JP2005302341A - Separator for electronic component and its manufacturing method - Google Patents
Separator for electronic component and its manufacturing method Download PDFInfo
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- JP2005302341A JP2005302341A JP2004112702A JP2004112702A JP2005302341A JP 2005302341 A JP2005302341 A JP 2005302341A JP 2004112702 A JP2004112702 A JP 2004112702A JP 2004112702 A JP2004112702 A JP 2004112702A JP 2005302341 A JP2005302341 A JP 2005302341A
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- separator
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- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 239000011347 resin Substances 0.000 claims abstract description 176
- 229920005989 resin Polymers 0.000 claims abstract description 176
- 239000000463 material Substances 0.000 claims abstract description 59
- 238000002844 melting Methods 0.000 claims abstract description 58
- 230000008018 melting Effects 0.000 claims abstract description 58
- 239000000758 substrate Substances 0.000 claims abstract description 52
- 239000002245 particle Substances 0.000 claims abstract description 43
- 239000000945 filler Substances 0.000 claims abstract description 30
- 239000003990 capacitor Substances 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims description 67
- 238000000034 method Methods 0.000 claims description 54
- 239000004745 nonwoven fabric Substances 0.000 claims description 41
- 238000001035 drying Methods 0.000 claims description 34
- -1 polyethylene naphthalate Polymers 0.000 claims description 30
- 239000003973 paint Substances 0.000 claims description 21
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 17
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- 239000011247 coating layer Substances 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 229920002978 Vinylon Polymers 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 229920002239 polyacrylonitrile Polymers 0.000 claims 1
- 238000013021 overheating Methods 0.000 abstract description 4
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 76
- 239000000835 fiber Substances 0.000 description 34
- 239000011148 porous material Substances 0.000 description 33
- 238000000576 coating method Methods 0.000 description 29
- 239000011248 coating agent Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 14
- 230000007547 defect Effects 0.000 description 13
- 229920000139 polyethylene terephthalate Polymers 0.000 description 12
- 239000005020 polyethylene terephthalate Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000009826 distribution Methods 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000009816 wet lamination Methods 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229920003043 Cellulose fiber Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 238000007606 doctor blade method Methods 0.000 description 3
- 238000007756 gravure coating Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 229920002972 Acrylic fiber Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 240000000907 Musa textilis Species 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000012644 addition polymerization Methods 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
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 240000004308 marijuana Species 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 229920006297 regenerated protein fiber Polymers 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
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- 238000004381 surface treatment Methods 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Cell Separators (AREA)
Abstract
Description
本発明は、電子部品、すなわちリチウムイオン二次電池、ポリマーリチウム二次電池、リチウム金属電池、アルミニウム電解コンデンサ又は電気二重層キャパシタ等の電子部品に使用され、特に耐熱性が要求される大型のリチウム系電池、あるいは電気二重層キャパシタに好適に用いられるセパレータおよびその製造方法に関するものである。 The present invention is used for electronic parts such as lithium ion secondary batteries, polymer lithium secondary batteries, lithium metal batteries, aluminum electrolytic capacitors or electric double layer capacitors, and particularly large-sized lithium that requires heat resistance. The present invention relates to a separator suitably used for a system battery or an electric double layer capacitor and a method for producing the same.
近年、産業機器、民生機器に関わらず、電気・電子機器の需要の増加、及びハイブリッド自動車の開発により、電子部品であるリチウムイオン二次電池、ポリマーリチウム二次電池、アルミニウム電解コンデンサ及び電気二重層キャパシタの需要が著しく増加している。これらの電気・電子機器は小型化、高機能化が日進月歩で進行しており、リチウムイオン二次電池、ポリマーリチウム二次電池、アルミニウム電解コンデンサ及び電気二重層キャパシタにおいても、小型化、高機能化が要求されている。 In recent years, lithium ion secondary batteries, polymer lithium secondary batteries, aluminum electrolytic capacitors and electric double layers, which are electronic components, have been developed due to increasing demand for electrical and electronic equipment, regardless of industrial equipment and consumer equipment, and the development of hybrid vehicles. The demand for capacitors has increased significantly. These electric and electronic devices are steadily becoming smaller and more functional. Lithium ion secondary batteries, polymer lithium secondary batteries, aluminum electrolytic capacitors, and electric double layer capacitors are also becoming smaller and more functional. Is required.
リチウムイオン二次電池及びポリマーリチウム二次電池は、活物質とリチウム含有酸化物とポリフッ化ビニリデン等のバインダーを１−メチル−２−ピロリドンと混合しアルミニウム製集電体上にシート化した正極と、リチウムイオンを吸蔵放出し得る炭素質材料とポリフッ化ビニリデン等のバインダーを１−メチル−２−ピロリドンと混合して銅製集電体上にシート化した負極と、ポリフッ化ビニリデンやポリエチレン等より成る多孔質電解質膜とを、正極、電解質膜、負極の順に捲回もしくは積層して形成された電極体に駆動用電解液を含浸させ、アルミニウムケースにより封止された構造のものである。また、アルミニウム電解コンデンサは、エッチングした後、化成処理を施して誘電体皮膜を形成したアルミニウム製正極箔と、エッチングされたアルミニウム製負極箔とを、セパレータを介して捲回もしくは積層した電極体に駆動用電解液を含浸し、アルミニウムケースと封口体により封止し、短絡しないように正極リードと負極リードを封止体を貫通させて外部に引き出した構造のものである。また、電気二重層キャパシタは、活性炭と導電剤及びバインダーを混錬したものをアルミニウム製正極、負極各集電極の両面に貼り付け、セパレータを介して捲回又は積層した電極体に駆動用電解液を含浸し、アルミニウムケースと封止体により梱包され、短絡しないように正極リードと負極リードを封止体を貫通させて外部に引き出した構造のものである。 A lithium ion secondary battery and a polymer lithium secondary battery are prepared by mixing an active material, a lithium-containing oxide, a binder such as polyvinylidene fluoride with 1-methyl-2-pyrrolidone, and forming a sheet on an aluminum current collector. A negative electrode formed by mixing a carbonaceous material capable of occluding and releasing lithium ions and a binder such as polyvinylidene fluoride with 1-methyl-2-pyrrolidone to form a sheet on a copper current collector, and polyvinylidene fluoride or polyethylene. An electrode body formed by winding or laminating a porous electrolyte membrane in the order of a positive electrode, an electrolyte membrane, and a negative electrode is impregnated with a driving electrolyte and sealed with an aluminum case. In addition, an aluminum electrolytic capacitor is an electrode body obtained by etching or laminating an aluminum positive electrode foil having a dielectric film formed thereon by etching and an etched aluminum negative electrode foil with a separator interposed therebetween. It is impregnated with a driving electrolyte solution, sealed with an aluminum case and a sealing body, and has a structure in which a positive electrode lead and a negative electrode lead are passed through the sealing body and pulled out so as not to be short-circuited. In addition, the electric double layer capacitor is obtained by mixing a mixture of activated carbon, a conductive agent, and a binder on both surfaces of an aluminum positive electrode and a negative electrode, and winding or laminating the electrode body through a separator. And is packed with an aluminum case and a sealing body, and has a structure in which a positive electrode lead and a negative electrode lead are passed through the sealing body and pulled out so as not to be short-circuited.
従来、上記リチウムイオン二次電池及びポリマーリチウム二次電池のセパレータとしては、ポリオレフィン、ポリエステル、ポリアミド、ポリイミド等の多孔質膜や不織布が使用されており、アルミニウム電解コンデンサ及び電気二重層キャパシタのセパレータとしては、セルロースパルプからなる紙やセルロース繊維、ポリエステル繊維、ポリエチレンテレフタレート繊維、アクリル繊維等からなる不織布が使用されている。 Conventionally, as separators for the lithium ion secondary battery and polymer lithium secondary battery, porous films and nonwoven fabrics such as polyolefin, polyester, polyamide, and polyimide have been used, and as separators for aluminum electrolytic capacitors and electric double layer capacitors. Are made of paper made of cellulose pulp, and non-woven fabric made of cellulose fiber, polyester fiber, polyethylene terephthalate fiber, acrylic fiber, or the like.
ところで、上記リチウムイオン二次電池、ポリマーリチウム二次電池、アルミニウム電解コンデンサ及び電気二重層キャパシタは、前述の通り小型化が進んでいるためにセパレータも薄膜化が要求されている。しかしながら、従来のセパレータで薄膜化を進めると、正極、負極間で微小短絡が発生したり、電子部品を駆動させるために必要な駆動用電解液を十分保持できなくなるだけでなく、機械的強度の低下により製造工程での作業性、生産性を損ない、製品の信頼性の低下などの問題が発生する。十分な機械的強度を持たせながら薄膜化するためには、セパレータの空隙率を低下させればよいが、空隙率を低下させると、内部抵抗の上昇を伴ない、高機能化の要求を満たすことができなくなる。 By the way, since the lithium ion secondary battery, the polymer lithium secondary battery, the aluminum electrolytic capacitor, and the electric double layer capacitor are miniaturized as described above, the separator is also required to be thin. However, when the film thickness is reduced with the conventional separator, not only does the micro short circuit occur between the positive electrode and the negative electrode, and the driving electrolyte necessary for driving the electronic component cannot be sufficiently retained, but also the mechanical strength is increased. Due to the decrease, workability and productivity in the manufacturing process are impaired, and problems such as a decrease in product reliability occur. In order to achieve a thin film with sufficient mechanical strength, it is sufficient to reduce the porosity of the separator. However, if the porosity is reduced, the internal resistance increases and the demand for higher functionality is met. I can't do that.
一方、リチウムイオン二次電池やリチウムポリマー二次電池などの比較的エネルギー密度が高い二次電池は、車載用途や、コジェネレーションにおける蓄電に応用され始めている。ところが、例えば、車載用途の場合は、使用温度域が比較的高温まで求められるほか、高レートで連続使用する場合に温度が上がりやすいなど、従来のセパレータには、これまでの要求以上の耐熱安定性が求められており、現状主流のポリオレフィン樹脂を用いたセパレータ等ではその要求を満たすものではない。すなわち、ポリオレフィン樹脂を用いたセパレータでは、過熱時の安全性確保のため、１２０〜１３０℃程度で溶融しイオン伝導を抑制する必要があるため、高温環境におけるシュリンクを起こしやすいという問題がある。このシュリンクを抑制する方法としては、例えば特許文献１では、耐熱性が良好な不織布を選択して、これにポリエチレン粒子や繊維などを複合することにより、シュリンク性を抑えつつシャットダウン機能をあわせ持たせる技術が開示されている。特許文献１では、例えばポリエチレン粒子などのフィラー粒子は、偏析させる方がシャットダウン機能は発現しやすいとされているが、しかし、フィラー粒子を偏析させた場合には、特に製造工程等のハンドリング時にフィラー粒子が脱落しやすく、その部分が塗工欠陥となってピンホールなどのセパレータの欠陥を発生しやすいという問題があり、また、低融点の繊維を予め不織布に混抄した場合にはシュリンクしやすくなる等の不具合が生じることがある。
本発明は、上記のような実状に鑑みて提案されたものであり、その目的は、作業性、生産性を損なうことなく、リチウムイオン二次電池、ポリマーリチウム二次電池、アルミニウム電解コンデンサ及び電気二重層キャパシタの種々の実用特性を良好に保ちつつ、過熱時にも熱収縮が極めて少なく高信頼特性を得ることを可能とする電子部品用セパレータおよびその製造方法を提供することにある。 The present invention has been proposed in view of the above circumstances, and its purpose is not to impair workability and productivity, but a lithium ion secondary battery, a polymer lithium secondary battery, an aluminum electrolytic capacitor, and an electric capacitor. It is an object of the present invention to provide a separator for electronic parts and a method for manufacturing the same which can obtain highly reliable characteristics with extremely little heat shrinkage even during overheating while maintaining various practical characteristics of the double layer capacitor.
