时每层之间空气逸出的空间较小,发生经时皱纹,若最大粗糙度SRmax大于1800nm,则因投入过多颗粒而在生产时过滤器压力增加,生产率降低。
在一实施例中,双轴拉伸聚酯膜的雾度优选为4%以上。此时,若雾度低于4%,则与此对应地颗粒含量小,因此空气逸出不利,从而经时发生皱纹。
在一实施例中,双轴拉伸聚酯膜在表面的峰值计数SPC中在0.1mm2面积内的高度为0.15μm以上的突起数优选为100个以上。此时,若突起数少于100个,则当堆叠膜时,空气在各层之间逸出的空间较小,因此经时发生皱纹。
在一实施例中,双轴拉伸聚酯膜的厚度优选为10μm至16μm。此时,若厚度小于10μm,则卷绕卷时会产生皱纹,且空气逸出不利,因此经时发生皱纹。然而,双轴拉伸聚酯膜越厚,经时越不易发生皱纹,因此对上述上限值没有限制。
根据本发明的一实施例的双轴拉伸聚酯膜的制备方法包括:第一步骤,将无机颗粒与聚酯树脂混合、挤出及双轴拉伸,从而制备母卷;第二步骤,将上述母卷分切成预定的宽度;以及第三步骤,以预定的卷绕张力、卷绕面压及卷绕速度再卷绕,从而制备再卷绕的双轴拉伸聚酯膜卷。
首先,在通过将无机颗粒与聚酯树脂混合、挤出及双轴拉伸来制备母卷的第一步骤中,将无机颗粒添加到聚酯树脂中,混合、挤出并在MD和TD方向上双轴拉伸,从而制备双轴拉伸聚酯膜。此时,无机颗粒的平均粒径优选为3.0μm至5.0μm,并且无机颗粒的含量相对于100重量%的整个双轴拉伸聚酯膜优选为0.0008重量%至0.0015重量%。另外,为了便于后续工艺,优选将第一步骤中制备的聚酯膜卷绕成母卷的形式。
其次,在将上述母卷分切成预定的宽度的第二步骤中,将以母卷形式卷绕的聚酯膜分切至所需宽度,即用户要求的宽度。此时,对通过分切实现的聚酯膜的宽度没有特别限制,而可以根据聚酯膜的使用用途和需要它的公司的需要自由调节。
其次,通过以预定的卷绕张力、卷绕面压及卷绕速度再卷绕来制备再卷绕的双轴拉伸聚酯膜卷的第三步骤为将通过分切具有预定宽度的聚酯膜以6.5kg/m至8.5kg/m的卷绕张力、35kg/m至50kg/m的卷绕面压及300m/min至350m/min的卷绕速度再卷绕的步骤。由此,能够防止在上述条件下再卷绕双轴拉伸聚酯膜的状态下经时发生皱纹。
同时,第二步骤和第三步骤可以各自作为单独的工艺执行,为了工艺方便,可以具有在第二步骤的分切工艺过程中同时执行第三步骤的一个工艺形式。
在上述双轴拉伸聚酯膜的制备方法中,省略了与图1的双轴拉伸聚酯膜相同的重复内容。
在一实施例中,对卷绕有上述双轴拉伸聚酯膜的母卷(Master Roll)进行分切(Slitting)并为了提供给用户而再卷绕时,以6.5kg/m至8.5kg/m的卷绕张力、35kg/m至50kg/m的卷绕面压及300m/min至350m/min的卷绕速度最终卷绕的卷的硬度优选满足90点至95点。此时,若卷的硬度小于90点,则卷下垂,且在膜的宽度方向上出现横向皱纹,若卷的硬度大于95点,则经时发生皱纹。
当如上所述再卷绕时,若卷绕张力小于6.5kg/m且卷绕面压小于35kg/m,则因张力和面压而卷绕母卷时出现横向皱纹且发生卷绕截面脱落,导致卷绕不正常,无法生产产品。相反,若卷绕张力大于8.5kg/m且卷绕面压大于50kg/m,则因进入不同膜层间的空气量增加而加速皱纹的发生。
另外,若卷绕速度小于300m/min,则卷的硬度增加,由此经时发生皱纹,而若卷绕速度大于350m/min,则卷绕速度变得过快,进入不同膜层之间的空气量增加,加速皱纹的发生。
如上所述,根据本发明的一实施例的双轴拉伸聚酯膜被卷绕并制备成母卷,并且当分切后再卷绕以提供给用户时,在6.5kg/m至8.5kg/m的卷绕张力、35kg/m至50kg/m的卷绕面压及300m/min至350m/min的卷绕速度的设定条件下卷绕,以使膜内空气(Air)顺畅地逸出,从而防止随着时间的经过出现皱纹。
