JP5398016B2 - Microporous membrane, method for producing the same, and separator for non-aqueous electrolyte secondary battery - Google Patents

Description

  The present invention relates to a microporous membrane, particularly a microporous membrane suitable as a separator for a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery, and a method for producing the same.

  The microporous membrane is used as a packaging film, a microfiltration membrane, a battery separator, a capacitor separator, a fuel cell material, and the like, and is particularly used as a lithium ion secondary battery separator. In recent years, lithium ion secondary batteries have been applied not only to small electronic devices such as mobile phones and notebook computers, but also to hybrid cars, plug-in hybrid cars, electric vehicles, small electric motorcycles, and the like. In particular, it will be highly safe, cycleable, and easy to create batteries for in-vehicle applications that will continue to expand rapidly worldwide, especially for electric vehicles and consumer computers. In order to satisfy these requirements, separators are also required to be easy to make, such as safety, cycleability, battery winding property, etc., and to improve the productivity of the separator itself. . In particular, with regard to cycle performance, stable performance under high temperature use is achieved, with regard to safety, withstand voltage characteristics are improved, and with regard to battery winding performance and productivity of the separator itself, there is moderate surface slipperiness. It has been demanded.

  Conventionally, as a microporous membrane, particularly a separator for a lithium ion secondary battery, a microporous membrane made of polyethylene excellent in ease of molding and chemical stability has been used. In addition, for the purpose of imparting heat resistance to polyethylene microporous membranes and preventing deterioration at high temperatures, polypropylene separators having a melting point higher than that of polyethylene are also used, and multilayer separators combining these are also proposed. Yes.

For example, Patent Document 1 describes a method for producing a three-layer porous film by a coextrusion method. This document discloses a technique in which the surface layer is mainly made of polypropylene and the intermediate layer is mainly made of polyethylene. However, microporous membranes with polypropylene on the surface generally have high friction and poor sliding with metal pins and rolls, which adversely affects the winding performance of the battery and the productivity of the separator itself at the film production site. .
As a technique for eliminating such influences, for example, Patent Documents 1 to 7 propose a method of arranging or applying a layer made of a material having good slipperiness on the surface of a separator.

JP 09-219184 A Japanese Patent No. 3483846 Japanese Patent No. 3235669 Japanese Patent No. 342296 Japanese Patent No. 4052495 JP 2000-204174 A JP 07-216118 A

However, all of the separators described in the above-mentioned patent documents still have room for improvement from the viewpoints of cycle performance at high temperatures, safety, productivity, and battery winding performance. These separators are obtained by a method of applying a slip agent or providing a layer made of a resin having a good slip property in order to improve the slip property. There is a problem that microporous clogging is caused by the above, and the latter has a problem of canceling out high temperature cycle characteristics. In addition, Patent Document 6 and the like disclose that a low molecular weight antioxidant is mixed and a sliding effect is aimed at, but simply adding a low molecular weight antioxidant does not improve the slipping effect. It can be seen that there is almost no decrease in the coefficient of friction from the results of the examples.
In view of the above circumstances, an object of the present invention is to provide a microporous membrane excellent in high-temperature cycle performance, productivity, and battery winding property when used as a separator, and a method for producing the same.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention are single-layer microporous membranes containing a specific amount of polypropylene, the surface of which has a dynamic friction coefficient adjusted to a specific range. The present inventors have found that the above-mentioned problems can be solved by using, and that the performance is further improved by using a multilayer microporous membrane including this single-layer microporous membrane. Moreover, the manufacturing method of such a microporous film was discovered and it came to complete this invention.

That is, the present invention is as follows.
[1]
A microporous membrane comprising a resin composition containing a mixture of polypropylene and polyethylene as a main component,
The proportion of the polypropylene in the mixture is 50% by mass or more,
A microporous membrane having a surface dynamic friction coefficient of 0.55 or less.
[2]
The microporous membrane according to the above [1], wherein the polypropylene content on the surface is 60% by mass or less and (total polypropylene content) − (polypropylene content on the surface) ≧ 10% by mass.
[3]
A multilayer microporous membrane comprising the microporous membrane according to [1] or [2] as a surface layer.
[4]
A method for producing a microporous membrane according to the above [1] or [2],
(1) A step of preparing a mixture by mixing polypropylene and polyethylene containing a polyethylene component having a molecular weight (Mw) of less than 10,000,
(2) a step of bleeding the polyethylene component having a molecular weight (Mw) of less than 10,000 on the surface of the sheet when the sheet is formed by a casting method after the mixture is extruded by an extruder.
Manufacturing method.
[5]
[4] The above step (4), wherein the step (1) further comprises a step of adding a mixture of a plasticizer and a low molecular weight polyethylene to a mixture of polypropylene and a polyethylene component having a molecular weight (Mw) of less than 10,000. The manufacturing method as described.
[6]
A separator for a nonaqueous electrolyte secondary battery comprising the microporous membrane according to [1] or [2] or the multilayer microporous membrane according to [3].

  According to the present invention, a microporous membrane excellent in high-temperature cycle performance, productivity, and battery winding property, particularly when used as a separator, and a method for producing the same are provided.

Side surface sectional drawing of the die | dye used in the Example is shown. The upper surface sectional drawing of the die | dye used in the Example is shown. The schematic of a battery winding property evaluation jig is shown.

  Hereinafter, a mode for carrying out the present invention (hereinafter abbreviated as “the present 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 microporous membrane of the present embodiment is
A microporous membrane comprising a resin composition containing a mixture of polypropylene and polyethylene as a main component,
The proportion of the polypropylene in the mixture is 50% by mass or more,
The surface dynamic friction coefficient is 0.55 or less.
The microporous membrane of the present embodiment is a single-layer microporous membrane, and can be formed into a multilayer microporous membrane by stacking with other microporous membranes.

  In the present embodiment, the “main component” is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more as a proportion of the specific component in the matrix component. This means that it may be 100% by mass.

  Polypropylene can contribute to providing high temperature cycleability and safety when the microporous membrane is used as a separator of a lithium ion secondary battery, and 50 mass in a mixture of polypropylene and polyethylene. % Or more. From the viewpoint of further improving the cycle performance of the lithium ion secondary battery, it is preferably contained in an amount of 61% by mass or more, and from the viewpoint of improving the safety of the lithium ion secondary battery after high temperature storage, it is contained by 71% by mass or more. It is preferable.

  The polypropylene is not particularly limited. For example, propylene homopolymers such as isotactic polypropylene (IPP), syndiotactic polypropylene, and atactic polypropylene, propylene, ethylene, butene, and carbon number of 5 or more. And a random copolymer (RPP), a block copolymer (BPP), a terpolymer and the like obtained by copolymerizing with a comonomer such as α-olefin. Among these, when it is desired to impart heat resistance, IPP having high crystallinity is preferable, and RPP and BPP that are easily stretched are preferable from the viewpoint of imparting strength.