上記課題を達成するための本発明の電子部品用セパレータは、融点が１８０℃以上の物質からなる多孔質基材と、その少なくとも一面及び／又は内部に設けられた樹脂構造体とよりなり、１８０℃以上の融点を有するか、または実質的に融点を有しないフィラー粒子を含有することを特徴とする。 The separator for electronic parts of the present invention for achieving the above object comprises a porous substrate made of a substance having a melting point of 180 ° C. or higher, and a resin structure provided on at least one surface and / or inside thereof. It is characterized by containing filler particles having a melting point of 0 ° C. or higher or substantially not having a melting point.
また、本発明の電子部品用セパレータの製造方法は、１８０℃以上の融点を有するか、または実質的に融点を有しないフィラー粒子を含む、融点が１８０℃以上の物質からなる多孔質基材に、多孔質樹脂構造体を形成するための樹脂を含有する塗料を塗工した後、乾燥することによって該多孔質基材の表面および／または内部に多孔質樹脂構造体を形成することを特徴とする。そしてその第１の態様としては、樹脂フィルム上に、予め１８０℃以上の融点を有するか、または実質的に融点を有しないフィラー粒子を含む、融点が１８０℃以上の物質からなる不織布または網状物を重ね、その上に、多孔質樹脂構造体を形成するための樹脂を含有する塗料を塗工した後、乾燥することによって、前記多孔質樹脂構造体と不織布または網状物とを一体化し、その後樹脂フィルムを除去することを特徴とし、また、第２の態様としては、樹脂フィルム上に、多孔質樹脂構造体を形成するための樹脂を含有する塗料を塗工して塗布層を形成した後に、１８０℃以上の融点を有するか、または実質的に融点を有しないフィラー粒子を含む、融点が１８０℃以上の物質からなる不織布または網状物を塗布層の上に積層し、次いで乾燥して不織布または網状物と一体化した多孔質樹脂構造体を形成し、その後樹脂フィルムを除去することを特徴とする。 In addition, the method for manufacturing a separator for electronic parts according to the present invention provides a porous substrate made of a substance having a melting point of 180 ° C. or higher, including filler particles having a melting point of 180 ° C. or higher or substantially not having a melting point. Characterized in that a porous resin structure is formed on the surface and / or inside of the porous substrate by applying a paint containing a resin for forming the porous resin structure and then drying. To do. And as the 1st aspect, the nonwoven fabric or net-like material which consists of a substance with melting | fusing point more than 180 degreeC which contains the filler particle which has melting | fusing point more than 180 degreeC previously or has substantially no melting point on the resin film And then, after applying a paint containing a resin for forming the porous resin structure, the porous resin structure and the nonwoven fabric or network are integrated by drying, and thereafter The resin film is removed, and as a second aspect, a coating layer containing a resin for forming a porous resin structure is applied on the resin film to form a coating layer. A non-woven fabric or network made of a material having a melting point of 180 ° C. or higher, containing filler particles having a melting point of 180 ° C. or higher, or substantially no melting point, is laminated on the coating layer, and then dried. To form a porous resin structure integrated with a nonwoven fabric or a net-like material, characterized by thereafter removing the resin film.
本発明の電子部品用セパレータは、種々の実用特性を良好に保ちつつ、過熱時にも熱収縮が極めて少なく高信頼特性を得ることが可能であって、作業性、生産性に優れたものである。したがって、本発明の電子部品用セパレータは、リチウムイオン二次電池、ポリマーリチウム二次電池、リチウム金属電池、アルミニウム電解コンデンサ又は電気二重層キャパシタ等の電子部品において、耐短絡性に優れ、低インピーダンス化と高耐熱性化を両立した優れたものであり、これらの電子部品に好適に使用される。特に、本発明の電子部品用セパレータにおける多孔質基材は、耐熱寸法安定性に優れたものであるので、耐熱寸法安定性を確実に付与することができ、したがって、耐熱性が要求される大型のリチウム系電池、あるいは電気二重層キャパシタに好適に用いることができる。 The separator for electronic parts of the present invention is excellent in workability and productivity because it can obtain highly reliable characteristics with extremely little heat shrinkage even during overheating while keeping various practical characteristics good. . Therefore, the separator for electronic parts of the present invention is excellent in short circuit resistance and low impedance in electronic parts such as lithium ion secondary batteries, polymer lithium secondary batteries, lithium metal batteries, aluminum electrolytic capacitors or electric double layer capacitors. And excellent heat resistance, and is suitably used for these electronic components. In particular, since the porous substrate in the separator for electronic parts of the present invention is excellent in heat-resistant dimensional stability, it can reliably impart heat-resistant dimensional stability, and thus a large-size material that requires heat resistance. It can be suitably used for a lithium-based battery or an electric double layer capacitor.
本発明の電子部品用セパレータを構成する多孔質基材としては、融点が１８０℃以上の物質からなるものであって、具体的には、セルロースパルプからなる紙、綿、***、黄麻等の靭皮繊維、マニラ麻等の葉脈繊維等のセルロース繊維からなる紙の他、レーヨン、キュプラ等の再生セルロース繊維及び再生タンパク繊維等の再生繊維、酢酸セルロース繊維及びプロミックス等の半合成繊維、ナイロンアラミド繊維、ポリエチレンテレフタレート繊維及びポリエチレンナフタレート繊維等のポリエステル繊維、アクリル繊維、ポリエチレン及びポリプロピレン等のポリオレフィン繊維、ポリビニルアルコール繊維、ポリ塩化ビニル繊維、ポリ塩化ビニリデン繊維、ポリ塩化ビニル系繊維、ポリウレタン繊維、ポリオキシメチレン繊維、ポリテトラフルオロエチレン繊維、ポリパラフェニレンベンズビスチアゾール繊維、ポリイミド繊維、ポリアミド繊維等、ビニロン繊維、セラミック繊維および金属繊維等からなる不織布および網状物をあげることができる。また、上記繊維を構成する物質からなる樹脂フィルムであって、フィルム面に対して垂直方向に設けられた、フィルムの一面から他面の間に実質上遮蔽構造を有しない貫通孔のみからなる孔を有する微多孔樹脂フィルムをあげることができる。上記不織布は、公知の技術を用いて製造することができる。すなわち、湿式、乾式、乾式パルプ式、スパンボンド式、メルトブロー式、フラッシュ紡糸式、トウ開繊式などにより得ることができる。また、貫通孔を設けた微多孔樹脂フィルムは、レーザー照射により樹脂フィルムに孔を設ける方法を用いることによって製造することができる。本発明に用いる上記の多孔質基材を構成する物質は融点が１８０℃を超すものであることが必要である。融点が１８０℃以下であると、加熱時に熱溶融しシュリンクしやすいために、電極間での短絡を起こすという問題が生じる。 The porous substrate constituting the separator for electronic parts of the present invention is made of a substance having a melting point of 180 ° C. or more, and specifically, tough paper such as paper made of cellulose pulp, cotton, cannabis, and jute. In addition to paper made of cellulose fibers such as leather fibers and leaf fibers of Manila hemp, regenerated cellulose fibers such as rayon and cupra, regenerated fibers such as regenerated protein fibers, cellulose acetate fibers and semi-synthetic fibers such as promix, nylon aramid fibers Polyester fiber such as polyethylene terephthalate fiber and polyethylene naphthalate fiber, Acrylic fiber, Polyolefin fiber such as polyethylene and polypropylene, Polyvinyl alcohol fiber, Polyvinyl chloride fiber, Polyvinylidene chloride fiber, Polyvinyl chloride fiber, Polyurethane fiber, Polyoxy Methylene fiber, polytet Fluoroethylene fibers, polyparaphenylene benzimidazole bis benzothiazole fibers, polyimide fibers, polyamide fibers, vinylon fibers, may be mentioned nonwoven fabric and net-like material made of ceramic fibers and metal fibers. Also, a resin film made of a material constituting the fiber, the hole being formed in a direction perpendicular to the film surface and consisting only of through-holes having substantially no shielding structure between one surface and the other surface of the film The microporous resin film which has can be mention | raise | lifted. The said nonwoven fabric can be manufactured using a well-known technique. That is, it can be obtained by a wet method, a dry method, a dry pulp method, a spun bond method, a melt blow method, a flash spinning method, a tow opening method, or the like. Moreover, the microporous resin film provided with the through-hole can be manufactured by using a method of providing a hole in the resin film by laser irradiation. The substance constituting the porous substrate used in the present invention needs to have a melting point exceeding 180 ° C. If the melting point is 180 ° C. or lower, the heat melts during heating and the resin tends to shrink, which causes a problem of causing a short circuit between the electrodes.
また、多孔質基材の少なくとも一面、内部、または少なくとも一面と内部に設けられた樹脂構造体を構成する樹脂としては、具体的には、ポリフッ化ビニリデン、フッ化ビニリデンを含む共重合体、ポリアクリロニトリル、アクリロニトリルを含む共重合体、ポリメタクリル酸メチル、メタクリル酸メチルを含む共重合体、ポリスチレン、スチレンを含む共重合体、ポリエチレンオキサイド、エチレンオキサイドを含む共重合体、ポリイミドアミド、ポリフェニルスルフォン、ポリエーテルスルフォン、ポリエーテルエーテルケトンおよびポリテトラフルオロエチレンの少なくとも１種類からなるものがあげられる。これらの樹脂は、公知の技術を用いて製造することができる。すなわち、ホモポリマーの場合は、それぞれの樹脂のモノマーの付加重合反応、例えば、ラジカル重合、カチオン重合、アニオン重合、光・放射線重合、縣濁重合法、乳化重合法、塊状重合法などによって得ることができ、また、コポリマーの場合は、それぞれの樹脂のモノマーと他のモノマーを上記と同様な重合方法により共重合させることによって得ることができる。 Further, at least one surface of the porous substrate, the inside, or the resin constituting the resin structure provided on at least one surface and the inside, specifically, polyvinylidene fluoride, a copolymer containing vinylidene fluoride, Acrylonitrile, copolymer containing acrylonitrile, polymethyl methacrylate, copolymer containing methyl methacrylate, polystyrene, copolymer containing styrene, polyethylene oxide, copolymer containing ethylene oxide, polyimide amide, polyphenyl sulfone, Examples include those composed of at least one of polyether sulfone, polyether ether ketone, and polytetrafluoroethylene. These resins can be produced using known techniques. That is, in the case of a homopolymer, it can be obtained by addition polymerization reaction of each resin monomer, for example, radical polymerization, cationic polymerization, anionic polymerization, light / radiation polymerization, suspension polymerization method, emulsion polymerization method, bulk polymerization method, etc. In the case of a copolymer, it can be obtained by copolymerizing the monomer of each resin and another monomer by the same polymerization method as described above.
