JP6398498B2 - Battery separator using polyolefin laminated porous membrane and method for producing the same - Google Patents

Description

The present invention relates to a battery separator using a polyolefin laminated porous membrane suitable for lamination of a modified porous layer. It is a battery separator useful as a lithium ion battery separator.

  Thermoplastic resin microporous membranes are widely used as material separation, selective permeation and isolation materials. For example, battery separators used in lithium ion secondary batteries, nickel-hydrogen batteries, nickel-cadmium batteries, polymer batteries, separators for electric double layer capacitors, reverse osmosis filtration membranes, ultrafiltration membranes, microfiltration membranes, etc. Filters, moisture permeable waterproof clothing, medical materials, etc. In particular, a polyethylene porous membrane is suitably used as a separator for a lithium ion secondary battery. The reason for this is not only the characteristics of having ion permeability by impregnating with an electrolyte solution, excellent electrical insulation, electrolyte solution resistance and oxidation resistance, but also current at a temperature of about 120 to 150 ° C. when the battery is abnormally heated. This is because it also has a hole closing effect that blocks excessive temperature rise. However, if the temperature continues to rise even after the pores are closed for some reason, a film breakage may occur at a certain temperature due to a decrease in the viscosity of the polyethylene constituting the film and a contraction of the film. This phenomenon is not limited to polyethylene, and even when other thermoplastic resins are used, the phenomenon cannot be avoided beyond the melting point of the resin constituting the porous film.

  In particular, lithium-ion battery separators are deeply involved in battery characteristics, battery productivity, and battery safety. Excellent mechanical characteristics, heat resistance, permeability, dimensional stability, pore clogging characteristics (shutdown characteristics), molten film breakage Characteristics (meltdown characteristics) are required. Furthermore, in order to improve the cycle characteristics of the battery, it is required to improve the adhesion with the electrode material and to improve the electrolyte permeability to improve the productivity. For this reason, various studies have been made to stack various modified porous layers on a porous membrane. As the modified porous layer, a polyamide-imide resin, a polyimide resin, a polyamide resin and / or a fluorine-based resin excellent in electrode adhesion, which have both heat resistance and electrolyte solution permeability are preferably used. The modified porous layer in the present invention refers to a layer containing a resin that imparts or improves at least one function such as heat resistance, adhesion to an electrode material, and electrolyte permeability.

  Furthermore, in order to improve battery capacity, it is necessary to increase the area that can be filled in the container not only in the electrode but also in the separator, and it is predicted that further thinning will progress. However, as the porous film becomes thinner, it tends to be deformed in the plane direction. Therefore, a battery separator in which a modified porous layer is laminated on a thin porous film is modified during processing, the slit process, or the battery assembly process. The porous porous layer may peel off, making it more difficult to ensure safety.

  In addition, in order to reduce costs, the battery assembly process is expected to increase in speed, and even in such high-speed processing, there are few troubles such as peeling of the modified porous layer, and high adhesion that can withstand high-speed processing. Is required. However, in order to improve the adhesion, if the resin contained in the modified porous layer is sufficiently permeated into the polyolefin porous membrane as a base material, there is a problem that the increase in the air resistance increases. It was.

  In Patent Document 1, polyvinylidene fluoride is applied to a polyethylene porous membrane having a thickness of 9 μm, and a part of the polyvinylidene fluoride resin appropriately bites into the pores of the polyethylene porous membrane so as to express an anchor effect. A composite porous membrane having a peel strength (T-type peel strength) at the interface between the porous membrane and the polyvinylidene fluoride coating layer is disclosed as 1.0 to 5.3 N / 25 mm.

  In Patent Document 2, a heat-resistant porous layer containing a thickening agent of acrylic resin and N-vinylacetamide or a water-soluble cellulose derivative and plate boehmite on a corona discharge-treated polyethylene porous film having a thickness of 16 μm. There is disclosed a separator having a polyethylene porous membrane and a heat-resistant porous layer having a peel strength at 180 ° (T-type peel strength) of 1.1 to 3.0 N / 10 mm.

In Patent Document 3, an ultrahigh molecular weight polyethylene (UHM) having a weight average molecular weight of 2.0 × 10 ⁶ is used.
High-density polyethylene (HDPE) with 20% by weight (WPE) and a weight average molecular weight of 3.5 × 10 ⁵
) A polyethylene solution consisting of 30 parts by weight of a polyethylene composition comprising 80% by weight and an antioxidant and 70 parts by weight of liquid paraffin was extruded from an extruder at 190 ° C., and the gel was drawn off with a cooling roll adjusted to 50 ° C. A technique for producing a porous film by obtaining a shaped molded article and then biaxially stretching so as to be 5 × 5 times is disclosed.

  In Patent Document 4, a polyethylene solution similar to that in Patent Document 3 is extruded from an extruder, and taken up by a cooling roll adjusted to 0 ° C., to obtain a gel-like molded product, and then biaxially drawn at a draw ratio of 5 × 5 times. A technique for producing a microporous film by stretching is disclosed.

  In Example 1 of Patent Document 5, 47.5 parts by mass of polyethylene having a viscosity average molecular weight of 200,000, 2.5 parts by mass of polypropylene having a viscosity average molecular weight of 400,000, 50 parts by mass of a composition comprising an antioxidant, and liquid paraffin While extruding a polyethylene solution consisting of 50 parts by mass from an extruder at 200 ° C. and taking it up with a cooling roll adjusted to 25 ° C., a gel-like molded product was obtained, and then biaxially so as to be 7 × 6.4 times Stretching to obtain a polyolefin resin porous membrane. Next, a multilayer porous membrane obtained by laminating a coating layer made of polyvinyl alcohol and alumina particles on the surface of the polyolefin resin porous membrane is disclosed.

  In Example 6 of Patent Document 6, a polyethylene solution having a weight average molecular weight of 41.50 million, a weight average molecular weight of 560,000, a polyethylene composition of 30% by weight and a mixed solvent of liquid paraffin and decalin of 70% by weight is used as an extruder. To 148 ° C., and cooled in a water bath to obtain a gel-like molded product, and then biaxially stretched to 5.5 × 11.0 times to obtain a polyethylene porous membrane. Next, a separator for a non-aqueous secondary battery obtained by further laminating a coating layer made of a meta-type wholly aromatic polyamide and alumina particles on the surface of the polyethylene porous membrane is disclosed.

  Patent Document 7 discloses a polyolefin microporous membrane in which unevenness of an oblique lattice pattern is formed by passing a gel sheet before stretching between an embossing roll and a backup roll.

  However, in response to the demands for high-speed processing and separator thinning associated with cost reduction and capacity increase, which are expected to proceed rapidly in the future, these conventional technologies locally perform slit processing and battery assembly processing. Since the modified porous layer is peeled off, it is expected that ensuring safety will become increasingly difficult. In particular, if the polyolefin resin porous membrane serving as the base material becomes thin, it becomes difficult to obtain a sufficient anchor effect of the modified porous layer for the polyolefin resin porous membrane, and thus it becomes more difficult to ensure safety.

JP 2012-037662 A Republished 2010-104127 JP 2003-003006 A JP 2004-083866 A Japanese Patent No. 4931083 Japanese Patent No. 4460028 International Publication No. 2008/053898

Assuming that battery separators will become increasingly thinner and lower in cost, the present inventors have extremely high peel strength from the modified porous layer and are suitable for high-speed processing in the slit process and battery assembly process. An object of the present invention is to provide a polyolefin laminated porous membrane suitable for modified porous layer lamination and a battery separator in which the modified porous layer is laminated.
In this specification, the peel strength between the polyolefin laminated porous membrane and the modified porous layer in the separator is a value measured by the following method (hereinafter, sometimes referred to as 0 ° peel strength).

   FIG. 1 schematically shows a side view of a laminated sample of a polyolefin porous membrane and a modified porous layer in a state of being pulled by a tensile tester (not shown). 1 is a laminated sample, 2 is a polyolefin laminated porous film, 3 is a modified porous layer, 4 is a double-sided pressure-sensitive adhesive tape, 5 and 5 'are aluminum plates, and the arrows in the figure are tensile directions. A sample (1) (battery) cut into a 50 mm width × 100 mm length on a double-sided adhesive tape (4) of the same size on an aluminum plate (5) having a size of 50 mm × 25 mm and a thickness of 0.5 mm. The surface of the polyolefin laminated porous membrane (2) of the separator for use is attached so that 40 mm overlaps from the end of one side of the 25 mm length of the aluminum plate (5), and the protruding portion is cut off. Next, a double-sided adhesive tape is attached to one side of an aluminum plate (5 ′) having a length of 100 mm, a width of 15 mm, and a thickness of 0.5 mm. From the end of one side of the aluminum plate (5) on the 25 mm-long sample side. Paste so that 20mm overlaps. Thereafter, the aluminum plate (5) and the aluminum plate (5 ′) are pulled in parallel in opposite directions using a tensile tester at a tensile rate of 10 mm / min, and the strength when the modified porous layer is peeled is measured. If the peel strength is 100 N / 15 mm or more in this evaluation method, the laminated modified porous layer is being transported or processed even if the polyolefin porous membrane has a thickness of 10 μm or less, for example. The peeling phenomenon hardly occurs.

  The T-type peel strength or 180 ° peel strength conventionally used as a method for measuring peel strength is to peel the coating layer from the polyethylene porous film perpendicularly or obliquely backward from the surface of the polyethylene porous film. It is the peel force at the time. According to this evaluation method, it is possible to evaluate the abrasion resistance in the slit process and the battery assembly process more practically as compared with these conventional evaluation methods.

In order to solve the above problems, the present invention has the following configuration.
(1) A polyolefin laminated porous membrane having a layer configuration of A / B / A composed of a polyolefin microporous membrane and having a layer configuration of A / B / A, and the density of both the A layer and the B layer is 0.94 g / cm ³ . The high-density polyethylene exceeds the main component, and the layer A contains from 10% by weight to 40% by weight of ultrahigh molecular weight polyethylene having a weight average molecular weight of 1 × 10 ⁶ or more and less than 4 × 10 ⁶ , and the layer B has a weight average The ultrahigh molecular weight polyethylene having a molecular weight of 1 × 10 ⁶ or more and less than 4 × 10 ^{6 is} contained in an amount of 1 to 40% by mass, and the terminal vinyl group concentration of the high-density polyethylene of the A layer is 0.00 per 10,000 carbon atoms. is 2 or more, projections made of polyethylene on the surface of the polyolefin porous laminated film, 5μm ≦ W ≦ 50μm (W is the size of the projections) and 0.5μm ≦ H ≦ 3.0μm (H is the projection It viewed Is), three per side / cm ² or more, and dotted erratically at 200 spots / cm ^2, the protrusion is grown raised portions of the surface layer of the polyolefin multilayer porous membrane A separator for a battery in which a modified porous layer is laminated on at least a surface of a polyolefin laminated porous film having a film thickness of 20 μm or less and having at least protrusions .

( 2 ) The battery separator as described in the item ( 1 ), wherein the modified porous layer contains a polyamideimide resin, a polyimide resin or a polyamide resin.