如上所述,根据本发明的一实施例的双轴拉伸聚酯膜通过上述物理性质抑制经时发生的皱纹,从而防止在隔膜贴合加工时皱纹转移至隔膜的问题,因此能够用作二次电池隔膜的夹层衬片。
因此,本领域技术人员将容易理解,本发明的范围还延伸至用作二次电池隔膜的夹层衬片的双轴拉伸聚酯膜、包括其的二次电池隔膜以及包括上述二次电池隔膜的二次电池。
在下文中,将通过实施例更详细地说明本发明。提供本实施例仅用于具体说明本发明,而本发明的范围不受这些实施例的限制。
[实施例]
[实施例1]
混合0.00087重量%的平均粒径为3.75μm的无机颗粒(SiO2)和99.99913重量%的聚酯树脂(PET A9039,东丽先端素材株式会社)。其次,将混合的聚酯树脂真空干燥,通过挤出机在275℃至285℃的温度下熔融,通过使用T型模(T-DIE)经由进料段挤出,然后在冷却辊上通过静电施加法(pinning)粘合在流延鼓上,通过冷却和凝固获得未经拉伸的片材,在加热至片材的玻璃化转变温度或其以上温度的辊通过辊与辊之间的圆周速度比差对上述片材进行单轴拉伸(纵向拉伸)。此时,纵向拉伸倍率为4.5倍。其次,在单轴拉伸后,在与纵向垂直的横向上进行4.1倍的双轴拉伸。此时,基于拉幅机,在拉伸区域中的初始阶段的拉伸温度被设定为100℃至120℃,在拉伸区域中的中间阶段的拉伸温度被设定为120℃至140℃,在拉伸热定型区域中的温度被设定为200℃至240℃。
如上所述制备聚酯膜母卷,此时,双轴拉伸聚酯膜的厚度为12μm。
其次,将制备的聚酯膜母分切成1,120mm的宽度,并以7.6kg/m的卷绕张力、48kg/m的卷绕面压及340m/min的卷绕速度再卷绕,从而制备双轴拉伸聚酯膜卷。
[实施例2]
除了无机颗粒含量为0.0008重量%之外,以与实施例1相同的方法制备双轴拉伸聚酯膜卷。
[实施例3]
除了无机颗粒含量为0.0015重量%之外,以与实施例1相同的方法制备双轴拉伸聚酯膜卷。
[实施例4]
除了无机颗粒的尺寸为3μm之外,以与实施例1相同的方法制备双轴拉伸聚酯膜卷。
[实施例5]
除了无机颗粒的尺寸为5μm之外,以与实施例1相同的方法制备双轴拉伸聚酯膜卷。
[实施例6]
除了卷绕张力为6.5kg/m之外,以与实施例1相同的方法制备双轴拉伸聚酯膜卷。
[实施例7]
除了卷绕张力为8.5kg/m之外,以与实施例1相同的方法制备双轴拉伸聚酯膜卷。
[实施例8]
除了卷绕面压为35kg/m之外,以与实施例1相同的方法制备双轴拉伸聚酯膜卷。
[实施例9]
除了卷绕面压为50kg/m之外,以与实施例1相同的方法制备双轴拉伸聚酯膜卷。
[比较例]
[比较例1]
除了无机颗粒的尺寸为2.9μm之外,以与实施例1相同的方法制备双轴拉伸聚酯膜卷。
[比较例2]
除了无机颗粒含量为0.0016重量%之外,以与比较例1相同的方法制备双轴拉伸聚酯膜卷。
[比较例3]
除了无机颗粒的尺寸为5.1μm之外,以与实施例1相同的方法制备双轴拉伸聚酯膜卷。
[比较例4]
除了无机颗粒含量为0.0007重量%之外,以与实施例1相同的方法制备双轴拉伸聚酯膜卷。
[比较例5]
除了无机颗粒含量为0.0016重量%之外,以与实施例1相同的方法制备以制备膜。
[比较例6]
除了卷绕张力为8.6kg/m之外,以与实施例1相同的方法制备双轴拉伸聚酯膜卷。
[比较例7]
除了卷绕张力为6.4kg/m之外,以与实施例1相同的方法制备膜。
[比较例8]
除了卷绕面压为51kg/m之外,以与实施例1相同的方法制备双轴拉伸聚酯膜卷。
[比较例9]
除了卷绕面压为34kg/m之外,以与实施例1相同的方法制备膜。
[比较例10]
除了卷绕速度为290m/min之外,以与实施例1相同的方法制备双轴拉伸聚酯膜卷。
对实施例1至9和比较例1至10中制备的双轴拉伸聚酯膜卷的物理性能通过以下实验例进行评价,其结果如表1所示。
