JP2016072197A - Separator for power storage device, and electrochemical element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a separator for power storage device excellent in productivity, adhesion to an electrode, stickiness of the outermost surface of the separator and handling ability, and cycle characteristics, while having a long battery capacity life, and capable of being manufactured by one time coating.SOLUTION: The separator for power storage device has a porous substrate layer (A), and a porous layer (B) containing an inorganic filler (b-2) and a resin binder (b-1). The resin binder (b-1) contains more than one kind of resin binder, and the surface softening temperature of the porous layer (B) is in a range of 30-60°C. In a hole having an area of 0.01 μmor more in the cross section of the porous layer (B), the ratio of holes having an angle θ of 60-120 degrees, formed by the long axis of each hole and an axis in parallel with the interface of the porous substrate layer (A) and porous layer (B), is 30% or more.SELECTED DRAWING: None

Description

  The present invention relates to an electricity storage device separator and an electrochemical element.

In power storage devices such as lithium ion secondary batteries and electric double layer capacitors, a separator made of a microporous film is provided between the positive and negative electrodes. As a function of the separator, for example, in order to prevent direct contact between the positive and negative electrodes, permeate ions, etc., from the viewpoint of safety,
"Fuse characteristics" that immediately stop the battery reaction when the storage device is abnormally heated,
"Short characteristics" that maintain the original shape even at high temperatures and prevent dangerous situations where the cathode and anode materials react directly
Etc. are required.
As a material constituting such a separator, for example, non-woven fabric, paper, polyethylene terephthalate, polyolefin and the like are known.

In recent years, there has been a demand for improving the adhesion between an electrode and a separator from the viewpoint of uniform charge / discharge current and suppression of lithium dendrite growth in an electricity storage device. If the close contact between the separator and the electrode is improved, the charge / discharge current is expected to be uniform and the growth of lithium dendrite is expected to be suppressed. As a result, the charge / discharge cycle life of the electricity storage device may be improved. It will be expected.
Under such circumstances, attempts have been made to apply an adhesive polymer to a microporous membrane made of polyolefin for the purpose of improving the adhesion of the separator (see, for example, Patent Documents 1 and 2).

JP 2007-59271 A JP 2011-54502 A Special table 2009-518809 JP 2012-38597 A International Publication No. 2014/017651

According to the techniques of Patent Documents 1 and 2 described above, certain effects are certainly recognized for improving the cycle characteristics of the electricity storage device. However, these techniques are not satisfactory in terms of lithium ion permeability, and also cause a problem that “stickiness” occurs on the surface of the separator and handling properties are lowered.
In this regard, Patent Document 3 discloses a technique in which two or more kinds of resin binders are mixed and used in order to achieve both adhesion to the electrode and suppression of stickiness on the separator surface;
Patent Document 4 discloses a technique for controlling the migration of two or more types of resin binders;
Patent Document 5 discloses a technique in which two types of resin binders are applied in layers.
Each is disclosed.

  However, the attempts in the above Patent Documents 3 to 5 have all been successful as attempts to improve industrially meaningful forms, such as some of which have not achieved the target and some have lost productivity. Not.

  The present invention has been made in order to overcome the above-described present situation. Therefore, the object of the present invention is excellent in adhesion with the electrode, adhesive strength with the porous base material layer, and binding strength of the inorganic filler, does not cause stickiness, has excellent handling properties, and is even better. The object is to provide an electricity storage device separator exhibiting cycle characteristics with excellent productivity.

The inventors of the present invention have made extensive studies to achieve the above object. As a result, when manufacturing a separator having a porous layer composed of an inorganic filler and a resin binder on the porous base material layer, a plurality of types having different specific gravity and glass transition temperature may be mixed and used as the resin binder. Thus, the migration of the resin binder is controlled to a desired mode by the difference in specific gravity of the plurality of types of resin binders, and the surface softening temperature of the formed porous layer can be controlled within the optimum range, and thus the above-mentioned problem can be solved. I found.
That is, the present invention is as follows.

