JP5511214B2 - Multilayer porous membrane - Google Patents
Multilayer porous membrane Download PDFInfo
- Publication number
- JP5511214B2 JP5511214B2 JP2009090754A JP2009090754A JP5511214B2 JP 5511214 B2 JP5511214 B2 JP 5511214B2 JP 2009090754 A JP2009090754 A JP 2009090754A JP 2009090754 A JP2009090754 A JP 2009090754A JP 5511214 B2 JP5511214 B2 JP 5511214B2
- Authority
- JP
- Japan
- Prior art keywords
- porous membrane
- less
- multilayer porous
- polyolefin resin
- multilayer
- 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 title claims description 120
- 229920005672 polyolefin resin Polymers 0.000 claims description 68
- 239000011256 inorganic filler Substances 0.000 claims description 38
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 38
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- 239000011347 resin Substances 0.000 claims description 27
- -1 polypropylene Polymers 0.000 claims description 25
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- 239000002245 particle Substances 0.000 claims description 15
- 239000004743 Polypropylene Substances 0.000 claims description 12
- 229920001155 polypropylene Polymers 0.000 claims description 12
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 150000004678 hydrides Chemical class 0.000 claims description 9
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
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- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
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- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Secondary Cells (AREA)
- Laminated Bodies (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Cell Separators (AREA)
Description
本発明は、多層多孔膜に関する。 The present invention relates to a multilayer porous membrane.
ポリオレフィン樹脂多孔膜は優れた電気絶縁性、イオン透過性を示すことから電池やコンデンサー等におけるセパレータとして広く利用されている。特に近年では携帯機器の多機能化、軽量化に伴いその電源として高出力密度、高容量密度のリチウムイオン二次電池が使用されており、このような電池用セパレータにも主としてポリオレフィン樹脂多孔膜が用いられている。
近年、リチウムイオン二次電池は、携帯電話、ノート型パーソナルコンピュータなどの小型機器用電源として用いられている。この電池に用いられるセパレータには、イオン透過性に優れることが要求される。また、電池の安全性を確保するために、電池が１３０〜１５０℃程度まで過熱された際にシャットダウンできることもセパレータに要求される。ここで、「シャットダウン」とは、電池内の温度が上昇した際に、多孔膜を構成するポリマーの溶融によってその連通孔が閉塞し、膜の電気抵抗が増大してリチウムイオンの流れが遮断される現象である。
Polyolefin resin porous membranes are widely used as separators in batteries, capacitors and the like because they exhibit excellent electrical insulation and ion permeability. In recent years, lithium ion secondary batteries with a high output density and a high capacity density have been used as power sources in recent years with the increase in functionality and weight of portable devices. Polyolefin resin porous membranes are mainly used for such battery separators. It is used.
In recent years, lithium ion secondary batteries have been used as power sources for small devices such as mobile phones and notebook personal computers. The separator used for this battery is required to have excellent ion permeability. Moreover, in order to ensure the safety | security of a battery, it is requested | required of a separator that it can shut down when a battery is overheated to about 130-150 degreeC. Here, “shutdown” means that when the temperature in the battery rises, the communication hole is blocked by melting of the polymer constituting the porous film, the electric resistance of the film is increased, and the flow of lithium ions is blocked. It is a phenomenon.
そして、これらの要求を満足するために、セパレータとしてはポリオレフィンを主成分とする多孔膜が主に採用されている。
一方、リチウムイオン二次電池は高い出力密度、容量密度を持つ反面、電解液に有機溶媒を用いているために短絡や過充電などの異常事態に伴う発熱によって電解液が分解し、最悪の場合には発火に至ることがある。高いエネルギーを有する電池においては熱暴走時の発熱量が大きく、シャットダウン温度を超えても温度が上昇し続けた場合、セパレータの破膜（「ショート」と表記することがある）により両極が短絡し、さらなる発熱を引き起こす危険性がある。
In order to satisfy these requirements, a porous film mainly composed of polyolefin is mainly employed as the separator.
On the other hand, lithium-ion secondary batteries have high output density and capacity density, but the use of organic solvents in the electrolyte causes the electrolyte to decompose due to heat generation due to abnormal situations such as short-circuiting and overcharging. May lead to fire. In a battery with high energy, the amount of heat generated during thermal runaway is large, and if the temperature continues to rise even if the shutdown temperature is exceeded, both electrodes are short-circuited due to a separator film (sometimes referred to as “short”). Risk of causing further fever.
このような問題を解決するために、セパレータと電極の間に絶縁性無機フィラーを主成分とする層を形成する方法等が提案されている（特許文献１〜７）。 In order to solve such a problem, a method of forming a layer mainly composed of an insulating inorganic filler between a separator and an electrode has been proposed (Patent Documents 1 to 7).
しかしながら、良好な耐熱性（耐ショート性）と良好なイオン透過性とを両立するセパレータを実現する観点からは、なお改良の余地があった。
本発明は、良好な耐熱性と良好なイオン透過性とを両立する多層多孔膜を提供することを目的とする。
However, there is still room for improvement from the viewpoint of realizing a separator that has both good heat resistance (short-circuit resistance) and good ion permeability.
An object of the present invention is to provide a multilayer porous membrane that has both good heat resistance and good ion permeability.
本発明者は、前記課題を解決するため鋭意検討した結果、本発明に到達した。すなわち、本発明は下記の通りである。
［１］ポリオレフィン樹脂多孔膜の少なくとも片面に無機フィラーと樹脂製バインダとを含む多孔層を備え、
前記ポリオレフィン樹脂多孔膜の膜厚が０．１μｍ以上１５μｍ以下、
平均孔径が０．０４μｍ以上０．１μｍ以下、
熱収縮応力の最大値が、ＭＤ、ＴＤ共に８ｇ以下、
前記多孔層のＲ値が０．０１ｇ／ｍ2以上０．５２ｇ／ｍ2以下、
前記多孔層の層厚が２μｍ以上７μｍ以下、
前記無機フィラーの平均粒径が０．１μｍ以上１．５μｍ以下、
前記樹脂製バインダがスチレン−ブタジエン共重合体及びその水素化物、アクリロニトリル−ブタジエン共重合体及びその水素化物、アクリロニトリル−ブタジエン−スチレン共重合体及びその水素化物、メタクリル酸エステル−アクリル酸エステル共重合体、スチレン−アクリル酸エステル共重合体、アクリロニトリル−アクリル酸エステル共重合体、エチレンプロピレンラバー、ポリビニルアルコール、ポリ酢酸ビニルからなる群から選ばれる少なくとも１種
である多層多孔膜。
［２］前記ポリオレフィン樹脂中の総ポリオレフィンに対するポリプロピレンの割合が、１〜３５質量％である［１］に記載の多層多孔膜。
［３］多層多孔膜の膜厚が５μｍ以上１９μｍ以下である［１］又は［２］に記載の多層多孔膜。
［４］ポリオレフィン樹脂多孔膜の熱収縮応力の最大値がＭＤ、ＴＤ共に６ｇ以下である［１］〜［３］のいずれかに記載の多層多孔膜。
［５］前記多層多孔膜の１５０℃での熱収縮率が長さ方向（ＭＤ）、幅方向（ＴＤ）共に１５％以下である［１］〜［４］のいずれかに記載の多層多孔膜。
［６］前記ポリオレフィン樹脂多孔膜のＭＤ熱収縮最大応力と、ＴＤ熱収縮最大応力との比が０．５以上３．０以下である［１］〜［５］のいずれかに記載の多層多孔膜。
［７］前記無機フィラーがアルミニウム酸化物である［１］〜［６］のいずれかに記載
の多層多孔膜。
［８］前記無機フィラーが層状ケイ酸塩鉱物である［１］〜［６］のいずれかに記載の多層多孔膜。
［９］前記多孔層の層厚が、多層多孔膜の膜厚に占める割合が７０％以下である［１］〜［８］のいずれかに記載の多層多孔膜。
［１０］［１］〜［９］のいずれかに記載の多層多孔膜を用いた捲回体。
［１１］［１］〜［９］のいずれかに記載の多層多孔膜を用いた非水電解液電池用セパレータ。
［１２］［１１］に記載の電池用セパレータと、正極と、負極と、電解液とを用いた非水電解液電池。
The inventor of the present invention has arrived at the present invention as a result of intensive studies to solve the above-mentioned problems. That is, the present invention is as follows.
[1] A porous layer containing an inorganic filler and a resin binder on at least one surface of a polyolefin resin porous membrane,
The polyolefin resin porous membrane has a thickness of 0.1 μm or more and 15 μm or less,
The average pore diameter is 0.04 μm or more and 0.1 μm or less ,
The maximum value of heat shrinkage stress is 8 g or less for both MD and TD.
The R value of the porous layer is 0.01 g / m 2 or more and 0.0. 52 g / m 2 or less ,
The layer thickness of the porous layer is 2 μm or more and 7 μm or less,
The average particle size of the inorganic filler is 0.1 μm or more and 1.5 μm or less,
The resin binder is a styrene-butadiene copolymer and its hydride, acrylonitrile-butadiene copolymer and its hydride, acrylonitrile-butadiene-styrene copolymer and its hydride, methacrylic acid ester-acrylic acid ester copolymer A multilayer porous membrane that is at least one selected from the group consisting of styrene-acrylic acid ester copolymer, acrylonitrile-acrylic acid ester copolymer, ethylene propylene rubber, polyvinyl alcohol, and polyvinyl acetate.
[2] The multilayer porous membrane according to [1], wherein the ratio of polypropylene to the total polyolefin in the polyolefin resin is 1 to 35% by mass.
[ 3 ] The multilayer porous membrane according to [1] or [2], wherein the multilayer porous membrane has a thickness of 5 μm or more and 19 μm or less.
[ 4 ] The multilayer porous membrane according to any one of [1] to [3], wherein the maximum value of heat shrinkage stress of the polyolefin resin porous membrane is 6 g or less for both MD and TD .
[ 5 ] The multilayer porous membrane according to any one of [1] to [4], wherein the thermal shrinkage rate at 150 ° C. of the multilayer porous membrane is 15% or less in both the length direction (MD) and the width direction (TD). .
[ 6 ] The multilayer porous material according to any one of [1] to [ 5 ], wherein the ratio of the maximum MD thermal shrinkage stress and the maximum TD thermal shrinkage stress of the polyolefin resin porous membrane is 0.5 or more and 3.0 or less. film.
[ 7 ] The multilayer porous membrane according to any one of [1] to [ 6 ], wherein the inorganic filler is an aluminum oxide .
[ 8 ] The multilayer porous membrane according to any one of [1] to [ 6 ], wherein the inorganic filler is a layered silicate mineral .
[ 9 ] The multilayer porous membrane according to any one of [1] to [ 8 ], wherein the thickness of the porous layer accounts for 70% or less of the thickness of the multilayer porous membrane.
[ 10 ] A wound body using the multilayer porous membrane according to any one of [1] to [ 9 ].
[ 11 ] A separator for a non-aqueous electrolyte battery using the multilayer porous membrane according to any one of [1] to [ 9 ].