( 3 ) The battery separator as described in ( 1 ), wherein the modified porous layer contains a fluororesin.

( 4 ) The battery separator as described in any one of ( 1 ) to ( 3 ), wherein the modified porous layer contains inorganic particles or crosslinked polymer particles.

( 5 ) The battery separator according to any one of ( 1 ) to ( 4 ), wherein the polyolefin laminated porous film has a thickness of 16 μm or less.

( 6 ) The battery separator according to any one of ( 1 ) to ( 4 ), wherein the polyolefin laminated porous membrane has a thickness of 12 μm or less.

( 7 ) The manufacturing method of the separator for batteries as described in any one of (1 )-( 6 ) term | claim including the following processes (a)-(f).
(A) Step of preparing a polyolefin resin solution by adding a molding solvent to the polyolefin resin constituting the A layer and then melt-kneading
However, the polyolefin resin constituting the layer A includes an ultrahigh molecular weight polyethylene having a weight average molecular weight of 1 × 10 ⁶ or more and less than 4 × 10 ⁶ and a high density polyethylene having a weight average molecular weight of 1 × 10 ⁴ to 5 × 10 ⁵ , The content of ultrahigh molecular weight polyethylene is 10% by mass or more and 40% by mass or less, and the high density polyethylene has a terminal vinyl group concentration of 0.2 or more per 10,000 carbon atoms.
(B) A step of preparing a polyolefin resin solution by adding a molding solvent to the polyolefin resin constituting the B layer and then melt-kneading.
However, the polyolefin resin constituting the B layer comprises a high density polyethylene having a weight-average molecular weight 1 × 10 ultra-high molecular weight of ⁶ or more and less than 4 × 10 ⁶ polyethylene and the weight average molecular weight ^of 1 × 10 ⁴ from 5 × 10 ^5, ultra Content of high molecular weight polyethylene is 1 mass% or more and 40 mass% or less.
(C) Extrude the polyolefin solutions A and B obtained in the steps (a) and (b) from a die, and at least one of them is a cooling roll having a surface from which the molding solvent is removed by the molding solvent removing means. (D) The step of stretching the gel-like molded product in MD (machine direction) and TD (width direction) to obtain a stretched molded product (e) The stretched molded product (F) A step of heat-treating the laminated porous molded product to obtain a polyolefin laminated porous membrane

(8) the (c) means for removing the molding solvent in step is characterized in that the doctor blade (7) The method of producing a separator for batteries according to claim.

According to the present invention, it is possible to obtain a battery separator in which a modified porous layer in which peeling does not occur even during high-speed transport is laminated on a polyolefin laminated porous membrane having extremely excellent adhesion between modified porous layers.

Schematic which shows the measuring method of 0 degree peeling strength. Schematic which shows the spherulite structure and crystal nucleus of polyethylene in a polyethylene porous membrane. The microscope picture of the ring-shaped trace derived from the spherulite of polyethylene in a polyethylene porous membrane. Schematic which shows the process of forming a gel-like molded object, extruding a polyethylene resin solution from the die | dye installed in the front-end | tip of an extruder, and cooling with a cooling roll.

  The present invention can be obtained by highly controlling the cooling rate of a polyolefin resin solution extruded from an extruder through a die in a process for producing a polyolefin laminated porous membrane using a specific polyolefin resin solution. , A polyolefin laminated porous membrane having a moderate shape and a number of protrusions on the surface, and when the modified porous layer is laminated on the polyolefin laminated porous membrane, excellent peel strength from the modified porous layer And a polyolefin porous laminate film having a small increase in air resistance.

  The protrusions referred to in the present invention are essentially different from protrusions obtained by adding, for example, inorganic particles to a polyolefin laminated porous membrane. Protrusions obtained by adding inorganic particles to polyolefin laminated porous membranes are usually extremely small in height, and if one tries to form projections with a height of 0.5 μm or more by the same means, polyolefin laminated porous membranes It is necessary to add particles having a particle size equal to or greater than the thickness of the film. However, when such particles are added, the strength of the polyolefin laminated porous membrane is lowered, which is not realistic.

  The protrusions referred to in the present invention are those in which a part of the surface layer of the polyolefin laminated porous membrane is grown to a moderately raised shape, and do not deteriorate the basic characteristics of the polyolefin laminated porous membrane. .

  Further, the irregularly scattered protrusions referred to in the present invention are regularity or periodicity obtained by passing through an embossing roll before or after the stretching step in the production of the polyolefin porous film. The arrangement is clearly different. Press work such as embossing is basically not preferred because it forms protrusions by compressing portions other than the protrusions and tends to cause a decrease in air resistance and electrolyte permeability.

The moderately shaped protrusion as used in the present invention means a protrusion having a size of 5 μm or more and 50 μm or less and a height of 0.5 μm or more. That is, 5 μm ≦ W ≦ 50 μm (W is the size of the protrusion) and 0.5 μm ≦ H (H is the height of the protrusion). Such a protrusion functions as an anchor when the modified porous layer is laminated on the porous film, and as a result, the battery separator having a high 0 ° peel strength can be obtained. On the other hand, the upper limit of the height is not particularly limited, but 3.0 μm is sufficient. The more the protrusions are sufficiently high, the higher the 0 ° peel strength described above tends to be. That is, the 0 ° peel strength is affected by the number of protrusions having a height of 0.5 μm or more and the average height thereof. The lower limit of the number of projections (per one side) is 3 / cm ² , preferably 5 / cm ² , more preferably 10 / cm ² . The upper limit of the number of protrusions is 200 / cm ² , preferably 150 / cm ² . The lower limit of the height of the protrusion is 0.5 μm, preferably 0.8 μm, more preferably 1.0 μm.
In addition, the magnitude | size and height of a processus | protrusion in this invention say the value measured with the measuring method mentioned later.

  The increase in the air resistance referred to in the present invention means the difference between the air resistance of the polyolefin laminated porous membrane as the base material and the air resistance of the battery separator in which the modified porous layer is laminated. And 100 seconds / 100 cc Air or less is preferable.

  The outline of the polyolefin laminated porous membrane and battery separator of the present invention will be described below, but the present invention is not limited to these representative examples.

First, the polyolefin laminated porous membrane of the present invention will be described.
The polyolefin laminated porous membrane of the present invention is a laminated porous membrane comprising at least two layers.

  The polyolefin laminated porous membrane of the present invention has a thickness (total thickness) of 20 μm or less. A preferable upper limit is 16 μm, more preferably 12 μm. The lower limit is 7 μm, preferably 9 μm. If the thickness of the polyolefin laminated porous membrane is within the above preferred range, practical membrane strength and pore blocking function can be retained, and the area per unit volume of the battery case is not restricted, and will proceed in the future. Suitable for increasing capacity of batteries.

  The upper limit of the air permeability resistance of the polyolefin laminated porous membrane is 300 sec / 100 cc Air, preferably 200 sec / 100 cc Air, more preferably 150 sec / 100 cc Air, and the lower limit is 50 sec / 100 cc Air, preferably 70 sec / 100 cc Air, more preferably 100 sec. / 100 cc Air.

  The upper limit of the porosity of the polyolefin laminated porous membrane is preferably 70%, more preferably 60%, and even more preferably 55%. The lower limit is preferably 30%, more preferably 35%, still more preferably 40%. When the air permeability resistance and the porosity are within the above preferred ranges, sufficient battery charge / discharge characteristics, particularly ion permeability (charge / discharge operating voltage) and battery life (closely related to the amount of electrolyte retained) In this case, the function as a battery can be sufficiently exerted, and sufficient mechanical strength and insulation can be obtained, so that the possibility of a short circuit during charge / discharge is reduced.

  The average pore size of the polyolefin laminated porous membrane is preferably 0.01 to 1.0 μm, more preferably 0.05 to 0.5 μm, and still more preferably 0.1 to 0.1 μm because it greatly affects the pore closing performance. 0.3 μm. When the average pore diameter of the laminated porous membrane made of polyolefin is within the above preferable range, the 0 ° peel strength of the modified porous layer can be sufficiently obtained by the anchor effect of the functional resin, and when the modified porous layer is laminated, The air resistance is not greatly deteriorated, the response to the temperature of the hole closing phenomenon is not slowed down, and the hole closing temperature due to the heating rate is not shifted to a higher temperature side.

Shutdown speed of the polyolefin multilayer porous film is preferably 2000sec / 100cccm ³ / 20μm or more. More preferably 3000sec / 100cccm ³ / 20μm or more. When the shutdown speed of the multilayer porous membrane made of polyolefin is within the above range, the multi-layer microporous membrane is used as a lithium battery separator, and the shut-off response at the time of overheating is good, so that the safety when used as a battery is improved. Excellent.

  As polyolefin resin which comprises the laminated porous membrane made from polyolefin, polyethylene and polypropylene are preferable. Further, it may be a single substance or a mixture of two or more different polyolefin resins, for example, a mixture of polyethylene and polypropylene, or a copolymer of different olefins. Among these, polyethylene is particularly preferable from the viewpoint of excellent pore closing performance. This is because, in addition to basic characteristics such as electrical insulation and ion permeability, it has a hole blocking effect that blocks current and suppresses excessive temperature rise at abnormal battery temperature rise.

  Hereinafter, polyethylene will be described in detail as an example of the polyolefin resin used in the present invention.

[1] Polyolefin resin in the first layer (A layer) The polyolefin microporous film constituting the A layer of the present invention is preferably a polyolefin resin mainly composed of polyethylene. The types of polyethylene, high density polyethylene such as density exceeding 0.94 g / cm ^3, density polyethylene in the range density of 0.93~0.94g / cm ^3, density of from 0.93 g / cm ³ Low low density polyethylene, linear low density polyethylene and the like can be mentioned, among which high density polyethylene is preferable. These polyethylenes may be not only ethylene homopolymers but also copolymers containing a small amount of other α-olefins. Examples of α-olefins other than ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, (meth) acrylic acid, esters of (meth) acrylic acid, styrene, etc. Is preferred.

Here, as high density polyethylene, it is preferable that the terminal vinyl group concentration by infrared spectroscopy is 0.2 or more per 10,000 carbon atoms. The lower limit is more preferably 0.4, further preferably 0.6, and most preferably 0.9. When the terminal vinyl group concentration is within the above range, good shutdown characteristics can be obtained. The weight average molecular weight (hereinafter referred to as Mw) of the high density polyethylene is not particularly limited, but is preferably 1 × 10 ⁴ to 5 × 10 ⁵ . When Mw is in the above range, both the stability of film formation and the shutdown characteristics can be achieved.

Moreover, it is preferable to contain an ultra high molecular weight polyethylene resin from a viewpoint of intensity | strength. The ultra high molecular weight polyethylene may be a copolymer containing not only a homopolymer of ethylene but also a small amount of the other α-olefins mentioned above. The Mw of the ultra high molecular weight polyethylene is preferably 1 × 10 ⁶ or more and less than 4 × 10 ⁶ . The content of ultrahigh molecular weight polyethylene is 100% by mass with respect to the entire polyolefin resin, and the lower limit is preferably 10% by mass, more preferably 18% by mass. The upper limit is preferably 40% by mass. When the Mw is 4 × 10 ⁶ or more, the viscosity of the melt becomes too high, so that there may be a problem in the film forming process such that the resin cannot be extruded from the die. When Mw is in the above range, both the stability of film formation and strength can be achieved.