[1] A porous substrate layer (A);
An electrical storage device separator having a porous layer (B) containing an inorganic filler (b-2) and a resin binder (b-1),
The resin binder (b-1) contains two or more kinds of resin binders,
The surface of the porous layer (B) has a surface softening temperature in the range of 30 to 60 ° C., and in the holes having an area of 0.01 μm ² or more in the cross section of the porous layer (B), the long axis of each hole and the porous substrate The electrical storage characterized in that the proportion of pores having an angle θ of 60 degrees or more and 120 degrees or less formed by an axis parallel to the interface between the layer (A) and the porous layer (B) is 30% or more Device separator.
[2] The resin binder (b-1) is
A first resin binder (b-1-1) having a glass transition temperature of 30 ° C. or higher;
The separator for an electricity storage device according to [1], comprising a second resin binder (b-1-2) having a glass transition temperature of less than 30 ° C.
[3] The electricity storage device according to [1], wherein the specific gravity of the second resin binder (b-1-2) is larger than the specific gravity of the first resin binder (b-1-1). Separator.

[4] The separator for an electricity storage device according to any one of [1] to [3], wherein the air permeability is in a range of 10 to 500 seconds / 100 cc.
[5] The separator for an electricity storage device according to any one of [1] to [4], wherein the first resin binder (b-1-1) is a hollow particle.
[6] Of the resin binder (b-1) present in the thickness range (upper half region) of 0 to 50% from the outer surface of the porous layer (B), the first resin binder (b-1-1). ) Is 60 mass% or more, [1]-[5] separator for accumulation-of-electricity devices given in any 1 paragraph.

[7] Of the resin binder (b-1) present in the thickness range (lower half region) of 50% to 100% from the outer surface of the porous layer (B), the second resin binder (b-1-2) ) Is 60 mass% or more and 90 mass% or less, The separator for electrical storage devices as described in any one of [1]-[6].
[8] A laminate comprising the electricity storage device separator according to any one of [1] to [7] and an electrode.
[9] An electrochemical device comprising the laminate according to [8].

  ADVANTAGE OF THE INVENTION According to this invention, both the electrode adhesiveness and roll peelability are excellent, the battery capacity lifetime is long, and the separator for electrical storage devices which is excellent also in productivity, and the electrochemical element formed using this separator are provided.

It is explanatory drawing which shows the reference | standard which recognizes a hole part from the SEM image of a porous layer (B) cross section. It is explanatory drawing which shows the reference | standard which determines the angle of a hole.

Hereinafter, a mode for carrying out the present invention (hereinafter abbreviated as “this embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
In this specification, migration refers to the step of forming a porous layer (B) through immobilization of the coating layer and drying process after coating the coating liquid onto the porous substrate layer (A). , A phenomenon in which the resin binder moves to the outer surface side in the porous layer (B).
The separator for electrical storage devices of this embodiment has a porous base material layer (A) and a porous layer (B).

<Porous substrate layer (A)>
The porous substrate layer (A) in the present invention will be described.
As the porous substrate layer (A), those having a small electron conductivity, an ionic conductivity, a high resistance to an organic solvent, and a fine pore diameter are preferable.
As such a porous substrate layer (A), for example, a porous substrate layer containing a polyolefin resin; polyethylene terephthalate, polycycloolefin, polyethersulfone, polyamide, polyimide, polyimideamide, polyaramid, polycycloolefin, nylon, Examples thereof include a porous substrate layer containing a resin such as polytetrafluoroethylene; a polyolefin fiber woven (woven fabric); a polyolefin fiber nonwoven fabric; paper; and an aggregate of insulating substance particles. Among these, when a multilayer porous substrate layer, that is, a battery separator, is obtained through a coating process, the coating liquid is excellent in coating properties, the separator film thickness is reduced, From the viewpoint of increasing the active material ratio and increasing the volume per volume, a porous substrate film containing a polyolefin resin (hereinafter also referred to as “polyolefin resin porous substrate film”) is preferable.

  From the viewpoint of improving the shutdown performance when the porous substrate layer (A) is used as a battery separator, the polyolefin resin accounts for 50% by mass or more and 100% by mass or less of the resin component constituting the porous substrate layer (A). A porous substrate layer formed by the occupied polyolefin resin composition is preferred. The proportion of the polyolefin resin in the polyolefin resin composition is more preferably 60% by mass or more and 100% by mass or less, and further preferably 70% by mass or more and 100% by mass or less.

The polyolefin resin contained in the polyolefin resin composition is not particularly limited. For example, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene are used as monomers. Examples thereof include a homopolymer, a copolymer, or a multistage polymer. Moreover, these polyolefin resins may be used independently or may be used in mixture of 2 or more types.
Among these, polyethylene, polypropylene, copolymers thereof, and mixtures thereof are preferable as the polyolefin resin from the viewpoint of shutdown characteristics when used as a battery separator.
Specific examples of polyethylene include low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, and the like;
Specific examples of polypropylene include isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene and the like;
Specific examples of the copolymer include ethylene-propylene random copolymer, ethylene-propylene rubber, ethylene-butylene copolymer, ethylene-octene copolymer, etc.
Each is listed.