本発明において、上記樹脂構造体を構成する樹脂は、融点が１４５℃以上であることが好ましい。融点が１４５℃以下の場合、加熱時に熱溶融し多孔質を塞ぐ場合があり、また、電解液に溶解あるいはゲル化しやすい材質であると、更に目詰まりしやすくなるために、電池性能を低下させる可能性があり望ましくない。 In the present invention, the resin constituting the resin structure preferably has a melting point of 145 ° C. or higher. When the melting point is 145 ° C. or lower, the material may be melted by heat to close the porous material, and if it is a material that easily dissolves or gels in the electrolyte solution, it will become more clogged, thus reducing the battery performance. Possible and undesirable.
本発明においては、前記の樹脂構造体を形成する樹脂は、アミド系溶媒またはケトン系溶媒またはフラン系溶媒に可溶であることが望ましい。本発明で特に好適に用いられるフッ化ビニリデン系樹脂はアミド系溶媒で溶解した場合において、成膜性が非常に良好であるため、特に好適に用いることができるが、塗工面の乾燥効率を向上する上では、ケトン系溶媒やフラン系溶媒に可溶である樹脂を用いることが望ましい。本発明では、乾燥速度や成膜状態を見ながら、上記の溶媒を適宜混合して用いてもよい。 In the present invention, the resin forming the resin structure is desirably soluble in an amide solvent, a ketone solvent, or a furan solvent. The vinylidene fluoride resin particularly preferably used in the present invention has a very good film formability when dissolved in an amide solvent, and can be used particularly preferably, but improves the drying efficiency of the coated surface. Therefore, it is desirable to use a resin that is soluble in a ketone solvent or a furan solvent. In the present invention, the above solvents may be appropriately mixed and used while observing the drying rate and the film formation state.
また、本発明においては、前記の樹脂構造体は多孔質樹脂構造体であることが望ましい。樹脂構造体が多孔質ではない場合は、電解液の抽液性が低下するほか、イオン伝導性が低下する。前記多孔質樹脂構造体の各孔は、セパレータの一面から他面に多数の孔の繋がりによって通じており、各孔の孔径はセパレータの膜厚より小さいことが好ましい。孔径がセパレータの膜厚と同等以上であると、微小短絡を起こしやすく電池歩留まりを低下する原因となり好ましくない。 In the present invention, the resin structure is preferably a porous resin structure. When the resin structure is not porous, the bleedability of the electrolytic solution is lowered and the ionic conductivity is lowered. Each hole of the porous resin structure communicates from one side of the separator to the other side by a number of holes connected, and the diameter of each hole is preferably smaller than the film thickness of the separator. If the pore diameter is equal to or greater than the film thickness of the separator, a micro short circuit is likely to occur, which causes a decrease in battery yield.
多孔質基材および／または樹脂構造体に含有させるフィラー粒子は、１８０℃以上の融点を有するか、または実質的に融点を有しないことが必要である。融点が１８０℃よりも低い場合は、加熱時に熱溶融し多孔質構造体の細孔を塞ぐ場合があり、また、電解液に溶解あるいはゲル化しやすい材質であると、更に目詰まりしやすくなるために、電池性能を低下させる可能性があり望ましくない。本発明において用いることができるフィラー粒子としては、例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）、架橋ポリメチルメタクリレート（ＰＭＭＡ）、シリカ、アルミナ、バンゾグアナミン、ナイロン、ガラス、シリコーン、架橋スチレン、ポリウレタンなどの微粒子があげられる。これらの微粒子の一次平均粒子径は１０μｍ以下の範囲が好ましい。フィラー粒子を多孔質基材および／または樹脂構造体に含有させるには、フィラー粒子を含有する塗料を用いて樹脂構造体を形成したり、不織布を作製する際に繊維間にフィラー粒子をすきこんだり、フィラー粒子と不織布を結着するための樹脂を含む樹脂溶液に不織布を浸漬することで、不織布にフィラー粒子を予め固着する方法をあげることができる。 The filler particles contained in the porous base material and / or the resin structure must have a melting point of 180 ° C. or higher or substantially have no melting point. When the melting point is lower than 180 ° C., the material may be melted by heat to close the pores of the porous structure, and if the material is easily dissolved or gelled in the electrolytic solution, clogging is more likely to occur. In addition, the battery performance may be lowered, which is not desirable. Examples of filler particles that can be used in the present invention include polytetrafluoroethylene (PTFE), cross-linked polymethyl methacrylate (PMMA), silica, alumina, vanzoguanamine, nylon, glass, silicone, cross-linked styrene, and polyurethane. Fine particles. The primary average particle diameter of these fine particles is preferably in the range of 10 μm or less. In order to incorporate the filler particles in the porous substrate and / or the resin structure, the filler particles are used to form the resin structure, or when the nonwoven fabric is produced, the filler particles are squeezed between the fibers. Alternatively, the filler particles can be fixed in advance to the nonwoven fabric by immersing the nonwoven fabric in a resin solution containing a resin for binding the filler particles and the nonwoven fabric.
また、フィラー粒子の含有量は、多孔質基材に対して、０．５ｇ／ｍ２〜１００ｇ／ｍ２の範囲が好ましい。 The content of filler particles, a porous substrate, the range of 0.5g / m 2 ~100g / m 2 is preferred.
本発明においては、セパレータに存在する孔は、バブルポイント法による孔径が０．１〜１５μｍ、より好ましくは０．５〜５μｍである。孔径が０．１μｍより小さいと、イオン伝導性を阻害する場合があり好ましくないほか、電解液の含浸性が低下する傾向や、微小なデンドライトの成長を阻害する場合があり好ましくない。一方、１５μｍより大きいと、特にセパレータを薄膜化した場合に短絡などの不具合を生ずる場合があり好ましくない。 In the present invention, the pores present in the separator have a pore diameter of 0.1 to 15 μm, more preferably 0.5 to 5 μm, according to the bubble point method. When the pore size is smaller than 0.1 μm, ion conductivity may be inhibited, which is not preferable. In addition, the impregnation property of the electrolytic solution tends to decrease, and the growth of minute dendrites may be inhibited. On the other hand, if it is larger than 15 μm, it is not preferable because a problem such as a short circuit may occur particularly when the separator is thinned.
また、本発明のセパレータは,上記のように樹脂構造体が多孔質樹脂構造体であることが好ましいが、その場合、セパレータの片面からもう一方の面に向かって、孔が連通して繋がっていることが望まれる。しかしながら、セパレータ面の実質的に垂直方向にピンホール状の貫通孔を有さないことが望ましい。ここで、貫通孔とはセパレータのいずれか一方の面から、もう一方の面を実質的に垂直に見た時に、セパレータを構成する部材で全く覆われずに、貫通して見える部分を意味する。このような貫通孔を有するセパレータは、短絡を起こしやすく、したがって、充放電性能を著しく阻害する場合がある。 Further, in the separator of the present invention, the resin structure is preferably a porous resin structure as described above, but in that case, holes are connected and connected from one side of the separator to the other side. It is hoped that However, it is desirable not to have a pinhole-shaped through hole in a direction substantially perpendicular to the separator surface. Here, the through-hole means a portion that can be seen through from one of the surfaces of the separator when the other surface is viewed substantially vertically without being covered by the member constituting the separator. . A separator having such a through-hole tends to cause a short circuit, and thus may significantly impede charge / discharge performance.
本発明において、セパレータの膜厚としては特に限定されるものではないが、電子部品の小型化を可能にする為には５０μｍ以下が好適である。ただし、５μｍ未満になると強度が非常に弱くなり、好ましくない。 In the present invention, the film thickness of the separator is not particularly limited, but is preferably 50 μm or less in order to enable downsizing of electronic components. However, when the thickness is less than 5 μm, the strength becomes very weak, which is not preferable.
次に、本発明の電子部品用セパレータの製造方法について説明する。本発明の電子部品用セパレータは、１８０℃以上の融点を有するか、または実質的に融点を有しないフィラー粒子を含む、融点が１８０℃以上の物質からなる上記の多孔質基材に、上記の樹脂構造体形成するための樹脂を含有する塗料を塗工した後、乾燥することによって多孔質基材の表面および／または内部に樹脂構造体を形成することによって製造することができる。 Next, the manufacturing method of the separator for electronic components of this invention is demonstrated. The separator for an electronic component according to the present invention includes the above porous base material made of a substance having a melting point of 180 ° C. or higher, containing filler particles having a melting point of 180 ° C. or higher or substantially not having a melting point. It can manufacture by forming the resin structure in the surface and / or the inside of a porous base material by applying the coating material containing the resin for resin structure formation, and drying.
本発明の上記の方法においては、前記樹脂構造体を塗工法によってのみ形成し、塗工後の塗面に含まれる溶媒を除去する工程において、他の溶媒による溶媒置換や抽出などの手段を用いず、実質的に乾燥工程の１パスだけで多孔質の樹脂構造体を形成することができる。 In the above method of the present invention, the resin structure is formed only by a coating method, and in the step of removing the solvent contained in the coated surface after coating, means such as solvent substitution or extraction with another solvent are used. However, a porous resin structure can be formed substantially in only one pass of the drying process.