[ 12 ] A nonaqueous electrolyte battery using the battery separator according to [ 11 ], a positive electrode, a negative electrode, and an electrolytic solution.
本発明によれば、良好な耐熱性と良好なイオン透過性とを両立する多層多孔膜が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the multilayer porous membrane which balances favorable heat resistance and favorable ion permeability is provided.
以下、本発明を実施するための最良の形態（以下、「実施形態」と略記する。）について詳細に説明する。尚、本発明は、以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。
本実施形態の多層多孔膜は、ポリオレフィン樹脂多孔膜の少なくとも片面に無機フィラーと樹脂製バインダとを含む多孔層を備え、前記ポリオレフィン樹脂多孔膜の膜厚が０．１μｍ以上１５μｍ以下、平均孔径が０．０４μｍ以上０．１μｍ以下であり、前記多孔層のＲ値が０．０１ｇ／ｍ２以上０．６ｇ／ｍ２以下であることを特徴とする。
なお、「Ｒ値」とは、後述する方法で測定された、単位面積当たりに積層された多孔層重量（いわゆる「目付け」）の最大値と最小値の差である。
Hereinafter, the best mode for carrying out the present invention (hereinafter abbreviated as “embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
The multilayer porous membrane of this embodiment comprises a porous layer containing an inorganic filler and a resin binder on at least one surface of a polyolefin resin porous membrane, the polyolefin resin porous membrane has a thickness of 0.1 μm to 15 μm, and an average pore size. It is 0.04 μm or more and 0.1 μm or less, and the R value of the porous layer is 0.01 g / m 2 or more and 0.6 g / m 2 or less.
The “R value” is a difference between the maximum value and the minimum value of the weight of the porous layer laminated per unit area (so-called “weight per unit area”) measured by a method described later.
［ポリオレフィン樹脂多孔膜］
前記ポリオレフィン樹脂多孔膜は、電池用セパレータとして用いた場合のシャットダウン性能などの観点から、ポリオレフィン樹脂を５０質量％以上、好ましくは７０〜１００質量％含むポリオレフィン樹脂組成物にて形成される。なお本実施形態においては、ポリオレフィン樹脂が１００質量％である場合にも便宜上、ポリオレフィン樹脂組成物と記載する。
[Polyolefin resin porous membrane]
The polyolefin resin porous membrane is formed of a polyolefin resin composition containing 50% by mass or more, preferably 70 to 100% by mass of a polyolefin resin, from the viewpoint of shutdown performance when used as a battery separator. In this embodiment, even when the polyolefin resin is 100% by mass, it is described as a polyolefin resin composition for convenience.
ポリオレフィン樹脂とは、通常の押出、射出、インフレーション、及びブロー成形等に使用するポリオレフィン樹脂をいい、エチレン、プロピレン、１-ブテン、４-メチル-１-ペンテン、１−ヘキセン、及び１-オクテン等のホモ重合体及び共重合体、多段重合体等を使用することができる。また、これらのホモ重合体及び共重合体、多段重合体の群から選んだポリオレフィンを単独、もしくは混合して使用することもできる。前記重合体の代表例としては、低密度ポリエチレン、線状低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、超高分子量ポリエチレン、アイソタクティックポリプロピレン、アタクティックポリプロピレン、エチレン−プロピレンランダム共重合体、ポリブテン、エチレンプロピレンラバー等が挙げられる。 Polyolefin resin refers to polyolefin resin used for normal extrusion, injection, inflation, blow molding, etc., such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. Homopolymers and copolymers, multistage polymers, and the like can be used. In addition, polyolefins selected from the group of these homopolymers, copolymers, and multistage polymers can be used alone or in combination. Representative examples of the polymer include low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ultrahigh molecular weight polyethylene, isotactic polypropylene, atactic polypropylene, ethylene-propylene random copolymer, polybutene. And ethylene propylene rubber.
ポリオレフィン樹脂には耐熱性向上の観点からポリプロピレンを含有させることが好ましい。ポリプロピレン含有量が大きいほど多孔膜の耐熱性は高まる傾向にあるが、ポロプロピレン含有量が数質量％程度でも十分な耐熱性向上効果がある。一方、本実施形態の多層多孔膜を電池用セパレータとして使用する場合、シャットダウン温度において膜が熱溶融して多孔が閉塞することが求められる。ポリプロピレンは比較的高い融点を有するが、ポリプロピレン含有量を一定量以下とすることは、シャットダウンを適切に生じさせること、又は、より低い温度でシャットダウンを生じさせる観点から好ましい。
したがって、耐熱性と良好なシャットダウン機能の両立の観点から、ポリオレフィン樹脂中の総ポリオレフィンに対するポリプロピレンの割合は、１〜３５質量％であることが好ましく、より好ましくは３〜２０質量％、さらに好ましくは４〜１０質量％である。
The polyolefin resin preferably contains polypropylene from the viewpoint of improving heat resistance. Although the heat resistance of the porous film tends to increase as the polypropylene content increases, there is a sufficient heat resistance improvement effect even if the polypropylene content is about several mass%. On the other hand, when the multilayer porous membrane of this embodiment is used as a battery separator, it is required that the membrane is thermally melted at the shutdown temperature to close the pores. Polypropylene has a relatively high melting point, but the polypropylene content is preferably not more than a certain amount from the viewpoint of appropriately causing shutdown or causing shutdown at a lower temperature.
Therefore, from the viewpoint of achieving both heat resistance and a good shutdown function, the ratio of polypropylene to the total polyolefin in the polyolefin resin is preferably 1 to 35% by mass, more preferably 3 to 20% by mass, and still more preferably. It is 4-10 mass%.
ポリオレフィン樹脂の粘度平均分子量（Ｍｖ）としては、５万〜３００万であることが好ましい。このＭｖは、得られる多孔膜の機械的強度を高める観点から５万以上であることが好ましく、生産時の成形性を良好にする観点から３００万以下であることが好ましい。同様の観点から、Ｍｖは１０万〜１００万であるとより好ましく、２０万〜８０万であると更に好ましい。また、多孔膜の機械的強度を制御するために、Ｍｖの異なるポリオレフィンを２種以上混合したものを用いてもよい。さらに、Ｍｖが１００万未満であれば、電池用セパレータとして使用した場合に、温度上昇時に孔を閉塞しやすく良好なシャットダウン機能が得られやすいので好ましい。 The viscosity average molecular weight (Mv) of the polyolefin resin is preferably 50,000 to 3,000,000. The Mv is preferably 50,000 or more from the viewpoint of increasing the mechanical strength of the resulting porous film, and preferably 3 million or less from the viewpoint of improving the moldability during production. From the same viewpoint, Mv is more preferably 100,000 to 1,000,000, and further preferably 200,000 to 800,000. Moreover, in order to control the mechanical strength of the porous membrane, a mixture of two or more polyolefins having different Mvs may be used. Furthermore, if Mv is less than 1,000,000, it is preferable that when used as a battery separator, it is easy to close the hole when the temperature rises and a good shutdown function is easily obtained.
なお、前記ポリオレフィン樹脂組成物には、本実施形態の利点を損なわない範囲で必要に応じて、フェノール系やリン系やイオウ系等の酸化防止剤、ステアリン酸カルシウムやステアリン酸亜鉛等の金属石鹸類、紫外線吸収剤、光安定剤、帯電防止剤、防曇剤、着色顔料等の添加剤を混合して使用できる。
前記ポリオレフィン樹脂多孔膜の膜厚としては、０．１μｍ以上１５μｍ以下が好ましく、より好ましくは１μｍ以上１４μｍ以下、さらに好ましくは３μｍ以上１３μｍ以下、最も好ましくは５μｍ以上１３μｍ以下である。得られる多層多孔膜の機械的強度の観点から０．１μｍ以上が好ましく、後述の無機フィラー含有樹脂溶液塗布量のばらつき抑制及び電池の高容量化の観点から１５μｍ以下が好ましい。１５μｍ以下の膜厚のポリオレフィン樹脂多孔膜を用いることは、無機フィラー含有樹脂溶液塗布時の張力を低減でき、塗布量のばらつき及び得られる多層多孔膜の反りを抑制できる観点から好ましい。
The polyolefin resin composition includes, as necessary, antioxidants such as phenolic, phosphorous, and sulfur-based agents, and metal soaps such as calcium stearate and zinc stearate within a range that does not impair the advantages of the present embodiment. In addition, additives such as ultraviolet absorbers, light stabilizers, antistatic agents, antifogging agents, and coloring pigments can be mixed and used.
The thickness of the polyolefin resin porous membrane is preferably from 0.1 μm to 15 μm, more preferably from 1 μm to 14 μm, still more preferably from 3 μm to 13 μm, and most preferably from 5 μm to 13 μm. From the viewpoint of mechanical strength of the obtained multilayer porous membrane, 0.1 μm or more is preferable, and from the viewpoint of suppressing variation in the coating amount of the inorganic filler-containing resin solution described later and increasing the capacity of the battery, 15 μm or less is preferable. The use of a polyolefin resin porous film having a thickness of 15 μm or less is preferable from the viewpoint of reducing the tension during coating of the inorganic filler-containing resin solution, and suppressing variations in coating amount and warpage of the resulting multilayer porous film.
ポリオレフィン樹脂多孔膜の孔径としては、０．０４μｍ以上０．１μｍ以下が好ましく、より好ましくは０．０５μｍ以上０．０９μｍ以下、さらに好ましくは０．０６μｍ以上０．０９μｍ以下、最も好ましくは０．０７μｍ以上０．０９μｍ以下である。後述の無機フィラー含有樹脂溶液塗布後の透気度上昇抑制、及び塗布量のばらつき抑制の観点から０．０４μｍ以上０．１μｍ以下が好ましい。
ポリオレフィン樹脂多孔膜の気孔率としては、好ましくは２５％以上６０％以下、より好ましく３０％以上５５％以下、更に好ましくは３５％以上５０％以下である。後述の無機フィラー含有樹脂溶液塗布後の透気度上昇抑制の観点から２５％以上が好ましく、塗布量のばらつき抑制の観点から６０％以下が好ましい。
The pore diameter of the polyolefin resin porous membrane is preferably 0.04 μm or more and 0.1 μm or less, more preferably 0.05 μm or more and 0.09 μm or less, further preferably 0.06 μm or more and 0.09 μm or less, and most preferably 0.07 μm. It is 0.09 μm or less. From the viewpoints of suppressing an increase in air permeability after applying an inorganic filler-containing resin solution, which will be described later, and suppressing variations in coating amount, 0.04 to 0.1 μm is preferable.
The porosity of the polyolefin resin porous membrane is preferably 25% to 60%, more preferably 30% to 55%, and still more preferably 35% to 50%. 25% or more is preferable from the viewpoint of suppressing air permeability increase after application of the inorganic filler-containing resin solution described later, and 60% or less is preferable from the viewpoint of suppressing variation in coating amount.