Among these, polyethylene, particularly high-density polyethylene, is preferably used as the polyolefin resin from the viewpoint of satisfying the required performance of a low melting point and high strength when used as a battery separator. In the present invention, high density polyethylene means polyethylene having a density of 0.942 to 0.970 g / cm ³ . In the present invention, the density of polyethylene refers to a value measured according to the D) density gradient tube method described in JIS K7112 (1999).

  Moreover, when a porous base material layer (A) is a polyolefin resin porous base material film | membrane, it is preferable to use the mixture of polyethylene and a polypropylene as polyolefin resin from a viewpoint of improving heat resistance. In this case, the ratio of polypropylene to the total polyolefin resin in the polyolefin resin composition is preferably 1 to 35% by mass, more preferably 3 to 20% by mass from the viewpoint of achieving both heat resistance and a good shutdown function. %, More preferably 4 to 10% by mass.

  Arbitrary additives can be contained in the polyolefin resin composition. Examples of additives include polymers other than polyolefin resins; inorganic materials; antioxidants such as phenols, phosphorus and sulfur; metal soaps such as calcium stearate and zinc stearate; ultraviolet absorbers; light stabilizers An antistatic agent, an antifogging agent, a coloring pigment, and the like. The total addition amount of these additives is preferably 20 parts by mass or less with respect to 100 parts by mass of the polyolefin resin from the viewpoint of improving the shutdown performance, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass. Or less.

Since the porous base material layer (A) has a porous structure in which a large number of very small holes are gathered to form a dense communication hole, it has excellent ion conductivity and at the same time withstand voltage characteristics, Moreover, it has a feature of high strength.
The porous substrate layer (A) may be a single layer made of the above-described material or may be a laminated layer.

  The film thickness of the porous substrate layer (A) is preferably from 0.1 μm to 100 μm, more preferably from 1 μm to 50 μm, and even more preferably from 3 μm to 25 μm. From the viewpoint of mechanical strength, 0.1 μm or more is preferable, and from the viewpoint of increasing the capacity of the electricity storage device, 100 μm or less is preferable. The film thickness of the porous substrate layer (A) can be adjusted by controlling the die lip interval, the draw ratio in the drawing step, and the like.

The average pore diameter of the porous substrate layer (A) is preferably 0.03 μm or more and 0.70 μm or less, more preferably 0.04 μm or more and 0.20 μm or less, still more preferably 0.05 μm or more and 0.10 μm or less, particularly preferably. It is 0.06 μm or more and 0.09 μm or less. From the viewpoint of high ion conductivity and withstand voltage, 0.03 to 0.70 μm is preferable. The average pore diameter of the porous substrate layer (A) can be measured by a measurement method described later.
The average pore diameter should be adjusted by controlling the composition ratio, the extrusion sheet cooling rate, the stretching temperature, the stretching ratio, the heat setting temperature, the stretching ratio at the time of heat setting, the relaxation rate at the time of heat setting, or a combination thereof. Can do.

The porosity of the porous substrate layer (A) is preferably 25% to 95%, more preferably 30% to 65%, and still more preferably 35% to 55%. 25% or more is preferable from the viewpoint of improving ion conductivity, and 95% or less is preferable from the viewpoint of withstand voltage characteristics. The porosity of the porous substrate layer (A) can be measured by the method described later.
When the porous substrate layer (A) is composed of a polyolefin resin porous substrate film, the porosity is the mixing ratio of the polyolefin resin composition and the plasticizer, the stretching temperature, the stretching ratio, the heat setting temperature, the stretching ratio during heat setting. It can be adjusted by controlling the relaxation rate during heat setting, or by combining these.

  When the porous substrate layer (A) is a polyolefin resin porous substrate film, the viscosity average molecular weight of the polyolefin resin porous substrate film is preferably 30,000 or more and 12,000,000 or less, more preferably It is 50,000 or more and less than 2,000,000, more preferably 100,000 or more and less than 1,000,000. A viscosity average molecular weight of 30,000 or more is preferable because the melt tension at the time of melt molding becomes large, the moldability becomes good, and the strength tends to become high due to entanglement between polymers. On the other hand, a viscosity average molecular weight of 12,000,000 or less is preferable because uniform melt kneading is facilitated and the formability of the sheet, particularly thickness stability, tends to be excellent. Furthermore, when it is set as the separator for electrical storage devices, it is preferable for the viscosity average molecular weight to be less than 1,000,000 because it tends to close a hole when the temperature rises and a good shutdown function tends to be obtained.