As the viscosity average molecular weight (Mv) of polypropylene, melt kneading is facilitated, and as a result, fisheye defects tend to be improved when the resin composition is made into a microporous film. More preferably, it is 700,000 or less, More preferably, it is 600,000 or less. From the viewpoint of strength, the viscosity average molecular weight of polypropylene is 100,000 or more, more preferably 200,000 or more.
Here, the fish eye is a small amount generated in a film-like or sheet-like product as defined in Polymer Editorial Board, Polymer Dictionary, Taiseisha, 2000, 6th edition, 337 pages, etc. This name was given because it is a spherical lump, and many of them show transparency like fish eyes. Fisheye is distinguished from its production factors, with unmelted lumps resulting from insufficient kneading of molding materials, lumps due to part of the raw material gelling, lumps due to partial deterioration of the material being molded, and foreign matter as the core. Various things, such as a thing, are mentioned. However, in this specification, the fish eye originates from the material used as the raw material for the microporous membrane, and excludes those having foreign matter as the core. In addition, the foreign material includes, for example, cellulose, dust, metal pieces, resin carbide, plastics of different types, lint, and pieces of paper.

  Also preferred is a resin composition obtained by blending 0.5-30% by mass of polypropylene, BPP, or RPP with reduced stereoregularity using a metallocene catalyst or the like with respect to IPP. By using such polypropylene, the permeability tends to be improved when a microporous film is formed by a wet method described later.

  The microporous membrane of the present embodiment needs to contain polyethylene as a resin component. The proportion of polyethylene in the mixture of polypropylene and polyethylene is less than 50% by mass from the viewpoint of improving high-temperature cycle performance, and is preferably 35% by mass or less from the viewpoint of safety. On the other hand, polyethylene has the effect of increasing the productivity of the microporous membrane. From this viewpoint, the ratio of polyethylene is preferably 15% by mass or more, and more preferably 20% by mass or more.

  Examples of the polyethylene include high density polyethylene, ultra high molecular weight polyethylene, linear low density polyethylene, high pressure method low density polyethylene, and mixtures thereof. Further, polyethylene having a narrow molecular weight distribution using a metallocene catalyst, high-density polyethylene, or polyethylene by multistage polymerization may be used. Among these, from the viewpoint of reducing thermal shrinkage when a microporous membrane is used as a separator, it is preferable to use linear high-density polyethylene, ultrahigh molecular weight polyethylene, or a mixture thereof by ion polymerization. The ultra high molecular weight polyethylene here refers to polyethylene having a viscosity average molecular weight of 500,000 or more. The proportion of ultra high molecular weight polyethylene in the total polyethylene is preferably 5 to 50% by mass, and more preferably 9 to 40% by mass from the viewpoint of dispersibility.

  The viscosity average molecular weight (Mv) of polyethylene (when using a plurality of types of polyethylene, the total viscosity average molecular weight) is preferably 200,000 or more, more preferably from the viewpoint of improving the strength of the microporous membrane. Is over 300,000. The upper limit of the viscosity average molecular weight (Mv) is preferably 10 million or less, more preferably 5 million or less, from the viewpoints of extrusion moldability and stretchability.

  The molecular weight distribution of polyethylene (Mw / Mn) improves the kneadability when mixing and kneading inorganic fillers, etc., and from the viewpoint of suppressing the occurrence of granular defects in which the inorganic filler is secondarily aggregated, Preferably it is 5 or more, More preferably, it is 8 or more.

  The polyethylene used for the microporous membrane of the present embodiment preferably contains a polyethylene component having a molecular weight of less than 10,000. Here, the polyethylene component having a molecular weight of less than 10,000 is a portion having a molecular weight of less than 10,000 in a molecular weight distribution chart measured by a gel permeation chromatography (GPC) method, and the ratio is determined from the area ratio on the chart. Can be sought. When a polyethylene component having a molecular weight of less than 10,000 is formed under a specific condition, a part of the polyethylene component moves to the surface of the microporous membrane, and as a result, has an action of reducing the amount of polypropylene on the surface. As a method of incorporating such a polyethylene component having a molecular weight of less than 10,000 into the polyethylene, it may be prepared by setting polymerization conditions so as to contain a large amount of low molecular weight components during the polymerization of polyethylene. You may mix and produce the polyethylene component whose molecular weight is less than 10,000.

  The content of the polyethylene component having a molecular weight of less than 10,000 is preferably 5% by mass or more with respect to the total polyethylene amount. If the content is within this range, friction is reduced during the formation of the microporous membrane, and the microporous membrane is reduced. Productivity tends to improve. More preferably, the content is 10% by mass or more. When the content is within this range, the winding property of the battery tends to be improved when the microporous membrane is used as a separator for a lithium ion secondary battery. Furthermore, when it is 20% by mass or more, winding at higher speed becomes possible, and the productivity of the battery tends to be improved. On the other hand, from the viewpoint of improving the strength of the microporous membrane, it is preferably 50% by mass or less. Further, from the viewpoint of further improving friction reduction, it is preferable that the polyethylene component having a molecular weight of less than 1000 is contained at 1% by mass or more.

  In addition to polypropylene and polyethylene, the resin composition in the present embodiment includes other resin components, inorganic fillers, antioxidants, dispersing aids, antistatic agents, processing stabilizers, additives such as crystal nucleating agents, Additives such as organic fillers may be mixed. The proportion of these components in the resin composition is preferably 5% by mass or less, more preferably 2% by mass or less, and may be substantially 0% by mass.

  In the microporous membrane of this embodiment, as a resin other than polypropylene and polyethylene, for the purpose of improving the film-forming property, polybutene-1 resin, propylene-based and ethylene-based elastomers, particularly random copolymerization of propylene and ethylene A combined elastomer may be mixed. Polymethylpentene-1 resin can also be used, and those having a melt flow rate (MFR) of 0.1 to 10 g / 10 min are preferably used.

  Other than the above, engineering plastic resins such as polyphenylene ether, polyamide resins such as nylon 6, nylon 6-12, and aramid resin, polyimide resins, polyester resins such as PET and PBT, polycarbonate resins, and polyvinylidene fluoride (PVDF) Fluorine-based resins, copolymers of ethylene and vinyl alcohol, copolymers of C2-C12 α-olefin and carbon monoxide and hydrogenated products thereof, hydrogenated products of styrene-based polymers, styrene and α-olefins A copolymer of styrene and an aliphatic monounsaturated fatty acid, a copolymer of acrylic acid and its derivatives, a copolymer of styrene and a conjugated diene unsaturated monomer, and A thermoplastic resin selected from these hydrogenated materials can be used.

  In this Embodiment, you may mix an inorganic filler with said resin component. Examples of the inorganic filler that can be used include alumina (for example, α-alumina), silica, titania, zirconia, magnesia, ceria, yttria, zinc oxide, iron oxide, and other oxide ceramics; silicon nitride, nitriding Nitride ceramics such as titanium and boron nitride; silicon carbide, calcium carbonate, aluminum sulfate, aluminum hydroxide, potassium titanate, talc, kaolin clay, kaolinite, halloysite, pyrophyllite, montmorillonite, sericite, mica, candy Ceramics such as sight, bentonite, asbestos, zeolite, calcium silicate, magnesium silicate, diatomaceous earth, and silica sand; glass fiber etc. may be used, and these may be used alone or in combination. Also good.

