JP2000212324A5 - - Google Patents
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- JP2000212324A5 JP2000212324A5 JP1999014373A JP1437399A JP2000212324A5 JP 2000212324 A5 JP2000212324 A5 JP 2000212324A5 JP 1999014373 A JP1999014373 A JP 1999014373A JP 1437399 A JP1437399 A JP 1437399A JP 2000212324 A5 JP2000212324 A5 JP 2000212324A5
- Authority
- JP
- Japan
- Prior art keywords
- microporous membrane
- polyolefin
- lyophilic
- sulfonate
- surfactant
- 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.)
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- 239000012528 membrane Substances 0.000 description 25
- 229920000098 polyolefin Polymers 0.000 description 16
- -1 alkylphenyl sulfonate Chemical compound 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- 239000002563 ionic surfactant Substances 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 6
- 239000002736 nonionic surfactant Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- WVJHONXZLYKXFP-UHFFFAOYSA-N 2-amino-6-methylbenzenesulfonic acid Chemical compound CC1=CC=CC(N)=C1S(O)(=O)=O WVJHONXZLYKXFP-UHFFFAOYSA-N 0.000 description 2
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000002085 persistent Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- CQVPPLWYIDMWDA-UHFFFAOYSA-N OS(=O)(=O)c1ccccc1.CCCCCCCCCCCC[Na] Chemical compound OS(=O)(=O)c1ccccc1.CCCCCCCCCCCC[Na] CQVPPLWYIDMWDA-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001451 Polypropylene glycol Polymers 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000004432 carbon atoms Chemical group C* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
Description
【特許請求の範囲】
【請求項１】 重量平均分子量５０万以上のポリオレフィン又は当該ポリオレフィンを含むポリオレフィン組成物からなるポリオレフィン微多孔膜を、スルホン酸型イオン性界面活性剤及び重量平均分子量１５００以上のポリエーテル系非イオン性界面活性剤の２種類の界面活性剤で処理し、かつ微多孔膜の含水量が絶乾時の膜の２重量％以下であることを特徴とする親液性微多孔膜。
【請求項２】 前記スルホン酸型イオン性界面活性剤が、アミノトルエンスルホン酸、グリコールエーテルスルホン酸塩、アルキルフェニルスルホン酸塩、アルキルジフェニルスルホン酸塩、アルキルビニルスルホン酸塩、ポリオキシエチレンノニルフェニルスルホン酸塩、アルキルアリルスルホン酸塩、アルキルナフタレンスルホン酸塩等のいずれかから少なくとも１種類選ばれたものであることを特徴とする請求項１記載の親液性微多孔膜。
【請求項３】 前記重量平均分子量が１５００以上のポリエーテル系非イオン性界面活性剤が、重量平均分子量が１５００以上のポリエチレングリコール、ポリプロピレングリコール、ポリアクリレート、ポリメタクリレート、ポリアニリン、ポリピロール、ポリアセチレン、ポリアクリロニトリルのいずれかから少なくとも１種類選ばれたものであることを特徴とする請求項１記載の親液性微多孔膜。
【請求項４】 重量平均分子量５０万以上のポリオレフィン又は当該ポリオレフィンを含むポリオレフィン組成物からなるポリオレフィン微多孔膜をスルホン酸型イオン性界面活性剤及び重量平均分子量１５００以上のポリエーテル系非イオン性界面活性剤のとを溶解させた溶液と接触させた後、微多孔膜の含水量が絶乾時の膜の２重量％以下になるように乾燥又は熱処理することを特徴とする親液性微多孔膜の製造方法。
【請求項５】 請求項１ないし３いずれかに記載の親液性微多孔膜を用いた電池セパレータ。
【請求項６】 請求項１ないし３いずれかに記載の親液性微多孔膜を電池セパレータとして用いた電池。
【請求項７】 請求項１ないし３いずれかに記載の親液性微多孔膜を用いたフィルター。
[Claims]
1. A polyolefin microporous membrane comprising a polyolefin having a weight average molecular weight of 500,000 or more or a polyolefin composition containing the polyolefin,acidTreated with two types of surfactants, i.e., an ionic surfactant and a polyether-based nonionic surfactant having a weight average molecular weight of 1500 or more, and the water content of the microporous membrane is 2% by weight of the membrane when completely dried. A lyophilic microporous membrane characterized by the following.