  Furthermore, when the content of ultrahigh molecular weight polyethylene is within the preferred range, a sufficiently high protrusion can be obtained. When the modified porous layer is laminated by the protrusions, the protrusions function as anchors, and extremely strong peeling resistance can be obtained against the force applied in parallel to the surface direction of the polyethylene porous film. Further, even when the thickness of the polyethylene porous film is reduced, sufficient tensile strength can be obtained. The tensile strength is preferably 100 MPa or more. There is no particular upper limit.

  The specific molecular weight distribution (Mw / Mn) of Mw and number average molecular weight (Mn) of the polyethylene resin is preferably in the range of 5 to 200, more preferably 10 to 100. When the range of Mw / Mn is within the above preferred range, it is easy to extrude the polyethylene solution, and when the thickness of the polyethylene porous film is reduced, sufficient mechanical strength can be obtained. Mw / Mn is used as a measure of molecular weight distribution, that is, in the case of polyethylene consisting of a single substance, the larger this value, the wider the molecular weight distribution. The Mw / Mn of polyethylene composed of a single substance can be appropriately adjusted by multistage polymerization of polyethylene. Moreover, Mw / Mn of the mixture of polyethylene can be suitably adjusted by adjusting the molecular weight and mixing ratio of each component.

[2] Polyolefin resin in the second layer (B layer) The polyolefin microporous membrane constituting the B layer of the present invention is preferably a polyolefin resin mainly composed of high-density polyethylene. These polyethylenes may be not only ethylene homopolymers but also copolymers containing a small amount of other α-olefins as in the case of the A layer.

  Here, as high density polyethylene, it is preferable that the terminal vinyl group density | concentration by an infrared spectroscopy is less than 0.2 per 10,000 carbon atoms. The upper limit is more preferably 0.15, and still more preferably 0.1. When the terminal vinyl group concentration is in the above range, both good permeability and strength can be achieved.

  Similarly to the A layer, the B layer preferably contains ultrahigh molecular weight polyethylene from the viewpoint of strength and formation of protrusions. The upper limit of the content of ultrahigh molecular weight polyethylene is 40% by weight, more preferably 30% by weight, still more preferably 10% by weight, and the lower limit is 1% by weight, more preferably 2% by weight, still more preferably 5% by weight. is there.

  The specific molecular weight distribution (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyethylene resin of the B layer together with the A layer is preferably in the range of 5 to 200, and is preferably 10 to 100. It is more preferable. When the range of Mw / Mn is the above preferred range, it is easy to extrude a polyethylene solution, and a sufficient number of protrusions can be obtained. Further, when the thickness of the polyethylene porous film is reduced, sufficient Mechanical strength is obtained. Mw / Mn is used as a measure of molecular weight distribution, that is, in the case of polyethylene consisting of a single substance, the larger this value, the wider the molecular weight distribution. The Mw / Mn of polyethylene composed of a single substance can be appropriately adjusted by multistage polymerization of polyethylene. Moreover, Mw / Mn of the mixture of polyethylene can be suitably adjusted by adjusting the molecular weight and mixing ratio of each component.

  The present inventors consider the mechanism by which the projections are formed in the present invention as follows. The resin solution of the melted polyethylene resin and the molding solvent is extruded from the die, and at the same time, the crystallization of polyethylene is started. The crystallization speed is increased by contacting the cooling roll and quenching. At this time, a spherulite having a symmetric structure having a crystal nucleus is formed (FIG. 2). When the heat transfer rate between the chill roll surface and the molten polyethylene resin is relatively low, the crystallization rate is low, resulting in spherulites with relatively small crystal nuclei. When the heat transfer rate is high, the spherulite has a relatively large crystal nucleus. The crystal nuclei of these spherulites become protrusions during TD (width direction) and / or MD (machine direction) stretching, which is a subsequent process. Spherulites appear as ring-shaped marks on the surface of the polyethylene porous membrane (FIG. 3).

  As long as the polyethylene laminated porous membrane is within a range that satisfies the above-mentioned various characteristics, a production method according to the purpose can be freely selected. There are foaming methods, phase separation methods, dissolution recrystallization methods, stretched pore opening methods, powder sintering methods, etc., among these porous membrane production methods. Among these, phase separation is performed in terms of uniform micropores and cost. The method is preferred.

  As a manufacturing method by the phase separation method, for example, polyethylene and a molding solvent are heated and melt-kneaded, and the obtained molten mixture is extruded from a die and cooled to form a gel-like molded product, and the obtained gel-like molding is obtained. Examples include a method of obtaining a porous film by stretching the product in at least a uniaxial direction and removing the molding solvent.

[3] Method for Producing Polyolefin Laminated Microporous Membrane A method for producing a polyolefin laminated porous membrane of the present invention will be described.
The method for producing a polyolefin laminated porous membrane of the present invention includes the following steps (a) to (f).
(A) Step of adding a molding solvent to the polyolefin resin constituting the A layer, then melt-kneading to prepare a polyolefin resin solution (b) Melting after adding the molding solvent to the polyolefin resin constituting the B layer Step (c) of kneading and preparing a polyolefin resin solution The polyolefin resin solutions A and B obtained in steps (a) and (b) are extruded from a die, and at least one of them is molded by a solvent removing means for molding. Step (d): Forming a laminated gel-like molded product by cooling with a cooling roll having a surface from which the solvent has been removed, and stretching the laminated gel-like molded product in MD (machine direction) and TD (width direction) Step (e) of obtaining a stretched molded product (e) Extracting and removing the molding solvent from the layered stretched molded product and drying to obtain a layered porous molded product (f) Heat treatment of the layered porous molded product And further obtaining a polyolefin multilayer porous membrane (a) ~ a (f) before halfway, hydrophilic treatment after, also add other steps neutralization treatment. Moreover, a redrawing process can also be provided after the (f) process.

Hereinafter, each step will be described using an example in which a polyethylene resin is used as the polyolefin resin.
(A), (b) A step of adding a molding solvent to the polyethylene resin constituting the A layer and the B layer, and then melt-kneading to prepare polyethylene resin solutions A and B. As a molding solvent, polyethylene is sufficient If it can melt | dissolve, it will not specifically limit. For example, nonane, decane, undecane, dodecane, liquid paraffin and other aliphatic or cyclic hydrocarbons, or mineral oil fractions with boiling points corresponding to these, gel-like molded products with a stable solvent content Nonvolatile solvents such as liquid paraffin are preferred for obtaining. The dissolution by heating is performed by a method in which the polyethylene composition is completely dissolved and stirred and uniformly mixed in an extruder. The temperature varies depending on the polymer and solvent to be used when it is dissolved in an extruder or in a solvent while stirring, but is preferably in the range of 140 to 250 ° C, for example.

  The concentration of the polyethylene resin is 25 to 40 parts by weight, preferably 28 to 35 parts by weight, with the total of the polyethylene resin and the molding solvent being 100 parts by weight. When the concentration of the polyethylene resin is within the above preferable range, a sufficient number of crystal nuclei for forming protrusions are formed, and a sufficient number of protrusions are formed. In addition, swell and neck-in are suppressed at the die outlet when extruding the polyethylene resin solution, and the moldability and self-supporting property of the extruded product are maintained.

  When a difference is provided between the resin concentrations of the resin solutions A and B, a laminated microporous film having a structure (gradient structure) in which the average pore diameter is changed in the film thickness direction can be obtained. The average pore diameter of the layer formed using the resin solution having the lower concentration is larger than the average pore diameter of the layer formed using the resin solution having the higher concentration. The concentration of the resin solution A or B can be appropriately selected according to the physical properties required for the laminated microporous membrane, but the preferable average pore diameter is 0.01 to 0.05 μm for the inner layer. When the surface layer average pore diameter is 1.2 to 5.0 times that of the dense structure layer, the balance between ion permeability and pin puncture strength can be improved.

  The method of melt kneading is not particularly limited, but it is usually carried out by uniformly kneading in an extruder. This method is suitable for preparing highly concentrated solutions of polyethylene. The melting temperature is preferably within the range of the melting point of polyethylene + 10 ° C to + 100 ° C. In general, the melting temperature is preferably in the range of 160 to 230 ° C, and more preferably in the range of 170 to 200 ° C. Here, the melting point refers to a value obtained by differential scanning calorimetry (DSC) based on JIS K7121. The molding solvent may be added before the start of kneading, or may be added from the middle of the extruder during the kneading and further melt kneaded, but it is preferably added before the start of kneading and preliminarily formed into a solution. In melt kneading, it is preferable to add an antioxidant to prevent oxidation of polyethylene.

(C) A cooling roll having a surface obtained by extruding the polyolefin resin solutions A and B obtained in steps (a) and (b) from a die and removing at least one of the molding solvents by a molding solvent removing means. The step of cooling and forming a laminated gel-like molded product The polyolefin resin solutions A and B melt-kneaded by an extruder are pushed up from a die directly or through another extruder, and are cooled by a cooling roll. Cool to form a laminated gel-like molded product. As a method for obtaining a laminated gel-like molded product, it is desirable to separately prepare gel-like molded products to be laminated, and then stick them together through a calender roll or the like (sticking method), or supply a polyolefin solution separately to an extruder as desired. Any method may be used such as a method of melting at a temperature of 5 ° C, joining in a polymer tube or die, coextrusion and laminating, and then forming a laminated gel-like molded product (coextrusion method). From the viewpoint of adhesion, it is preferable to use a coextrusion method.

  The polyolefin resin solution extruded from the die is brought into contact with a rotating cooling roll set at a surface temperature of 20 ° C. to 40 ° C. with a refrigerant to form a gel-like molded product. The extruded polyethylene resin solution is preferably cooled to 25 ° C. or lower. Here, the cooling rate in the temperature range where crystallization is substantially performed becomes important. For example, a polyethylene resin solution extruded at a cooling rate of 10 ° C./second or more in a temperature range where crystallization is substantially performed is cooled to obtain a gel-like molded product. A preferable cooling rate is 20 ° C./second or more, more preferably 30 ° C./second or more, and further preferably 50 ° C./second or more. By carrying out such cooling, the structure in which the polyethylene phase is microphase-separated by the solvent is fixed, and spherulites having relatively large nuclei are formed on the surface of the gel-like molded product in contact with the cooling roll. Appropriately shaped protrusions can be formed. The cooling rate can be estimated by simulating from the extrusion temperature of the gel-shaped molded product, the thermal conductivity of the gel-shaped molded product, the thickness of the gel-shaped molded product, the molding solvent, the cooling roll, and the heat transfer coefficient of air.