ポリオレフィン樹脂多孔膜の熱収縮応力の最大値としては、ＭＤ、ＴＤ共に８ｇ以下であることが好ましく、より好ましくは６ｇ以下、更に好ましくは４ｇ以下、最も好ましくは３ｇ以下である。８ｇ以下のポリオレフィン樹脂多孔膜を採用することは、優れた耐熱性と透過性を同時に達成する観点から好ましい。
ポリオレフィン樹脂多孔膜の熱収縮応力のＭＤとＴＤの比としては、０．５以上３．０以下であることが好ましく、より好ましくは０．６以上２．５以下、更に好ましくは０．７以上２．０以下である。０．５以上３．０以下のポリオレフィン樹脂多孔膜を採用することは、ＭＤ方向、ＴＤ方向共に熱収縮率の小さい多層多孔膜を得る観点から好ましい。
なお、ポリオレフィン樹脂多孔膜の膜厚、孔径、気孔率、熱収縮応力の最大値、熱収縮応力のＭＤとＴＤの比については、延伸時の倍率や温度で調整する方法、熱固定時の倍率や温度で調整する方法、等により調整可能である。
The maximum value of the heat shrinkage stress of the polyolefin resin porous membrane is preferably 8 g or less for both MD and TD, more preferably 6 g or less, still more preferably 4 g or less, and most preferably 3 g or less. Adopting a polyolefin resin porous membrane of 8 g or less is preferable from the viewpoint of simultaneously achieving excellent heat resistance and permeability.
The ratio of MD and TD of the heat shrinkage stress of the polyolefin resin porous membrane is preferably 0.5 or more and 3.0 or less, more preferably 0.6 or more and 2.5 or less, and still more preferably 0.7 or more. 2.0 or less. Employing a polyolefin resin porous membrane of 0.5 or more and 3.0 or less is preferable from the viewpoint of obtaining a multilayer porous membrane having a small thermal shrinkage in both the MD direction and the TD direction.
The film thickness, pore diameter, porosity, maximum value of heat shrinkage stress, and the ratio of MD and TD of heat shrinkage stress are the method of adjusting by the magnification and temperature during stretching, and the magnification during heat fixation. It can be adjusted by a method of adjusting by temperature or temperature.
［多孔層］
前記多孔層は無機フィラーと樹脂製バインダとを含み、樹脂製バインダにより無機フィラーとポリオレフィン樹脂多孔膜及び／又は無機フィラー同士が結着された多孔構造である。
前記多孔層に含まれる無機フィラーとしては、２００℃以上の融点をもち、電気絶縁性が高く、かつリチウムイオン二次電池の使用範囲で電気化学的に安定であるものが好ましい。例えば、アルミナ、シリカ、チタニア、ジルコニア、マグネシア、セリア、イットリア、酸化亜鉛、酸化鉄などの酸化物系セラミックス、窒化ケイ素、窒化チタン、窒化ホウ素等の窒化物系セラミックス、シリコンカーバイド、炭酸カルシウム、硫酸アルミニウム、水酸化アルミニウム、チタン酸カリウム、タルク、カオリナイト、ディカイト、ナクライト、ハロイサイト、パイロフィライト、ハロイサイト、パイロフィライト、モンモリロナイト、セリサイト、マイカ、アメサイト、ベントナイト、アスベスト、ゼオライト、ケイ酸カルシウム、ケイ酸マグネシウム、ケイ藻土、ケイ砂等のセラミックス、ガラス繊維などが挙げられ、これらを単独で用いてもよいし、複数を混合して用いてもよい。
[Porous layer]
The porous layer includes an inorganic filler and a resin binder, and has a porous structure in which the inorganic filler is bonded to the polyolefin resin porous film and / or the inorganic filler by the resin binder.
The inorganic filler contained in the porous layer is preferably one having a melting point of 200 ° C. or higher, high electrical insulation, and electrochemically stable in the range of use of the lithium ion secondary battery. For example, oxide ceramics such as alumina, silica, titania, zirconia, magnesia, ceria, yttria, zinc oxide, iron oxide, nitride ceramics such as silicon nitride, titanium nitride, boron nitride, silicon carbide, calcium carbonate, sulfuric acid Aluminum, aluminum hydroxide, potassium titanate, talc, kaolinite, dickite, nacrite, halloysite, pyrophyllite, halloysite, pyrophyllite, montmorillonite, sericite, mica, amicite, bentonite, asbestos, zeolite, calcium silicate And ceramics such as magnesium silicate, diatomaceous earth, and silica sand, and glass fibers. These may be used alone or in combination.
無機フィラーとしては、中でも、多層多孔膜の耐熱性、透過性の観点から、カオリナイト、ディカイト、ナクライト、ハロイサイト、パイロフィライト、タルクなどの層状ケイ酸塩鉱物、アルミナなどのアルミニウム酸化物が好ましい。また、カオリナイト等のカオリン鉱物で主に構成されているカオリンには焼成カオリン、湿式カオリンがあるが、いずれも好ましく用いることができる。
前記無機フィラーの平均粒径としては、より薄い多孔層での耐熱性発現の観点から、好ましくは０．１μｍ以上１．５μｍ以下、より好ましくは０．２μｍ以上１．５μｍ、更に好ましくは０．２μｍ以上１．２μｍ以下である。
Among inorganic fillers, layered silicate minerals such as kaolinite, dickite, nacrite, halloysite, pyrophyllite, and talc, and aluminum oxides such as alumina are preferable from the viewpoint of heat resistance and permeability of the multilayer porous membrane. . The kaolin mainly composed of kaolin minerals such as kaolinite includes calcined kaolin and wet kaolin, both of which can be preferably used.
The average particle size of the inorganic filler is preferably 0.1 μm or more and 1.5 μm or less, more preferably 0.2 μm or more and 1.5 μm, and still more preferably 0.8 μm, from the viewpoint of heat resistance development in a thinner porous layer. It is 2 μm or more and 1.2 μm or less.
前記多孔層に含まれる樹脂製バインダとしては、無機フィラーを結着でき、リチウムイオン二次電池の電解液に対して不溶であり、かつリチウムイオン二次電池の使用範囲で電気化学的に安定であることが好ましい。
より具体的には、例えば、ポリエチレンやポリプロピレンなどのポリオレフィン、ポリフッ化ビニリデンやポリテトラフルオロエチレンなどの含フッ素樹脂、フッ化ビニリデン−ヘキサフルオロプロピレン−テトラフルオロエチレン共重合体やエチレン−テトラフルオロエチレン共重合体などの含フッ素ゴム、スチレン−ブタジエン共重合体及びその水素化物、アクリロニトリル−ブタジエン共重合体及びその水素化物、アクリロニトリル−ブタジエン−スチレン共重合体及びその水素化物、メタクリル酸エステル−アクリル酸エステル共重合体、スチレン−アクリル酸エステル共重合体、アクリロニトリル−アクリル酸エステル共重合体、エチレンプロピレンラバー、ポリビニルアルコール、ポリ酢酸ビニルなどのゴム類、ポリフェニレンエーテル、ポリスルホン、ポリエーテルスルホン、ポリフェニレンスルフィド、ポリエーテルイミド、ポリアミドイミド、ポリアミド、ポリエステルなどの融点及び／又はガラス転移温度が１８０℃以上の樹脂が挙げられる。
As the resin binder contained in the porous layer, an inorganic filler can be bound, it is insoluble in the electrolyte of the lithium ion secondary battery, and it is electrochemically stable within the range of use of the lithium ion secondary battery. Preferably there is.
More specifically, for example, polyolefins such as polyethylene and polypropylene, fluorine-containing resins such as polyvinylidene fluoride and polytetrafluoroethylene, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymers and ethylene-tetrafluoroethylene copolymers. Fluorine-containing rubber such as polymer, styrene-butadiene copolymer and its hydride, acrylonitrile-butadiene copolymer and its hydride, acrylonitrile-butadiene-styrene copolymer and its hydride, methacrylic acid ester-acrylic acid ester Copolymers, styrene-acrylic acid ester copolymers, acrylonitrile-acrylic acid ester copolymers, rubbers such as ethylene propylene rubber, polyvinyl alcohol, polyvinyl acetate, polyphenylene Ether, polysulfone, polyether sulfone, polyphenylene sulfide, polyetherimide, polyamideimide, polyamide, melting point and / or glass transition temperature of such polyesters are 180 ° C. or more resins.
なお、樹脂製バインダに使用するポリオレフィンの粘度平均分子量は、１０００以上１２００万未満が好ましく、より好ましくは２０００以上２００万未満、さらに好ましくは５０００以上１００万未満である。
前記樹脂製バインダが、前記無機フィラーと前記樹脂製バインダとの総量に占める割合としては、両者の結着性の点から、体積分率で好ましくは０．５％以上、より好ましくは０．７％以上、更に好ましくは１．２％以上であり、特に好ましくは１．５％以上であり、最も好ましくは１．７％以上であり、上限として好ましくは８％以下である。当該比率を０．５％以上とすることは、無機フィラーを十分に結着させ、剥離、欠落等が生じにくくする観点（良好な取り扱い性を十分に確保する観点）から好適である。一方、当該比率を８％以下とすることは、セパレータの良好なイオン透過性を実現する観点から好適である。
In addition, the viscosity average molecular weight of polyolefin used for the resin binder is preferably 1000 or more and less than 12 million, more preferably 2000 or more and less than 2 million, and still more preferably 5000 or more and less than 1 million.
The proportion of the resin binder in the total amount of the inorganic filler and the resin binder is preferably 0.5% or more, more preferably 0.7% in terms of volume fraction, from the viewpoint of the binding properties of both. % Or more, more preferably 1.2% or more, particularly preferably 1.5% or more, most preferably 1.7% or more, and the upper limit is preferably 8% or less. Setting the ratio to 0.5% or more is preferable from the viewpoint of sufficiently binding the inorganic filler and making it difficult to cause peeling, missing, and the like (to ensure sufficient handling properties). On the other hand, setting the ratio to 8% or less is preferable from the viewpoint of realizing good ion permeability of the separator.
前記多孔層の層厚は、耐熱性向上の点から０．５μｍ以上が好ましく、透過性や電池の高容量化の点から１０μｍ以下が好ましく、より好ましくは１μｍ以上９μｍ以下、更に好ましくは１．５μｍ以上８μｍ以下、最も好ましくは２μｍ以上７μｍ以下である。
また、前記無機フィラーが前記多孔層中に占める質量分率は、耐熱性の点から５０％以上１００％未満であることが好ましく、５５％以上９９．９９％以下であることがより好ましく、６０％以上９９．９％以下であることがさらに好ましく、６５％以上９９％以下であることが特に好ましい。
更に、前記多孔層の層厚が、多層多孔膜の膜厚に占める割合としては、多層多孔膜の反り防止の観点から、好ましくは７０％以下、より好ましくは５０％以下であり、耐熱性発現の観点から、下限として好ましくは５％以上、より好ましくは１０％以上である。
The thickness of the porous layer is preferably 0.5 μm or more from the viewpoint of improving heat resistance, preferably 10 μm or less, more preferably 1 μm or more and 9 μm or less, further preferably 1. It is 5 μm or more and 8 μm or less, and most preferably 2 μm or more and 7 μm or less.