There is no restriction | limiting in particular as a method of manufacturing the polyolefin resin porous substrate film as a porous substrate layer (A), A well-known manufacturing method is employable. For example;
(1) A method in which a polyolefin resin composition and a pore-forming material are melt-kneaded and formed into a sheet, and then stretched as necessary, and then the pore-forming material is extracted to make it porous.
(2) A method in which a polyolefin resin composition is melt-kneaded and extruded at a high draw ratio and then made porous by peeling the polyolefin resin crystal interface by heat treatment and stretching,
(3) A method in which a polyolefin resin composition and an inorganic material are melt-kneaded and formed on a sheet, and thereafter the surface is made porous by peeling the interface between the polyolefin resin and the inorganic material by stretching,
(4) After dissolving the polyolefin resin composition, it is immersed in a poor solvent for the polyolefin resin to solidify the polyolefin resin and at the same time remove the solvent to make it porous.

  Hereinafter, as an example of a method for producing a polyolefin resin porous substrate film as the porous substrate layer (A), a polyolefin resin composition and a pore-forming material are melt-kneaded to form a sheet, and then the pore-forming material is extracted. How to do will be described.

  First, the polyolefin resin composition and the hole forming material are melt-kneaded. As the melt-kneading method, for example, the polyolefin resin and, if necessary, other additives are put into a resin kneading apparatus such as an extruder, kneader, lab plast mill, kneading roll, Banbury mixer, etc., while the resin component is heated and melted. A method of introducing and kneading the pore-forming material at an arbitrary ratio is mentioned.

Examples of the pore forming material include a plasticizer, an inorganic material, or a combination thereof.
Although it does not specifically limit as a plasticizer, It is preferable to use the non-volatile solvent which can form a uniform solution above melting | fusing point of polyolefin. Specific examples of such a non-volatile solvent include, for example, hydrocarbons such as liquid paraffin and paraffin wax; esters such as dioctyl phthalate and dibutyl phthalate; higher alcohols such as oleyl alcohol and stearyl alcohol. . Note that these plasticizers may be recovered and reused after extraction by an operation such as distillation. Further, preferably, before being put into the resin kneading apparatus, the polyolefin resin, other additives and plasticizer are previously kneaded in advance at a predetermined ratio using a Henschel mixer or the like. More preferably, in pre-kneading, only a part of the plasticizer is added, and the remaining plasticizer is appropriately heated in a resin kneader and kneaded while side-feeding. By using such a kneading method, the dispersibility of the plasticizer is increased, and when the sheet-shaped molded body of the melt-kneaded product of the resin composition and the plasticizer is stretched in a later step, a high magnification is obtained without breaking the film. Tend to stretch.

  Among the plasticizers, liquid paraffin is highly compatible with polyolefin resins such as polyethylene and polypropylene, and even when the melt-kneaded product is stretched, the interface between the resin and the plasticizer does not easily peel, and uniform stretching is possible. Is preferable because it tends to be easily implemented.

  The ratio of the polyolefin resin composition and the plasticizer is not particularly limited as long as they can be uniformly melt-kneaded and formed into a sheet shape. For example, the mass fraction of the plasticizer in the composition comprising the polyolefin resin composition and the plasticizer is preferably 20 to 90 mass%, more preferably 30 to 80 mass%. When the mass fraction of the plasticizer is 90% by mass or less, the melt tension at the time of melt molding tends to be sufficient for improving moldability. On the other hand, when the mass fraction of the plasticizer is 20% by mass or more, even when the mixture of the polyolefin resin composition and the plasticizer is stretched at a high magnification, the polyolefin molecular chain is not broken, and the pore structure is uniform and fine. Are easily formed, and the strength is also easily increased.

  The inorganic material is not particularly limited. For example, oxide ceramics such as alumina, silica (silicon oxide), titania, zirconia, magnesia, ceria, yttria, zinc oxide, iron oxide; silicon nitride, titanium nitride, nitriding Nitride ceramics such as boron; silicon carbide, calcium carbonate, aluminum sulfate, aluminum hydroxide, potassium titanate, talc, kaolin clay, kaolinite, halloysite, pyrophyllite, montmorillonite, sericite, mica, amicite, bentonite Ceramics such as asbestos, zeolite, calcium silicate, magnesium silicate, diatomaceous earth, and silica sand; glass fibers. These may be used alone or in combination of two or more. Among these, silica, alumina, and titania are preferable from the viewpoint of electrochemical stability, and silica is particularly preferable from the viewpoint of easy extraction.