  Further, in the present invention, it is important to remove as much as possible the forming solvent adhering to the surface of the cooling roll in the part in contact with the polyethylene resin solution A and / or B extruded from the die. That is, as shown in FIG. 4, the polyethylene resin solution is cooled by being wound around a rotating cooling roll to become a gel-like molded product, but is formed on the surface of the cooling roll after being separated as a gel-like molded product. The solvent for use is attached, and it usually comes into contact with the polyethylene resin solution again as it is. However, if a large amount of the forming solvent adheres to the surface of the cooling roll, the cooling rate becomes slow due to the heat insulating effect, and it becomes difficult to form protrusions. Therefore, it is important to remove the forming solvent as much as possible before the cooling roll comes into contact with the polyethylene resin solution again.

  The method for removing the molding solvent, that is, the method for removing the molding solvent from the cooling roll is not particularly limited, but the doctor blade is placed on the cooling roll so as to be parallel to the width direction of the gel-like molded article and passed through the doctor blade. A method is preferably employed in which the molding solvent is scraped off to the extent that the cooling roll surface is invisible until immediately after the gel-like molded product comes into contact. Alternatively, it can be removed by means such as blowing with compressed air, suction, or a combination of these methods. Among them, the method of scraping off using a doctor blade is preferable because it can be carried out relatively easily, and it is more preferable to use a plurality of doctor blades in order to improve the removal efficiency of the forming solvent.

  The material of the doctor blade is not particularly limited as long as it is resistant to the forming solvent, but is preferably made of resin or rubber rather than metal. This is because in the case of metal, the cooling roll may be scratched. Examples of the resin doctor blade include polyester, polyacetal, and polyethylene.

  Even if the temperature of the cooling roll is set to less than 20 ° C., this alone does not provide a sufficient cooling rate due to the heat insulating effect of the molding solvent, but also causes the gel-like molded product to adhere to the condensation due to the condensation on the cooling roll. It may cause surface roughness.

  The thickness of the polyethylene resin solution during extrusion is 1500 μm or less, more preferably 1000 μm or less, and still more preferably 800 μm or less. When the thickness of the polyethylene resin solution at the time of extrusion is within the above range, the cooling rate on the surface on the side of the cooling roll is preferably not slow.

  Here, when a laminated gel-like molded product is obtained by the bonding method, if at least one of the polyolefin resin solutions to be the A layer or the B layer is formed as a gel-like molded product under the above cooling conditions. Good. In addition, when bonding together, it is necessary to laminate | stack so that the surface which contacted the cooling roll of the layer formed on the said cooling conditions may become the surface. Further, when a laminated gel-like molded product is obtained by the coextrusion method, the polyolefin resin solution laminated and extruded from the die may be formed as a laminated gel-like molded product under the above cooling conditions.

  The structure of the layer may be at least two layers of A layer and B layer from the viewpoint of physical properties balance such as shutdown characteristics and strength and permeability, but from the viewpoint of the balance between the front and back of the final film, the A layer A three-layer structure of / B layer / A layer or B layer / A layer / B layer is more preferable. From the viewpoint of adhesion to the modified porous layer, the protrusion may be formed on either the A layer or the B layer, but from the viewpoint of shutdown, the surface layer is the A layer and the inner layer is the B layer. In particular, it is preferable because of excellent shutdown characteristics.

  Here, the ratio of the A layer is preferably 30% by mass or more and 80% by mass or less with respect to the mass of all layers. The lower limit is more preferably 40% by mass, and the upper limit is more preferably 70% by mass. If the ratio of the A layer is within the above range, the balance between good shutdown characteristics, permeability and puncture strength can be made good.

(D) Step of stretching the laminated gel-like molded product in MD (machine direction) and TD (width direction) to obtain a stretched molded product Next, this laminated gel-like molded product is stretched to obtain a stretched molded product. Stretching is performed by heating the gel-like molded product and performing normal tenter method, roll method, or a combination of these methods at a predetermined magnification in two directions of MD and TD. Stretching may be either MD and TD (machine direction and width direction) simultaneous stretching (simultaneous biaxial stretching) or sequential stretching. In the sequential stretching, the order of MD and TD is not limited, and at least one of MD and TD may be stretched in multiple stages. The stretching temperature is the melting point of the polyolefin composition + 10 ° C. or less. Further, the draw ratio varies depending on the thickness of the original fabric, but is preferably 9 times or more, more preferably 16 to 400 times in terms of surface magnification. For MD and TD simultaneous stretching (simultaneous biaxial stretching), stretching at the same MD and TD magnifications such as 3 × 3, 5 × 5, and 7 × 7 is preferable. When the surface magnification is in the above preferred range, stretching is sufficient and a highly elastic, high strength porous membrane can be obtained. Moreover, a desired air resistance can be obtained by adjusting the stretching temperature.

(E) Step of extracting and removing the molding solvent from the laminated stretched molded product and drying to obtain a laminated porous molded product Next, the stretched molded product is treated with a washing solvent to remove the remaining molding solvent. Thus, a laminated porous membrane is obtained. Cleaning solvents include hydrocarbons such as pentane, hexane and heptane, chlorinated hydrocarbons such as methylene chloride and carbon tetrachloride, fluorinated hydrocarbons such as ethane trifluoride, and ethers such as diethyl ether and dioxane. Volatile ones can be used. These washing solvents are appropriately selected according to the molding solvent used for dissolving polyethylene, and used alone or in combination. The cleaning method can be performed by a method of immersing and extracting in a cleaning solvent, a method of showering the cleaning solvent, a method of sucking the cleaning solvent from the opposite side of the stretched molded product, or a method of a combination thereof. Washing as described above is performed until the residual solvent in the stretched molded product, which is a stretched molded product, is less than 1% by weight. Thereafter, the cleaning solvent is dried. The cleaning solvent can be dried by heat drying, air drying, or the like.

(F) Step of heat-treating the laminated porous molded product to obtain a polyethylene porous membrane The laminated porous molded product obtained by drying is further subjected to heat treatment to obtain a laminated porous membrane. The heat treatment temperature is preferably 90 to 150 ° C. When the heat treatment temperature is in the above preferred range, the resulting polyolefin laminated porous membrane has a sufficient heat shrinkage reduction and a sufficient air resistance. The residence time of the heat treatment step is not particularly limited, but is usually 1 second to 10 minutes, preferably 3 seconds to 2 minutes or less. For the heat treatment, any of a tenter method, a roll method, a rolling method, and a free method can be adopted.

  Further, in the heat treatment step, it is preferable to contract in at least one direction of MD and TD while fixing in both directions of MD (machine direction) and TD (width direction). If the MD and TD are fixed in both directions and the MD and TD are not contracted in at least one direction, the heat shrinkage reduction is deteriorated. The shrinkage rate of shrinking in at least one direction of MD and TD is 0.01 to 50%, preferably 3 to 20%. When the shrinkage rate is within the above preferable range, the thermal shrinkage rate at 105 ° C. and 8 hours is improved, and the air resistance is maintained. Further, in order to improve the puncture strength such as the puncture strength, TD or MD or re-stretching of about 5% to 20% in both directions may be performed before the heat setting treatment.

  Furthermore, you may perform a hydrophilic treatment to an extending | stretching molded object, a porous molded object, or a microporous film as needed. By performing the hydrophilic treatment, for example, when coating the heat resistant resin layer, the adhesion between the microporous high membrane surface and the heat resistant resin layer and the uniformity of the coating film can be further improved. The hydrophilic treatment can be performed by monomer grafting, surfactant treatment, corona discharge or the like. Monomer grafting is preferably performed after the crosslinking treatment. The corona discharge treatment can be performed in air, nitrogen, or a mixed atmosphere of carbon dioxide and nitrogen.

Next, the modified porous layer used in the present invention will be described.
The modified porous layer is preferably laminated on the side having the projections of the polyolefin laminated porous membrane. When a modified porous layer is provided on both sides, in a later process such as a slitting process or a conveying process, the protrusion of the polyethylene porous film is placed on the side where the stress parallel to the modified porous layer surface is more intense by contact with a roll or bar. It is preferable that the modified porous layer is laminated on the surface side to have the effect of the present invention.

  The modified porous layer as used in the present invention is particularly limited as long as it is a layer containing a resin that imparts or improves at least one function such as heat resistance, adhesion to an electrode material, and electrolyte permeability, that is, a functional resin. However, the modified porous layer preferably contains inorganic particles or crosslinked polymer particles in addition to the functional resin.

  For example, from the viewpoint of improving heat resistance, the functional resin is preferably a heat resistant resin having a glass transition temperature or melting point of 150 ° C. or higher, more preferably 180 ° C. or higher, and still more preferably 210 ° C. or higher. There is no particular upper limit on the glass transition temperature or melting point. When the glass transition temperature is higher than the decomposition temperature, the decomposition temperature may be within the above range. When the lower limit of the glass transition temperature is within the above preferred range, a sufficient heat-resistant film breaking temperature can be obtained, and high safety can be ensured.

  As the heat resistant resin, for example, a resin mainly composed of polyamideimide, polyimide or polyamide can be suitably used. Among these, a resin mainly composed of polyamideimide is particularly preferable. These resins may be used alone or in combination with other materials.

  From the viewpoint of electrode adhesion, the functional resin is composed of a vinylidene fluoride homopolymer, a vinylidene fluoride / fluorinated olefin copolymer, a vinyl fluoride homopolymer, and a vinyl fluoride / fluorinated olefin copolymer. It is preferable to use one or more selected from the group. Particularly preferred is polytetrafluoroethylene. These polymers have electrode adhesion, high affinity with non-aqueous electrolytes, appropriate heat resistance, and high chemical and physical stability against non-aqueous electrolytes. Even when used, the affinity with the electrolyte can be sufficiently maintained. Polyvinylidene fluoride (PVDF) is preferred.

Hereinafter, the polyamideimide resin will be described in detail as an example of the functional resin.
In general, the polyamideimide resin is synthesized by a conventional method such as an acid chloride method using trimellitic acid chloride and diamine or a diisocyanate method using trimellitic anhydride and diisocyanate, but the diisocyanate method is preferable from the viewpoint of production cost. .

  Examples of the acid component used for the synthesis of the polyamide-imide resin include trimellitic anhydride (chloride). A part of the acid component can be replaced with another polybasic acid or an anhydride thereof. For example, tetracarboxylic acids such as pyromellitic acid, biphenyltetracarboxylic acid, biphenylsulfonetetracarboxylic acid, benzophenonetetracarboxylic acid, biphenylethertetracarboxylic acid, ethylene glycol bistrimellitate, propylene glycol bistrimellitate and their anhydrides, Aliphatic dicarboxylic acids such as oxalic acid, adipic acid, malonic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, dicarboxypolybutadiene, dicarboxypoly (acrylonitrile-butadiene), dicarboxypoly (styrene-butadiene), 1,4 -Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 4,4'-dicyclohexylmethanedicarboxylic acid, alicyclic dicarboxylic acids such as dimer acid, terephthalic acid, isophthalic acid Aromatic dicarboxylic acids such as phosphoric acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, naphthalene dicarboxylic acid and the like can be mentioned. Among these, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid are preferable from the viewpoint of the resistance to electrolytic solution, and dimer acid, dicarboxypolybutadiene having a molecular weight of 1000 or more and dicarboxypoly (acrylonitrile) from the shutdown characteristics. Butadiene) and dicarboxypoly (styrene-butadiene) are preferred.