The mass fraction of the inorganic filler in the porous layer is preferably 50% or more and less than 100%, more preferably 55% or more and 99.99% or less, from the viewpoint of heat resistance. % To 99.9%, more preferably 65% to 99%.
Furthermore, the ratio of the layer thickness of the porous layer to the film thickness of the multilayer porous membrane is preferably 70% or less, more preferably 50% or less, from the viewpoint of preventing warpage of the multilayer porous membrane. In view of the above, the lower limit is preferably 5% or more, more preferably 10% or more.
［多層多孔膜］
本実施形態の多層多孔膜は、ポリオレフィン樹脂多孔膜の少なくとも片面に無機フィラーと樹脂製バインダとを含む多孔層を備える多層構造を有する。
多孔層のＲ値としては、０．０１ｇ／ｍ２以上０．６ｇ／ｍ２であり、より好ましくは０．０１ｇ／ｍ２以上０．５５ｇ／ｍ２である。多層多孔膜の耐熱性、透過性のばらつき抑制の観点、多層多孔膜の反りや弛みの発生抑制の観点から、０．６ｇ／ｍ２以下が好ましい。なお、Ｒ値は前記無機フィラー種や粒径、多孔層の厚みによって異なるが、ポリオレフィン樹脂多孔膜の膜厚や孔径により制御することが可能である。
多層多孔膜の透気度は、自己放電性の点から１０秒／１００ｃｃ以上が好ましく、充放電特性の点から６５０秒／１００ｃｃ以下が好ましい。より好ましくは２０秒／１００ｃｃ以上５００秒／１００ｃｃ以下、更に好ましくは３０秒／１００ｃｃ以上４５０秒／１００ｃｃ以下、特に好ましくは５０秒／１００ｃｃ以上４００秒／１００ｃｃ以下の範囲である。
[Multilayer porous membrane]
The multilayer porous membrane of this embodiment has a multilayer structure including a porous layer containing an inorganic filler and a resin binder on at least one surface of a polyolefin resin porous membrane.
The R value of the porous layer is 0.01 g / m 2 or more and 0.6 g / m 2 , more preferably 0.01 g / m 2 or more and 0.55 g / m 2 . From the viewpoint of suppressing the heat resistance and permeability variation of the multilayer porous membrane and suppressing the occurrence of warpage and slack of the multilayer porous membrane, 0.6 g / m 2 or less is preferable. In addition, although R value changes with the said inorganic filler seed | species, a particle size, and the thickness of a porous layer, it is possible to control by the film thickness and pore diameter of a polyolefin resin porous membrane.
The air permeability of the multilayer porous membrane is preferably 10 seconds / 100 cc or more from the viewpoint of self-discharge, and preferably 650 seconds / 100 cc or less from the viewpoint of charge / discharge characteristics. More preferably, it is in the range of 20 seconds / 100 cc to 500 seconds / 100 cc, more preferably 30 seconds / 100 cc to 450 seconds / 100 cc, particularly preferably 50 seconds / 100 cc to 400 seconds / 100 cc.
なお、基材であるポリオレフィン樹脂多孔膜の透気度に対して、多孔層を形成した後の多層多孔膜の透気度の増加率としては、１００％以下であることが好ましく、７０％以下であることがより好ましく、５０％以下であることが特に好ましい。本実施形態の多層多孔膜を電池用セパレータとして使用する場合、透気度の増加によりイオン透過性が減少することから、１００％以下であることが好ましい。
多層多孔膜の最終的な膜厚は、機械強度の点から２μｍ以上が好ましく、電池の高容量化の点から２０μｍ以下の範囲が好ましい。より好ましくは５μｍ以上１９μｍ以下、さらに好ましくは８μｍ以上１８μｍ以下、最も好ましくは１０μｍ以上１７μｍ以下の範囲である。
The rate of increase in the air permeability of the multilayer porous film after forming the porous layer is preferably 100% or less, and preferably 70% or less with respect to the air permeability of the polyolefin resin porous film as the substrate. It is more preferable that it is 50% or less. When the multilayer porous membrane of this embodiment is used as a battery separator, it is preferably 100% or less because ion permeability decreases due to an increase in air permeability.
The final film thickness of the multilayer porous membrane is preferably 2 μm or more from the viewpoint of mechanical strength, and preferably 20 μm or less from the viewpoint of increasing the capacity of the battery. More preferably, it is 5 μm or more and 19 μm or less, more preferably 8 μm or more and 18 μm or less, and most preferably 10 μm or more and 17 μm or less.
多層多孔膜の１５０℃での熱収縮率は、ＭＤ、ＴＤ共に０％以上１５％以下であることが好ましく、０％以上１０％以下であることがより好ましく、０％以上５％以下であることが特に好ましい。ＭＤ方向、ＴＤ方向共に１５％以下であると電池の異常発熱時においてもセパレータの破膜を防ぐことが出来るので、正負極間の接触を抑制し得るため、より良好な安全性能が得られる傾向があるので好ましい。
多層多孔膜のシャットダウン温度は、１２０℃以上１６０℃以下が好ましく、より好ましくは１２０℃以上１５０℃以下の範囲である。１６０℃以下であると、電池が発熱した場合などにおいても、電流遮断を速やかに促進し、より良好な安全性能が得られる傾向にあるので好ましい。一方、１２０℃以上であると例えば１００℃前後での高温化の使用、熱処理等を実施できるので好ましい。
多層多孔膜のショート温度は、１８０℃以上が好ましく、１９０℃以上がより好ましく、最も好ましくは２００℃以上である。１８０℃以上であると電池異常発熱においても放熱するまで正負極間の接触を抑制し得るため、より良好な安全性能が得られる傾向があるので好ましい。
The thermal shrinkage rate at 150 ° C. of the multilayer porous membrane is preferably 0% or more and 15% or less for both MD and TD, more preferably 0% or more and 10% or less, and 0% or more and 5% or less. It is particularly preferred. When both the MD direction and the TD direction are 15% or less, it is possible to prevent the separator from being broken even when the battery is abnormally heated. Therefore, it is possible to suppress contact between the positive and negative electrodes, and thus better safety performance tends to be obtained. This is preferable.
The shutdown temperature of the multilayer porous membrane is preferably 120 ° C. or higher and 160 ° C. or lower, more preferably 120 ° C. or higher and 150 ° C. or lower. When the temperature is 160 ° C. or lower, even when the battery generates heat, current interruption is promptly promoted, and better safety performance tends to be obtained, which is preferable. On the other hand, it is preferable that the temperature is 120 ° C. or higher because, for example, use of a high temperature around 100 ° C., heat treatment, etc. can be performed.
The short-circuit temperature of the multilayer porous membrane is preferably 180 ° C. or higher, more preferably 190 ° C. or higher, and most preferably 200 ° C. or higher. When the temperature is 180 ° C. or higher, contact between the positive and negative electrodes can be suppressed until the heat is dissipated even in abnormal battery heat generation.
［多層多孔膜の製造方法］
本実施形態の多層多孔膜の製造方法については特に制限されないが、ポリオレフィン樹脂多孔膜を製造した後、その少なくとも片面に、無機フィラーと樹脂製バインダとを含有する分散液を塗布することによって製造することができる。
ポリオレフィン樹脂多孔膜の製造方法としては、例えば、ポリオレフィン樹脂と可塑剤とを溶融混練してシート状に成形後、可塑剤を抽出することで多孔化させる方法、ポリオレフィン樹脂を溶融混練して高ドロー比で押出した後、熱処理と延伸によってポリオレフィン結晶界面を剥離させることで多孔化させる方法、ポリオレフィン樹脂と無機充填材とを溶融混練してシート上に成形後、延伸によってポリオレフィン樹脂と無機充填材との界面を剥離させることで多孔化させる方法、ポリオレフィン樹脂を溶解後、ポリオレフィン樹脂に対する貧溶媒に浸漬させポリオレフィン樹脂を凝固させると同時に溶剤を除去することで多孔化させる方法など、公知の方法が挙げられる。
[Method for producing multilayer porous membrane]
The method for producing the multilayer porous membrane of the present embodiment is not particularly limited, but after producing a polyolefin resin porous membrane, it is produced by applying a dispersion containing an inorganic filler and a resin binder on at least one surface thereof. be able to.
As a method for producing a polyolefin resin porous membrane, for example, a method in which a polyolefin resin and a plasticizer are melt-kneaded and formed into a sheet shape and then made porous by extracting the plasticizer, and a polyolefin resin is melt-kneaded to obtain a high draw rate. After extruding at a ratio, the polyolefin crystal interface is peeled off by heat treatment and stretching, a polyolefin resin and an inorganic filler are melt-kneaded and molded on a sheet, and then stretched to form a polyolefin resin and an inorganic filler. Known methods such as a method of making the surface porous by peeling off the interface, a method of dissolving the polyolefin resin and then immersing it in a poor solvent for the polyolefin resin to solidify the polyolefin resin and simultaneously removing the solvent to make it porous It is done.
前記分散液は、前記無機フィラーと樹脂製バインダを溶媒に溶解又は分散させて形成される。
このような溶媒としては、例えば、Ｎ−メチルピロリドンやＮ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、水、エタノール、トルエン、熱キシレン、ヘキサンなどを挙げることができる。
また、無機フィラー含有樹脂溶液を安定化させるため、あるいはポリオレフィン樹脂多孔膜への塗工性を向上させるために、界面活性剤等の分散剤、増粘剤、湿潤剤、消泡剤、酸やアルカリを含めたＰＨ調製剤等の各種添加剤を加えてもよい。これらの添加剤は、溶媒除去や可塑剤抽出の際に除去できるものが好ましいが、リチウムイオン二次電池の使用範囲において電気化学的に安定で、電池反応を阻害しないものであれば、電池内に残存してもよい。
The dispersion is formed by dissolving or dispersing the inorganic filler and a resin binder in a solvent.
Examples of such a solvent include N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, water, ethanol, toluene, hot xylene, and hexane.
Further, in order to stabilize the inorganic filler-containing resin solution or to improve the coating property to the polyolefin resin porous membrane, a dispersant such as a surfactant, a thickener, a wetting agent, an antifoaming agent, an acid, Various additives such as a pH adjusting agent including an alkali may be added. These additives are preferably those that can be removed upon solvent removal or plasticizer extraction. However, if they are electrochemically stable in the range of use of the lithium ion secondary battery and do not inhibit the battery reaction, May remain.
なお、無機フィラーと樹脂製バインダとを溶媒に溶解又は分散させる方法としては、例えば、ボールミル、ビーズミル、遊星ボールミル、振動ボールミル、サンドミル、コロイドミル、アトライター、ロールミル、高速インペラー分散、ディスパーザー、ホモジナイザー、高速衝撃ミル、超音波分散、撹拌羽根等による機械撹拌等が挙げられる。
このような分散液を前記ポリオレフィン樹脂多孔膜に塗布する方法については、必要とする層厚や塗布面積を実現できる方法であれば特に限定しない。例えば、グラビアコーター法、小径グラビアコーター法、リバースロールコーター法、トランスファロールコーター法、キスコーター法、ディップコータ−法、ナイフコータ−法、エアドクタコーター法、ブレードコーター法、ロッドコーター法、スクイズコーター法、キャストコーター法、ダイコーター法、スクリーン印刷法、スプレー塗布法等が挙げられる。また、用途に応じて無機フィラー含有樹脂溶液をポリオレフィン樹脂多孔膜の片面だけに塗布してもよいし、両面に塗布してもよい。
Examples of the method for dissolving or dispersing the inorganic filler and the resin binder in a solvent include, for example, a ball mill, a bead mill, a planetary ball mill, a vibrating ball mill, a sand mill, a colloid mill, an attritor, a roll mill, a high-speed impeller dispersion, a disperser, and a homogenizer. , High-speed impact mill, ultrasonic dispersion, mechanical stirring by stirring blades, and the like.