  The ratio between the polyolefin resin composition and the inorganic material is preferably 5% by mass or more, more preferably 10% by mass or more with respect to the total mass from the viewpoint of obtaining good separability. From the viewpoint of ensuring strength, the content is preferably 99% by mass or less, and more preferably 95% by mass or less.

  Next, the melt-kneaded product is formed into a sheet shape. As a method for producing a sheet-like molded product, for example, a melt-kneaded product is extruded into a sheet shape via a T-die or the like, and brought into contact with a heat conductor to cool to a temperature sufficiently lower than the crystallization temperature of the resin component. And then solidify. Examples of the heat conductor used for cooling and solidifying include metals, water, air, and plasticizers. Among these, it is preferable to use a metal roll because of its high heat conduction efficiency. In addition, when the extruded kneaded product is brought into contact with a metal roll, sandwiching it between the rolls further increases the efficiency of heat conduction, and the sheet is oriented to increase the film strength and improve the surface smoothness of the sheet. This is more preferable. The die lip interval when the melt-kneaded product is extruded from the T die into a sheet is preferably 200 μm or more and 3,000 μm or less, and more preferably 500 μm or more and 2,500 μm or less. When the die lip interval is 200 μm or more, the mess and the like are reduced, and there is little influence on the film quality such as streaks and defects, and the risk of film breakage and the like in the subsequent stretching process can be reduced. On the other hand, when the die lip interval is 3,000 μm or less, the cooling rate is fast and cooling unevenness can be prevented, and the thickness stability of the sheet can be maintained.

  Moreover, you may roll a sheet-like molded object. Rolling can be performed, for example, by a pressing method using a double belt press or the like. By performing rolling, the orientation of the surface layer portion can be particularly increased. The rolling surface magnification is preferably more than 1 and 3 or less, more preferably more than 1 and 2 or less. When the rolling ratio exceeds 1, the plane orientation increases and the film strength of the finally obtained porous base material layer (A) tends to increase. On the other hand, when the rolling ratio is 3 times or less, the orientation difference between the surface layer portion and the center is small, and a uniform porous structure tends to be formed in the thickness direction of the film.

  Next, the pore-forming material is removed from the sheet-like molded body to obtain a porous substrate layer (A). As a method for removing the hole forming material, for example, a method of extracting the hole forming material by immersing the sheet-shaped molded body in an extraction solvent and sufficiently drying it may be mentioned. The method for extracting the hole forming material may be either a batch type or a continuous type. In order to suppress shrinkage of the film constituting the porous base material layer (A), it is preferable to constrain the end of the sheet-like molded body during a series of steps of immersion and drying. Moreover, it is preferable to make the pore formation material residual amount in a porous base material layer (A) less than 1 mass% with respect to the mass of the whole porous base material layer (A).

  As the extraction solvent used when extracting the pore-forming material, it is preferable to use a solvent which is a poor solvent for the polyolefin resin and a good solvent for the pore-forming material and has a boiling point lower than the melting point of the polyolefin resin. . Examples of such an extraction solvent include hydrocarbons such as n-hexane and cyclohexane; halogenated hydrocarbons such as methylene chloride and 1,1,1-trichloroethane; non-chlorine such as hydrofluoroether and hydrofluorocarbon. Halogenated solvents; alcohols such as ethanol and isopropanol; ethers such as diethyl ether and tetrahydrofuran; ketones such as acetone and methyl ethyl ketone. These extraction solvents may be recovered and reused by an operation such as distillation. Moreover, when using an inorganic material as a pore formation material, aqueous solution, such as sodium hydroxide and potassium hydroxide, can be used as an extraction solvent.