(2) The sulfonic acid type ionic surfactants include aminotoluenesulfonic acid, glycol ether sulfonate, alkylphenyl sulfonate, alkyl diphenyl sulfonate, alkyl vinyl sulfonate, polyoxyethylene nonylphenyl sulfonate, alkyl 2. The lyophilic microporous membrane according to claim 1, wherein the membrane is at least one selected from the group consisting of an allyl sulfonate and an alkylnaphthalene sulfonate.
(3) The polyether-based nonionic surfactant having a weight average molecular weight of 1500 or more is selected from polyethylene glycol, polypropylene glycol, polyacrylate, polymethacrylate, polyaniline, polypyrrole, polyacetylene, and polyacrylonitrile having a weight average molecular weight of 1500 or more. The lyophilic microporous membrane according to claim 1, wherein at least one kind is selected.
Claims4A polyolefin microporous membrane comprising a polyolefin having a weight average molecular weight of 500,000 or more or a polyolefin composition containing the polyolefin is sulfone-coated.acidAfter contact with a solution in which a water-soluble ionic surfactant and a polyether-based nonionic surfactant having a weight-average molecular weight of 1500 or more are dissolved, the water content of the microporous membrane is 2% of the membrane when absolutely dry % Or less, and drying or heat-treating the lyophilic microporous membrane.
Claims5Claim 1Or one of threeA battery separator using the lyophilic microporous membrane according to the above.
Claims6Claim 1Or one of threeA battery using the lyophilic microporous membrane as described above as a battery separator.
Claims7Claim 1Or one of threeA filter using the lyophilic microporous membrane according to the above.
【０００５】
【課題を解決するための手段】
本発明者らは、上記課題を達成すべく鋭意研究を行った結果、特定の分子量を持つポリオレフィンから得られた微多孔膜を特定の２種類の界面活性剤で処理し、さらに膜の含水量を特定量以下にすることにより、即効性・持続性を併せ持つ電解液等への浸透性のよい親液性微多孔膜が得られることを見出し、本発明を完成した。すなわち、本発明は、重量平均分子量５０万以上のポリオレフィン又は当該ポリオレフィンを含むポリオレフィン組成物からなるポリオレフィン微多孔膜を、スルホン酸型イオン性界面活性剤及び重量平均分子量１５００以上のポリエーテル系非イオン性界面活性剤の２種類の界面活性剤で処理し、かつ微多孔膜の含水量が絶乾時の膜の２重量％以下であることを特徴とする親液性微多孔膜であり、またその製造方法である。
[0005]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above object, and as a result, treated a microporous membrane obtained from a polyolefin having a specific molecular weight with two specific surfactants, and further treated the water content of the membrane. It has been found that, by setting the content of the lipophilic substance to a specific amount or less, a lyophilic microporous membrane having both immediate effect and durability and good permeability to an electrolytic solution or the like can be obtained, and completed the present invention. That is, the present invention provides a polyolefin microporous membrane comprising a polyolefin having a weight average molecular weight of 500,000 or more or a polyolefin composition containing the polyolefin, a sulfonic acid type ionic surfactant and a polyether nonionic having a weight average molecular weight of 1500 or more. A lyophilic microporous membrane characterized in that it is treated with two kinds of surfactants, and the water content of the microporous membrane is not more than 2% by weight of the membrane at the time of absolute drying; The manufacturing method.
２．界面活性剤処理
本発明の親液性微多孔膜は、上記で得られたポリオレフィン微多孔膜を２種類の界面活性剤で処理し、乾燥して得られる。
（１）界面活性剤
ポリオレフィン微多孔膜の処理に用いる界面活性剤は、即効性を有するスルホン酸型イオン性界面活性剤と持続性を有するポリエーテル型非イオン性界面活性剤の双方を使用しなければならない。スルホン酸型イオン性界面活性剤だけでは、電池セパレータとして使用した時に、電解液との濡れ性に劣り、また、ポリエーテル型非イオン性界面活性剤だけでは、電解液の濡れ性に劣るため、双方の界面活性剤の使用が必須である。
2. Surfactant treatment The lyophilic microporous membrane of the present invention is obtained by treating the polyolefin microporous membrane obtained above with two kinds of surfactants and drying.