The method for applying such a dispersion to the polyolefin resin porous membrane is not particularly limited as long as it can realize a required layer thickness and application area. For example, gravure coater method, small diameter gravure coater method, reverse roll coater method, transfer roll coater method, kiss coater method, dip coater method, knife coater method, air doctor coater method, blade coater method, rod coater method, squeeze coater method, Examples thereof include a cast coater method, a die coater method, a screen printing method, and a spray coating method. Moreover, according to a use, you may apply | coat an inorganic filler containing resin solution only to the single side | surface of a polyolefin resin porous film, and may apply | coat to both surfaces.
なお、塗布に先立ち、ポリオレフィン樹脂多孔膜表面を積極的に表面処理すると、無機フィラー含有樹脂溶液がより均一に塗布し易くなる上に、塗布後の無機フィラー含有樹脂層とポリオレフィン樹脂多孔膜表面との接着性が向上するため、より好ましい。
表面処理の方法は、ポリオレフィン樹脂多孔膜の多孔質構造が著しく損なわれなければ特に限定しないが、例えばコロナ放電処理法、機械的粗面化法、溶剤処理法、酸処理法、紫外線酸化法などが挙げられる。
前記分散液を塗布後、溶媒を除去することが好ましい。溶媒を除去する方法としては、例えば、ポリオレフィン樹脂多孔膜を固定しながらその融点以下の温度にて乾燥する方法、低温で減圧乾燥する方法、樹脂製バインダに対する貧溶媒に浸漬して樹脂製バインダを凝固させると同時に溶媒を抽出する方法、などが挙げられる。
If the surface of the polyolefin resin porous membrane is positively treated prior to application, the inorganic filler-containing resin solution can be more uniformly applied, and the inorganic filler-containing resin layer after application and the polyolefin resin porous membrane surface This is more preferable because of improving the adhesiveness.
The surface treatment method is not particularly limited as long as the porous structure of the polyolefin resin porous membrane is not significantly impaired. For example, corona discharge treatment method, mechanical surface roughening method, solvent treatment method, acid treatment method, ultraviolet oxidation method, etc. Is mentioned.
It is preferable to remove the solvent after applying the dispersion. As a method for removing the solvent, for example, a method of drying the polyolefin resin porous film at a temperature below its melting point, a method of drying under reduced pressure at a low temperature, a resin binder immersed in a poor solvent for a resin binder And a method of extracting the solvent at the same time as coagulation.
本実施形態の多層多孔膜は、良好な耐熱性、イオン透過性（透気度）を両立し得る。このような多層多孔膜を非水電解液電池用セパレータとして用いた場合、安全性能や出力特性等に優れた非水電解液電池を実現し得る。
なお、上述した各種パラメータについては、特に断りの無い限り、後述する実施例における測定法に準じて測定される値である。
The multilayer porous membrane of this embodiment can achieve both good heat resistance and ion permeability (air permeability). When such a multilayer porous membrane is used as a separator for a non-aqueous electrolyte battery, a non-aqueous electrolyte battery excellent in safety performance and output characteristics can be realized.
The various parameters described above are values measured according to the measurement methods in the examples described later unless otherwise specified.
次に、実施例及び比較例を挙げて本実施の形態をより具体的に説明するが、本実施の形態はその要旨を超えない限り、以下の実施例に限定されるものではない。なお、実施例中の物性は以下の方法により測定した。
（１）粘度平均分子量Ｍｖ
ＡＳＴＭ−Ｄ４０２０に基づき、デカリン溶媒における１３５℃での極限粘度［η］（ｄｌ／ｇ）を求める。ポリエチレンのＭｖは次式により算出した。
［η］＝６．７７×１０−４Ｍｖ０．６７
ポリプロピレンについては、次式によりＭｖを算出した。
Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless it exceeds the gist. In addition, the physical property in an Example was measured with the following method.
(1) Viscosity average molecular weight Mv
Based on ASTM-D4020, the intrinsic viscosity [η] (dl / g) at 135 ° C. in a decalin solvent is determined. Mv of polyethylene was calculated by the following formula.
[Η] = 6.77 × 10 −4 Mv 0.67
For polypropylene, Mv was calculated by the following formula.
［η］＝１．１０×１０−４Ｍｖ０．８０ [Η] = 1.10 × 10 −4 Mv 0.80
（２）膜厚、層厚（μｍ）
ダイヤルゲージ（尾崎製作所社製、商品名「ＰＥＡＣＯＣＫ Ｎｏ．２５」）にて測定した。ＭＤ方向１００ｍｍ×ＴＤ方向１００ｍｍの寸法を有するサンプルを切り出し、格子状に９箇所（３点×３点）の局所膜厚を測定した。得られた９箇所の局所膜厚の相加平均値を膜厚とした。なお多孔層の層厚は、多層多孔膜の膜厚とポリオレフィン樹脂多孔膜の膜厚（多孔層を剥離して測定）との差から算出した。
(2) Film thickness, layer thickness (μm)
It was measured with a dial gauge (manufactured by Ozaki Seisakusho, trade name “PEACOCK No. 25”). A sample having a dimension of 100 mm in the MD direction × 100 mm in the TD direction was cut out, and the local film thickness was measured at nine locations (3 points × 3 points) in a lattice shape. The arithmetic average value of the nine local thicknesses obtained was taken as the film thickness. The thickness of the porous layer was calculated from the difference between the thickness of the multilayer porous membrane and the thickness of the polyolefin resin porous membrane (measured by peeling the porous layer).
（３）透気度（秒／１００ｃｃ）、透気度増加率（％）
ＪＩＳ Ｐ−８１１７準拠のガーレー式透気度計（東洋精機製Ｇ−Ｂ２（商標））を用いた。内筒重量は５６７ｇで、直径２８．６ｍｍ、６４５ｍｍ２の面積を空気１００ｍｌが通過する時間を測定し、透気度を測定した。
一方、透気度増加率は、以下の式にて算出した。
透気度増加率（％）＝１００×（多層多孔膜の透気度−ポリオレフィン樹脂多孔膜の
透気度）／ポリオレフィン樹脂多孔膜の透気度
(3) Air permeability (second / 100cc), Air permeability increase rate (%)
A Gurley type air permeability meter (G-B2 (trademark) manufactured by Toyo Seiki Co.) conforming to JIS P-8117 was used. The inner cylinder weight was 567 g, the time required for 100 ml of air to pass through an area of 28.6 mm in diameter and 645 mm 2 was measured, and the air permeability was measured.
On the other hand, the air permeability increase rate was calculated by the following formula.
Permeability increase rate (%) = 100 × (Air permeability of multilayer porous membrane−Polyolefin resin porous membrane
Air permeability) / Air permeability of polyolefin resin porous membrane
（４）気孔率（％）
１０ｃｍ×１０ｃｍ角の試料をポリオレフィン樹脂多孔膜から切り取り、その体積（ｃｍ３）と質量（ｇ）を求め、膜密度を０．９５（ｇ／ｃｍ３）として次式を用いて計算した。
気孔率＝（１−質量／体積／０．９５）×１００
(4) Porosity (%)
A 10 cm × 10 cm square sample was cut out from the polyolefin resin porous membrane, its volume (cm 3 ) and mass (g) were determined, and the membrane density was calculated as 0.95 (g / cm 3 ) using the following formula.
Porosity = (1−mass / volume / 0.95) × 100
（５）平均孔径（μｍ）
孔径ｄ（μｍ）は、空気の透過速度定数Ｒｇａｓ（ｍ３／（ｍ２・ｓｅｃ・Ｐａ））、水の透過速度定数Ｒｌｉｑ（ｍ３／（ｍ２・ｓｅｃ・Ｐａ））、空気の分子速度ν（ｍ／ｓｅｃ）、水の粘度η（Ｐａ・ｓｅｃ）、標準圧力Ｐｓ（＝１０１３２５Ｐａ）から次式を用いて算出した。
ｄ＝２ν×（Ｒｌｉｑ／Ｒｇａｓ）×（１６η／３Ｐｓ）×１０６
Ｒｇａｓは透気度から次式を用いて求めた。
Ｒｇａｓ＝０．０００１／（透気度×（６．４２４×１０−４）×（０．０１２７６×
１０１３２５））
また、Ｒｌｉｑは透水度（ｃｍ３／（ｃｍ２・ｓｅｃ・Ｐａ））から次式を用いて求めた。
Ｒｌｉｑ＝透水度／１００
なお、透水度は次のように求めた。直径４１ｍｍのステンレス製の透液セルに、あらかじめアルコールに浸しておいたポリオレフィン樹脂多孔膜をセットし、該膜のアルコールを水で洗浄した後、約５００００Ｐａの差圧で水を透過させ、１２０ｓｅｃ間経過した際の透水量（ｃｍ３）より、単位時間・単位圧力・単位面積当たりの透水量を計算し、これを透水度とした。
(5) Average pore diameter (μm)
The pore diameter d (μm) is determined by air permeation rate constant R gas (m 3 / (m 2 · sec · Pa)), water permeation rate constant R liq (m 3 / (m 2 · sec · Pa)), air The molecular velocity ν (m / sec), the water viscosity η (Pa · sec), and the standard pressure P s (= 101325 Pa) were calculated using the following equation.
d = 2ν × (R liq / R gas ) × (16η / 3Ps) × 10 6
R gas was obtained from the air permeability using the following equation.
R gas = 0.0001 / (air permeability × (6.424 × 10 −4 ) × (0.01276 ×
101325))
R liq was determined from the water permeability (cm 3 / (cm 2 · sec · Pa)) using the following equation.
R liq = water permeability / 100
The water permeability was determined as follows. A polyolefin resin porous membrane previously immersed in alcohol was set in a stainless steel liquid-permeable cell having a diameter of 41 mm, and after washing the alcohol of the membrane with water, water was allowed to permeate at a differential pressure of about 50000 Pa for 120 sec. The water permeability per unit time, unit pressure, and unit area was calculated from the water permeability (cm 3 ) at the time, and this was used as the water permeability.