  In addition, a urethane group can be introduced into the molecule by replacing part of the trimellitic acid compound with glycol. Examples of glycols include alkylene glycols such as ethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, and hexanediol, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and one or more of the above dicarboxylic acids. And polyesters having terminal hydroxyl groups synthesized from one or two or more of the above-mentioned glycols. Among these, polyethylene glycol and polyesters having terminal hydroxyl groups are preferred because of the shutdown effect. Moreover, these number average molecular weights are preferably 500 or more, and more preferably 1000 or more. The upper limit is not particularly limited, but is preferably less than 8000.

  When replacing a part of the acid component with at least one of the group consisting of dimer acid, polyalkylene ether, polyester and butadiene rubber containing any of carboxyl group, hydroxyl group and amino group at the end, 1 to 60 mol% is preferably replaced.

  As the diamine (diisocyanate) component used for the synthesis of the polyamide-imide resin, those having o-tolidine and tolylenediamine as components are preferable. Aliphatic components such as ethylenediamine, propylenediamine, and hexamethylenediamine are used as components to replace a part thereof. Diamines and their diisocyanates, alicyclic diamines such as 1,4-cyclohexanediamine, 1,3-cyclohexanediamine and dicyclohexylmethanediamine, and their diisocyanates, m-phenylenediamine, p-phenylenediamine, 4,4'-diamino Aromatic diamines such as diphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, benzidine, xylylenediamine, naphthalenediamine, and their diisocyanates Doo and the like, reactivity among these, cost, and most preferably dicyclohexylmethane diamine and its diisocyanates terms of electrolyte solution resistance, 4,4'-diaminodiphenylmethane, naphthalene diamines and these diisocyanates are preferred. In particular, o-tolidine diisocyanate (TODI), 2,4-tolylene diisocyanate (TDI) and blends thereof are preferred. In particular, in order to improve the peel strength at 0 ° of the modified porous layer, o-tolidine diisocyanate (TODI) having high rigidity is 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol%, based on the total isocyanate. More than mol%.

  Polyamideimide resin is easy to stir in a polar solvent such as N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone while heating to 60-200 ° C. Can be manufactured. In this case, amines such as triethylamine and diethylenetriamine, alkali metal salts such as sodium fluoride, potassium fluoride, cesium fluoride, sodium methoxide, and the like can be used as a catalyst as necessary.

  When the polyamideimide resin is used in the present invention, the logarithmic viscosity is preferably 0.5 dl / g or more. When the logarithmic viscosity of the polyamideimide resin is within the above preferred range, sufficient meltdown characteristics can be obtained and the polyolefin laminated porous membrane can be prevented from becoming brittle. Also, the peel strength at 0 ° is improved by the anchor effect. On the other hand, the upper limit is preferably less than 2.0 dl / g in consideration of workability and solvent solubility.

  The modified porous layer of the present invention is obtained by applying a resin solution (hereinafter sometimes referred to as varnish) that is soluble in a functional resin and dissolved in a water-miscible solvent to a predetermined base material, The functional resin and the solvent are phase-separated, and the resin is solidified by adding it to a water bath (hereinafter, this water bath may be referred to as a coagulation bath). If necessary, a phase separation aid may be added to the varnish.

  Solvents that can be used to dissolve the functional resin include N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), hexamethyltriamide phosphate (HMPA), N, N-dimethyl. Examples include formamide (DMF), dimethyl sulfoxide (DMSO), γ-butyrolactone, chloroform, tetrachloroethane, dichloroethane, 3-chloronaphthalene, parachlorophenol, tetralin, acetone, acetonitrile, etc. You can choose.

  The solid content concentration of the varnish is not particularly limited as long as it can be uniformly applied, but is preferably 50% by weight or more and 98% by weight or less, and more preferably 80% by weight or more and 95% by weight or less. When the solid content concentration of the varnish is within the above preferred range, the modified porous layer is prevented from becoming brittle, and a sufficient peel strength of 0 ° of the modified porous layer can be obtained.

  Examples of the phase separation aid used in the present invention include water, ethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, alkylene glycol such as hexanediol, polyalkylene glycol such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, water-soluble At least one selected from water-soluble polyester, water-soluble polyurethane, polyvinyl alcohol, carboxymethyl cellulose and the like.

  The amount of the phase separation aid added is in the range of 10 to 90 wt%, more preferably 20 to 80 wt%, and still more preferably 30 to 70% with respect to the weight of the varnish solution. By mixing these phase separation aids into the varnish, it is possible to mainly control the air permeability resistance, the surface porosity, and the layer structure formation rate. If it is in the above preferred range, a significant increase in the phase separation rate is observed. Further, it prevents the resin solution from becoming cloudy at the mixing stage and causing the resin component to precipitate.

  In order to reduce the curl of the polyolefin laminated porous membrane by laminating the modified porous layer, it is important to add inorganic particles or crosslinked polymer particles to the varnish. By adding inorganic particles or crosslinked polymer particles to the varnish, the effect of preventing internal short circuit (dendrite prevention effect) caused by the growth of dendritic crystals of the electrode inside the battery, reducing the heat shrinkage rate, imparting slipperiness, etc. The effect of can also be acquired. The upper limit of the amount of these particles added is preferably 98% by weight, more preferably 95% by weight. The lower limit is preferably 80% by weight, more preferably 85% by weight. When the amount of particles added is in the above preferred range, the curl reduction effect is sufficient, the ratio of the functional resin to the total volume of the modified porous layer is optimal, and sufficient 0 ° of the modified porous layer is obtained. Peel strength is obtained.

  Inorganic particles include calcium carbonate, calcium phosphate, amorphous silica, crystalline glass filler, kaolin, talc, titanium dioxide, alumina, silica-alumina composite oxide particles, barium sulfate, calcium fluoride, lithium fluoride, zeolite , Molybdenum sulfide, mica and the like. Examples of the heat-resistant crosslinked polymer particles include crosslinked polystyrene particles, crosslinked acrylic resin particles, and crosslinked methyl methacrylate particles.

  The average particle diameter of these particles is preferably 1.5 times or more and 50 times or less than the average pore diameter of the polyolefin laminated porous membrane. More preferably, it is 2.0 times or more and 20 times or less. If the average particle size of the particles is within the above-mentioned preferable range, the pores of the polyolefin laminated porous membrane are blocked in a state where the heat-resistant resin and the particles are mixed, and as a result, the air resistance is maintained, and the battery is assembled. In the process, the particles are prevented from falling off and causing a serious defect of the battery.

  The shape of the particle includes a true sphere shape, a substantially spherical shape, a plate shape, a needle shape, and a polyhedral shape, but is not particularly limited.

  The film thickness of the modified porous layer is 1 to 5 μm, preferably 1 to 4 μm, and more preferably 1 to 3 μm. When the film thickness of the modified porous layer is within the above preferred range, the battery separator obtained by laminating the modified porous layer can ensure the film breaking strength and insulation when melted / shrinked at the melting point or higher, and A sufficient pore blocking function can be obtained and abnormal reactions can be prevented. Moreover, the winding volume can be suppressed, which is suitable for increasing the battery capacity. In addition, suppressing curling leads to improved productivity in the battery assembly process.

  The porosity of the modified porous layer is preferably 30 to 90%, more preferably 40 to 70%. When the porosity of the modified porous layer is within the above preferred range, the battery separator obtained by laminating the modified porous layer has a low electrical resistance of the membrane, a large current flows easily, and the membrane strength is maintained. The

  The upper limit of the total film thickness of the battery separator obtained by laminating the modified porous layer is preferably 25 μm, more preferably 20 μm. The lower limit is preferably 6 μm or more, more preferably 7 μm or more. When the total thickness of the battery separator is within the above preferable range, the battery separator obtained by laminating the modified porous layer can ensure sufficient mechanical strength and insulation. Moreover, a reduction in capacity can be avoided by reducing the electrode area that can be filled in the container.

  The air resistance of the battery separator is one of the most important characteristics, and is preferably 50 to 600 sec / 100 cc Air, more preferably 100 to 500 sec / 100 cc Air, and further preferably 100 to 400 sec / 100 cc Air. When the air permeability resistance of the battery separator is within the above preferable range, sufficient insulation is obtained, and foreign matter clogging, short circuit and film breakage are prevented. Further, by suppressing the film resistance, charge / discharge characteristics and life characteristics within a practically usable range can be obtained.

Next, a method for laminating the modified porous layer of the battery separator of the present invention will be described.
The method of laminating the modified porous layer on the polyolefin laminated porous membrane may be a method (direct method) in which the varnish is directly applied to the polyolefin laminated porous membrane and converted into a modified porous layer (direct method), After applying the varnish to a film (for example, a polypropylene film or a polyester film) and placing it in a specific humidity environment, the functional resin component and the solvent component are phase-separated to form a modified porous layer, and then a polyolefin laminated porous A method (transfer method) in which the film is transferred to a material film and laminated is also possible.

In the present invention, a preferred method of laminating the modified porous layer includes steps (i) and (ii) in the production process.
Step (i): After applying a varnish containing a functional resin and inorganic particles or cross-linked polymer particles on the polyolefin laminated porous membrane, the absolute humidity is 0.5 g / m ³ or more and the absolute humidity is less than 6 g / m ³ . A step of forming a functional resin film on the polyolefin laminated porous film by passing through a low humidity zone and a high humidity zone having an absolute humidity of 7.0 g / m ³ or more and an absolute humidity of less than 25.0 g / m ³ .
Step (ii): The composite membrane obtained by laminating the functional resin film obtained in step (i) is immersed in a coagulation bath to convert the functional resin membrane into a modified porous layer, washed, dried, and battery A step of obtaining a separator for use.

Further details will be described.
A functional resin solution in which the functional resin is dissolved in a solvent that is soluble in the functional resin and miscible with water and a varnish mainly composed of the inorganic particles or the crosslinked polymer particles are applied to the polyolefin laminated porous membrane. Then, the modified porous layer can be obtained by placing in a specific humidity environment, allowing the varnish to phase-separate, and then adding to a water bath (coagulation bath) to coagulate the functional resin.

In the present invention, the low humidity zone has an absolute humidity of less than 6 g / m ³ , a preferred upper limit is 4 g / m ³ , more preferably 3 g / m ³ , and a lower limit is 0.5 g / m ³ , preferably It is a zone adjusted to 0.8 g / m ³ . When the absolute humidity is in the above preferred range, the phase separation is sufficiently performed and becomes porous, and the increase in the air resistance is suppressed. Further, in parallel with the phase separation, solidification of the resin constituting the modified porous layer is suppressed, and the penetration of the resin component constituting the modified porous layer into the polyolefin laminated porous membrane is sufficiently performed. A peel strength of 0 ° of the modified porous layer is obtained. Further, if the passage time in the low humidity zone is less than 3 seconds, the phase separation is not sufficiently performed, and if it exceeds 20 seconds, the resin constituting the modified porous layer is solidified, which is not preferable.