また、本発明において、樹脂構造体を形成するための塗料として、樹脂構造体を形成する樹脂を実質的に溶解する溶媒（良溶媒）を少なくとも１種以上含み、かつ、上記樹脂を実質的には溶解しない溶媒（貧溶媒）を少なくとも１種以上含むものを用いることによって、多孔質樹脂構造体を形成することが可能である。多孔質フィルムを貧溶媒を用いて乾燥工程だけで作る技術は、古くから知られているが、本発明者等は、両溶媒の乾燥のしやすさや、乾燥工程における風量設定によって、膜性能が大きく変化することや、製造効率に多大な影響があることを見出した。すなわち、加熱・送風乾燥によるセパレータ性能への影響は非常に大きく、具体的には、両溶媒の沸点や蒸気圧で決まる乾燥速度、及び、両溶媒の乾燥のタイミング、送風量が非常に重要であることを見出した。本発明においては、良溶媒及び貧溶媒を用い、乾燥条件を後述のように適宜制御することにより効率的に多孔質構造体を形成することができる。塗料のハンドリング性からは、塗料粘度をある程度低くすることが重要であるため、比較的低粘度である補助的な良溶媒を、これとは異なる主たる良溶媒と併用することで塗料粘度を低減することが望ましい。このような補助的良溶媒の選択は、上記の溶媒粘度のほか、貧溶媒との乾燥バランスや、溶媒同士の共沸を考慮して選択すればよい。本発明において、補助的良溶媒は１種類に限らず複数種用いてもよく、また、実質的に樹脂を溶かさない貧溶媒でなければ、上記の選択指針によって適宜選択すればよく、いずれのものも使用できる。 In the present invention, the paint for forming the resin structure includes at least one solvent (good solvent) that substantially dissolves the resin that forms the resin structure, and substantially contains the resin. It is possible to form a porous resin structure by using at least one solvent that does not dissolve (poor solvent). The technology of making a porous film only by a drying process using a poor solvent has been known for a long time, but the present inventors have determined that the film performance depends on the ease of drying of both solvents and the air volume setting in the drying process. It has been found that there is a large change and a great influence on the production efficiency. In other words, the effect on the separator performance by heating and blowing drying is very large. Specifically, the drying speed determined by the boiling points and vapor pressures of both solvents, the timing of drying both solvents, and the blowing rate are very important. I found out. In the present invention, a porous structure can be efficiently formed by using a good solvent and a poor solvent and appropriately controlling the drying conditions as described below. Since it is important to reduce the viscosity of the paint to some extent from the handleability of the paint, an auxiliary good solvent having a relatively low viscosity is used in combination with a main good solvent different from this to reduce the paint viscosity. It is desirable. Such an auxiliary good solvent may be selected in consideration of the drying balance with the poor solvent and the azeotropy of the solvents in addition to the above solvent viscosity. In the present invention, the auxiliary good solvent is not limited to one type, and a plurality of types may be used. If the solvent is not a poor solvent that does not substantially dissolve the resin, it may be appropriately selected according to the above selection guidelines. Can also be used.
良溶媒および貧溶媒としては、種々の溶剤が使用できるが、共沸や、乾燥の温度差及び蒸気圧の差が大きい組み合わせは、大径のピンホールの発生頻度を高める点で好ましくなく、また製造効率上も望ましくない。良溶媒と貧溶媒の沸点差は、５０℃以内、更に好ましくは、３０℃以内とすることが製造効率上好ましい。５０℃を超す範囲では、製造のプロセス速度があげられないほか、乾燥エネルギーが大きくなり好ましくない。また、５０℃を超す範囲では、乾燥条件を段階的に設定する場合には、プロセス方向への瞬時の条件切り替えが実質的に不可能となるために、大量生産には向いていない。 Various solvents can be used as the good solvent and the poor solvent, but a combination with a large difference in azeotropic or drying temperature difference and vapor pressure is not preferable in terms of increasing the frequency of occurrence of large-diameter pinholes. It is not desirable in terms of manufacturing efficiency. The difference in boiling point between the good solvent and the poor solvent is preferably 50 ° C. or less, more preferably 30 ° C. or less in view of production efficiency. When the temperature exceeds 50 ° C., the manufacturing process speed cannot be increased, and the drying energy increases, which is not preferable. Also, in the range exceeding 50 ° C., when the drying conditions are set stepwise, instantaneous condition switching in the process direction becomes virtually impossible, and is not suitable for mass production.
溶媒として吸湿性が高いものを用いて塗料を得る場合には、できる限り水分の混入を防ぐことが必要であり、本発明では、カールフィッシャー法による測定で水分量が０．７重量％以下、より好ましくは、０．５重量％以下のものが好ましく使用される。水分量が０．７重量％を超すと、ゲル化が早期に進み塗料の保存期間が極端に短くなったり、成膜性に悪影響を与える場合があり好ましくない。 When obtaining a paint using a highly hygroscopic solvent as the solvent, it is necessary to prevent the mixing of moisture as much as possible, in the present invention, the moisture content is 0.7 wt% or less by measurement by the Karl Fischer method, More preferably, 0.5% by weight or less is preferably used. If the water content exceeds 0.7% by weight, gelation progresses early and the storage period of the paint becomes extremely short, and the film formability may be adversely affected.
本発明において、フィラー粒子として、ポリフッ化ビニリデン粒子を含むセパレータを作製する際には、フィラー粒子ができるだけ溶融しない温度条件が好ましいが、ポリフッ化ビニリデンを溶解する溶媒は沸点が高いものが多いために、実質的には７０〜１８０℃の加熱温度が必要となる。このため、乾燥風量を多くすることにより乾燥を早期に行いつつ、更にはプロセス速度を上げることによって、できるだけ短時間で乾燥を終了するようにすればよい。加熱温度が７０℃以下であると、乾燥効率が悪く製造効率があがらず、一方、１８０℃を超える範囲では、フィラー粒子や樹脂構造体が溶融する場合があり、多孔質樹脂構造体を形成する場合には問題となるので、上記の範囲の加熱温度が好ましい。また、一般的には、乾燥条件は段階的な設定を行い、良溶媒を先に乾燥させた後に貧溶媒を乾燥させることが多孔質樹脂構造体を作る上では好ましいが、セパレータの膜性能上は、共沸するものでなければ、両溶媒は必ずしもはっきりと分けて乾燥しなくてもよく、多孔質構造体の空隙率や、孔径の制御を適宜行いつつ乾燥条件を決定することが望ましい。本発明では、上記のように溶媒処方の組み合わせ、乾燥温度および送風量の条件を適宜選択すること等で、セパレータの電池性能へ与える負の影響を最小化することと、製造効率向上の両立が実現できる。また、本発明では、上記の如く、溶媒などにより貧溶媒や残留溶媒を除去する工程を設けることなく、塗工後に乾燥工程を一度経るだけで、セパレータに最適な多孔質膜を簡便に形成することができるので、製造効率が非常に良好なことから、安価で良質なセパレータを大量に提供することが可能となる。 In the present invention, when producing a separator containing polyvinylidene fluoride particles as filler particles, a temperature condition in which the filler particles do not melt as much as possible is preferable, but many solvents that dissolve polyvinylidene fluoride have high boiling points. In practice, a heating temperature of 70 to 180 ° C. is required. For this reason, it is only necessary to finish the drying in as short a time as possible by increasing the process speed while increasing the drying speed at an early stage. When the heating temperature is 70 ° C. or lower, the drying efficiency is poor and the production efficiency does not increase. On the other hand, in the range exceeding 180 ° C., the filler particles and the resin structure may be melted to form a porous resin structure. In this case, a heating temperature in the above range is preferable because it causes a problem. In general, the drying conditions are set stepwise, and it is preferable to dry the poor solvent after the good solvent is dried first, in order to make a porous resin structure. If they are not azeotropic, the two solvents do not necessarily need to be clearly separated and dried, and it is desirable to determine the drying conditions while appropriately controlling the porosity and pore diameter of the porous structure. In the present invention, it is possible to minimize the negative influence on the battery performance of the separator and to improve the production efficiency by appropriately selecting the combination of the solvent formulation, the drying temperature and the air blowing amount as described above. realizable. In addition, in the present invention, as described above, a porous film that is optimal for a separator can be easily formed by performing a drying process once after coating without providing a process for removing a poor solvent or a residual solvent with a solvent or the like. Therefore, since the production efficiency is very good, it is possible to provide a large amount of inexpensive and high-quality separators.
本発明において、塗工に際しては、ディップコート法、スプレーコート法、ロールコート法、ドクターブレード法、グラビアコート法、スクリーン印刷法等により塗布又はキャスティング法等を用いることができるが、多孔質基材を載置するための保持材を用いて塗工を行なうのが好ましい。保持材としては、ポリプロピレンやポリエチレンテレフタレート等の樹脂フィルム、ガラス板等を挙げることができる。保持材には離型処理、易接着処理等の表面処理を施してもよい。これらの保持材の中でも柔軟性を有する樹脂フィルムが電子部品用セパレータの表面保護膜の機能も有するため好ましい。また、保持材として柔軟性を有する樹脂フィルムを用いた場合は、乾燥工程後、樹脂フィルムに電子部品用セパレータが保持されたままの状態の積層物を巻き取って保管・搬送することも可能となるため好ましい。 In the present invention, for coating, a dip coating method, a spray coating method, a roll coating method, a doctor blade method, a gravure coating method, a screen printing method, or the like can be used. It is preferable to perform the coating using a holding material for placing the material. Examples of the holding material include resin films such as polypropylene and polyethylene terephthalate, glass plates, and the like. The holding material may be subjected to a surface treatment such as a mold release treatment or an easy adhesion treatment. Among these holding materials, a resin film having flexibility is preferable because it also has a function of a surface protective film of a separator for electronic parts. In addition, when a flexible resin film is used as the holding material, it is possible to wind up and store and transport the laminate with the electronic component separator held on the resin film after the drying step. Therefore, it is preferable.
本発明のセパレータの製造方法の第１の態様においては、樹脂フィルム上に、予め１８０℃以上の融点を有するか、または実質的に融点を有しないフィラー粒子を含む、融点が１８０℃以上の物質からなる不織布または網状物を重ね、その上に、多孔質樹脂構造体を形成するための樹脂を含有する塗料を塗工した後、乾燥することによって、前記多孔質樹脂構造体と不織布または網状物とを一体化し、その後樹脂フィルムを除去する。また、第２の態様においては、樹脂フィルム上に、多孔質樹脂構造体を形成するための樹脂を含有する塗料を塗工して塗布層を形成した後に、１８０℃以上の融点を有するか、または実質的に融点を有しないフィラー粒子を含む、融点が１８０℃以上の物質からなる不織布または網状物を塗布層の上に積層し（ウェットラミネーション）、次いで乾燥して不織布または網状物と一体化した多孔質樹脂構造体を形成し、その後樹脂フィルムを除去する。 In the first aspect of the method for producing a separator of the present invention, a substance having a melting point of 180 ° C. or higher, which contains filler particles having a melting point of 180 ° C. or higher in advance or substantially having no melting point on the resin film. The porous resin structure and the nonwoven fabric or network are coated with a coating material containing a resin for forming a porous resin structure, and then dried. And then the resin film is removed. In the second embodiment, on the resin film, a coating containing a resin for forming a porous resin structure is applied to form a coating layer, and then has a melting point of 180 ° C. or higher, Alternatively, a nonwoven fabric or network made of a material having a melting point of 180 ° C. or higher, containing filler particles having substantially no melting point, is laminated on the coating layer (wet lamination), and then dried to be integrated with the nonwoven fabric or network. The formed porous resin structure is formed, and then the resin film is removed.