Moreover, it is preferable to extend | stretch the film | membrane which comprises the said sheet-like molded object or a porous base material layer (A). The stretching may be performed before extracting the hole forming material from the sheet-like molded body. Moreover, you may carry out with respect to the film | membrane which comprises the porous base material layer (A) which extracted the hole formation material from the said sheet-like molded object. Furthermore, it may be performed before and after extracting the hole forming material from the sheet-like molded body.
As the stretching treatment, either uniaxial stretching or biaxial stretching can be suitably used, but biaxial stretching is preferable from the viewpoint of improving the strength and the like of the obtained porous base material layer (A). When the sheet-like molded body is stretched at a high magnification in the biaxial direction, the molecules are oriented in the plane direction, and the finally obtained porous base material layer is difficult to tear and has a high puncture strength. Examples of the stretching method include simultaneous biaxial stretching, sequential biaxial stretching, multistage stretching, and multiple stretching. Simultaneous biaxial stretching is preferable from the viewpoints of improvement of puncture strength, uniformity of stretching, and shutdown property. Further, sequential biaxial stretching is preferred from the viewpoint of easy control of plane orientation.

  Here, simultaneous biaxial stretching means stretching in MD (machine direction (length direction) when continuously forming the porous substrate layer (A)) and TD (MD of the porous substrate layer (A) of 90 °. In the direction crossing at an angle of 2), and the stretching ratio in each direction may be different. Sequential biaxial stretching refers to a stretching method in which MD and TD are stretched independently. When MD or TD is stretched, the other direction is fixed in an unconstrained state or a constant length. State.

  The draw ratio is preferably in the range of 20 times to 100 times in terms of surface magnification, and more preferably in the range of 25 times to 70 times. The draw ratio in each axial direction is preferably in the range of 4 to 10 times in MD, 4 to 10 times in TD, 5 to 8 times in MD, and 5 to 8 times in TD. More preferably, it is the range. When the total area magnification is 20 times or more, there is a tendency that sufficient strength can be imparted to the resulting porous base material layer (A). It tends to prevent and achieve high productivity.

  In order to suppress shrinkage of the film constituting the porous substrate layer (A), heat treatment can be performed for the purpose of heat setting after the stretching step or after the film is formed. Further, the membrane constituting the porous substrate layer (A) may be subjected to a post-treatment such as a hydrophilic treatment with a surfactant or the like, or a crosslinking treatment with ionizing radiation or the like.

  The film constituting the porous base material layer (A) is preferably subjected to heat treatment for the purpose of heat setting from the viewpoint of suppressing shrinkage. As a heat treatment method, a stretching operation performed at a predetermined temperature atmosphere and a predetermined stretching rate for the purpose of adjusting physical properties and / or a relaxation performed at a predetermined temperature atmosphere and a predetermined relaxation rate for the purpose of reducing stretching stress. Operation is mentioned. The relaxation operation may be performed after the stretching operation. These heat treatments can be performed using a tenter or a roll stretching machine.

The stretching operation is performed by stretching the film MD and / or TD by 1.1 times or more, more preferably 1.2 times or more, so that the porous substrate layer (A) having higher strength and high porosity can be obtained. It is preferable from a viewpoint obtained.
The relaxation operation is an operation for reducing the film to MD and / or TD. The relaxation rate is a value obtained by dividing the dimension of the film after the relaxation operation by the dimension of the film before the relaxation operation. When both MD and TD are relaxed, it is a value obtained by multiplying the MD relaxation rate and the TD relaxation rate. The relaxation rate is preferably 1.0 or less, more preferably 0.97 or less, and still more preferably 0.95 or less. The relaxation rate is preferably 0.5 or more from the viewpoint of film quality. The relaxation operation may be performed in both the MD and TD directions, but only one of the MD and TD may be performed.

  The stretching and relaxation operations after this plasticizer extraction are preferably performed at TD. The temperature in the stretching and relaxation operation is preferably lower than the melting point of the polyolefin resin (hereinafter also referred to as “Tm”), and more preferably in the range of 1 ° C. to 25 ° C. lower than Tm. When the temperature in the stretching and relaxation operation is in the above range, it is preferable from the viewpoint of the balance between the reduction in thermal shrinkage and the porosity.

[Physical properties of porous substrate layer (A)]
The puncture strength of the porous substrate layer (A) in the present embodiment is not particularly limited, but is preferably 200 g / 20 μm or more, more preferably 300 g / 20 μm or more, preferably 2,000 g / 20 μm or less, more preferably It is 1,000 g / 20 μm or less. It is preferable that the puncture strength is 200 g / 20 μm or more from the viewpoint of suppressing film breakage due to the dropped active material or the like during winding of the electricity storage device. Moreover, it is preferable also from a viewpoint of suppressing the concern which short-circuits by the expansion / contraction of the electrode accompanying charging / discharging. On the other hand, setting it to 2,000 g / 20 μm or less is preferable from the viewpoint of reducing width shrinkage due to orientation relaxation during heating. Here, the puncture strength is measured by the method described in Examples below.
The puncture strength can be adjusted by adjusting the draw ratio and the draw temperature.