（６）ＭＤ（ＴＤ）熱収縮最大応力（ｇ）
島津製作所製ＴＭＡ５０（商標）を用いて測定した。ＭＤ（ＴＤ）方向の値を測定する場合は、ＴＤ（ＭＤ）方向に幅３ｍｍに切り出したサンプルを、チャック間距離が１０ｍｍとなるようにチャックに固定し、専用プローブにセットする。初期荷重を１．０ｇとし、３０℃から２００℃まで１０℃／ｍｉｎの昇温速度で加熱し、その時発生する荷重（ｇ）を測定し、その最大値をＭＤ（ＴＤ）最大熱収縮応力（ｇ）とした。
(6) MD (TD) heat shrinkage maximum stress (g)
It measured using Shimadzu Corporation TMA50 (trademark). When measuring the value in the MD (TD) direction, a sample cut to a width of 3 mm in the TD (MD) direction is fixed to the chuck so that the distance between the chucks is 10 mm, and set on a dedicated probe. The initial load is 1.0 g, the sample is heated from 30 ° C. to 200 ° C. at a heating rate of 10 ° C./min, the load (g) generated at that time is measured, and the maximum value is the MD (TD) maximum heat shrinkage stress ( g).
（７）ＭＤ／ＴＤ熱収縮応力比
（６）で測定したＭＤ方向及びＴＤ方向の最大熱収縮応力を用いて以下の式より算出した。
ＭＤ／ＴＤ熱収縮応力比＝ＭＤ最大熱収縮応力／ＴＤ最大熱収縮応力
(7) MD / TD heat shrinkage stress ratio It computed from the following formula | equation using the maximum heat shrinkage stress of MD direction and TD direction measured by (6).
MD / TD heat shrinkage stress ratio = MD maximum heat shrinkage stress / TD maximum heat shrinkage stress
（８）平均粒径
無機フィラーの平均粒径は、レーザー式粒度分布測定装置（日機装（株）製マイクロトラックＭＴ３３００ＥＸ）を用いて粒径分布を測定し、累積頻度が５０％となる粒径を平均粒径とした。
(8) Average particle size The average particle size of the inorganic filler is determined by measuring the particle size distribution using a laser-type particle size distribution measuring device (Microtrack MT3300EX manufactured by Nikkiso Co., Ltd.), and the particle size at which the cumulative frequency is 50%. The average particle size was taken.
（９）ＭＤ（ＴＤ）１５０℃熱収縮率
多層多孔膜をＭＤ方向に１００ｍｍ、ＴＤ方向に１００ｍｍに切り取り、１５０℃のオーブン中に１時間静置する。このとき、サンプルを２枚の紙にはさむことで、温風が直接サンプルにあたらないようにした。サンプルをオーブンから取り出し冷却した後、長さ（ｍｍ）を測定し、以下の式にてＭＤ及びＴＤの熱収縮率を算出した。
ＭＤ熱収縮率（％）＝（１００―加熱後のＭＤの長さ）／１００×１００
ＴＤ熱収縮率（％）＝（１００―加熱後のＴＤの長さ）／１００×１００
(9) MD (TD) 150 ° C. Heat Shrinkage The multilayer porous membrane is cut to 100 mm in the MD direction and 100 mm in the TD direction, and left in an oven at 150 ° C. for 1 hour. At this time, the sample was sandwiched between two sheets of paper so that the hot air was not directly applied to the sample. After the sample was taken out of the oven and cooled, the length (mm) was measured, and the thermal contraction rate of MD and TD was calculated by the following formula.
MD thermal shrinkage (%) = (100−MD length after heating) / 100 × 100
TD heat shrinkage rate (%) = (100−length of TD after heating) / 100 × 100
（１０）シャットダウン温度、ショート温度
ａ．正極の作製
正極活物質としてリチウムコバルト複合酸化物（ＬｉＣｏＯ２）を９２．２質量％、導電材としてリン片状グラファイトとアセチレンブラックをそれぞれ２．３質量％、バインダとしてポリフッ化ビニリデン（ＰＶＤＦ）３．２質量％をＮ−メチルピロリドン（ＮＭＰ）中に分散させてスラリーを調製した。このスラリーを正極集電体となる厚さ２０μｍのアルミニウム箔の片面にダイコーターで塗布し、１３０℃で３分間乾燥後、ロールプレス機で圧縮成形する。この時、正極の活物質塗布量は２５０ｇ／ｍ２、活物質かさ密度は３．００ｇ／ｃｍ３になるようにした。
(10) Shutdown temperature, short-circuit temperature a. Production of positive electrode 92.2% by mass of lithium cobalt composite oxide (LiCoO 2 ) as a positive electrode active material, 2.3% by mass of flake graphite and acetylene black as a conductive material, and polyvinylidene fluoride (PVDF) 3 as a binder A slurry was prepared by dispersing 2% by mass in N-methylpyrrolidone (NMP). This slurry is applied to one side of a 20 μm thick aluminum foil serving as a positive electrode current collector with a die coater, dried at 130 ° C. for 3 minutes, and then compression molded with a roll press. At this time, the active material coating amount of the positive electrode was 250 g / m 2 , and the active material bulk density was 3.00 g / cm 3 .
ｂ．負極の作製
負極活物質として人造グラファイト９６．６質量％、バインダとしてカルボキシメチルセルロースのアンモニウム塩１．４質量％とスチレン−ブタジエン共重合体ラテックス１．７質量％を精製水中に分散させてスラリーを調製する。このスラリーを負極集電体となる厚さ１２μｍの銅箔の片面にダイコーターで塗布し、１２０℃で３分間乾燥後、ロールプレス機で圧縮成形した。この時、負極の活物質塗布量は１０６ｇ／ｍ２、活物質かさ密度は１．３５ｇ／ｃｍ３になるようにした。
b. Preparation of Negative Electrode 96.6% by mass of artificial graphite as a negative electrode active material, 1.4% by mass of ammonium salt of carboxymethyl cellulose and 1.7% by mass of styrene-butadiene copolymer latex as a binder were dispersed in purified water to prepare a slurry. To do. This slurry was applied to one side of a 12 μm thick copper foil serving as a negative electrode current collector with a die coater, dried at 120 ° C. for 3 minutes, and then compression molded with a roll press. At this time, the active material coating amount of the negative electrode was set to 106 g / m 2 , and the active material bulk density was set to 1.35 g / cm 3 .
ｃ．非水電解液
プロピレンカーボネート：エチレンカーボネート：γ−ブチルラクトン＝１：１：２（体積比）の混合溶媒に、溶質としてＬｉＢＦ４を濃度１．０ｍｏｌ／Ｌとなるように溶解させて調製した。
c. Nonaqueous Electrolytic Solution Prepared by dissolving LiBF 4 as a solute at a concentration of 1.0 mol / L in a mixed solvent of propylene carbonate: ethylene carbonate: γ-butyllactone = 1: 1: 2 (volume ratio).
ｄ．評価
熱電対を繋いだセラミックスプレート上に、６５ｍｍ×２０ｍｍに切り出し非水電解液に１分以上浸漬した負極を載せ、この上に中央部に直径１６ｍｍの穴をあけた５０ｍｍ×５０ｍｍに切り出した厚さ９μｍのアラミドフィルムを載せ、この上に４０ｍｍ×４０ｍｍに切り出し非水電解液に１時間以上浸漬した試料の多孔膜をアラミドフィルムの穴部を覆うように載せ、この上に６５ｍｍ×２０ｍｍに切り出し非水電解液に１分以上浸漬した正極を負極に接触しないように載せ、その上にカプトンフィルム、更に厚さ約４ｍｍのシリコンゴムを載せた。
これをホットプレート上にセットした後、油圧プレス機にて４．１ＭＰａの圧力をかけた状態で、１５℃／ｍｉｎの速度で昇温し、この際の正負極間のインピーダンス変化を交流１Ｖ、１ｋＨｚの条件下で２００℃まで測定した。この測定において、インピーダンスが１０００Ωに達した時点の温度をシャットダウン温度とし、孔閉塞状態に達した後、再びインピーダンスが１０００Ωを下回った時点の温度をショート温度とした。
d. Evaluation On a ceramic plate connected with a thermocouple, a negative electrode cut into 65 mm × 20 mm and immersed in a non-aqueous electrolyte for 1 minute or more is placed, and a thickness cut into 50 mm × 50 mm with a hole having a diameter of 16 mm is formed on the negative electrode. Place a 9 μm thick aramid film, cut it into 40 mm × 40 mm, place a porous film of the sample soaked in non-aqueous electrolyte for 1 hour or more so as to cover the hole of the aramid film, and cut it into 65 mm × 20 mm A positive electrode immersed in a non-aqueous electrolyte for 1 minute or longer was placed so as not to contact the negative electrode, and a Kapton film and a silicon rubber having a thickness of about 4 mm were placed thereon.
After this was set on a hot plate, the temperature was raised at a rate of 15 ° C./min with a pressure of 4.1 MPa applied by a hydraulic press machine, and the impedance change between the positive and negative electrodes at this time was AC 1V, Measurement was performed up to 200 ° C. under the condition of 1 kHz. In this measurement, the temperature at which the impedance reached 1000Ω was taken as the shutdown temperature, and the temperature at which the impedance again fell below 1000Ω after reaching the hole closed state was taken as the short-circuit temperature.
（１１）Ｒ値
作製した多層多孔膜から１０００ｍｍ２の寸法を有するサンプルを１０箇所切り出し、１０箇所の多孔層の単位面積当たりの重量（Ｗ）の最大値（ＷＭＡＸ）と最小値（ＷＭＩＮ）を用いて、以下の式よりＲ値を算出した。
Ｒ値＝ＷＭＡＸ―ＷＭＩＮ
Ｗは多層多孔膜の重量を測定した後、多孔層を除去したポリオレフィン樹脂多孔膜の重量を測定し、以下の式より算出した。
Ｗ（ｇ／ｍ2）＝（多層多孔膜重量―ポリオレフィン樹脂多孔膜重量）×１０００
(11) R value 10 samples having a size of 1000 mm 2 are cut out from the produced multilayer porous membrane, and the maximum value (W MAX ) and the minimum value (W MIN ) of the weight (W) per unit area of the 10 porous layers ) Was used to calculate the R value from the following equation.
R value = W MAX- W MIN
W measured the weight of the multilayer porous membrane, then measured the weight of the polyolefin resin porous membrane from which the porous layer had been removed, and was calculated from the following equation.
W (g / m 2 ) = (multilayer porous membrane weight−polyolefin resin porous membrane weight) × 1000
［実施例１］
Ｍｖが７０万のポリエチレンを４７質量部、Ｍｖ３０万のポリエチレンを４６質量部、Ｍｖ４０万のポリプロピレンを７質量部とを、タンブラーブレンダーを用いてドライブレンドした。得られた純ポリマー混合物９９質量部に酸化防止剤としてペンタエリスリチル−テトラキス−［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］を１質量部添加し、再度タンブラーブレンダーを用いてドライブレンドすることにより、ポリマー等混合物を得た。得られたポリマー等混合物は窒素で置換を行った後に、二軸押出機へ窒素雰囲気下でフィーダーにより供給した。また流動パラフィン（３７．７８℃における動粘度７．５９×１０−５ｍ２／ｓ）を押出機シリンダーにプランジャーポンプにより注入した。
[Example 1]
47 parts by mass of polyethylene having an Mv of 700,000, 46 parts by mass of polyethylene having an Mv of 300,000, and 7 parts by mass of polypropylene having an Mv of 400,000 were dry blended using a tumbler blender. To 99 parts by mass of the obtained pure polymer mixture, 1 part by mass of pentaerythrityl-tetrakis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] as an antioxidant was added, and the tumbler was added again. A dry blend was performed using a blender to obtain a polymer mixture. The obtained mixture of polymers and the like was substituted with nitrogen and then fed to the twin-screw extruder with a feeder under a nitrogen atmosphere. Further, liquid paraffin (kinematic viscosity at 37.78 ° C .: 7.59 × 10 −5 m 2 / s) was injected into the extruder cylinder by a plunger pump.