  The proportion of the inorganic filler in the resin composition is preferably 10 to 90% by mass, more preferably 20 to 55% by mass.

  Although it does not specifically limit as a particle diameter of an inorganic filler, A various thing can be used according to the objective. For example, in order to improve wettability with an organic solvent, when using a hydrophobic inorganic filler or the like, in order to improve the dispersibility in the resin and the surface area, those having a relatively small average particle diameter, for example, 5 nm to 1 μm, Preferably about 5-100 nm is used. On the other hand, when an inorganic filler having an average particle diameter of 1 μm to 10 μm is used, the strength of the film tends to be improved, and when an inorganic filler having an average particle diameter of 1.5 μm to 5 μm is used, The uneven thickness at the time of film tends to improve.

  Examples of the antioxidant include phenolic antioxidants such as “Irganox 1010”, “Irganox 1076”, and “BHT” (both are trademarks, manufactured by Ciba Specialty Chemicals), phosphorus-based and sulfur-based antioxidants. A secondary antioxidant, a hindered amine weathering agent, and the like can be used alone or in accordance with the purpose. In particular, a combination of a phenolic antioxidant and a phosphorus antioxidant is preferably used. Specifically, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butylhydroxyphenyl) propionate 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butylhydroxybenzyl) benzene, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2 , 4-di-t-butylphenyl) -4,4′-biphenylene phosphite is preferred. In addition, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenzo [d, f] [1,3, 2] Dioxyphosphine and the like are also suitable. The blending amount of the antioxidant is preferably 100 ppm to 10000 ppm with respect to the resin constituting the microporous membrane. When the phenolic antioxidant and the phosphorus antioxidant are used in combination, the phenolic / phosphorous type is used. The ratio is preferably 1/3 to 3/1.

  In the present embodiment, it is preferable to use a crystal nucleating agent for the purpose of controlling the crystallinity of polypropylene and controlling the formation of micropores, particularly when a microporous membrane is produced by extrusion. Although it does not specifically limit as a kind of crystal nucleating agent, Carboxylic acid metal salts, such as general benzyl sorbitol type | system | group ("Gerol" (trademark made by Shin Nippon Rika Co., Ltd.)), phosphoric acid metal salt, aluminum t-butylbenzoate Is mentioned. Specific examples thereof include bis (p-ethylbenzylidene) sorbitol, bis (4-methylbenzylidene) sorbitol, bis (3,4-dimethylbenzylidene) sorbitol, bisbenzylidenesorbitol, and the like. The compounding amount of the crystal nucleating agent is preferably 100 ppm or more based on the amount of polypropylene, from the viewpoint that crystallization proceeds rapidly and moldability is easy, although it depends on the desired crystallization conditions. From the viewpoint of preventing excessive bleeding due to the crystal nucleating agent, it is preferably 10,000 ppm or less. A more preferable amount of the crystal nucleating agent is 100 to 2,000 ppm with respect to polypropylene. In the production of microporous membranes using ordinary plasticizers, when liquid paraffin or phthalate ester plasticizers are used, microporous membranes using polyethylene tend to exhibit permeability, but polypropylene is polyethylene. As compared with, the pores become smaller and the permeability tends to be inferior. As a means for eliminating the permeability of this polypropylene, a method of adjusting the pores to an appropriate size is effective, and the phase separation rate is adjusted by using a crystal nucleating agent, so that an appropriate pore structure can be easily formed. .

  In addition, as a dispersion aid for polypropylene and polyethylene, for example, a hydrogenated styrene-butadiene elastomer, an elastomer copolymerized with ethylene and propylene, or the like can be used as necessary. The amount of these dispersing aids is not particularly limited, but is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total amount of polypropylene and polyethylene.

  Antistatic agents include amines such as alkyldiethanolamine and hydroxyalkylethanolamine, amine esters such as stearyl diethanolamine monofatty acid ester, alkyloamides such as lauric acid diethanolamide and stearic acid diethanolamide, glycerin and diethanolamine. Examples include glycerin mono-fatty acid esters, anionic antistatic agents such as alkylbenzene sulfonic acid, and polyoxyethylene alkyl ethers. These may be used alone or in combination. The blending amount of the antistatic agent is not particularly limited, but is preferably about 500 to 10,000 ppm with respect to the resin constituting the microporous membrane.

  The microporous membrane of the present embodiment has a surface dynamic friction coefficient adjusted to 0.55 or less, and if it is within this range, the winding property of the battery and the productivity of the separator itself at the film forming site are improved. In addition, safety when used as a separator of a lithium ion secondary battery is improved. The mechanism of safety improvement is not clear, but it is estimated that the friction reduces, making it difficult for static electricity to occur during the film-forming process and battery winding, and reducing wrinkles and adhesion of foreign objects due to static electricity. Is done. The dynamic friction coefficient is preferably 0.45 or less, and safety is further improved when the coefficient is in this range. The dynamic friction coefficient is more preferably 0.35 or less, and the battery winding speed can be increased within this range.

The microporous membrane of the present embodiment preferably has a surface polypropylene content of 60% by mass or less. When the polypropylene content on the surface is within this range, the friction on the surface is reduced, and the safety, productivity, and winding property tend to be improved. The polypropylene content on the surface is more preferably 45% by mass or less, and further preferably 30% by mass or less from the viewpoint of winding property. Further, in the microporous membrane of the present embodiment, the difference between the total polypropylene content (containing PP amount) contained as a resin component of the microporous membrane and the surface polypropylene content (surface PP amount) is (containing PP amount). − (Surface PP amount) ≧ 10% by mass is preferable. When the (containing PP amount)-(surface PP amount) is within this range, the PP amount on the surface is sufficient while at the same time having a PP amount sufficient to impart high temperature safety and cycleability to the microporous membrane. Since the amount is small, friction is reduced and the productivity of the microporous membrane tends to be excellent. More preferably, (the amount of PP contained) − (the amount of PP on the surface) ≧ 30% by mass, and in this range, when the microporous membrane is used as a separator of a lithium ion secondary battery, It tends to be very good. Particularly preferably, (contained PP amount) − (surface PP amount) ≧ 50 mass%, and within this range, the battery tends to be excellent in high-speed winding property.
Here, the polypropylene content on the surface can be determined by using the value of the dynamic friction coefficient on the surface of the microporous membrane, as described in Examples described later.

The method for producing the microporous membrane of the present embodiment is not particularly limited,
(1) A step of preparing a mixture by mixing polypropylene and polyethylene containing a polyethylene component having a molecular weight (Mw) of less than 10,000,
(2) A step of bleeding the polyethylene component having a molecular weight of less than 10,000 on the surface of the sheet when the sheet is formed by a casting method after the mixture is extruded by an extruder.
Is preferred.

  Bleed here is a phenomenon in which the low molecular weight component of the resin moves to the surface of the microporous membrane, and as a result, the amount of the low molecular weight component on the surface of the microporous membrane increases compared to the inside.