[实验例]
(1)经时发生的皱纹评价
将卷绕有根据实施例和比较例制备的双轴拉伸聚酯膜的膜卷包装并储存,经过2天后,拆开包装并用肉眼确认卷绕的卷的表面状况,以确定是否出现皱纹。此时,卷绕的膜的长度为8,200m,并且如下进行评价。
良好:在膜的整个宽度上不发生经时皱纹。
差:在膜的整个宽度上发生经时皱纹。
(2)卷绕的卷(Roll)的硬度
按照JIS K 7312标准,利用由ASKER公司制造的精密硬度计(型号:Type C)来置于卷绕的膜卷表面,分别测量卷的左端和右端的硬度各一次,以确定硬度值。
(3)SRa、SRz、SRmax测量(膜表面粗糙度)
利用由株式会社小坂研究所(Kosaka Laboratory Ltd.)制造的三维表面粗糙度测量仪(型号:SE3500K)测量单张膜表面的SRa、SRz、SRmax值。
(4)SPC突起数
利用由株式会社小坂研究所制造的三维表面粗糙度测量仪(型号:SE3500K)测量单张膜表面的SPC(峰值计数(Peak Count)),计算在0.1mm2的测量面积内高度为0.15μm以上的突起的数量。
(5)雾度测量
利用日本电色工业株式会社(NIPPON DENSHOKU INDUSTRIES Co.,LTD)的雾度计(型号:COH-300A)测量一张膜的雾度。
表1
分类 | 经时皱纹 | 卷硬度 | SRa | SRz | SRmax | SPC突起数 | 雾度 |
实施例1 | 良好 | 92 | 53nm | 825nm | 1218nm | 160 | 4.40% |
实施例2 | 良好 | 91 | 51nm | 812nm | 1433nm | 143 | 4.10% |
实施例3 | 良好 | 90 | 67nm | 1239nm | 1580nm | 250 | 5.50% |
实施例4 | 良好 | 94 | 48nm | 807nm | 1175nm | 128 | 4.20% |
实施例5 | 良好 | 90 | 75nm | 1222nm | 1753nm | 200 | 6.10% |
实施例6 | 良好 | 91 | 53nm | 825nm | 1218nm | 160 | 4.40% |
实施例7 | 良好 | 94 | 53nm | 825nm | 1218nm | 160 | 4.40% |
实施例8 | 良好 | 91 | 53nm | 825nm | 1218nm | 160 | 4.40% |
实施例9 | 良好 | 93 | 53nm | 825nm | 1218nm | 160 | 4.40% |
比较例1 | 差 | 97 | 41nm | 802nm | 1027nm | 90 | 3.90% |
比较例2 | 差 | 96 | 45nm | 825nm | 1099nm | 160 | 5.20% |
比较例3 | 良好 | 88 | 81nm | 1312nm | 1826nm | 263 | 5.90% |
比较例4 | 差 | 96 | 39nm | 799nm | 1065nm | 92 | 3.90% |
比较例5 | 良好 | 88 | 62nm | 1236nm | 1335nm | 123 | 5.30% |
比较例6 | 差 | 96 | 53nm | 825nm | 1218nm | 160 | 4.40% |
比较例8 | 差 | 97 | 53nm | 825nm | 1218nm | 160 | 4.40% |
比较例10 | 差 | 96 | 53nm | 825nm | 1218nm | 160 | 4.40% |