本発明においては、上記いずれの方法も好適に用いられるが、例えば多孔質基材の空隙率が大きい場合は、後者の方法が好ましい。すなわち、前者の場合は、樹脂フィルム上に多孔質基材を重ねた上に塗料を塗工するために、多孔質基材を構成する例えば繊維間の空隙に空気が残存しやすく、塗工欠点となる場合があるためである。しかしながら、前者の製法は、塗料を樹脂フィルムに塗工後、湿潤状態にある塗工面の上に多孔質基材をウェットラミネーションによって重ねる後者の方法と比べて、予め多孔質基材を樹脂フィルムと同軸に巻いておくことが可能であるため、後者のように多孔質基材を別に巻きだすための巻き出し機構が不要であり、より効率の良い製造が可能である。それ故、空隙率が比較的低く成膜性に問題のない多孔質基材を用いる場合には、前者の方法が適している。多孔質基材の空隙率は電池設計を優先して決めるべきであり、その設計要求によって多孔質基材の複合方法を適宜選択すればよい。後者の方法では、例えば多孔質基材の空隙率の大小に関わらず、塗工欠点のない均質なセパレータを製造することが可能であるが、本発明では、上記の空隙率に代表される多孔質基材の諸物性によって、製造方法を適宜選択することにより、いずれの製法でも均質なセパレータを製造することが可能である。 In the present invention, any of the above methods is preferably used. For example, when the porosity of the porous substrate is large, the latter method is preferable. That is, in the former case, in order to apply the paint on the porous base material on the resin film, air easily remains, for example, in the gaps between the fibers constituting the porous base material. This is because there is a case of becoming. However, in the former method, the porous substrate and the resin film are preliminarily compared with the latter method in which the porous substrate is stacked by wet lamination on the wet coated surface after the coating is applied to the resin film. Since it can be wound on the same axis, an unwinding mechanism for unwinding the porous substrate as in the latter case is unnecessary, and more efficient production is possible. Therefore, the former method is suitable when using a porous substrate having a relatively low porosity and no problem in film formability. The porosity of the porous substrate should be determined with priority given to battery design, and the composite method of the porous substrate may be appropriately selected according to the design requirements. In the latter method, for example, it is possible to produce a homogeneous separator having no coating defects regardless of the porosity of the porous substrate, but in the present invention, the porosity represented by the above porosity is used. A homogeneous separator can be produced by any production method by appropriately selecting the production method depending on various physical properties of the porous substrate.
本発明においては、上記の多孔質基材との複合方法において、前記樹脂フィルムの物性が非常に重要である。すなわち、本発明では、多孔質構造体と樹脂フィルムとの剥離強度が０．１〜７５（ｇ／２０ｍｍ）であり、より好ましくは０．１〜４０（ｇ／２０ｍｍ）である樹脂フィルムを用いることが好ましい。剥離強度は、樹脂フィルム上に形成された多孔質樹脂構造体の端部を剥離した後、その剥離端部とこれと同じ側に位置する樹脂フィルムの端部とをテンシロンの上下のチャックにそれぞれ固定し、引っ張り強度を測定した場合に得られる引っ張り荷重の５点平均値を、試験片の幅で割った値である。 In the present invention, the physical properties of the resin film are very important in the composite method with the porous substrate. That is, in the present invention, a resin film having a peel strength between the porous structure and the resin film of 0.1 to 75 (g / 20 mm), more preferably 0.1 to 40 (g / 20 mm) is used. It is preferable. The peel strength is determined by peeling the end of the porous resin structure formed on the resin film, and then attaching the peel end and the end of the resin film located on the same side to the upper and lower chucks of Tensilon respectively. It is a value obtained by dividing the five-point average value of the tensile load obtained when fixing and measuring the tensile strength by the width of the test piece.
特にウェットラミネーションを用いる上記第２の態様の場合には、前記の如く多孔質基材を複合する前に樹脂フィルム上に塗料を塗工するが、剥離強度が０．１ｇ／２０ｍｍ未満のような比較的離型性が良好な樹脂フィルムでは、塗料粘度が低い場合には塗工直後の湿潤状態にある塗工面が安定せず塗料の単位面積あたりの塗布量が、塗工直後からウェットラミネーションを実施するまでの間で変動してしまい、セパレータの面方向で多孔質構造体の単位面積あたりの重量が変動してしまう。この現象は本質的には、樹脂フィルムの表面張力に由来するものである。また、これとは別に、樹脂フィルムの剥離強度が０．１ｇ／２０ｍｍ未満の場合には、乾燥工程においてセパレータが樹脂フィルムから剥離する場合があり好ましくない。一方、７５ｇ／２０ｍｍを超すような接着性が高い樹脂フィルムでは、上記のような変動は認められないが、樹脂フィルムからセパレータを効率的に剥離し取り出すことが困難となるため好ましくない。 In particular, in the case of the second aspect using wet lamination, the paint is applied on the resin film before combining the porous substrate as described above, but the peel strength is less than 0.1 g / 20 mm. For resin films with relatively good releasability, when the paint viscosity is low, the wet coated surface immediately after coating is not stable, and the amount of coating per unit area of the paint is reduced to wet lamination immediately after coating. It will change until it implements, and the weight per unit area of a porous structure will change in the surface direction of a separator. This phenomenon is essentially derived from the surface tension of the resin film. Apart from this, when the peel strength of the resin film is less than 0.1 g / 20 mm, the separator may peel off from the resin film in the drying step, which is not preferable. On the other hand, in the resin film having high adhesiveness exceeding 75 g / 20 mm, the above-mentioned fluctuation is not recognized, but it is not preferable because it is difficult to efficiently peel and remove the separator from the resin film.
一方、樹脂フィルム上に多孔質基材を重ねておいた上に塗工する本発明の上記第１の態様の塗工方法においては、塗料が直接的に多孔質基材上に塗工されるために塗料は塗工後において多孔質基材に絡むため流動しにくく、樹脂フィルムの剥離強度が０．１ｇ／２０ｍｍ未満の場合であっても、ウェットラミネーションを用いる上で生じる上記の重量バラツキの問題点は発生しないが、乾燥工程においてセパレータが樹脂フィルムから剥離する場合があるので、０．１ｇ／２０ｍｍ未満の場合はやはり好ましくない。一方、剥離強度が７５ｇ／２０ｍｍを超す樹脂フィルムを用いる場合には、ウェットラミネーションを使用する場合と同じく、樹脂フィルムからセパレータを効率的に剥離し取り出すことが困難となるため好ましくない。 On the other hand, in the coating method according to the first aspect of the present invention in which the coating is performed after the porous substrate is overlaid on the resin film, the paint is directly coated on the porous substrate. Therefore, the coating material is difficult to flow because it is entangled with the porous substrate after coating, and even when the peel strength of the resin film is less than 0.1 g / 20 mm, the above-mentioned weight variation that occurs when using wet lamination is used. Although no problem occurs, the separator may be peeled off from the resin film in the drying step, so that the case of less than 0.1 g / 20 mm is not preferable. On the other hand, when a resin film having a peel strength exceeding 75 g / 20 mm is used, it is not preferable because it is difficult to efficiently peel and remove the separator from the resin film, as in the case of using wet lamination.
また、上記範囲にある樹脂フィルムを用いる別の利点として、以下に述べる内容がセパレータの孔径を制御する上で重要である。すなわち、上記のいずれの複合方法においても共通するが、剥離強度を０．１ｇ／２０ｍｍに近い低い範囲に設計する場合は、樹脂フィルムの接するセパレータ面側の孔径が、塗工表層にあたるセパレータ面の孔径に比べて大きくなり、逆に７５ｇ／２０ｍｍに近く高い範囲に設計する場合は、樹脂フィルムの接するセパレータ面側の孔径が、塗工表層にあたるセパレータ面の孔径に比べて小さくなる。また、０．１ｇ／２０ｍｍ未満の場合は、樹脂面に接する側のセパレータ面の孔が閉塞する場合があり、７５ｇ／２０ｍｍを超す範囲では、塗工表層にあたるセパレータ面の孔が閉塞しやすくなる場合がある。この現象の原因は必ずしも明らかではないが、多孔質基材の表面張力が異なる材質を用いた場合でも同様の孔径の表裏非対称性が生ずることから、表面張力の強さによって生ずるものと考えられる。したがって、本発明では、電池設計からの要求から多孔質基材の材質を固定しても、その多孔質基材に複合される多孔質の表裏における孔径の対称性を、樹脂フィルムの表面性で制御することが可能となる。つまり、本発明では、従来は多孔質基材の材質によって必ずしも上記の表裏孔径の対象性が制御できなかったことに比較して、セパレータ材料としては残らない樹脂フィルムの剥離強度を設定することによって孔径の対称性を制御することができる。 Further, as another advantage of using the resin film in the above range, the following contents are important in controlling the pore diameter of the separator. That is, although it is common to any of the above-described composite methods, when the peel strength is designed in a low range close to 0.1 g / 20 mm, the pore diameter on the separator surface side in contact with the resin film is that of the separator surface corresponding to the coating surface layer. On the contrary, when designing in a high range close to 75 g / 20 mm, the hole diameter on the separator surface side in contact with the resin film is smaller than that on the separator surface corresponding to the coating surface layer. In addition, if it is less than 0.1 g / 20 mm, the hole on the separator surface on the side in contact with the resin surface may be blocked, and if it exceeds 75 g / 20 mm, the hole on the separator surface corresponding to the coating surface layer is likely to be blocked. There is a case. Although the cause of this phenomenon is not necessarily clear, even when materials having different surface tensions of the porous base material are used, the same front and back asymmetry of the pore diameter occurs, and it is considered that this phenomenon is caused by the strength of the surface tension. Therefore, in the present invention, even if the material of the porous base material is fixed due to the demand from the battery design, the symmetry of the pore diameter on the front and back surfaces of the porous composite to the porous base material is the same as the surface property of the resin film. It becomes possible to control. In other words, in the present invention, by setting the peel strength of the resin film that does not remain as a separator material, compared to the conventional case where the objectivity of the front and back hole diameters cannot always be controlled by the material of the porous substrate. The symmetry of the hole diameter can be controlled.
本発明の電子部品用セパレータの好ましい具体例は、多孔質樹脂構造体がポリフッ化ビニリデンまたはフッ化ビニリデン共重合体等のフッ化ビニリデン樹脂を用いて形成された場合である。そのようなセパレータは次のようにして作製することができる。 A preferred specific example of the separator for electronic parts of the present invention is a case where the porous resin structure is formed using a vinylidene fluoride resin such as polyvinylidene fluoride or a vinylidene fluoride copolymer. Such a separator can be produced as follows.