(1) Surfactant As the surfactant used for treating the polyolefin microporous membrane, both a sulfonic acid type ionic surfactant having an immediate effect and a polyether type nonionic surfactant having a persistent effect are used. There must be. The sulfonic acid type ionic surfactant alone has poor wettability with the electrolytic solution when used as a battery separator, and the polyether type nonionic surfactant alone has poor wettability of the electrolytic solution. The use of both surfactants is essential.
本発明で用いるスルホン酸型イオン性界面活性剤としては、アミノトルエンスルホン酸、グリコールエーテルスルホン酸塩、アルキルフェニルスルホン酸塩、アルキルジフェニルスルホン酸塩、アルキルビニルスルホン酸塩、ポリオキシエチレンノニルフェニルスルホン酸塩、アルキルアリルスルホン酸塩、アルキルナフタレンスルホン酸塩等が挙げられ、中でもでアルキル基の炭素数が８〜１３であり、かつ塩がアルカリ金属であるアルキルフェニルスルホン酸塩が好ましく、特にドデシルベンゼンスルホン酸ナトリウム等が好ましい。 Examples of the sulfonic acid type ionic surfactant used in the present invention include aminotoluenesulfonic acid, glycol ether sulfonate, alkylphenyl sulfonate, alkyl diphenyl sulfonate, alkyl vinyl sulfonate, and polyoxyethylene nonylphenyl sulfonate. Acid salts, alkyl allyl sulfonates, alkyl naphthalene sulfonates, etc., among which alkyl phenyl sulfonates in which the alkyl group has 8 to 13 carbon atoms and the salt is an alkali metal are preferred, and especially dodecyl Sodium benzenesulfonate and the like are preferred.
【００４７】
【発明の効果】
本発明の親液性微多孔膜は、特定な特性を持つポリオレフィン微多孔膜に即効性の処理剤であるスルホン酸型イオン系界面活性剤と持続性の処理剤であるポリエーテル系非イオン性界面活性剤を一定比率で混合し塗布することにより、即効性・持続性を併せ持つ電解液への浸透性の良い膜であり、電池セパレータ、フィルター等に用いることができる。特に有機系電解液の電池セパレータの場合は、アセンブリでの電解液浸透が早く生産速度が向上し、かつ残留水分が少ないため、劣化が少なく、ポリマー電池セパレータとして用いることができる。
[0047]
【The invention's effect】
The lyophilic microporous membrane of the present invention is a sulfonic acid type ionic surfactant which is a quick-acting agent for a polyolefin microporous film having specific properties, and a polyether-based nonionic which is a persistent agent. more to mixing a surfactant to scale coating, a permeable film of good to electrolyte having both fast-acting and sustainability, it is possible to use battery separators, filter or the like. In particular, in the case of a battery separator of an organic electrolyte solution, the electrolyte solution permeates quickly in the assembly, the production rate is improved, and the residual moisture is small, so that the battery separator is less deteriorated and can be used as a polymer battery separator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11014373A JP2000212324A (en) | 1999-01-22 | 1999-01-22 | Lypophilic finely porous membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11014373A JP2000212324A (en) | 1999-01-22 | 1999-01-22 | Lypophilic finely porous membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000212324A JP2000212324A (en) | 2000-08-02 |
| JP2000212324A5 true JP2000212324A5 (en) | 2006-02-23 |
Family
ID=11859258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11014373A Pending JP2000212324A (en) | 1999-01-22 | 1999-01-22 | Lypophilic finely porous membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000212324A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4781499B2 (en) * | 2000-01-28 | 2011-09-28 | 日東電工株式会社 | Manufacturing method of battery separator |
| JP4846911B2 (en) * | 2001-02-08 | 2011-12-28 | 東レ東燃機能膜合同会社 | Extractant composition for thermoplastic resin porous molded body, and method for producing thermoplastic resin porous molded body |
| JP4711319B2 (en) * | 2001-02-13 | 2011-06-29 | 日立マクセル株式会社 | Non-aqueous secondary battery |
| KR20090050686A (en) * | 2007-11-16 | 2009-05-20 | 에스케이에너지 주식회사 | Microporous polyethylene film with improved strength, permeability and surface energy |
| JP2010100845A (en) * | 2008-09-29 | 2010-05-06 | Toray Ind Inc | Method for producing porous polyolefin film |
| WO2013047600A1 (en) * | 2011-09-26 | 2013-04-04 | 旭化成イーマテリアルズ株式会社 | Microporous membrane |
-
1999
- 1999-01-22 JP JP11014373A patent/JP2000212324A/en active Pending
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