Here, the polyethylene containing a polyethylene component having a molecular weight (Mw) of less than 10,000 preferably contains a low molecular weight component as a by-product during polymerization. Thereby, the dispersibility at the time of mixing a low molecular weight component becomes favorable, and the strength reduction of a microporous film is suppressed. Here, the polyethylene component having a molecular weight (Mw) of less than 10,000 is the ratio of the weight of less than 10,000 in the polyethylene GPC chart. In addition to the above, the polyethylene containing a polyethylene component having a molecular weight of less than 10,000 is a mixture of a polyethylene having a weight average molecular weight of less than 10,000, a low molecular weight polyethylene such as an ethylene polymer, a commercially available wax, or the like with ordinary polyethylene. But you can. In particular, when a sheet is formed by a cast method after adding a mixture of a plasticizer and a low molecular weight polyethylene to a mixture of polypropylene and polyethylene containing a component having a molecular weight (Mw) of less than 10,000 and extruding with an extruder. A method of bleeding a polyethylene component having a molecular weight of less than 10,000 on the surface of the sheet is simple. Further, according to this method, a polyethylene component having a molecular weight of less than 10,000 is easily transferred to the surface of the microporous membrane, thereby suppressing the amount of polypropylene on the surface. Therefore, the object of the present invention can be easily achieved.
In order to promote bleeding, it is preferable to expose the sheet formed by the casting method to a temperature atmosphere in which low molecular weight components easily move to the surface of the sheet for a certain period of time. For example, after cooling and solidifying the sheet coming out of the die at the time of cast molding, it is promoted by holding the resin film at a temperature not lower than the melting point of the resin −50 ° C. for a certain time, for example, 10 seconds or more. The holding temperature and time vary somewhat depending on the properties of the resin, the thickness of the sheet, and the film forming environment temperature. Even after film formation, bleeding is promoted by aging at room temperature for several days.

  The amount of the polyethylene component having a molecular weight (Mw) of less than 10,000 is 1 to 20% by mass based on the entire resin component, from the viewpoint of battery winding property and prevention of strength reduction due to an excessive low molecular weight component. preferable. Furthermore, it is preferable that the amount of the polyethylene component having a molecular weight of less than 10,000 is 5 to 10% by mass with respect to the entire resin component from the viewpoint of high-speed battery winding property and prevention of film contamination due to excessive bleeding.

  Also, after adding a mixture of a plasticizer such as phthalate ester and liquid paraffin and low molecular weight polyethylene to a resin component such as polypropylene and polyethylene and extruding with an extruder, the cast sheet is stretched uniaxially or biaxially. In the wet method of forming a microporous film through a process, a process of removing a plasticizer, a process of stretching after removing the plasticizer, and a process of heat setting, a polyethylene component having a weight average molecular weight of less than 10,000 is dissolved in the plasticizer. Or what was swell-dispersed may be mixed. With this method, it becomes easy to dispose (bleed) the low molecular weight component of polyethylene on the surface of the microporous membrane.

The multilayer microporous membrane in the present embodiment includes the microporous membrane in the present embodiment described above as a surface layer. For example, when the microporous membrane in the present embodiment is (A layer), Combined with any (B layer) or (C layer), (A layer) / (B layer) two-layer structure, (A layer) / (B layer) / (A layer) or (A layer) / Arbitrary layer structures such as a three-layer structure of (B layer) / (C layer) and a five-layer structure of (A layer) / (B layer) / (C layer) / (B layer) / (A layer) sell. Here, the layer composition of (B layer) or (C layer) is not particularly specified. For example, (B layer) and (C layer) include (A layer) such as high-density polyethylene, ultrahigh molecular weight polyethylene, and polypropylene. A composition in which a resin used in the above is singly or mixed, and a composition in which a filler or an additive is further mixed are suitably used.
Among these, the strength of the microporous membrane is improved by using a high-density polyethylene with a Mv of 100,000 or more in the (B layer) or a composition containing mainly high-density polyethylene and a small amount of ultra-high molecular weight polyethylene and polypropylene. And handling becomes very good.

The method for producing the multilayer microporous membrane of the present embodiment may be a known method such as a co-extrusion method, a method of laminating each layer individually and then laminating them, and the above-described (A layer) and (B layer). In the case of a multi-layer microporous film containing, preferably, it is produced by a method comprising the following (Step 1) and (Step 2).
(Step 1) The resin composition A of (A layer) and the resin composition B of (B layer) are extruded together in a molten state to form a multilayer film in which (A layer) and (B layer) are multilayered. Multilayer film forming step (Step 2) After the multilayer film forming step, a multilayer microporous film forming step in which both the (A layer) and (B layer) are microporous. Here, for step 1, (A layer) In addition to (B layer), a third (C layer) may be included.

An example of (Step 1) is given. For example, the resin composition A of (A layer) and the resin composition B of (B layer) are kneaded by separate extruders. As a method of kneading the resin composition A or B, the raw material resin and, optionally, a plasticizer is preliminarily kneaded with a Henschel mixer, a tumbler mixer or the like, and the kneaded product is put into an extruder, Examples of the method include introducing a plasticizer at a desired ratio as required, while heating and melting, and further kneading. Such a method tends to be able to obtain a sheet having a better dispersibility of the resin composition, and is preferable from the viewpoint that each layer can be stretched without breaking even at a high magnification. (Step 2) is a step (wet method) in which a plasticizer and an inorganic filler are blended in the resin composition A and the resin composition B, respectively, and a plasticizer and an inorganic filler are extracted after film formation to form a multilayer microporous film. ), A plasticizer and an inorganic filler may be added to the resin composition A and the resin composition B. In the case where (Step 2) is a step of opening using a crystal interface between the resin composition A and the resin composition B or an interface between the inorganic filler and the resin composition (dry method), the resin composition Opening can be carried out without adding a plasticizer to A and the resin composition B.
Another preferred embodiment in (Step 1) is a case where the resin composition having the same composition is used for both the A layer and the B layer, and the molten resin stream extruded by one extruder is used as two or more resin streams. And a method in which each molten resin flow is spread in the coat hanger part in the die, and the respective films are stacked in the die to form a multilayer state and pushed out of the die from the lip port. It is. In this case, since a multilayer film can be obtained with one extruder, it tends to be excellent in terms of prevention of thermal deterioration and economy.

The method for stacking the multilayer microporous membrane of the present embodiment is not particularly limited, and may be a co-extrusion method using a plurality of ordinary extruders and one die, or a method described in JP-T 2009-543711 May be used. In addition, a production apparatus called a super nanolayer manufactured by Clawren may be used, but as described above, the molten resin stream extruded from one extruder is divided into two or more resin streams, and each In the film state in which the molten resin flow spreads in the coat hanger portion in the die, the respective films are stacked in the die to form a multilayer state, and the manufacturing method including pushing out from the die through the lip port is preferable. According to this method, the apparatus is simple and the manufacturing cost can be reduced. As shown in FIGS. 1 and 2, a specific example of this method includes a distribution unit 1 that divides a molten resin flow into two or more resin flows, and a crossing direction of the divided molten resin flows. In the method of using a device comprising an expansion portion 2 that spreads in a coat hanger shape and a stacking portion 3 in which the respective films are stacked in a mold to form a multilayer state, and then discharged out of the die from the extrusion mold lip port 4. According to this method, in addition to the simplicity of the apparatus, the joining of the layers is performed after the resin spreads in the same manner as in the multi-manifold type coextrusion die, so that the uneven thickness is excellent and the flow is excellent. Since the path is simple, there is an advantage that there is little generation of deteriorated gel due to resin retention or the like.
1 shows a side sectional view of a die used in the above method, and FIG. 2 shows a top sectional view (XX sectional view of FIG. 1).