The air permeability of the porous substrate layer (A) in the present embodiment is not particularly limited, but is preferably 10 sec / 100 cc or more, more preferably 50 sec / 100 cc or more, preferably 1,000 sec / 100 cc or less, more preferably Is 500 sec / 100 cc or less. The air permeability is preferably 10 sec / 100 cc or more from the viewpoint of suppressing self-discharge of the electricity storage device. On the other hand, setting it to 1,000 sec / 100 cc or less is preferable from the viewpoint of obtaining good charge / discharge characteristics. Here, the air permeability is measured by the method described in Examples below.
The air permeability can be adjusted by changing the stretching temperature and the stretching ratio.

  The short temperature which is an index of heat resistance of the porous substrate layer (A) in the present embodiment is preferably 150 ° C. or higher, more preferably 160 ° C. or higher, further preferably 180 ° C. or higher, and most preferably. Is 200 ° C. or higher. When the short-circuit temperature is set to 150 ° C. or higher, it is preferable from the viewpoint of the safety of the electricity storage device when the electricity storage device separator is used.

<Porous layer (B)>
The porous layer (B) in the power storage device separator of the present embodiment includes an inorganic filler (b-2) and a resin binder (b-1). The resin binder (b-1) includes two or more types of resin binders.

[Inorganic filler (b-2)]
Although it does not specifically limit as an inorganic filler (b-2) used for the said porous layer (B), Heat resistance and electrical insulation are high, and it is electrochemically stable in the use range of a lithium ion secondary battery. Some are preferred.
Examples of the inorganic filler (b-2) include an aluminum compound, a magnesium compound, and other compounds.
Examples of the aluminum compound include aluminum oxide, aluminum silicate, aluminum hydroxide, aluminum hydroxide oxide, sodium aluminate, aluminum sulfate, aluminum phosphate, and hydrotalcite.
Examples of the magnesium compound include magnesium sulfate and magnesium hydroxide.

Other compounds include oxide ceramics, nitride ceramics, clay minerals, silicon carbide, calcium carbonate, barium titanate, asbestos, zeolite, calcium silicate, magnesium silicate, diatomaceous earth, silica sand, glass fiber, etc. Is mentioned. Examples of the oxide ceramics include silica, titania, zirconia, magnesia, ceria, yttria, zinc oxide, iron oxide and the like. Examples of nitride ceramics include silicon nitride, titanium nitride, boron nitride and the like. Examples of the clay mineral include talc, montmorillonite, sericite, mica, amicite, bentonite and the like.
These may be used alone or in combination.

  Among these, aluminum oxide, aluminum hydroxide oxide, and aluminum silicate are preferable from the viewpoints of electrochemical stability and heat resistance. A specific example of aluminum oxide is alumina. Specific examples of the aluminum hydroxide oxide include boehmite. Specific examples of aluminum silicate include kaolinite, dickite, nacrite, halloysite, and pyrophyllite.

  As the aluminum oxide, alumina is more preferable from the viewpoint of electrochemical stability. By using particles mainly composed of alumina as the inorganic filler (b-2) constituting the porous layer (B), a very lightweight porous layer (B) is realized while maintaining high permeability. In addition, even with a thinner porous layer (B) thickness, thermal shrinkage of the separator at high temperatures is suppressed, and excellent heat resistance tends to be exhibited. Alumina has many crystal forms such as α-alumina, β-alumina, γ-alumina, and θ-alumina, and any of them can be suitably used. Of these, α-alumina is most preferable because it is thermally and chemically stable.

  As the aluminum hydroxide oxide, boehmite is more preferable from the viewpoint of preventing an internal short circuit due to generation of lithium dendrite. Realizing a very lightweight porous layer (B) while maintaining high permeability by adopting particles mainly composed of boehmite as the inorganic filler (b-2) constituting the porous layer (B) In addition, even with a thinner porous layer thickness, the thermal contraction of the separator at a high temperature is suppressed, and excellent heat resistance tends to be exhibited. Synthetic boehmite that can reduce ionic impurities that adversely affect the characteristics of the electrochemical device is more preferred.