すなわち、まずフッ化ビニリデン樹脂を溶媒に分散させる。溶媒としてはフッ化ビニリデン樹脂が溶解するもの（良溶媒）を選択しなければならない。良溶媒の例として、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、１−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルスルホキシド等が挙げられる。分散、溶解方法としては市販の攪拌機を使用して行うことができる。フッ化ビニリデン樹脂は、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、１−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルスルホキシドに室温で容易に溶解するので、特に加熱する必要はない。その後、フッ化ビニリデン樹脂が溶解しない溶媒（貧溶媒）を更に混合する。貧溶媒としては、良溶媒より沸点の高い溶媒を選択するのが好ましい。貧溶媒の例として、フタル酸ジブチル、エチレングリコール、ジエチレングリコール、グリセリン等があげられる。フッ化ビニリデン樹脂の濃度としては、得るべきセパレータの特性を考慮に入れ適宜変更する必要がある。 That is, first, vinylidene fluoride resin is dispersed in a solvent. As the solvent, a solvent capable of dissolving the vinylidene fluoride resin (good solvent) must be selected. Examples of the good solvent include N, N-dimethylacetamide, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, N, N-dimethylsulfoxide and the like. As a dispersion and dissolution method, a commercially available stirrer can be used. Since vinylidene fluoride resin is easily dissolved in N, N-dimethylacetamide, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, and N, N-dimethylsulfoxide at room temperature, there is no need for heating. Thereafter, a solvent (poor solvent) in which the vinylidene fluoride resin does not dissolve is further mixed. As the poor solvent, it is preferable to select a solvent having a boiling point higher than that of the good solvent. Examples of the poor solvent include dibutyl phthalate, ethylene glycol, diethylene glycol, glycerin and the like. The concentration of the vinylidene fluoride resin needs to be appropriately changed in consideration of the characteristics of the separator to be obtained.
上記の操作によって得られるフッ化ビニリデン樹脂及び貧溶媒等を溶解した塗料において、溶媒として吸湿性が高いものを用いる場合には、できる限り水分の混入を防ぐことが必要であり、本発明では、カールフィッシャー法による測定で水分量が０．７重量％以下、より好ましくは、０．５重量％以下のものが使用される。水分量が０．７重量％を超すと、ゲル化が早期に進み塗料の保存期間が極端に短くなったり、成膜性に悪影響を与える場合があり好ましくない。 In a paint in which a vinylidene fluoride resin and a poor solvent obtained by the above operation are dissolved, when using a highly hygroscopic solvent as a solvent, it is necessary to prevent moisture from being mixed as much as possible. A water content of 0.7% by weight or less, more preferably 0.5% by weight or less is used as measured by the Karl Fischer method. If the water content exceeds 0.7% by weight, gelation progresses early and the storage period of the paint becomes extremely short, and the film formability may be adversely affected.
上記不織布または網状物等の繊維状基材に、予め上記のフィラー粒子を含有させておき、これに上記のようにして得られた塗料を塗布する。その一例として、繊維状基材を保持材上に重ね合わせ、その繊維状基材上に、前記で得たフッ化ビニリデン樹脂及び貧溶媒等を溶解した塗料を塗布する。保持材としてはポリプロピレンやポリエチレンテレフタレート等の樹脂フィルム、ガラス板等を用いることができる。これらの保持材の中でも柔軟性を有する樹脂フィルムが電子部品用セパレータの表面保護膜の機能も有するため好ましい。保持材として柔軟性を有する樹脂フィルムを用いた場合は、乾燥工程後、樹脂フィルムに電子部品用セパレータが保持されたままの状態の積層物を巻き取って保管・搬送することも可能となるため好ましい。 The filler particles described above are preliminarily contained in a fibrous base material such as the nonwoven fabric or the net-like material, and the paint obtained as described above is applied thereto. As an example, a fibrous base material is superposed on a holding material, and a coating material in which the vinylidene fluoride resin obtained above and a poor solvent are dissolved is applied onto the fibrous base material. As the holding material, a resin film such as polypropylene or polyethylene terephthalate, a glass plate, or the like can be used. Among these holding materials, a resin film having flexibility is preferable because it also has a function of a surface protective film of a separator for electronic parts. When a flexible resin film is used as the holding material, it is possible to wind up and store and transport the laminate with the electronic component separator held on the resin film after the drying step. preferable.
フッ化ビニリデン樹脂を繊維状基材上に塗布する方法としては、前記したディップコート法、スプレーコート法、ロールコート法、ドクターブレード法、グラビアコート法、スクリーン印刷法等により塗布又はキャスティング法等を用いることができる。これにより、繊維状基材の内部にフッ化ビニリデン樹脂が含まれる。次に、塗布された繊維状基材上のフッ化ビニリデン樹脂を含む塗布層から溶媒を乾燥により蒸発させることにより、本発明の電子部品用セパレータを得ることができる。この場合、繊維状基材の内部にポリフッ化ビニリデンが含まれていると共に、繊維状基材の片面又は両面にポリフッ化ビニリデンよりなる膜状物が形成されていてもよい。本発明の電子部品用セパレータは、保持材から剥離して使用される。 As a method for applying the vinylidene fluoride resin on the fibrous base material, the above-described dip coating method, spray coating method, roll coating method, doctor blade method, gravure coating method, screen printing method, etc. may be used. Can be used. Thereby, the vinylidene fluoride resin is contained inside the fibrous base material. Next, the separator for electronic parts of the present invention can be obtained by evaporating the solvent from the coating layer containing the vinylidene fluoride resin on the coated fibrous base material by drying. In this case, polyvinylidene fluoride is contained in the fibrous base material, and a film-like material made of polyvinylidene fluoride may be formed on one side or both sides of the fibrous base material. The separator for electronic parts of the present invention is used after being peeled from the holding material.
また、他の方法として、上記の塗料を、例えば前記の、ポリエチレンテレフタレート繊維よりなる不織布に、ディップコート法、スプレーコート法、ロールコート法、ドクターブレード法、グラビアコート法、スクリーン印刷法等により塗布又はキャスティング法等により塗布して、シート状の被覆物を得る。塗布により得られたシート状の被覆物から溶媒を乾燥により蒸発または揮散させることにより、多孔性のシートが形成され、本発明のセパレータを得ることができる。この場合、繊維状基材の内部にポリフッ化ビニリデンが含まれていると共に、繊維状基材の片面又は両面にポリフッ化ビニリデンよりなる膜状物が形成されていてもよい。 Further, as another method, the above-mentioned paint is applied to the nonwoven fabric made of polyethylene terephthalate fiber, for example, by a dip coating method, a spray coating method, a roll coating method, a doctor blade method, a gravure coating method, a screen printing method, or the like. Or it apply | coats by the casting method etc. and a sheet-like coating material is obtained. A porous sheet is formed by evaporating or volatilizing the solvent from the sheet-like coating obtained by coating by drying, and the separator of the present invention can be obtained. In this case, polyvinylidene fluoride is contained in the fibrous base material, and a film-like material made of polyvinylidene fluoride may be formed on one side or both sides of the fibrous base material.
次に、本発明を実施例によって説明する。なお、以下の実施例において、セパレータと樹脂フィルムとが直接接しない面及び接する面の両方の孔径をバブルポイント法で測定し、両者を比較の上、孔径が小さい方を、孔径の測定値とした。厚さ方向の孔径分布は電子顕微鏡により観察した。なお、本発明における多孔質樹脂構造体の孔径は、塗料化及び乾燥条件やプレス条件を適宜選択することにより制御した。 Next, the present invention will be described by examples. In the following examples, the pore diameter of both the surface where the separator and the resin film are not in direct contact with each other and the surface in contact with each other was measured by the bubble point method. did. The pore size distribution in the thickness direction was observed with an electron microscope. In addition, the pore diameter of the porous resin structure in the present invention was controlled by appropriately selecting coating and drying conditions and pressing conditions.
重量平均分子量３０万のフッ化ビニリデンホモポリマーを１−メチル−２−ピロリドンに溶解し、フタル酸ジブチルを添加してフッ化ビニリデンホモポリマー成分が１５重量％になるように調整した溶液を準備した。この溶液中に含まれる水分量をカールフィッシャー法で測定したところ、０．６％であった。次にポリエチレンテレフタレートからなる樹脂フィルム面に、予め融点が２６０℃の繊維のみからなるポリエチレンテレフタレート繊維よりなる厚さ１０μｍの不織布に一次平均粒子径０．２５μｍで融点が３２０℃のＰＴＦＥ粒子を５ｇ／ｍ２保持させておいたものを載置し、その不織布に上記溶液をキャスティング法により塗布した。次に、不織布の内部に含まれる溶液中の溶剤を熱により蒸発させ、不織布の繊維間にフッ化ビニリデンホモポリマーよりなる多孔質樹脂構造体を有する厚さが２２μｍのセパレータを作製した。なお、多孔質樹脂構造体に対する上記樹脂フィルムの剥離強度は１５ｇ／２０ｍｍであった。 A vinylidene fluoride homopolymer having a weight average molecular weight of 300,000 was dissolved in 1-methyl-2-pyrrolidone, and a solution prepared by adding dibutyl phthalate to adjust the vinylidene fluoride homopolymer component to 15% by weight was prepared. . The amount of water contained in this solution was measured by the Karl Fischer method and found to be 0.6%. Next, a PTFE particle having a primary average particle diameter of 0.25 μm and a melting point of 320 ° C. is applied to a non-woven fabric having a thickness of 10 μm on a resin film surface made of polyethylene terephthalate in advance. What was kept m 2 was placed, and the solution was applied to the nonwoven fabric by a casting method. Next, the solvent in the solution contained inside the nonwoven fabric was evaporated by heat, and a separator having a porous resin structure made of vinylidene fluoride homopolymer between the fibers of the nonwoven fabric was produced. The peel strength of the resin film with respect to the porous resin structure was 15 g / 20 mm.
この電子部品用セパレータを電子顕微鏡で観察したところ、ピンホールなどの欠点は存在せず、前記多孔質樹脂構造体の細孔は、多孔質基材である不織布の片面から他面に多数の孔の繋がりによって通じており、各孔の孔径は繊維状基材の厚さより小さかった。また、セパレータの厚さ方向で孔径分布の傾斜は認められず、厚さ方向に均質な多孔質構造であることを確認した。バブルポイント法によりセパレータの孔径を測定したところ１．２μｍであった。 When the electronic component separator was observed with an electron microscope, there were no defects such as pinholes, and the pores of the porous resin structure consisted of a number of pores from one side of the nonwoven fabric to the other side. The hole diameter of each hole was smaller than the thickness of the fibrous base material. Moreover, the inclination of the pore diameter distribution was not recognized in the thickness direction of the separator, and it was confirmed that the porous structure was homogeneous in the thickness direction. When the pore diameter of the separator was measured by the bubble point method, it was 1.2 μm.
実施例１において、多孔質基材として、融点が２０５℃のビニロン繊維だけからなる厚さ１５μｍの不織布を用いた以外は、実施例１と同様にして電子部品用セパレータを作製した。この電子部品用セパレータを電子顕微鏡で観察したところ、ピンホールなどの欠点は存在せず、多孔質樹脂構造体は、多孔質基材の片面からもう一方の面に多数の孔の繋がりによって通じており、各孔の孔径は多孔質基材の厚さより小さかった。また、セパレータの厚さ方向で孔径分布の傾斜は認められず、厚さ方向に均質な多孔質構造であることを確認した。バブルポイント法によりこのセパレータの孔径を測定したところ１．０μｍであった。 In Example 1, a separator for electronic parts was produced in the same manner as in Example 1 except that a non-woven fabric having a thickness of 15 μm made of only vinylon fibers having a melting point of 205 ° C. was used as the porous substrate. When this electronic component separator was observed with an electron microscope, there were no defects such as pinholes, and the porous resin structure was communicated by connecting a large number of holes from one side of the porous substrate to the other side. The hole diameter of each hole was smaller than the thickness of the porous substrate. Moreover, the inclination of the pore diameter distribution was not recognized in the thickness direction of the separator, and it was confirmed that the porous structure was homogeneous in the thickness direction. When the pore diameter of this separator was measured by the bubble point method, it was 1.0 μm.