Next, the coating film is passed through the high humidity zone for 3 seconds or more and 10 seconds or less. In the present invention, the high humidity zone has a lower limit of absolute humidity of 6 g / m ³ , preferably 7 g / m ³ , more preferably 8 g / m ³ , and an upper limit of 25 g / m ³ , preferably 17 g / m ^3. More preferably, the zone is adjusted to 15 g / m ³ . When the absolute humidity is in the above preferred range, gelation (non-fluidization) is sufficiently performed, and the penetration of the resin component constituting the modified porous layer into the polyolefin laminated porous membrane does not proceed excessively, so An increase in the air resistance can be suppressed. In addition, excessive progress of solidification of the resin component is suppressed, and the penetration of the functional resin component into the polyolefin laminated porous membrane is prevented from becoming too small, and a sufficient peel strength of 0 ° is obtained.
The temperature conditions for both the low humidity zone and the high humidity zone are not particularly limited as long as the absolute humidity is within the above range, but 20 ° C. or more and 50 ° C. or less are preferable from the viewpoint of energy saving.

  Examples of the varnish application method include reverse roll coating method, gravure coating method, kiss coating method, roll brush method, spray coating method, air knife coating method, Meyer bar coating method, pipe doctor method, blade coating method. And a die coating method. These methods can be carried out alone or in combination.

  In the coagulation bath, the resin component and particles coagulate in a three-dimensional network. The immersion time in the coagulation bath is preferably 3 seconds or more. When the immersion time in the coagulation bath is within the above preferred range, the resin component is sufficiently coagulated. The upper limit is not limited, but 10 seconds is sufficient.

  Furthermore, the unwashed porous membrane is immersed in an aqueous solution containing 1 to 20% by weight, more preferably 5 to 15% by weight of a good solvent for the functional resin, and a washing step using pure water, 100 ° C. The final battery separator can be obtained through the drying process using the following hot air.

  For cleaning, general techniques such as heating, ultrasonic irradiation, and bubbling can be used. Furthermore, in order to keep the concentration in each bath constant and increase the cleaning efficiency, it is effective to remove the solution inside the porous membrane between baths. Specifically, a method of extruding the solution inside the porous layer with air or an inert gas, a method of physically squeezing out the solution inside the membrane with a guide roll, and the like can be mentioned.

  Although it is desirable to store the battery separator of the present invention in a dry state, when it is difficult to store in a completely dry state, it is preferable to perform a vacuum drying treatment at 100 ° C. or less immediately before use.

  The battery separator of the present invention includes a nickel-hydrogen battery, a nickel-cadmium battery, a nickel-zinc battery, a silver-zinc battery, a lithium secondary battery, a secondary battery such as a lithium polymer secondary battery, a plastic film capacitor, and a ceramic. Although it can be used as a separator for a capacitor, an electric double layer capacitor, etc., it is particularly preferably used as a separator for a lithium ion secondary battery. Hereinafter, a lithium ion secondary battery will be described as an example.

  In a lithium ion secondary battery, a positive electrode and a negative electrode are laminated via a separator, and the separator contains an electrolytic solution (electrolyte). The structure of the electrode is not particularly limited, and may be a known structure. For example, an electrode structure (coin type) in which disc-shaped positive electrodes and negative electrodes are opposed to each other, an electrode structure in which flat plate-like positive electrodes and negative electrodes are alternately stacked (stacked type), and belt-shaped positive electrodes and negative electrodes are stacked. It can be set as a structure such as a wound electrode structure (winding type).

The positive electrode usually has a current collector and a positive electrode active material layer containing a positive electrode active material capable of occluding and releasing lithium ions formed on the surface of the current collector. Examples of the positive electrode active material include transition metal oxides, composite oxides of lithium and transition metals (lithium composite oxides), inorganic compounds such as transition metal sulfides, and the like. Examples of the transition metal include V, Mn, Fe, Co, and Ni. Preferred examples of the lithium composite oxide in the positive electrode active material include lithium nickelate, lithium cobaltate, lithium manganate, and a layered lithium composite oxide based on an α-NaFeO ₂ type structure.

The negative electrode has a current collector and a negative electrode active material layer including a negative electrode active material formed on the surface of the current collector. Examples of the negative electrode active material include carbonaceous materials such as natural graphite, artificial graphite, cokes, and carbon black. The electrolytic solution can be obtained by dissolving a lithium salt in an organic solvent. Lithium salts include LiClO ₄ , LiPF ₆ , LiAsF ₆ , LiSbF ₆ , LiBF ₄ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ ) ₃ , Li ₂ B ₁₀ Cl ₁₀ , _{LiN (C 2 F 5 SO 2} ) 2, LiPF 4 (CF 3) 2, LiPF 3 (C2F 5) 3, lower aliphatic carboxylic acid lithium salts, and the like LiAlCl4. These may be used alone or in admixture of two or more. Examples of the organic solvent include high boiling point and high dielectric constant organic solvents such as ethylene carbonate, propylene carbonate, ethyl methyl carbonate, and γ-butyrolactone, and tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane, dioxolane, dimethyl carbonate, and diethyl carbonate. Examples include organic solvents having a low boiling point and a low viscosity. These may be used alone or in admixture of two or more. In particular, a high dielectric constant organic solvent has a high viscosity, and a low viscosity organic solvent has a low dielectric constant. Therefore, it is preferable to use a mixture of both.

  When assembling the battery, the separator of the present invention can be impregnated with an electrolytic solution to impart ion permeability to the separator. Usually, the impregnation treatment is performed by immersing the microporous membrane in an electrolytic solution at room temperature. For example, when assembling a cylindrical battery, first, a positive electrode sheet, a separator (composite porous membrane), and a negative electrode sheet are laminated in this order, and this laminate is wound from one end to form a wound electrode element. Next, a battery can be obtained by inserting this electrode element into a battery can, impregnating with the above electrolyte, and caulking a battery lid also serving as a positive electrode terminal provided with a safety valve via a gasket.

EXAMPLES Hereinafter, although an Example is shown and demonstrated concretely, this invention is not restrict | limited at all by these Examples. In addition, Example 8 and Examples 21-23 are reference examples. Moreover , the measured value in an Example is the value measured with the following method.

1. Number of protrusions The number and size of protrusions were measured after stabilizing the light source using a confocal microscope (HD100 manufactured by Lasertec) installed on a base isolation table.

(procedure)
(1) A 1 cm × 1 cm square frame was drawn with an ultrafine oil pen on the surface of the polyethylene porous membrane obtained in Examples and Comparative Examples that was in contact with the cooling roll during film formation.

  (2) The surface on which the square frame was drawn was placed on the sample stage, and was fixed to the sample stage using an electrostatic contact apparatus attached to the confocal microscope.

  (3) Using an objective lens having a magnification of 5 times, a ring-shaped trace derived from polyethylene spherulite as shown in FIG. The position of the sample stage was adjusted so that the darkest part of was positioned almost at the center of the monitor screen. When two ring-shaped marks were connected, the contact was made. The object of the projection height measurement was such that the major axis of the ring-shaped trace derived from the polyethylene spherulites was 0.2 mm or more. As for the major axis of the ring-shaped mark, the cursor was placed on both ends of the ring in the major axis direction in the two-dimensional image, and the length was read.

(4) Change the objective lens to a 20x lens and focus on the center of the monitor screen (in this device, the center of the monitor screen is displayed brightest), and this height position is used as the reference height (This device is called REF SET).

(5) The measurement range in the height direction was set to 15 μm above and below, with the reference height being 0 μm. Also, the scan time was 120 seconds, the STEP moving distance was 0.1 μm / Step, and the three-dimensional data was captured.

(6) After capturing the three-dimensional data, an image for data processing (referred to as a Z image in the present apparatus) was displayed and a smoothing process was performed (smoothing condition: filter size 3 × 3, matrix type SMOOTH3-0, one time). In addition, horizontal correction was performed on the horizontal correction screen as necessary.

(7) A cursor was placed in a horizontal direction at a position (the brightest part) passing through the highest protrusion in the data processing image, and a cross-sectional profile corresponding to the cursor was displayed on the cross-sectional profile image.

(8) In the cross-sectional profile image, the two cursors were aligned with the inflection points of the sleeves of the protrusions in the vertical direction, and the distance between the cursors was taken as the protrusion size.

(9) In the cross-sectional profile image, align the two cursors in the horizontal direction with the inflection points of the top of the protrusion and the sleeves of the protrusion (if the height of the inflection points of the sleeves of the protrusion is different) The distance between the cursors was the height of the protrusion.

(10) The above operation is repeated within the 1 cm × 1 cm square frame, and the number of protrusions having a size of 5 μm or more and 50 μm or less, a height of 0.5 μm or more and 3.0 μm or less is counted, and the number of protrusions per 1 cm ² is obtained. Further, the average height of the protrusions was obtained.

2. 0 ° Peel Strength of Modified Porous Layer FIG. 1 schematically shows the evaluation method. 1 is a laminated sample, 2 is a polyolefin laminated porous film, 3 is a modified porous layer, 4 is a double-sided pressure-sensitive adhesive tape, 5 and 5 'are aluminum plates, and the arrows in the figure are tensile directions. A double-sided adhesive tape (NW-K50 manufactured by Nichiban Co., Ltd.) 4 having the same size was attached to an aluminum plate 5 having a size of 50 mm × 25 mm and a thickness of 0.5 mm. A polyolefin laminated porous membrane 2 surface of sample 1 (battery separator) cut out to a width of 50 mm and a length of 100 mm is pasted thereon so that 40 mm overlaps from the end of one side of the 25 mm length of the aluminum plate 5. Attached and cut off the protruding part. Next, a double-sided adhesive tape is attached to one side of an aluminum plate 5 ′ having a length of 100 mm, a width of 15 mm, and a thickness of 0.5 mm, so that 20 mm overlaps from the end of one side of the 25 mm long sample side of the aluminum plate 5. Pasted on. Thereafter, the aluminum plate 5 and the aluminum plate 5 ′ sandwiching the sample are attached to a tensile tester (Autograph AGS-J 1kN, manufactured by Shimadzu Corporation), and the aluminum plate 5 and the aluminum plate 5 ′ are parallel and opposite to each other in a tensile speed of 10 mm. The strength when the modified porous layer was peeled was measured by pulling at / min. This measurement was performed for any three points with an interval of 30 cm or more in the longitudinal direction, and the average value was defined as the 0 ° peel strength of the modified porous layer.

3. Film thickness It calculated | required by averaging the measured value of 20 points | pieces using the contact-type film thickness meter (Mittoyo light-matic series 318). The measurement was performed under the condition of a weight of 0.01 N using a carbide spherical measuring element φ9.5 mm.