When the resin composition A and the resin composition B contain a plasticizer, the resin component concentration in the resin composition A is preferably 25 to 50% by mass, and the resin component concentration in the resin composition B is preferably 30 to 55% by mass. (The resin component concentration may be abbreviated as “PC” (polymer concentration).) The difference between the PC of (B layer) and the PC of (A layer) (PCB−PCA) is preferably 3 to 30 mass. %. Setting the ratio in the above range is preferable from the viewpoint of adjusting the physical properties of the multilayer microporous membrane to a specific range described later.
As the melt extruder used in the above (Step 1), it is preferable to use a twin-screw extruder, which can impart a strong shear, thereby further improving dispersibility. More preferably, L / D of the screw of a twin screw extruder is about 20-70, More preferably, it is 25-55. The screw may be provided with a full flight portion and generally a kneading portion such as a kneading disk or a rotor.

  In obtaining the multilayer film (step 1), it is preferable to use a die for coextrusion. In the case of a T die, a coat hanger type multi-manifold die in which the molten resin is spread in a film shape inside the die and then the layers are joined together Is particularly preferable from the viewpoint of thickness control. However, it is also possible to use a feed block die or a crosshead die. In the case of a circular die, a spiral die, and in the case of a multilayer film having five or more layers, a stack die is preferable from the viewpoint of preventing thermal deterioration, and is particularly preferable when it is desired to increase the adhesive strength between layers.

  In the above (Step 1), the resin composition A and the resin composition B are both extruded in a molten state, and it is preferable that they are stacked and multilayered in the die, but multilayered outside the die. May be.

The die attached to the tip of the extruder is not particularly limited, but a circular die, a T die, or the like is used. When using an inorganic filler or a resin composition that easily deteriorates, measures that prevent wear and adhesion caused by it, for example, Teflon (registered trademark) processing, ceramic processing on the flow path and lip Nickel processing, molybdenum processing, and hard chrome coating are preferably used.
Here, in (Step 1), when the resin composition A and the resin composition B are both extruded in a molten state, the melt viscosity A at the extrusion temperature of the resin composition A and the extrusion of the resin composition B The ratio of melt viscosity B at temperature is preferably 1/5 to 5/1, more preferably 1/2 to 2/1, as melt viscosity A / melt viscosity B. Setting the ratio in the above range is preferable from the viewpoint of suppressing interface disturbance at the time of resin merging and suppressing uneven thickness.

  The molten resin extruded from the die is introduced into, for example, a casting apparatus, but may be formed by bank molding or bankless molding. The thick original fabric obtained in the casting process can be used as the original fabric before stretching. Thereafter, the film is stretched for imparting high mechanical strength and a balance between physical and longitudinal properties. As the stretching method, biaxial stretching is preferable, and simultaneous biaxial stretching and sequential biaxial stretching are more preferable. The stretching temperature varies depending on the resin composition used, but is generally a temperature in the range between the Vicat softening point and the melting point of the main resin. From the viewpoint of film strength, the draw ratio is preferably in the range of 3 to 200 times, preferably 20 to 60 times in terms of area magnification.

  (Process 2) is a multilayer microporous film forming process in which both the (A layer) and (B layer) are microporous after the multilayer film forming process, and is performed by a wet method or a dry method as described above. . The extraction of the plasticizer and the inorganic filler may be performed by immersing the film in an extraction solvent and then sufficiently drying the film. As the extraction solvent in the case of extracting only the plasticizer, a solvent that is a poor solvent for the polyolefin and the inorganic filler, a good solvent for the plasticizer, and a boiling point lower than the melting point of the polyolefin is preferable. Examples of such extraction solvents include chlorinated solvents such as methylene chloride and 1,1,1-trichloroethane; ketones such as methyl ethyl ketone and acetone; hydrofluorocarbons, hydrofluoroethers, cyclic hydrofluorocarbons, perocarbons, perfluoros. Halogenous organic solvents such as ether; ethers such as diethyl ether and tetrahydrofuran; hydrocarbons such as n-hexane and cyclohexane; alcohols such as methanol and isopropyl alcohol. Among the above, methylene chloride is particularly preferable. Two or more of these extraction solvents may be used. The extraction step may be before or after the stretching step, or may be multistage extraction using a plurality of extraction tanks. Examples of the extraction solvent for the inorganic filler include alkaline water.

  Moreover, you may add heat fixation by heating extending | stretching as needed for adjustment of film | membrane physical properties, such as a film thickness and an air permeability, or the heat shrink prevention of a film. Examples of the stretching after extraction of the plasticizer and the inorganic filler include uniaxial stretching, simultaneous biaxial stretching, and sequential biaxial stretching, and simultaneous biaxial stretching and sequential biaxial stretching are preferable. The stretching temperature varies depending on the resin composition used, but is generally a temperature in the range between the Vicat softening point and the melting point of the main resin. The draw ratio is preferably more than 1 time and 10 times or less in terms of area magnification.

  Further, when heat treatment for dimensional stabilization is performed, from the viewpoint of reducing film shrinkage in a high temperature atmosphere, for example, using a biaxial stretching machine, a uniaxial stretching machine, or both, 100 ° C. or more and 150 ° C. or less. Heat treatment can be performed. Preferably, it is carried out by relaxing the magnification and / or stress in the width direction, the length direction, or both directions at a temperature below the melting point of the main resin.

  The multilayer microporous film thus obtained may be appropriately subjected to corona treatment or electron beam crosslinking treatment, and may be coated with an inorganic layer or an organic layer.

  The multilayer microporous film of the present embodiment preferably has a three-dimensional network structure in which pores are three-dimensionally complicated. The three-dimensional network structure means a structure in which the surface has a vein shape and the film structure of a cross section from an arbitrary three-dimensional coordinate axis direction is a sponge shape. Leaf vein is a state in which fibrils form a network structure. These can be confirmed by observing the surface and cross section with a scanning electron microscope. The fibril diameter of the three-dimensional network structure is preferably 0.01 μm or more and 0.3 μm or less, and this can also be observed with a scanning electron microscope.

Hereinafter, the physical properties of the microporous membrane of the present embodiment and the multilayer microporous membrane including the microporous membrane as a surface layer will be described.
When the microporous membrane of the present embodiment is used as a single layer membrane and as the surface layer of a multilayer microporous membrane, the thickness of the final microporous membrane as a whole is 5 to 50 μm. preferable. The air permeability of the final microporous membrane as a whole is preferably 500 seconds / 100 cc or less, and the puncture strength is preferably 150 g or more. When the air permeability and puncture strength are within the above ranges, the battery cycle and film strength are compatible when used as a separator.
Here, the “final microporous membrane” means a single layer when the microporous membrane is a single layer, and the entire multilayer when the microporous membrane is a multilayer multilayer microporous membrane. means.