実施例１において、融点が２００℃のポリエチレンテレフタレートからなる樹脂フィルムの垂直方向に向かって、その樹脂フィルムの一方の面から他方の面の間に実質上遮蔽構造を有しない貫通孔だけからなる厚さ１５μｍ微多孔樹脂フィルムを用いた以外は、実施例１と同様にして電子部品用セパレータを作製した。この電子部品用セパレータを電子顕微鏡で観察したところ、ピンホールなどの欠点は存在せず、多孔質樹脂構造体は、多孔質基材の片面からもう一方の面に多数の孔の繋がりによって通じており、各孔の孔径は微多孔樹脂フィルムの厚さより小さかった。また、セパレータの厚さ方向で孔径分布の傾斜は認められず、厚さ方向に均質な多孔質構造であることを確認した。バブルポイント法によりこのセパレータの孔径を測定したところ０．８μｍであった。 In Example 1, in the vertical direction of a resin film made of polyethylene terephthalate having a melting point of 200 ° C., a thickness consisting of only a through hole substantially having no shielding structure between one surface and the other surface of the resin film. A separator for electronic parts was produced in the same manner as in Example 1 except that a 15 μm microporous resin film was used. When this electronic component separator was observed with an electron microscope, there were no defects such as pinholes, and the porous resin structure was communicated by connecting a large number of holes from one side of the porous substrate to the other side. The hole diameter of each hole was smaller than the thickness of the microporous resin film. Moreover, the inclination of the pore diameter distribution was not recognized in the thickness direction of the separator, and it was confirmed that the porous structure was homogeneous in the thickness direction. When the pore diameter of this separator was measured by the bubble point method, it was 0.8 μm.
重量平均分子量５０万のポリメチルメタアクリレートをアセトンに溶解し、フタル酸ジブチルを添加してポリメチルメタアクリレートが１２重量％になるように調整した溶液を準備した。この溶液中に含まれる水分量をカールフィッシャー法で測定したところ、０．５％であった。この溶液を用いた以外は、実施例１と同様にして不織布と多孔質樹脂構造体が一体化した電子部品用セパレータを作製した。得られた電子部品用セパレータの厚さは２０μｍであった。この電子部品用セパレータを電子顕微鏡で観察したところ、ピンホールなどの欠点は存在せず、多孔質樹脂構造体は、多孔質基材の片面からもう一方の面に多数の孔の繋がりによって通じており、各孔の孔径は不織布の厚さより小さかった。また、セパレータの厚さ方向で孔径分布の傾斜は認められず、厚さ方向に均質な多孔質構造であることを確認した。バブルポイント法によりこのセパレータの孔径を測定したところ１．２μｍであった。 A solution prepared by dissolving polymethyl methacrylate having a weight average molecular weight of 500,000 in acetone and adding dibutyl phthalate to adjust the polymethyl methacrylate to 12% by weight was prepared. The amount of water contained in this solution was measured by the Karl Fischer method and found to be 0.5%. A separator for electronic parts in which a nonwoven fabric and a porous resin structure were integrated was produced in the same manner as in Example 1 except that this solution was used. The thickness of the obtained separator for electronic parts was 20 μm. When this electronic component separator was observed with an electron microscope, there were no defects such as pinholes, and the porous resin structure was communicated by connecting a large number of holes from one side of the porous substrate to the other side. The hole diameter of each hole was smaller than the thickness of the nonwoven fabric. Moreover, the inclination of the pore diameter distribution was not recognized in the thickness direction of the separator, and it was confirmed that the porous structure was homogeneous in the thickness direction. When the pore diameter of this separator was measured by the bubble point method, it was 1.2 μm.
実施例４において、アセトンをテトラヒドロフランに変えた以外は、実施例４と同様にして電子部品用セパレータを作製した。なお、使用した溶液中に含まれる水分量をカールフィッシャー法で測定したところ、０．６％であった。この溶液を用いた以外は、実施例４と同様にして不織布と多孔質構造体が一体化した電子部品用セパレータを得た。得られた電子部品用セパレータの厚さは２１μｍであった。この電子部品用セパレータを電子顕微鏡で観察したところ、ピンホールなどの欠点は存在せず、多孔質樹脂構造体は、多孔質基材の片面からもう一方の面に多数の孔の繋がりによって通じており、各孔の孔径は不織布の厚さより小さかった。また、セパレータの厚さ方向で孔径分布の傾斜は認められず、厚さ方向に均質な多孔質構造であることを確認した。バブルポイント法によりこのセパレータの孔径を測定したところ０．７μｍであった。 A separator for electronic parts was produced in the same manner as in Example 4 except that acetone was changed to tetrahydrofuran in Example 4. In addition, it was 0.6% when the moisture content contained in the used solution was measured by the Karl Fischer method. An electronic component separator in which the nonwoven fabric and the porous structure were integrated was obtained in the same manner as in Example 4 except that this solution was used. The thickness of the obtained separator for electronic parts was 21 μm. When this electronic component separator was observed with an electron microscope, there were no defects such as pinholes, and the porous resin structure was communicated by connecting a large number of holes from one side of the porous substrate to the other side. The hole diameter of each hole was smaller than the thickness of the nonwoven fabric. Moreover, the inclination of the pore diameter distribution was not recognized in the thickness direction of the separator, and it was confirmed that the porous structure was homogeneous in the thickness direction. It was 0.7 micrometer when the hole diameter of this separator was measured by the bubble point method.
実施例１において、多孔質樹脂構造体に対する剥離強度が２ｇ／２０ｍｍのポリエチレンテレフタレートからなる樹脂フィルムを用いた以外は、実施例１と同様にして電子部品用セパレータを作製した。得られた電子部品用セパレータの厚さは２０μｍであった。この電子部品用セパレータを電子顕微鏡で観察したところ、ピンホールなどの欠点は存在せず、前記多孔質樹脂構造体は、多孔質基材の片面からもう一方の面に多数の孔の繋がりによって通じており、各孔の孔径は多孔質基材の厚さより小さかった。また、セパレータの保持材と接する面では孔径が大きく、一方樹脂フィルムと接しない面は孔径が小さいことを確認した。バブルポイント法によりこのセパレータの孔径を測定したところ１．２μｍであった。 In Example 1, a separator for electronic parts was produced in the same manner as in Example 1 except that a resin film made of polyethylene terephthalate having a peel strength of 2 g / 20 mm with respect to the porous resin structure was used. The thickness of the obtained separator for electronic parts was 20 μm. When this electronic component separator was observed with an electron microscope, there were no defects such as pinholes, and the porous resin structure was communicated by connecting a number of holes from one side of the porous substrate to the other. The diameter of each hole was smaller than the thickness of the porous substrate. Moreover, it confirmed that the hole diameter was large in the surface which contact | connects the holding | maintenance material of a separator, and the hole diameter was small on the surface which does not contact | connect a resin film. When the pore diameter of this separator was measured by the bubble point method, it was 1.2 μm.
実施例１において、多孔質樹脂構造体に対する剥離強度が５５ｇ／２０ｍｍのポリエチレンテレフタレートからなる樹脂フィルムを用いた以外は、実施例１と同様にして電子部品用セパレータを得作製した。得られた電子部品用セパレータの厚さは２１μｍであった。この電子部品用セパレータを電子顕微鏡で観察したところ、ピンホールなどの欠点は存在せず、多孔質樹脂構造体は、多孔質基材の片面からもう一方の面に多数の孔の繋がりによって通じており、各孔の孔径は多孔質基材の厚さより小さかった。また、セパレータの樹脂フィルムと接する面では孔径が小さく、一方樹脂フィルムと接しない面は孔径が大きいことを確認した。バブルポイント法によりこのセパレータの孔径を測定したところ１．３μｍであった。 In Example 1, an electronic component separator was produced in the same manner as in Example 1 except that a resin film made of polyethylene terephthalate having a peel strength of 55 g / 20 mm with respect to the porous resin structure was used. The thickness of the obtained separator for electronic parts was 21 μm. When this electronic component separator was observed with an electron microscope, there were no defects such as pinholes, and the porous resin structure was communicated by connecting a large number of holes from one side of the porous substrate to the other side. The hole diameter of each hole was smaller than the thickness of the porous substrate. Further, it was confirmed that the surface of the separator in contact with the resin film had a small hole diameter, while the surface not in contact with the resin film had a large hole diameter. When the pore diameter of this separator was measured by the bubble point method, it was 1.3 μm.
実施例１において、樹脂フィルム面上に先に溶液を塗工し、塗面が湿潤状態にあるうちに、多孔質基材をウェットラミネートして多孔質基材と多孔質樹脂構造体を一体化した以外は、実施例１と同様にして電子部品用セパレータを作製した。得られた電子部品用セパレータの厚さは２３μｍであった。この電子部品用セパレータを電子顕微鏡で観察したところ、ピンホールなどの欠点は存在せず、多孔質樹脂構造体は、多孔質基材の片面からもう一方の面に多数の孔の繋がりによって通じており、各孔の孔径は多孔質基材の厚さより小さかった。また、セパレータの厚さ方向で孔径分布の傾斜は認められず、厚さ方向に均質な多孔質構造であることを確認した。バブルポイント法によりこのセパレータの孔径を測定したところ１．０μｍであった。 In Example 1, the solution was first applied onto the resin film surface, and the porous substrate and the porous resin structure were integrated by wet laminating the porous substrate while the coated surface was wet. A separator for electronic parts was produced in the same manner as in Example 1 except that. The thickness of the obtained separator for electronic parts was 23 μm. When this electronic component separator was observed with an electron microscope, there were no defects such as pinholes, and the porous resin structure was communicated by connecting a large number of holes from one side of the porous substrate to the other side. The hole diameter of each hole was smaller than the thickness of the porous substrate. Moreover, the inclination of the pore diameter distribution was not recognized in the thickness direction of the separator, and it was confirmed that the porous structure was homogeneous in the thickness direction. When the pore diameter of this separator was measured by the bubble point method, it was 1.0 μm.