4). Average pore diameter of the surface layer The average pore diameter in the surface layer of the polyolefin laminated porous membrane was measured by the following method. The sample was fixed on the measurement cell using double-sided tape, platinum or gold was vacuum-deposited for several minutes, and the surface of the film was subjected to SEM measurement at an appropriate magnification. Arbitrary ten places were selected on the image obtained by SEM measurement, and the average value of the pore diameters at these ten places was taken as the average pore diameter of the sample.

5. Air permeability resistance Gurley type densometer type B manufactured by Tester Sangyo Co., Ltd. is used to fix the polyolefin laminated porous membrane or battery separator so that wrinkles do not enter between the clamping plate and the adapter plate. And measured according to JIS P8117. The sample was a 10 cm square, the measurement points were a total of five points at the center and four corners of the sample, and the average value was used as the air resistance [sec / 100 cc Air]. When the length of one side of the sample is less than 10 cm, a value obtained by measuring five points at intervals of 5 cm may be used.

The increase width of the air permeability resistance was obtained from the following formula.
Air resistance increase range = (Y) − (X) sec / 100 cc Air
Air permeability resistance (X) sec / 100ccAir of laminated porous membrane made of polyolefin
Air permeability resistance of battery separator (Y) sec / 100ccAir

6). Shutdown speed
The air permeation resistance (sec / 100 cc Air) after the polyolefin microporous film having a thickness of T1 was brought into contact with a hot plate adjusted to a temperature of 135 ° C. for 10 seconds was measured. According to the formula: Gb = (Ga × 20) / T1, the air permeability resistance (sec / 100 cc Air / 20 μm) when the film thickness is 20 μm is converted into an index of the shutdown speed.

7). Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Mw and Mw / Mn were determined by gel permeation chromatography (GPC) method under the following conditions.
-Measuring device: GPC-150C manufactured by Waters Corporation
Column: Shodex UT806M manufactured by Showa Denko KK
-Column temperature: 135 ° C
Solvent (mobile phase): o-dichlorobenzene Solvent flow rate: 1.0 ml / min Sample concentration: 0.1% by mass (dissolution condition: 135 ° C./1 h)
・ Injection volume: 500μl
-Detector: Differential refractometer manufactured by Waters Corporation-Calibration curve: Prepared from a calibration curve obtained using a monodisperse polystyrene standard sample using a predetermined conversion constant.

8). Terminal Vinyl Group Concentration The terminal vinyl group concentration was determined by infrared spectroscopy. Specifically, a high-density polyethylene resin is heated and pressed at 210 ° C., then rapidly cooled at 25 ° C., formed into a sample with a thickness of about 1 mm, and then subjected to a Fourier transform infrared spectrophotometer (model number: FREEXACT-II). , Manufactured by HORIBA, Ltd.). Among the obtained spectra, the absorbance of the absorption peak at 910 cm ⁻¹ [A = log (I0 / I) (where A represents the absorbance, I0 represents the transmitted light intensity of the blank cell, and I represents the sample cell. Represents the transmitted light intensity)], and the number of terminal vinyl groups per 10,000 carbon atoms in high-density polyethylene (pieces / 10,000 C) was calculated from the following formula.
Terminal vinyl group concentration (pieces / 10,000 C) = (1.14 × absorbance A) / (polyethylene density (g / cm ³ ) × sample thickness (mm)].

9. Logarithmic viscosity A solution of 0.5 g of heat-resistant resin dissolved in 100 ml of NMP was measured at 25 ° C. using an Ubbelohde viscosity tube.

10. Melting point The peak temperature of the melting peak observed when 5 mg of a resin sample is heated at a heating rate of 20 ° C./min in a nitrogen gas atmosphere using a differential scanning calorimeter (DSC) DSC 6220 manufactured by SII Nanotechnology Inc. Was the melting point.

11. Glass transition temperature A resin solution or a resin solution in which a battery separator is dipped in a good solvent to dissolve only the modified porous layer is applied to a PET film (Toyobo E5001) or a polypropylene film (trade name “PYLEN, manufactured by Toyobo Co., Ltd.). (Registered trademark) -OT ") with a suitable gap, pre-dried at 120 ° C. for 10 minutes, peeled off, and fixed to a metal frame of an appropriate size with a heat-resistant adhesive tape. The film was dried at ° C. for 12 hours to obtain a dry film. A sample having a width of 4 mm and a length of 21 mm was cut from the obtained dry film, and measured at a measurement length of 15 mm, using a dynamic viscoelasticity measuring device (DVA-220 manufactured by IT Measurement Control Co., Ltd.), 110 Hz, temperature increase rate of 4 ° C./min Under the above conditions, at the refraction point of the storage elastic modulus (E ′) when measured in the range from room temperature to 450 ° C., an extension of the baseline below the glass transition temperature and a tangent line indicating the maximum inclination above the refraction point The temperature at the point of intersection was taken as the glass transition temperature.

12 Porosity A 10 cm square sample was prepared, and the porosity (%) was calculated from the results obtained by measuring the sample volume (cm ³ ) and mass (g) using the following equation.
Porosity = (1−mass / (resin density × sample volume)) × 100

13. Scratch resistance Both ends of the separators for roll batteries obtained in Examples and Comparative Examples were slit. The slitting was performed using a slitter (WA177A model manufactured by Nishimura Seisakusho Co., Ltd.) under conditions of a speed of 20 m / min and a tension of 50 N / 100 mm. During processing, the rolls that contact the coated surface were two hard chrome plating rolls (both free rolls). Next, using a magnifier with a scale of 10 times magnification (PEAK SCALELUPE × 10) while rewinding the slit-processed battery separator, peeling defects of the modified porous layer having a major axis of 0.5 mm or more Were evaluated according to the following criteria. The evaluation area was 100 mm wide × 500 m long. (When the width was less than 100 mm, the length was adjusted so that the same evaluation area was obtained.)
Judgment criteria ○ (very good): 10 or less △ (good): 11 to 30 × (defect): 31 or more

Example 1
It consists of 20% by weight of ultra high molecular weight polyethylene (UHMWPE) with a weight average molecular weight of 2 million and 80% by weight of high density polyethylene (HDPE) with a weight average molecular weight of 350,000 and a terminal vinyl group concentration of 0.9 / 10,000C. To 100 parts by weight of the composition (Mw / Mn = 24.5), 0.375 parts by weight of tetrakis [methylene-3- (3,5-ditertiarybutyl-4-hydroxyphenyl) -propionate] methane as an antioxidant was added. The added polyethylene composition A (melting point 135 ° C.) was obtained. 20 parts by weight of this polyethylene composition A was charged into a twin screw extruder. 80 parts by weight of liquid paraffin was supplied from the side feeder of this twin screw extruder, melt kneaded, and a polyethylene resin solution A was prepared in the extruder.

  On the other hand, ultra high molecular weight polyethylene (UHMWPE) with a weight average molecular weight of 2 million is 30% by weight and high density polyethylene (HDPE) with a weight average molecular weight of 300,000 and a terminal vinyl group concentration of 0.1 / 10,000C is 70% by weight. The composition (Mw / Mn = 24.5) consisting of 100 parts by weight of tetrakis [methylene-3- (3,5-ditertiarybutyl-4-hydroxyphenyl) -propionate] methane 0.375 wt. A polyethylene composition B (melting point: 135 ° C.) was added. 20 parts by weight of this polyethylene composition B was charged into a twin screw extruder. 80 parts by weight of liquid paraffin was supplied from the side feeder of this twin screw extruder, melted and kneaded, and a polyethylene resin solution B was prepared in the extruder.

  The obtained polyethylene resin solutions A and B were coextruded from a multilayer die so as to have a thickness of 1035 μm at 190 ° C. so that the layer configuration was A / B / A and the solution ratio was 1/2/1, A laminated gel-like molded product was formed while being taken up by a cooling roll having a diameter of 800 mm while maintaining the internal cooling water temperature at 25 ° C. At this time, one polyester doctor blade is inserted in the width direction of the gel-shaped molded article between the point where the laminated gel-shaped molded article is separated from the cooling roll and the point where the laminated polyethylene resin solution extruded from the die contacts the cooling roll. The liquid paraffin adhering to the cooling roll was scraped off in contact with the cooling roll in parallel with the cooling roll. Subsequently, the laminated gel-like molded product was simultaneously biaxially stretched 5 × 5 times while adjusting the temperature so as to obtain a desired air permeability resistance to obtain a stretched molded product. The obtained stretched molded product was washed with methylene chloride to extract and remove the remaining liquid paraffin, and dried to obtain a porous molded product. After that, the porous film is held on the tenter, reduced in width by 10% only in the TD (width direction) direction, and heat treated at 127 ° C. for 3 seconds, thickness 20 μm, porosity 45%, average pore diameter 0.18 μm, permeability A polyethylene laminated porous film having a gas resistance of 275 sec / 100 cc Air was obtained.

(Synthesis of heat-resistant resin)
In a four-necked flask equipped with a thermometer, a condenser tube, and a nitrogen gas inlet tube, 1 mole of trimellitic anhydride (TMA), 0.8 mole of o-tolidine diisocyanate (TODI), 2,4-tolylene diisocyanate (TDI) ) 0.2 mol and 0.01 mol of potassium fluoride were charged together with N-methyl-2-pyrrolidone so that the solid concentration was 14%, and stirred at 100 ° C. for 5 hours. The solution was diluted with N-methyl-2-pyrrolidone to synthesize a polyamideimide resin solution. The obtained polyamideimide resin had a logarithmic viscosity of 1.35 dl / g and a glass transition temperature of 320 ° C.

  A polyamide-imide resin solution, alumina particles having an average particle size of 0.5 μm, and N-methyl-2-pyrrolidone were blended in a weight ratio of 26:34:40, respectively, and zirconium oxide beads (manufactured by Toray Industries, Inc., trade name “Traceram (registered) (Trademark) beads ”(diameter: 0.5 mm) and placed in a polypropylene container, and dispersed in a paint shaker (manufactured by Toyo Seiki Seisakusho) for 6 hours. Subsequently, it filtered with the filter of 5 micrometers of filtration limits, and obtained varnish (a).

Varnish was applied to the surface of the polyethylene laminated porous membrane in contact with the cooling roll by blade coating, and a low humidity zone with a temperature of 25 ° C. and an absolute humidity of 1.8 g / m ³ was applied for 8 seconds, followed by a temperature of 25 ° C. After passing through a high humidity zone having an absolute humidity of 12 g / m ³ for 5 seconds, it was immersed in an aqueous solution containing 5% by weight of N-methyl-2-pyrrolidone for 10 seconds. Further, after washing with pure water, and further washing with pure water, the final thickness is 5 μm thicker than that of the polyethylene laminated porous membrane, and it is dried by passing through a hot air drying oven at 70 ° C. A battery separator was obtained.

Examples 2-3
Except that the blending ratio of the ultrahigh molecular weight polyethylene (UHMWPE) and the high density polyethylene (HDPE) of polyethylene compositions A and B and the ratio of each polyethylene composition to liquid paraffin were adjusted as shown in the table, the same as in Example 1. Thus, a battery separator was obtained.