溶融混練し、押し出される全混合物中に占める流動パラフィン量比が６５質量部となるように、フィーダー及びポンプを調整した。溶融混練条件は、設定温度２００℃であり、スクリュー回転数２４０ｒｐｍ、吐出量１２ｋｇ／ｈで行った。
続いて、溶融混練物を、Ｔ−ダイを経て表面温度２５℃に制御された冷却ロール上に押出しキャストすることにより、厚み１６００μｍのゲルシートを得た。
次に、同時二軸テンター延伸機に導き、二軸延伸を行った。設定延伸条件は、ＭＤ倍率７．０倍、ＴＤ倍率７．０倍、設定温度１２５℃である。
次に、メチルエチルケトン槽に導き、メチルエチルケトン中に充分に浸漬して流動パラフィンを抽出除去し、その後メチルエチルケトンを乾燥除去した。
The feeder and pump were adjusted so that the liquid paraffin content ratio in the total mixture melt-kneaded and extruded was 65 parts by mass. The melt kneading conditions were a set temperature of 200 ° C., a screw rotation speed of 240 rpm, and a discharge rate of 12 kg / h.
Subsequently, the melt-kneaded product was extruded and cast on a cooling roll controlled at a surface temperature of 25 ° C. through a T-die, to obtain a gel sheet having a thickness of 1600 μm.
Next, it led to the simultaneous biaxial tenter stretching machine, and biaxial stretching was performed. The set stretching conditions are an MD magnification of 7.0 times, a TD magnification of 7.0 times, and a set temperature of 125 ° C.
Next, the solution was introduced into a methyl ethyl ketone tank and sufficiently immersed in methyl ethyl ketone to extract and remove liquid paraffin, and then the methyl ethyl ketone was removed by drying.
次に、ＴＤテンターに導き、熱固定を行った。熱固定時の延伸温度・倍率は１２８℃・２．０倍で行い、その後の緩和時の温度・緩和率を１３３℃、０．８０とした。
ポリオレフィン樹脂多孔膜の表面に、コロナ放電処理（放電量５０Ｗ）を実施した後、当該処理面側に、アルミナ粒子（平均粒径０．７μｍ））９８．２重量部、ポリビニルアルコール（平均重合度１７００、ケン化度９９％以上）１．８重量部を１５０重量部の水にそれぞれ均一に分散させた水溶液を、上記ポリオレフィン樹脂多孔膜の表面にグラビアコーターを用いて塗布した後、６０℃にて乾燥して水を除去し、多孔膜上に厚さ４μｍの多孔層が形成した、総膜厚１６μｍの多層多孔膜を得た。結果を表１に併記する。
Next, it was led to a TD tenter and heat fixed. The stretching temperature and magnification during heat setting were 128 ° C. and 2.0 times, and the temperature and relaxation rate during the subsequent relaxation were 133 ° C. and 0.80.
After the corona discharge treatment (discharge amount 50 W) is performed on the surface of the polyolefin resin porous membrane, 98.2 parts by weight of alumina particles (average particle size 0.7 μm), polyvinyl alcohol (average polymerization degree) (1700, degree of saponification 99% or more) After applying an aqueous solution in which 1.8 parts by weight of water was uniformly dispersed in 150 parts by weight of water to the surface of the polyolefin resin porous film using a gravure coater, Water was removed by drying to obtain a multilayer porous membrane having a total thickness of 16 μm in which a porous layer having a thickness of 4 μm was formed on the porous membrane. The results are also shown in Table 1.
［実施例２〜４，６、参考実施例５］
表１に示す条件以外は実施例１の方法に準じて多層多孔膜を得た。結果を表１に併記する。
[Examples 2 to 4, 6 and Reference Example 5 ]
A multilayer porous membrane was obtained according to the method of Example 1 except for the conditions shown in Table 1. The results are also shown in Table 1.
［実施例７］
溶融混練物のキャストまでは実施例１に準じ、厚み１０００μｍのゲルシートを得た。
次に、同時二軸テンター延伸機に導き、二軸延伸を行った。設定延伸条件は、ＭＤ倍率７．０倍、ＴＤ倍率７．０倍、設定温度１２０℃である。
次に、メチルエチルケトン槽に導き、メチルエチルケトン中に充分に浸漬して流動パラフィンを抽出除去し、その後メチルエチルケトンを乾燥除去した。
次に、ＴＤテンターに導き、熱固定を行った。熱固定時の延伸温度・倍率は１１５℃・１．４倍で行い、その後の緩和時の温度・緩和率を１２５℃、０．７５とした。
その後、実施例１に準じて多層多孔膜を得た。
[Example 7]
A gel sheet having a thickness of 1000 μm was obtained according to Example 1 until the melt-kneaded material was cast.
Next, it led to the simultaneous biaxial tenter stretching machine, and biaxial stretching was performed. The set stretching conditions are an MD magnification of 7.0 times, a TD magnification of 7.0 times, and a set temperature of 120 ° C.
Next, the solution was introduced into a methyl ethyl ketone tank and sufficiently immersed in methyl ethyl ketone to extract and remove liquid paraffin, and then the methyl ethyl ketone was removed by drying.
Next, it was led to a TD tenter and heat fixed. The stretching temperature and magnification during heat setting were 115 ° C. and 1.4 times, and the temperature and relaxation rate during the subsequent relaxation were 125 ° C. and 0.75.
Thereafter, a multilayer porous membrane was obtained according to Example 1.
［実施例８〜１０，１２、参考実施例１１］
表１に示す条件以外は実施例６の方法に準じて多層多孔膜を得た。結果を表１に併記する。
[Examples 8 to 10, 12, Reference Example 11 ]
A multilayer porous membrane was obtained according to the method of Example 6 except for the conditions shown in Table 1. The results are also shown in Table 1.
［実施例１３］
溶融混練物のキャストまでは実施例１に準じ、厚み１２００μｍのゲルシートを得た。
次に、同時二軸テンター延伸機に導き、二軸延伸を行った。設定延伸条件は、ＭＤ倍率７．０倍、ＴＤ倍率７．０倍、設定温度１２５℃である。
次に、メチルエチルケトン槽に導き、メチルエチルケトン中に充分に浸漬して流動パラフィンを抽出除去し、その後メチルエチルケトンを乾燥除去した。
次に、ＴＤテンターに導き、熱固定を行った。熱固定時の延伸温度・倍率は１２５℃・１．６倍で行い、その後の緩和時の温度・緩和率を１３０℃、０．７０とした。
その後、実施例１に準じて多層多孔膜を得た。
[Example 13]
A gel sheet having a thickness of 1200 μm was obtained according to Example 1 until the melt-kneaded material was cast.
Next, it led to the simultaneous biaxial tenter stretching machine, and biaxial stretching was performed. The set stretching conditions are an MD magnification of 7.0 times, a TD magnification of 7.0 times, and a set temperature of 125 ° C.
Next, the solution was introduced into a methyl ethyl ketone tank and sufficiently immersed in methyl ethyl ketone to extract and remove liquid paraffin, and then the methyl ethyl ketone was removed by drying.
Next, it was led to a TD tenter and heat fixed. The stretching temperature and magnification during heat setting were 125 ° C. and 1.6 times, and the temperature and relaxation rate during the subsequent relaxation were 130 ° C. and 0.70.
Thereafter, a multilayer porous membrane was obtained according to Example 1.
［実施例１４］
溶融混練物のキャストまでは実施例１に準じ、厚み９００μｍのゲルシートを得た。
次に、同時二軸テンター延伸機に導き、二軸延伸を行った。設定延伸条件は、ＭＤ倍率７．０倍、ＴＤ倍率７．０倍、設定温度１２０℃である。
次に、メチルエチルケトン槽に導き、メチルエチルケトン中に充分に浸漬して流動パラフィンを抽出除去し、その後メチルエチルケトンを乾燥除去した。
次に、ＴＤテンターに導き、熱固定を行った。熱固定時の延伸温度・倍率は１１６℃・１．３倍で行い、その後の緩和時の温度・緩和率を１２６℃、０．７５とした。
その後、実施例１に準じて多層多孔膜を得た。
[Example 14]
A gel sheet having a thickness of 900 μm was obtained in accordance with Example 1 until the melt-kneaded material was cast.
Next, it led to the simultaneous biaxial tenter stretching machine, and biaxial stretching was performed. The set stretching conditions are an MD magnification of 7.0 times, a TD magnification of 7.0 times, and a set temperature of 120 ° C.
Next, the solution was introduced into a methyl ethyl ketone tank and sufficiently immersed in methyl ethyl ketone to extract and remove liquid paraffin, and then the methyl ethyl ketone was removed by drying.
Next, it was led to a TD tenter and heat fixed. The stretching temperature and magnification during heat setting were 116 ° C. and 1.3 times, and the temperature and relaxation rate during the subsequent relaxation were 126 ° C. and 0.75.
Thereafter, a multilayer porous membrane was obtained according to Example 1.
［実施例１５］
溶融混練物のキャストまでは実施例１に準じ、厚み１１００μｍのゲルシートを得た。
次に、同時二軸テンター延伸機に導き、二軸延伸を行った。設定延伸条件は、ＭＤ倍率７．０倍、ＴＤ倍率７．０倍、設定温度１２８℃である。
次に、メチルエチルケトン槽に導き、メチルエチルケトン中に充分に浸漬して流動パラフィンを抽出除去し、その後メチルエチルケトンを乾燥除去した。
次に、ＴＤテンターに導き、熱固定を行った。熱固定時の延伸温度・倍率は１３０℃・１．６倍で行い、その後の緩和時の温度・緩和率を１３０℃、０．８０とした。
その後、実施例１に準じて多層多孔膜を得た。
[Example 15]
A gel sheet having a thickness of 1100 μm was obtained according to Example 1 until the melt-kneaded material was cast.
Next, it led to the simultaneous biaxial tenter stretching machine, and biaxial stretching was performed. The set stretching conditions are an MD magnification of 7.0 times, a TD magnification of 7.0 times, and a set temperature of 128 ° C.
Next, the solution was introduced into a methyl ethyl ketone tank and sufficiently immersed in methyl ethyl ketone to extract and remove liquid paraffin, and then the methyl ethyl ketone was removed by drying.
Next, it was led to a TD tenter and heat fixed. The stretching temperature and magnification during heat setting were 130 ° C. and 1.6 times, and the temperature and relaxation rate during the subsequent relaxation were 130 ° C. and 0.80.
Thereafter, a multilayer porous membrane was obtained according to Example 1.