実施例１において、不織布に予め融点が１９０℃の架橋ＰＭＭＡからなる一次平均粒子径が２μｍのフィラー粒子を２０ｇ／ｍ２だけ保持させたものを多孔質基材として用いた以外は、実施例１と同様にして電子部品用セパレータを作製した。得られた電子部品用セパレータの厚さは２４μｍであった。この電子部品用セパレータを電子顕微鏡で観察したところ、ピンホールなどの欠点は存在せず、形成された多孔質樹脂構造体は、多孔質基材の片面からもう一方の面に多数の孔の繋がりによって通じており、各孔の孔径は多孔質基材の厚さより小さかった。また、セパレータの厚さ方向で孔径分布の傾斜は認められず、厚さ方向に均質な多孔質構造であることを確認した。バブルポイント法によりこのセパレータの孔径を測定したところ０．８μｍであった。 In Example 1, except for using those primary average particle diameter in advance melting the nonwoven fabric is made of 190 ° C. of the crosslinked PMMA was shown holding the filler particles of 2μm only 20 g / m 2 as a porous substrate, Example 1 In the same manner, a separator for electronic parts was produced. The thickness of the obtained separator for electronic parts was 24 μm. When this electronic component separator was observed with an electron microscope, there were no defects such as pinholes, and the formed porous resin structure had many holes connected from one side of the porous substrate to the other. The hole diameter of each hole was smaller than the thickness of the porous substrate. Moreover, the inclination of the pore diameter distribution was not recognized in the thickness direction of the separator, and it was confirmed that the porous structure was homogeneous in the thickness direction. When the pore diameter of this separator was measured by the bubble point method, it was 0.8 μm.
実施例１において、不織布にシリカからなる一次平均粒子径が５０ｎｍのフィラー粒子を３０ｇ／ｍ２だけ保持させたものを多孔質基材として用いた以外は、実施例１と同様にして電子部品用セパレータを作製した。得られた電子部品用セパレータの厚さは２０μｍであった。この電子部品用セパレータを電子顕微鏡で観察したところ、ピンホールなどの欠点は存在せず、多孔質樹脂構造体は、多孔質基材の片面からもう一方の面に多数の孔の繋がりによって通じており、各孔の孔径は多孔質基材の厚さより小さかった。また、セパレータの厚さ方向で孔径分布の傾斜は認められず、厚さ方向に均質な多孔質構造であることを確認した。バブルポイント法によりセパレータの孔径を測定したところ０．５μｍであった。 In Example 1, the same procedure as in Example 1 was used for an electronic component except that a nonwoven fabric in which only 30 g / m 2 of filler particles having a primary average particle diameter of 50 nm were made of silica was used as the porous substrate. A separator was produced. The thickness of the obtained separator for electronic parts was 20 μm. When this electronic component separator was observed with an electron microscope, there were no defects such as pinholes, and the porous resin structure was communicated by connecting a large number of holes from one side of the porous substrate to the other side. The hole diameter of each hole was smaller than the thickness of the porous substrate. Moreover, the inclination of the pore diameter distribution was not recognized in the thickness direction of the separator, and it was confirmed that the porous structure was homogeneous in the thickness direction. When the pore diameter of the separator was measured by the bubble point method, it was 0.5 μm.
［比較例１］
厚さ２５μｍの融点が１８５℃のポリエチレンテレフタレート繊維よりなる不織布を比較用のセパレータとして使用した。
［比較例２］
厚さ２０μｍのポリエチレン製延伸多孔質膜を比較用のセパレータとして使用した。
［比較例３］
融点が１９０℃の架橋ＰＭＭＡからなるフィラー粒子の代わりに、融点が１２４℃からなる一次平均粒子径が２μｍのポリエチレン粒子を用いた以外は、実施例９と同様にして比較用のセパレータを作製した。
[Comparative Example 1]
A nonwoven fabric made of polyethylene terephthalate fiber having a thickness of 25 μm and a melting point of 185 ° C. was used as a separator for comparison.
[Comparative Example 2]
A polyethylene stretched porous membrane with a thickness of 20 μm was used as a comparative separator.
[Comparative Example 3]
A comparative separator was prepared in the same manner as in Example 9, except that polyethylene particles having a melting point of 124 ° C. and a primary average particle diameter of 2 μm were used instead of filler particles made of crosslinked PMMA having a melting point of 190 ° C. .
［比較例４］
実施例１において、不織布として融点が１２５℃のポリエチレン繊維だけからなる不織布を用いた以外は、実施例１と同様にして比較用のセパレータを作製した。
［比較例５］
実施例１において、不織布として融点が２６０℃のポリエチレンテレフタレート繊維と融点が１３０℃のポリエチレンテレフタレート繊維とが混在した厚さ１０μｍの不織布を用い、融点が３２０℃のＰＴＦＥ粒子の代わりに融点が１２０℃のポリエチレン粒子を８０ｇ／ｍ２保持させた以外は、実施例１と同様にして比較用のセパレータを作製した。
上記実施例及び比較例で得られたセパレータを、リチウムイオン二次電池に使用した場合の特性を下記のように評価した。
[Comparative Example 4]
In Example 1, a comparative separator was prepared in the same manner as in Example 1 except that a non-woven fabric consisting only of polyethylene fibers having a melting point of 125 ° C. was used.
[Comparative Example 5]
In Example 1, a nonwoven fabric having a thickness of 10 μm in which polyethylene terephthalate fibers having a melting point of 260 ° C. and polyethylene terephthalate fibers having a melting point of 130 ° C. are mixed as the nonwoven fabric, and the melting point is 120 ° C. instead of PTFE particles having a melting point of 320 ° C. A comparative separator was prepared in the same manner as in Example 1 except that 80 g / m 2 of polyethylene particles were held.
The characteristics when the separators obtained in the above Examples and Comparative Examples were used in lithium ion secondary batteries were evaluated as follows.
〔耐熱寸法安定性〕
１０×１０ｃｍ２のサイズで、厚さが５ｍｍの２枚のガラス板間に、実施例及び比較例のセパレータを５×５ｃｍ２の正方形に切り出したサンプルを挟んだ後に、水平にしてアルミニウム製のバットに静置し、１５０℃の乾燥機に一晩放置して熱による面積変化を調べた。面積変化を、面積変化率＝（試験後の面積／試験前の面積：２５ｃｍ２）×１００％として評価した。その結果を表１に示す。
[Heat-resistant dimensional stability]
After sandwiching a sample of the separator of the example and the comparative example into a square of 5 × 5 cm 2 between two glass plates having a size of 10 × 10 cm 2 and a thickness of 5 mm, the sample is horizontally made of aluminum. The sample was left on a vat and left in a dryer at 150 ° C. overnight to examine the area change due to heat. The area change was evaluated as area change rate = (area after test / area before test: 25 cm 2 ) × 100%. The results are shown in Table 1.
以上の結果から、実施例の本発明のセパレータは、耐熱寸法安定性がいずれも良好であることが分かった。これに対して比較例のセパレータは、いずれも実施例に比べて劣るものであった。また、比較例１のセパレータは耐熱寸法安定性がかなり良好ではあるが、多孔質樹脂構造体が存在しないことから、若干劣る結果となったと思われる。 From the above results, it was found that the separators of the present invention of Examples all have good heat-resistant dimensional stability. In contrast, the separators of the comparative examples were all inferior to the examples. Further, although the separator of Comparative Example 1 has considerably good heat-resistant dimensional stability, it seems that the result is slightly inferior because there is no porous resin structure.
〔交流インピーダンス〕
上記セパレータを使用してコイン型セルを作製し、セルの交流インピーダンスを測定した。その結果を表２に示す。
A coin-type cell was produced using the separator, and the AC impedance of the cell was measured. The results are shown in Table 2.
上記の結果から、実施例の本発明のセパレータは、何れもイオン伝導度が優れたものであることが分かった。 From the above results, it was found that all of the separators of the present invention of the examples were excellent in ionic conductivity.
〔短絡性〕
次に、短絡性の試験を行なった。２枚のステンレス板（３×３ｃｍ２）にセパレータ（５×５ｃｍ２）を挟みステンレス電極間に８０Ｖの電位差を設けた状態で、両電極が対向する方向から加圧して、短絡を起こす圧力を調べた。その結果を表３に示す。
Next, a short circuit test was performed. With a separator (5 × 5 cm 2 ) sandwiched between two stainless steel plates (3 × 3 cm 2 ) and a potential difference of 80 V between the stainless steel electrodes, pressure is applied from the direction in which both electrodes face each other, causing a pressure that causes a short circuit. Examined. The results are shown in Table 3.
上記の結果から、実施例の本発明のセパレータは、短絡し難く、セパレータとしての本来の電気絶縁性は従来のセパレータ以上の性能を有していることが明らかとなった。一方、イオン伝導性においては比較的良好な結果を得た不織布だけからなる比較例のセパレータは電気絶縁性が非常に不十分な結果となった。 From the above results, it has been clarified that the separators of the present invention of the example are not easily short-circuited, and the original electrical insulation as a separator has performances higher than those of conventional separators. On the other hand, the separator of the comparative example which consists only of the nonwoven fabric which obtained the comparatively favorable result in ion conductivity resulted in the electrical insulation property being very inadequate.
以上の３種類の試験結果から、本発明の電子部品用セパレータは各特性を全て満足するものであるのに対して、比較用のセパレータは全ての特性を満足するものではなく、比較的高温域でも性能を維持すべき電気化学装置において使用されるセパレータとしては、いずれも不十分な性能であることが明らかとなった。 From the above three types of test results, the separator for electronic parts of the present invention satisfies all the characteristics, whereas the separator for comparison does not satisfy all the characteristics, and is in a relatively high temperature range. However, it has become clear that all of the separators used in electrochemical devices that should maintain performance are insufficient.
Claims (16)
The method for producing an electrophotographic separator according to any one of claims 10 to 12, wherein the amount of water contained in the paint is 0.7 wt% or less as measured by the Karl Fischer method.
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| JP2004112702A JP4974448B2 (en) | 2004-04-07 | 2004-04-07 | Manufacturing method of separator for electronic parts |
| US11/081,396 US20050208383A1 (en) | 2004-03-19 | 2005-03-16 | Electronic component separator and method for producing the same |
| KR1020050021791A KR100699215B1 (en) | 2004-03-19 | 2005-03-16 | Separator for electric component and method for producing the same |
| CNB2005100557143A CN100514711C (en) | 2004-03-19 | 2005-03-18 | Electronic component separator and method for producing the same |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001067536A1 (en) * | 2000-03-07 | 2001-09-13 | Teijin Limited | Lithium ion secondary cell, separator, cell pack, and charging method |
| JP2003007279A (en) * | 2001-06-21 | 2003-01-10 | Teijin Ltd | Separator for nonaqueous system secondary battery, and the nonaqueous system secondary battery |
| JP2004506542A (en) * | 2000-08-12 | 2004-03-04 | エルジー・ケミカル・カンパニー・リミテッド | Multi-component composite film and method for producing the same |
-
2004
- 2004-04-07 JP JP2004112702A patent/JP4974448B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001067536A1 (en) * | 2000-03-07 | 2001-09-13 | Teijin Limited | Lithium ion secondary cell, separator, cell pack, and charging method |
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| JP2003007279A (en) * | 2001-06-21 | 2003-01-10 | Teijin Ltd | Separator for nonaqueous system secondary battery, and the nonaqueous system secondary battery |
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