  The air permeability of the final microporous film as a whole is preferably 30 seconds / 100 cc or more from the viewpoint of mechanical strength and self-discharge, and preferably 400 seconds / 100 cc from the viewpoint of battery cycle characteristics and rate characteristics. It is as follows. The air permeability is more preferably 70 seconds / 100 cc or more and 230 seconds / 100 cc or less, and further preferably 100 seconds / 100 cc or more and 230 seconds / 100 cc or less. Here, the air permeability refers to a value measured with a Gurley air permeability meter “G-B2” (trademark, manufactured by Toyo Seiki Seisakusho Co., Ltd.) in accordance with JIS P-8117. In addition, the method for adjusting the air permeability to the above range depends on the production method of the microporous membrane, but the “wet method” in which a resin and a plasticizer are used as raw materials and the plasticizer is extracted and made porous after the film formation. In this case, a method of adjusting the mixing ratio of the resin and the plasticizer, a stretching ratio and temperature in the film forming process, a method of adjusting the stretching ratio and temperature in the heat setting process, and the like can be given. In addition, using a crystalline resin without using a plasticizer, the interface of the amorphous part between lamellae and the interface of the resin and an inorganic filler such as calcium carbonate are cleaved by longitudinal stretching at low temperature to make it porous. In the case of the “dry method”, a method of controlling the crystallization of the lamella by adjusting the draft ratio and the stretching speed can be mentioned.

  The final microporous membrane as a whole has a pin puncture strength of preferably 150 g or more, more preferably 300 g or more, and even more preferably 500 g or more, from the viewpoint of strength during battery assembly. Here, the puncture strength is obtained by conducting a puncture test using a handy compression tester “KES-G5” (trade name, manufactured by Kato Tech Co., Ltd.) under the conditions of a radius of curvature of the needle tip of 0.5 mm and a puncture speed of 2 mm / sec. This is the calculated value. Examples of the method for adjusting the puncture strength to the above range include a method of changing the orientation state of the microporous film. Specifically, in either case of the wet method or the dry method, the draw ratio or temperature The method of adjusting is mentioned. Another method is to use a high-strength resin as the raw material resin itself. For example, in the case of polyolefin, mixing ultrahigh molecular weight polyethylene having a weight average molecular weight of 500,000 or more, preferably 1,000,000 or more. Etc.

  The porosity of the final microporous membrane as a whole is preferably in the range of 25 to 69%. If the porosity is within the above range, the balance between membrane strength and permeability tends to be better. In particular, the balance of self-discharge suppression effect, prevention of fine short-circuiting, and cycle characteristics when used as a separator for a secondary battery or the like is good. Furthermore, the porosity is preferably 30 to 59% from the viewpoint of film strength, and preferably 30 to 49% from the viewpoint of suppressing fine short-circuiting. Examples of the method for adjusting the porosity within the above range include a method for adjusting the mixing ratio of the raw material resin and the plasticizer in the case of the wet method, and a method for adjusting the draw ratio in the case of the dry method.

The average pore diameter D of the final microporous membrane as a whole is preferably 0.02 μm or more and 0.1 μm or less from the viewpoint of achieving both ion permeability and microshort-circuit prevention. The average pore diameter D is more preferably 0.03 μm or more from the viewpoints of ion permeability and electrolyte absorbability, and more preferably 0.09 μm or less from the viewpoint of prevention of slight short circuit. As a method for adjusting the average pore size to the above range, in the case of a wet method, a combination of a resin and a plasticizer is adjusted, and a method in which the dispersion diameter of the plasticizer is increased or a poor compatibility is poor. Examples include a method using a solvent, and examples of the film forming conditions include a method of adjusting the draw ratio during the stretching step.
Furthermore, when the multilayer microporous membrane has a two-layer structure of (A) / (B) or a three-layer structure of (A) / (B) / (A), the average pore diameter DA of the A layer, The average pore diameter DB is not particularly specified, but the difference between DA and DB is preferably within 0.03 μm from the viewpoint of reducing the electrical resistance.

As a whole of the final microporous membrane, the range of the curvature is preferably 1.0 to 3.0, and if it is within this range, the balance between cycle performance and safety tends to be good. The range of the curvature is more preferably 1.5 to 2.5. As a method for adjusting the curvature to the above range, in the case of a wet method, a method for adjusting stretching conditions such as a stretching ratio and a stretching temperature, a method for appropriately selecting a combination of a resin and a plasticizer, and the like can be given.
Here, the average pore diameter and the curvature can be measured as follows.
It is known that the fluid inside the capillary follows the Knudsen flow when the mean free path of the fluid is larger than the pore size of the capillary, and the Poiseuille flow when it is small. Therefore, it is assumed that the air flow in the measurement of the permeability of the microporous membrane follows the Knudsen flow, and the water flow in the measurement of the permeability of the microporous membrane follows the Poiseuille flow.
In this case, the average pore diameter D (μm) and the curvature T (dimensionless) are the air permeation rate constant Rgas (m ³ / (m ² · sec · Pa)) and the water permeation rate constant Rliq (m ³ / (M ² · sec · Pa)), air molecular velocity ν (m / sec), water viscosity η (Pa · sec), standard pressure Ps (= 101325 Pa), porosity ε (%), film thickness L ( [mu] m) using the following formula.
D = 2ν × (Rliq / Rgas) × (16η / 3Ps) × 106
T = (D × (ε / 100) × ν / (3L × Ps × Rgas)) 1/2
Here, Rgas is obtained from the air permeability (sec) using the following equation.
Rgas = 0.0001 / (air permeability × (6.424 × 10 ⁻⁴ ) × (0.01276 × 101325))
Rliq is obtained from the water permeability (cm ³ / (cm ² · sec · Pa)) using the following equation.
Rliq = water permeability / 100
In addition, water permeability is calculated | required as follows. A microporous membrane previously immersed in alcohol is set in a stainless steel permeation cell having a diameter of 41 mm, and after the alcohol in the membrane is washed with water, water is allowed to permeate at a differential pressure of about 50000 Pa, and 120 seconds have elapsed. The water permeation amount per unit time, unit pressure, and unit area was calculated from the water permeation amount (cm ³ ) at the time, and this was taken as water permeability.
Ν is a gas constant R (= 8.314), an absolute temperature T (K), a circumference ratio π, and an average molecular weight M of air (= 2.896 × 10 ⁻² kg / mol), using the following formula. Desired.
ν = ((8R × T) / (π × M)) 1/2

  The microporous membrane according to the present embodiment and the multilayer microporous membrane including the microporous membrane according to the present embodiment as a surface layer are suitably used for a separator for a nonaqueous electrolyte secondary battery and the like, as well as various separation membranes. Can also be used.

  In addition, about the various parameters mentioned above, unless otherwise indicated, it measures according to the measuring method in the Example mentioned later.

  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. Judgment was performed on necessary items, and ◎ and ○ were accepted and × was rejected.

(1) The thickness of each layer and the total thickness (μm)
The thickness of each layer constituting the multilayer microporous film was measured by cross-sectional observation with a general scanning electron microscope (S4100, manufactured by Hitachi, Ltd.).
The total thickness of each layer was taken as the total thickness.