Example 4
A battery separator was obtained in the same manner as in Example 1 except that two polyester doctor blades were applied to the cooling roll at an interval of 20 mm.

Example 5
A battery separator was obtained in the same manner as in Example 1 except that three polyester doctor blades were each applied to the cooling roll at an interval of 20 mm.

Example 6
Varnish (b) was obtained with the blending ratio of polyamideimide resin solution (a), alumina particles having an average particle size of 0.5 μm, and N-methyl-2-pyrrolidone being 17:43:40 (weight ratio), respectively. A battery separator was obtained in the same manner as in Example 1 except that the varnish (b) was used.

Example 7
Varnish (c) was obtained by setting the blending ratio of the polyamideimide resin solution (a), alumina particles having an average particle size of 0.5 μm, and N-methyl-2-pyrrolidone to 39:22:39 (weight ratio), respectively. A battery separator was obtained in the same manner as in Example 1 except that the varnish (c) was used.

Example 8
A battery separator was obtained in the same manner as in Example 1 except that the polyethylene resin solutions A and B were coextruded so that the layer constitution was B / A / B and the solution ratio was 1/2/1.

Example 9
A battery separator was obtained in the same manner as in Example 1 except that the internal cooling water temperature of the cooling roll was maintained at 35 ° C.

Examples 10-12
A battery separator was obtained in the same manner as in Example 1 except that the ratio of the polyethylene composition A and the liquid paraffin was adjusted to the resin concentration shown in the table.

Examples 13-15
A battery separator having a final thickness of 22 μm was obtained in the same manner as in Example 1 except that the extrusion amounts of the polyethylene solutions A and B were adjusted so that the thickness of the polyethylene laminated porous membrane was as shown in the table.

Example 16
The alumina particles are replaced with crosslinked polymer particles (polymethyl methacrylate-based crosslinked product particles (product name Eposta (registered trademark) MA1002, manufactured by Nippon Shokubai Co., Ltd., average particle size: 2.5 μm)). -The varnish (d) was obtained by setting the blending ratio of methyl-2-pyrrolidone to 35:10:55 (weight ratio), respectively. A battery separator was obtained in the same manner as in Example 1 except that the varnish (d) was used.

Example 17
Fluorine-based resin solution (manufactured by Kureha Chemical Co., Ltd., trade name: KF polymer # 1120 (polyvinylidene fluoride (melting point: 175 ° C., 12% N-methylpyrrolidone solution) and alumina particles having an average particle size of 0.5 μm, N -Methyl-2-pyrrolidone was blended at a weight ratio of 31:34:45, respectively, and together with zirconium oxide beads (trade name "Traceram (registered trademark) beads", diameter 0.5 mm) manufactured by Toray Industries, Inc. The mixture was dispersed for 6 hours with a paint shaker (manufactured by Toyo Seiki Seisakusho), and then filtered through a filter having a filtration limit of 5 μm to obtain a varnish (e), except that varnish (e) was used. Similarly, a battery separator was obtained.

Examples 18-20
A battery separator was obtained in the same manner as in Example 1 except that the high-density polyethylene (HDPE) used for the polyethylene resin A was a polymer having a weight average molecular weight of 350,000 and a terminal vinyl group concentration shown in the table.

Example 21
Except that the blending ratio of the ultrahigh molecular weight polyethylene (UHMWPE) and the high density polyethylene (HDPE) of polyethylene compositions A and B and the ratio of each polyethylene composition to liquid paraffin were adjusted as shown in the table, the same as in Example 1. Thus, a battery separator was obtained.

Example 22
In the same manner as in Example 21, polyolefin solutions A and B were obtained. The obtained polyolefin solution A was extruded from a single-layer die so as to have a thickness of 350 μm at 190 ° C., and a gel-like molded product A was formed while being drawn by a cooling roll having a diameter of 800 mm with the internal cooling water temperature maintained at 25 ° C. . At this time, one polyester doctor blade is parallel to the width direction of the gel-shaped molded product between the point where the gel-shaped molded product is separated from the cooling roll and the point where the polyethylene resin solution extruded from the die contacts the cooling roll. The liquid paraffin adhering to the cooling roll was scraped off against the cooling roll. On the other hand, the polyolefin solution B was extruded from a single-layer die so as to have a thickness of 700 μm at 190 ° C., and a gel-like molded product B was formed while being drawn by a cooling roll having a diameter of 800 mm with the internal cooling water temperature maintained at 25 ° C. A doctor blade was not used for cooling the gel-like molded product B.

  The obtained gel-like molded products A and B were laminated in order of A / B / A so that the surface of the gel-like composition A in contact with the cooling roll was a surface layer, and pressure-bonded at 110 ° C. and 0.05 MPa. To obtain a laminated gel-like molded product. A battery separator was obtained in the same manner as in Example 1 except that the laminated gel-like molded product thus obtained was used.

Example 23
For batteries as in Example 21, except that the blending ratio of ultrahigh molecular weight polyethylene (UHMWPE) and high density polyethylene (HDPE) in polyethylene composition A and the ratio of polyethylene composition to liquid paraffin were adjusted as shown in the table. A separator was obtained.

Example 24
A battery separator having a final thickness of 9 μm was obtained in the same manner as in Example 2 except that the extrusion amounts of the polyethylene solutions A and B were adjusted so that the thickness of the polyethylene laminated porous membrane was as shown in the table.

Comparative Example 1
Using only the polyolefin solution A, a single-layer gel-like molded product was formed by extrusion from a single-layer die so as to have a thickness of 1035 μm at 190 ° C. A battery separator was obtained in the same manner as in Example 1 except that the molded product was used.

Comparative Example 2
Using only the polyolefin solution B, a single-layer gel-like molded product was formed by extruding from a single-layer die so as to have a thickness of 1035 μm at 190 ° C. A battery separator was obtained in the same manner as in Example 1 except that the molded product was used.

Example 3
Except that the blending ratio of the ultrahigh molecular weight polyethylene (UHMWPE) and the high density polyethylene (HDPE) of polyethylene compositions A and B and the ratio of each polyethylene composition to liquid paraffin were adjusted as shown in the table, the same as in Example 1. Thus, a battery separator was obtained.

Comparative Example 4
A battery separator was obtained in the same manner as in Example 1 except that the internal cooling water temperature of the cooling roll was kept at 0 ° C. and the doctor blade was not used.

Comparative Example 5
Instead of cooling the polyethylene resin solution extruded from the die with a cooling roll, a battery separator was obtained in the same manner as in Example 1 except that the polyethylene resin solution was immersed in water kept at 25 ° C. for 1 minute.

Comparative Example 6
The polyethylene resin solution extruded from the die was cooled with a cooling roll, and when the gel-like molded product was obtained, the doctor blade was not used and the liquid paraffin adhering to the cooling roll was not scraped off. Similarly, a battery separator was obtained.

Comparative Example 7
A battery separator was obtained in the same manner as in Example 1 except that the internal cooling water temperature of the cooling roll was kept at 50 ° C.

  Table 1 shows the properties of the polyolefin laminated porous films and battery separators obtained in Examples 1 to 22 and Comparative Examples 1 to 7.

DESCRIPTION OF SYMBOLS 1 Battery separator 2 Polyolefin laminated porous film 3 Modified porous layer 4 Double-sided adhesive tape 5 Aluminum plate 6 Polyethylene spherulite crystal nucleus 7 Die 8 Polyolefin resin solution 9 Cooling roll 10 Doctor blade 11 Gel-like molded product

Claims (8)

A polyolefin laminated porous membrane having a layer configuration of A / B / A composed of a microporous polyolefin membrane with A / B / A, and both A layer and B layer have a density exceeding 0.94 g / cm ^3. Polyethylene is the main component, and layer A contains from 10% by weight to 40% by weight of ultrahigh molecular weight polyethylene having a weight average molecular weight of 1 × 10 ⁶ or more and less than 4 × 10 ⁶ , and layer B has a weight average molecular weight of 1 × 10 ⁶ or more 4 × 10 ⁶ less than the ultra high molecular weight polyethylene 1 wt% or more, 40 wt% comprises less terminal vinyl group concentration of high-density polyethylene layer a to 0.2 per 10,000 carbon atoms , and the projection of polyethylene on the surface of the polyolefin porous laminated film, 5 [mu] m ≦ W ≦ 50 [mu] m (the size of W is the projection) and 0.5 [mu] m ≦ H ≦ 3.0 [mu] m (height H protrusions) Satisfied, per side 3 / cm ² or more, and dotted erratically at 200 spots / cm ^2, the projection, which has grown on the raised portions of the surface layer of the polyolefin multilayer porous membrane And a separator for a battery in which a modified porous layer is laminated on at least a surface of a polyolefin laminated porous film having a film thickness of 20 μm or less. The battery separator according to claim 1 , wherein the modified porous layer contains a polyamideimide resin, a polyimide resin, or a polyamide resin. The battery separator according to claim 1 , wherein the modified porous layer contains a fluororesin. The battery separator according to any one of claims 1 to 3 , wherein the modified porous layer contains inorganic particles or crosslinked polymer particles. The battery separator according to any one of claims 1 to 4 , wherein the polyolefin laminated porous membrane has a thickness of 16 µm or less. The battery separator according to any one of claims 1 to 4 , wherein the polyolefin laminated porous membrane has a thickness of 12 µm or less. Comprising the following steps (a) ~ (e), a manufacturing method for a battery separator according to any one of 請 Motomeko 1-6.
(A) Step of preparing a polyolefin resin solution by adding a molding solvent to the polyolefin resin constituting the A layer and then melt-kneading
However, the polyolefin resin constituting the layer A includes an ultrahigh molecular weight polyethylene having a weight average molecular weight of 1 × 10 ⁶ or more and less than 4 × 10 ⁶ and a high density polyethylene having a weight average molecular weight of 1 × 10 ⁴ to 5 × 10 ⁵ , The content of ultrahigh molecular weight polyethylene is 10% by mass or more and 40% by mass or less, and the high density polyethylene has a terminal vinyl group concentration of 0.2 or more per 10,000 carbon atoms.
(B) A step of preparing a polyolefin resin solution by adding a molding solvent to the polyolefin resin constituting the B layer and then melt-kneading.
However, the polyolefin resin constituting the B layer comprises a high density polyethylene having a weight-average molecular weight 1 × 10 ultra-high molecular weight of ⁶ or more and less than 4 × 10 ⁶ polyethylene and the weight average molecular weight ^of 1 × 10 ⁴ from 5 × 10 ^5, ultra Content of high molecular weight polyethylene is 1 mass% or more and 40 mass% or less.
(C) Extrude the polyolefin solutions A and B obtained in the steps (a) and (b) from a die, and at least one of them is a cooling roll having a surface from which the molding solvent is removed by the molding solvent removing means. (D) The step of stretching the gel-like molded product in MD (machine direction) and TD (width direction) to obtain a stretched molded product (e) The stretched molded product (F) A step of heat-treating the laminated porous molded product to obtain a polyolefin laminated porous membrane Method for producing a separator for batteries according to claim 7, wherein the means for removing the molding solvent in step (c) is a doctor blade.

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