［実施例１６］
Ｍｖが７０万のポリエチレンを５０質量部、Ｍｖ３０万のポリエチレンを５０質量部とを、タンブラーブレンダーを用いてドライブレンドし、その後、実施例１に準じて多層多孔膜を得た。
[Example 16]
50 parts by mass of polyethylene having an Mv of 700,000 and 50 parts by mass of polyethylene having an Mv of 300,000 were dry blended using a tumbler blender, and then a multilayer porous membrane was obtained according to Example 1.
［比較例１］
実施例１で基材に用いたポリオレフィン樹脂多孔膜について評価した。結果を表１に併記する。
[Comparative Example 1]
The polyolefin resin porous membrane used for the substrate in Example 1 was evaluated. The results are also shown in Table 1.
［比較例２］
実施例７で基材に用いたポリオレフィン樹脂多孔膜について評価した。結果を表１に併記する。
[Comparative Example 2]
The polyolefin resin porous membrane used for the substrate in Example 7 was evaluated. The results are also shown in Table 1.
［比較例３］
厚み２０００μｍのゲルシートを経る以外は、実施例１と同様にしてポリオレフィン樹脂多孔膜を得た。結果を表１に併記する。
その後、実施例１に準じて多層多孔膜を得た。
[Comparative Example 3]
A polyolefin resin porous membrane was obtained in the same manner as in Example 1 except that a gel sheet having a thickness of 2000 μm was passed. The results are also shown in Table 1.
Thereafter, a multilayer porous membrane was obtained according to Example 1.
［比較例４，５］
無機フィラーを表１記載の無機フィラーに変更する以外は、比較例３と同様にして比較例４の多層多孔膜を作製した。結果を表１に併記する。
[Comparative Examples 4 and 5]
A multilayer porous membrane of Comparative Example 4 was produced in the same manner as Comparative Example 3 except that the inorganic filler was changed to the inorganic filler described in Table 1. The results are also shown in Table 1.
［比較例６］
粘度平均分子量（Ｍｖ）２００万の超高分子量ポリエチレン１２質量部とＭｖ２８万の高密度ポリエチレン１２質量部とＭｖ１５万の直鎖状低密度ポリエチレン１６質量部とシリカ（平均粒径８．３μｍ）１７．６質量部と、可塑剤としてフタル酸ジオクチル（ＤＯＰ）を４２．４質量部を混合造粒した後、Ｔダイを装着した二軸押出機にて混練・押出し、厚さ９０μｍのシート状に成形した。該成形物から塩化メチレンにてＤＯＰを、水酸化ナトリウムにてシリカを抽出除去し多孔膜とした。該多孔膜を１１８℃に加熱のもと、縦方向に５．３倍延伸した後、横方向に１．８倍延伸した。
[Comparative Example 6]
12 parts by mass of ultrahigh molecular weight polyethylene having a viscosity average molecular weight (Mv) of 2 million, 12 parts by mass of high-density polyethylene of Mv 280,000, 16 parts by mass of linear low-density polyethylene of Mv 150,000 and silica (average particle size 8.3 μm) 17 After mixing and granulating 6 parts by mass and 42.4 parts by mass of dioctyl phthalate (DOP) as a plasticizer, the mixture is kneaded and extruded by a twin-screw extruder equipped with a T-die to form a sheet having a thickness of 90 μm. Molded. The molded product was subjected to extraction removal of DOP with methylene chloride and silica with sodium hydroxide to form a porous film. The porous membrane was heated to 118 ° C. and stretched 5.3 times in the longitudinal direction and then 1.8 times in the transverse direction.
ポリオレフィン樹脂多孔膜の表面に、コロナ放電処理（放電量５０Ｗ）を実施した後、当該処理面側に、アルミナ粒子（平均粒径０．７μｍ））９８．２重量部、ポリビニルアルコール（平均重合度１７００、ケン化度９９％以上）１．８重量部を１５０重量部の水にそれぞれ均一に分散させた水溶液を、上記ポリオレフィン樹脂多孔膜の表面にグラビアコーターを用いて塗布した後、６０℃にて乾燥して水を除去し、多孔膜上に厚さ５μｍの多孔層が形成した、総膜厚１６μｍの多層多孔膜を得た。結果を表１に併記する。 After the corona discharge treatment (discharge amount 50 W) is performed on the surface of the polyolefin resin porous membrane, 98.2 parts by weight of alumina particles (average particle size 0.7 μm), polyvinyl alcohol (average polymerization degree) (1700, degree of saponification 99% or more) After applying an aqueous solution in which 1.8 parts by weight of water was uniformly dispersed in 150 parts by weight of water to the surface of the polyolefin resin porous film using a gravure coater, Water was removed by drying to obtain a multilayer porous membrane having a total thickness of 16 μm in which a porous layer having a thickness of 5 μm was formed on the porous membrane. The results are also shown in Table 1.
［比較例７，８］
表１に示す条件以外は比較例７の方法に準じて多層多孔膜を得た。結果を表１に併記する。
[Comparative Examples 7 and 8]
A multilayer porous membrane was obtained according to the method of Comparative Example 7 except for the conditions shown in Table 1. The results are also shown in Table 1.
本発明の多層多孔膜は良好な耐熱性と良好なイオン透過性とを両立する。当該多層多孔膜は、非水電解液二次電池や電機二重層キャパシタ等の蓄電池用セパレータとして特に有用である。 The multilayer porous membrane of the present invention achieves both good heat resistance and good ion permeability. The multilayer porous membrane is particularly useful as a separator for storage batteries such as non-aqueous electrolyte secondary batteries and electric double layer capacitors.
Claims (12)
前記ポリオレフィン樹脂多孔膜の膜厚が０．１μｍ以上１５μｍ以下、
平均孔径が０．０４μｍ以上０．１μｍ以下、
熱収縮応力の最大値が、ＭＤ、ＴＤ共に８ｇ以下、
前記多孔層のＲ値が０．０１ｇ／ｍ2以上０．５２ｇ／ｍ2以下、
前記多孔層の層厚が２μｍ以上７μｍ以下、
前記無機フィラーの平均粒径が０．１μｍ以上１．５μｍ以下、
前記樹脂製バインダがスチレン−ブタジエン共重合体及びその水素化物、アクリロニトリル−ブタジエン共重合体及びその水素化物、アクリロニトリル−ブタジエン−スチレン共重合体及びその水素化物、メタクリル酸エステル−アクリル酸エステル共重合体、スチレン−アクリル酸エステル共重合体、アクリロニトリル−アクリル酸エステル共重合体、エチレンプロピレンラバー、ポリビニルアルコール、ポリ酢酸ビニルからなる群から選ばれる少なくとも１種
である多層多孔膜。 Provided with a porous layer containing an inorganic filler and a resin binder on at least one side of the polyolefin resin porous membrane,
The polyolefin resin porous membrane has a thickness of 0.1 μm or more and 15 μm or less,
The average pore diameter is 0.04 μm or more and 0.1 μm or less ,
The maximum value of heat shrinkage stress is 8 g or less for both MD and TD.
The R value of the porous layer is 0.01 g / m 2 or more and 0.0. 52 g / m 2 or less ,
The layer thickness of the porous layer is 2 μm or more and 7 μm or less,
The average particle size of the inorganic filler is 0.1 μm or more and 1.5 μm or less,
The resin binder is a styrene-butadiene copolymer and its hydride, acrylonitrile-butadiene copolymer and its hydride, acrylonitrile-butadiene-styrene copolymer and its hydride, methacrylic acid ester-acrylic acid ester copolymer A multilayer porous membrane that is at least one selected from the group consisting of styrene-acrylic acid ester copolymer, acrylonitrile-acrylic acid ester copolymer, ethylene propylene rubber, polyvinyl alcohol, and polyvinyl acetate.
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| JP5768359B2 (en) | 2010-11-17 | 2015-08-26 | ソニー株式会社 | Heat-resistant microporous membrane, battery separator, and lithium ion secondary battery |
| JP5618165B2 (en) * | 2010-11-26 | 2014-11-05 | トヨタ自動車株式会社 | Nonaqueous electrolyte secondary battery |
| US8980461B2 (en) * | 2011-02-03 | 2015-03-17 | Samsung Sdi Co., Ltd. | Separator for lithium secondary battery and lithium secondary battery including the same |
| JP5652683B2 (en) * | 2011-03-16 | 2015-01-14 | トヨタ自動車株式会社 | Nonaqueous electrolyte secondary battery and vehicle |
| JP6257122B2 (en) | 2011-10-04 | 2018-01-10 | 日産自動車株式会社 | Separator with heat-resistant insulation layer |
| KR101434379B1 (en) * | 2011-10-21 | 2014-08-27 | 데이진 가부시키가이샤 | Separator for non-aqueous rechargeable battery and non-aqueous rechargeable battery |
| JP6003041B2 (en) | 2011-11-10 | 2016-10-05 | 日産自動車株式会社 | Separator with heat-resistant insulation layer |
| JP6120828B2 (en) | 2012-03-28 | 2017-04-26 | 旭化成株式会社 | Porous membrane and multilayer porous membrane |
| CN104508864B (en) * | 2012-07-30 | 2017-04-19 | 帝人株式会社 | Non-aqueous electrolyte battery separator and non-aqueous electrolyte battery |
| CN104508861B (en) * | 2012-07-30 | 2018-06-15 | 帝人株式会社 | Separator for non-aqueous electrolyte battery and nonaqueous electrolyte battery |
| KR102183257B1 (en) * | 2012-08-07 | 2020-11-27 | 셀가드 엘엘씨 | Improved separator membranes for lithium ion batteries and related methods |
| CN104641490B (en) | 2012-09-19 | 2017-12-01 | 旭化成株式会社 | Separator and its manufacture method and lithium rechargeable battery |
| JP6084803B2 (en) * | 2012-10-10 | 2017-02-22 | ダイセルポリマー株式会社 | Thermoplastic resin composition for washing molding machine |
| JP6055302B2 (en) * | 2012-12-20 | 2016-12-27 | 大倉工業株式会社 | Heat-seal tape for bonding battery lead terminals that prevents shrinkage |
| JP6323449B2 (en) * | 2013-04-22 | 2018-05-16 | 東レ株式会社 | Laminated porous membrane, method for producing the same, and battery separator |
| KR102299957B1 (en) * | 2014-07-30 | 2021-09-08 | 에스케이이노베이션 주식회사 | Manufacturing method with good productivity for preparing porous multilayered polyolefin |
| JP2015181110A (en) * | 2015-04-20 | 2015-10-15 | ソニー株式会社 | Heat resistance microporous film, separator for lithium ion secondary batteries, and lithium ion secondary battery |
| CN108307884B (en) * | 2018-03-30 | 2024-04-26 | 孙琪 | Assembled heat preservation ventilative greenhouse film |
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| JP5286817B2 (en) * | 2007-02-27 | 2013-09-11 | 住友化学株式会社 | Separator |
| JP5286844B2 (en) * | 2007-03-23 | 2013-09-11 | 住友化学株式会社 | Separator |
| JP2008311221A (en) * | 2007-05-14 | 2008-12-25 | Sumitomo Chemical Co Ltd | Laminated porous film |
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