(2) Coefficient of dynamic friction Using a KES-SE friction tester manufactured by Kato Tech Co., Ltd., load 50 g, contact area 10 × 10 = 100 mm ² (0.5 mmφ hard stainless steel wire SUS304 piano wires without any gaps, and , 20 wound so as not to overlap), sample size of width 50 mm x measuring direction 200 mm in the MD and TD directions under the conditions of contact feed speed 1 mm / sec, tension 6 kPa, temperature 25 ° C., humidity 50% Each measurement was performed three times, and the average was obtained. In addition, the value of the dynamic friction coefficient in Table 1 represents the value of the surface in contact with the negative electrode when the battery was produced.

(3) Surface Polypropylene Content The polypropylene content on the surface of the microporous membrane of the present embodiment was determined by the following formula using the dynamic friction coefficient (μd) of the microporous membrane.
Surface polypropylene content [%] = [(μd−PEμd of microporous membrane) / (PPμd−PEμd)] * 100
Here, μd of the microporous membrane was measured in the above (2). PPμd is μd of a single polypropylene film, and 0.85 was used. PEμd is μd of a single polyethylene film, and 0.25 is used.

(4) Porosity (%)
The weight per unit area W (g / cm ² ) and the average density ρ (g / cm ³ ) of the components (resin and additive) constituting the microporous membrane were calculated from the mass of the 100 mm square microporous membrane sample. The following formula was calculated from the thickness d (cm).
Total layer porosity = (100−W / (d * ρ)) * 100 (%))

(5) Air permeability (sec / 100cc)
Based on JIS P-8117, it was measured with a Gurley type air permeability meter “G-B2” (trademark, manufactured by Toyo Seiki Seisakusho Co., Ltd.).
In addition, the value in a table | surface is the air permeability of 20 micrometers conversion calculated by the proportional calculation on the basis of total thickness.

(6) Puncture strength (g)
Using a handy compression tester “KES-G5” (trade name, manufactured by Kato Tech Co., Ltd.), the puncture test was performed under the conditions of a radius of curvature of the needle tip of 0.5 mm and a puncture speed of 2 mm / sec.
In addition, the value in a table | surface is the puncture strength of 20 micrometers conversion calculated by the proportional calculation on the basis of total thickness.

(7) Safety A Φ35mm electrode with a clean surface is sandwiched between a 50mm * 50mm film sample, and a voltage is applied to the electrode to raise it. The voltage value when a 0.5mA current flows and sparks is measured. And used as a safety indicator. This measurement was measured at least 15 times in the plane of the sample film, and the average value was recorded. An average value of 1.8 KV or more was rated as ◎, 1.0 KV or more as ◯, 0.8 KV or more as Δ, and less than 0.8 KV as x.

(8) Cyclicity After producing an electrode and an electrolytic solution as shown below, an evaluation battery was produced using the electrode and an electrolytic solution, and its cycle characteristics were evaluated.
(I) Production of positive electrode 100 parts by mass of lithium cobalt composite oxide LiCoO ₂ as a positive electrode active material, 2.5 parts by mass of flake graphite and acetylene black as a conductive agent, and polyvinylidene fluoride (PVDF) 3 as a binder A slurry was prepared by dispersing 5 parts by mass in N-methylpyrrolidone (NMP). This slurry was applied to both surfaces 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 . This was cut in accordance with the battery width to form a strip.
(Ii) Production of negative electrode As a negative electrode active material, 90 parts by mass of graphitized mesophase pitch carbon fiber (MCF) and 10 parts by mass of flake graphite, 1.4 parts by mass of ammonium salt of carboxymethyl cellulose as a binder and styrene-butadiene A slurry was prepared by dispersing 1.8 parts by mass of polymer latex in purified water. This slurry was applied to both sides 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 application amount of the negative electrode was 106 g / m ² , and the active material bulk density was 1.35 g / cm ³ . This was cut in accordance with the battery width to form a strip.
(Iii) Preparation of Nonaqueous Electrolyte Solution It was prepared by dissolving LiPF ₆ as a solute in a mixed solvent of ethylene carbonate: ethyl methyl carbonate = 1: 2 (volume ratio) to a concentration of 1.0 mol / liter.
(Iv) Production of battery for evaluation Electrode plate multilayer body by winding microporous membrane separator to be evaluated, strip-shaped positive electrode, and strip-shaped negative electrode in a spiral shape by overlapping the strip-shaped negative electrode, separator, strip-shaped positive electrode and separator in this order. Was made. The electrode plate multilayer body is pressed into a flat shape, and then accommodated in an aluminum container. The aluminum lead is led out from the positive electrode current collector, and the nickel lead is led out from the negative electrode current collector to the bottom of the container. The battery wound body was fabricated by welding to a battery.
(V) Cycle characteristics The above-described non-aqueous electrolyte solution was injected into the battery roll for evaluation produced as described above and sealed to produce a lithium ion battery.
This battery was charged to a charge end voltage of 4.2 V with a charge current of 1 A under a temperature of 40 ° C., and discharged to a discharge end voltage of 3 V with a charge current of 1 A. Charging / discharging was repeated with this as one cycle, and the capacity retention after 500 cycles with respect to the initial capacity was expressed as cycle characteristics and evaluated as follows. The capacity retention is ：: 90% or more, ◯: less than 90%, 60% or more, and x: less than 60%.

(9) Weight average molecular weight Weight average molecular weight Mw, number average molecular weight Mn, molecular weight distribution Mw / Mn
Measurement was performed under the following conditions using ALC / GPC 150C (trademark) manufactured by Waters, and a calibration curve was prepared using standard polystyrene. A molecular weight distribution curve in terms of polyethylene was obtained by multiplying each molecular weight component by 0.43 (Q factor of polyethylene / Q factor of polystyrene = 17.7 / 41.3).
Column: Tosoh GMH ₆ -HT (trademark) 2 + GMH ₆ -HTL (trademark) 2 Mobile phase: o-dichlorobenzene Detector: Differential refractometer Flow rate: 1.0 ml / min
Column temperature: 140 ° C

(10) Battery winding property In a 30 mm section in the longitudinal direction of a stainless plate chamfered at a length of 50 mm, a width of 10 mm, and a thickness of 1 mm, imitating a wound type battery, a width of 60 mm as a sample, A porous membrane having a length of 100 mm was wound 5 times in the longitudinal direction. The A end and the B end were attached to a tensile tester with a magnet plate interposed between them as shown in FIG. This was pulled at a pulling speed of 100 mm / min, and the value of resistance when the stainless steel plate was pulled out was regarded as battery winding property. At the time of pulling, the wound porous film is drawn out in a bamboo shoot shape, where x is taken out by 5 mm or more in the pulling direction, ◯ is from 1 mm to less than 5 mm, and ◎ is less than 1 mm.

(11) Microporous membrane productivity When the microporous membrane is cut in the transverse direction at the stage of rewinding the product using a turret in the final winder in the facility for producing the microporous membrane by the method of Example 1. In addition, the case where the film end on the cut product roll side adhered to the product roll due to static electricity or the like was rated as x, and the case where a clean wound body was obtained without breaking was marked as ◯.