由表1可知,在实施例1至9的情况下,可以确认将0.0008重量%至0.0015重量%的平均粒径为3.0μm至5.0μm的无机颗粒添加到聚酯树脂中并挤出和双轴拉伸以形成聚酯膜的母卷,然后分切并再卷时,将卷绕张力设定为6.5kg/m至8.5kg/m、将卷绕面压设定为35kg/m至50kg/m、将卷绕速度设定为300m/min至350m/min来制备再卷绕的卷,从而能够提供改善经时发生的皱纹的双轴拉伸聚酯膜。
另一方面,在比较例1的情况下,可以看出由于无机颗粒尺寸小和卷硬度高,经时发生皱纹,若SRmax低于最小范围,突起数小于100个,雾度小于4%。
另外,可知在比较例2中尽管添加了更多的小尺寸无机颗粒,但是卷的硬度高,经时发生皱纹,并且SRmax低于最小范围。
另外,在比较例3中,可知由于无机颗粒的尺寸过大,因此SRa、SRz及SRmax均超过最大值,并且因卷的硬度低而制备的膜的物理性能变软,卷向底部下沉,导致卷绕缺陷。
另外,在比较例4中,无机颗粒的尺寸与实施例1相同,但仅添加了低于标准含量的0.0007重量%的无机颗粒,因此SRa、SRz及SRmax均小于最小值,突起数小于100个,雾度小于4%,因卷的硬度过高而经时发生皱纹。
另外,在比较例5中,卷的硬度太低,导致膜变软,卷向底部下垂,发生卷绕缺陷,并且在生产过程中过滤器的压力过度增加,降低生产率。
另外,在比较例6中,将分切后的卷绕张力设定为较高的8.6kg/m,因此卷的硬度增加,与此相应地经时发生皱纹。
另外,在比较例8中,卷绕张力与实施例1相同,但由于将卷绕面压设定得较高,因此卷的硬度增加,经时发生皱纹。
另外,在比较例10中,由于以低卷绕速度卷绕,因此卷的硬度增加,与此相应地经时发生皱纹。
尤其,除了表1所示的以外,在卷绕张力或卷绕面压低的比较例7、9中,可以确认在制备膜后将膜卷绕时产生卷绕截面不良、挤压及折叠等卷绕缺陷。
以上对本发明的优选实施例进行了详细说明,但本发明的范围并不限定于此,利用所附发明要求保护范围中所定义的本发明的基本概念的本发明所属技术领域的普通技术人员的各种变形及改良形态也属于本发明的范围。
Claims (12)
1.一种双轴拉伸聚酯膜,其为包括无机颗粒和聚酯树脂的双轴拉伸聚酯膜,其特征在于,
将卷绕有上述双轴拉伸聚酯膜的母卷进行分切后,以6.5kg/m至8.5kg/m的卷绕张力、35kg/m至50kg/m的卷绕面压及300m/min至350m/min的卷绕速度再卷绕的卷的硬度为90点至95点。
2.根据权利要求1所述的双轴拉伸聚酯膜,其特征在于,
上述无机颗粒的平均粒径为3.0μm至5.0μm。
3.根据权利要求1所述的双轴拉伸聚酯膜,其特征在于,
上述无机颗粒的含量为0.0008重量%至0.0015重量%。
4.根据权利要求1所述的双轴拉伸聚酯膜,其特征在于,
上述双轴拉伸聚酯膜的中心线平均粗糙度SRa为40nm至80nm,十点平均粗糙度SRz为800nm至1300nm。
5.根据权利要求4所述的双轴拉伸聚酯膜,其特征在于,
上述双轴拉伸聚酯膜的最大粗糙度SRmax为1100nm至1800nm。
6.根据权利要求1所述的双轴拉伸聚酯膜,其特征在于,
上述双轴拉伸聚酯膜的雾度为4%以上。
7.根据权利要求1所述的双轴拉伸聚酯膜,其特征在于,
上述双轴拉伸聚酯膜在表面的峰值计数SPC中在0.1mm2面积内的高度为0.15μm以上的突起数为100个以上。
8.根据权利要求1所述的双轴拉伸聚酯膜,其特征在于,
上述无机颗粒为二氧化硅颗粒。
9.根据权利要求1所述的双轴拉伸聚酯膜,其特征在于,
上述双轴拉伸聚酯膜的厚度为10μm至16μm。
10.根据权利要求1至9中任一项所述的双轴拉伸聚酯膜,其特征在于,上述双轴拉伸聚酯膜用作二次电池隔膜的夹层衬片。
11.一种二次电池隔膜,其特征在于,包括根据权利要求1至9中任一项所述的双轴拉伸聚酯膜。
12.一种二次电池,其特征在于,包括根据权利要求11所述的二次电池隔膜。
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