Resins and inorganic fillers used in Examples and Comparative Examples are as follows.
PP1 Sun Allomer PB270A
PE1 A blend of 5% by mass of Asahi Kasei Sunfine SH810 with low molecular weight polyethylene (weight average molecular weight = 1000 not commercially available) manufactured by Asahi Kasei.
PE2 10% by mass of Asahi Kasei Sun Fine SH810 mixed with Asahi Kasei low molecular weight polyethylene (weight average molecular weight = 1000 not commercially available).
PE3 30% by mass of Asahi Kasei Sunfine SH810 mixed with Asahi Kasei low molecular weight polyethylene (weight average molecular weight = 1000 not commercially available).
PE4 Sun Fine SH810 manufactured by Asahi Kasei Corporation Weight average molecular weight = 250,000
Filler 1 Fumed silica R974 manufactured by Nippon Aerosil Co., Ltd.

[Example 1]
A production example of a multilayer microporous membrane having a three-layer structure of (A layer) / (B layer) / (A layer) = 5/10/5 μm is shown.
The raw material resin (resin component) and the inorganic filler were blended at the blending ratio (parts by mass) shown in Table 1. 0.5 parts by mass of bis (P-ethylbenzylidene) sorbitol as a crystal nucleating agent and tetrakis- [methylene- (3 ′, 5′-di-t-butyl-) as an antioxidant with respect to 100 parts by mass of the raw material resin 4′-hydroxyphenyl) propionate] 0.3 parts by mass of methane, and 10 parts by mass of liquid paraffin (dynamic viscosity at 37.8 ° C., 75.90 cSt, density 868 kg / m ³ ) as a plasticizer. These raw materials were stirred with a Henschel mixer to prepare the raw materials.
Next, the raw material of (A layer) and the raw material of (B layer) were put into separate twin-screw extruders (41 mm in diameter, L / D = 49). Liquid paraffin was injected into the middle part of the cylinders of both extruders so as to be 65% by mass in (A layer) and 64% by mass in (B layer). The mass% here is the ratio of liquid paraffin to the total composition including liquid paraffin and resin raw materials, additives, fillers and the like.
Adjusting the extrusion amount of both surface layers (A layer) and inner layer (B layer), using a co-extrusion die, the thickness ratio of (A layer) and (B layer) at the die outlet is as shown in Table 1. Was set to be.
A 250 mesh screen was disposed between the extruder and the die. The die used was a T-die capable of multi-manifold coextrusion. In the die, the surface layer was divided into approximately equal parts and stacked on both sides of the inner layer. The melted film raw material coming out of the die was cooled and solidified with a cast roll.
The sheet was stretched by a simultaneous biaxial stretching machine at 120 ° C. at an area magnification of 45 times, then immersed in methylene chloride, extracted after removing liquid paraffin, dried, and further subjected to 125 ° C. by a tenter stretching machine. The film was stretched 1.8 times in the transverse direction, and the stretched sheet was relaxed in the 10% width direction at 120 ° C. and heat-treated. Thereby, a multilayer microporous film having a three-layer structure was obtained. The physical properties of the obtained multilayer microporous film are shown in Table 1. Further, this multilayer microporous membrane was aged at a temperature of 40 ° C. for 48 hours or more in order to promote bleeding of low molecular weight components of polyethylene.
When this multilayer microporous membrane was used as a separator, it was extremely excellent in battery winding performance, cycle performance, safety, and separator productivity.

[Examples 2 to 13, Comparative Examples 1 to 5]
A multilayer microporous membrane was molded and evaluated by the same method as in Example 1 while changing each layer configuration and structural factors described in Tables 1 and 2. The amount of liquid paraffin added was in the range of 40% by mass to 80% by mass although it was different in each example. The simultaneous biaxial stretching machine was stretched at an area magnification of 45 times within a range of 115 ° C to 130 ° C. The liquid paraffin is extracted and dried, then dried, and further stretched 1.1 to 2.0 times in the transverse direction under the condition of 120 to 130 ° C by a tenter stretching machine, and this stretched sheet is relaxed in the width direction by 10% at 130 ° C. The heat treatment was performed. The physical properties of the obtained multilayer microporous film are shown in Tables 1 and 2. Although Examples 2, 4, and 5 have a sufficient amount of polypropylene disposed on the surface layer and excellent cycleability, the polypropylene content on the surface is small, so the battery winding property is particularly excellent. Since there was little generation of static electricity, it was particularly excellent in safety. Comparative Examples 1 to 4 are conventional techniques, which have good cycle characteristics, but have poor cycle characteristics because of the large polypropylene content on the surface. On the other hand, although the comparative example 5 had favorable battery winding property, it was inferior to cycling property. As described above, the multilayer microporous membrane of the present embodiment can achieve both cycle performance, safety, battery winding performance, and separator productivity, which cannot be realized by the conventional technology.

  The microporous membrane of the present embodiment has industrial applicability as a separator such as a lithium ion secondary battery capable of achieving both cycle performance, safety, battery winding performance, and separator productivity.

Claims (5)

A microporous membrane comprising a resin composition containing a mixture of polypropylene and polyethylene as a main component,
The proportion of the polypropylene in the mixture is 50% by mass or more,
Dynamic friction coefficient of the surface Ri der 0.55 or less,
The surface polypropylene content is 60% by mass or less, and (total polypropylene content) − (surface polypropylene content) ≧ 10% by mass,
Microporous membrane polypropylene content of the surface Ru value der obtained by the following equation.
Surface Polypropylene Content [%] = [(μd−PEμd of Microporous Film) / (PPμd−PEμd)] * 100
(Here, the dynamic friction coefficient (μd) of the microporous film is a load of 50 g, contact area 10 × 10 = 100 mm ² (made by hard stainless steel wire SUS304 of 0.5 mmφ, manufactured by Kato Tech Co., Ltd., KES-SE friction tester) . 20 piano wires wound so as not to overlap each other and not to overlap each other), contact feed speed 1 mm / sec, tension 6 kPa, temperature 25 ° C., humidity 50%, width 50 mm × measurement direction 200 mm The sample size was measured three times in the MD and TD directions, and the average value was obtained, and PPμd was a dynamic friction coefficient of a single polypropylene film, and 0.85 was used, and PEμd was a dynamic friction coefficient of a single polyethylene film. Yes, 0.25 was used.) A multilayer microporous membrane comprising the microporous membrane according to claim 1 as a surface layer. A method for producing a microporous membrane according to claim 1 ,
(1) A step of preparing a mixture by mixing polypropylene and polyethylene containing a polyethylene component having a molecular weight (Mw) of less than 10,000,
(2) a step of bleeding the polyethylene component having a molecular weight (Mw) of less than 10,000 on the surface of the sheet when the sheet is formed by a casting method after the mixture is extruded by an extruder.
Manufacturing method. In the step (1), a mixture of polypropylene and polyethylene containing a polyethylene component having a molecular weight (Mw) of less than 10,000,
The method according to claim 3 , further comprising the step of adding a mixture of a plasticizer and a polyethylene component having a weight average molecular weight of less than 10,000 . Claim 1 microporous membrane or a non-aqueous electrolyte secondary battery separator comprising a multi-layer, microporous membrane of claim 2 wherein the description.