  Among the aluminum silicates, kaolinite (hereinafter, also referred to as kaolin) mainly composed of kaolin mineral is preferable from the viewpoint of lightness and air permeability. Kaolin includes wet kaolin and calcined kaolin, which is calcined. However, calcined kaolin releases crystal water during the calcining process and removes impurities. Particularly preferred. As the inorganic filler (b-2) constituting the porous layer (B), by adopting particles containing calcined kaolin as a main component, a very lightweight porous layer (B) is maintained while maintaining high permeability. In addition to this, even with a thinner porous layer (B) thickness, thermal contraction of the separator at a high temperature is suppressed, and excellent heat resistance tends to be exhibited.

  The average particle size of the inorganic filler (b-2) is preferably from 0.1 μm to 10.0 μm, more preferably from 0.2 μm to 5.0 μm, and from 0.4 μm to 3. More preferably, it is 0 μm or less. It is preferable to adjust the average particle size of the inorganic filler (b-2) to the above range from the viewpoint of suppressing the air permeability of the separator and the heat shrinkage at a high temperature.

  As the particle size distribution of the inorganic filler (b-2), the minimum particle size is preferably 0.02 μm or more, more preferably 0.05 μm or more, and further preferably 0.1 μm or more. The maximum particle size is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 7 μm or less. The ratio of the maximum particle size / average particle size is preferably 50 or less, more preferably 30 or less, and still more preferably 20 or less. Adjusting the particle size distribution of the inorganic filler (b-2) to the above range is preferable from the viewpoint of suppressing thermal shrinkage of the separator at a high temperature. Moreover, you may have a several particle size peak between the maximum particle size and the minimum particle size. In addition, as a method of adjusting the particle size distribution of the inorganic filler (b-2), for example, the inorganic filler (b-2) is pulverized using a ball mill, a bead mill, a jet mill or the like, and adjusted to a desired particle size distribution. And a method of blending after adjusting the filler (b-2) having a plurality of particle size distributions.

  Examples of the shape of the inorganic filler (b-2) include a plate shape, a scale shape, a polyhedron, a needle shape, a columnar shape, a spherical shape, a spindle shape, a lump shape, and the like. The inorganic filler (b-2) having the above shape is used. You may use in combination of multiple types. Among these, a plate shape, a scale shape, and a polyhedron are preferable from the viewpoint of improving permeability.

  The proportion of the inorganic filler (b-2) in the porous layer (B) is the permeability and heat resistance of the separator, and the inorganic filler (b-2) is bound in the porous layer (B). It can determine suitably from viewpoints, such as the required amount of the resin binder (b-1) to make. The proportion of the inorganic filler (b-2) is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, from the viewpoint of the permeability and heat resistance of the separator. Especially preferably, it is 93 mass% or more, Most preferably, it is 96 mass% or more. From the viewpoint of the required amount of the resin binder (b-1) for binding the inorganic filler (b-2) in the porous layer (B), the proportion of the inorganic filler (b-2) is 100% by mass. It is preferably less than 9, more preferably 99.5% by mass or less, still more preferably 99% by mass or less, and particularly preferably 98% by mass or less.

  The inorganic filler (b-2) in the porous layer (B) is preferably present uniformly in the porous layer (B). As an index thereof, the amount of inorganic filler in the thickness range of 0 to 50% from the outer surface of the porous layer (B) (b-2U) / the amount of inorganic filler existing in the thickness range exceeding 50% to 100%. The ratio of (b-2D) is preferably 0.8 to 1.2, more preferably 0.85 to 1.15, and still more preferably 0.9 to 1.1. When the ratio is 0.8 to 1.2, the pore size distribution in the porous layer (B) becomes uniform, and the reproducibility of the cycle characteristics of the electricity storage device is improved.

The position of the inorganic filler (b-2) in the porous layer (B) can be known by using a technique combining a cross-sectional photograph of the porous layer (B) and element mapping. As the cross-sectional photograph, for example, an SEM (scanning electron microscope) image;
As the element mapping method, for example, EDX (energy dispersive X-ray spectroscopy) can be employed. In these analyses, it is possible to know the location of the inorganic filler (b-2) by mapping in the cross-sectional direction while paying attention to the metal element constituting the main component of the inorganic filler (b-2). . When the inorganic filler (b-2) is, for example, boehmite or kaolin, the position of the inorganic filler (b-2) can be known by mapping in the cross-sectional direction of the Al (aluminum) element constituting the main component.

[Resin binder (b-1)]
The resin binder (b-1) is a resin that plays a role in binding the inorganic filler (b-2) described above. Moreover, it is preferable that it is resin which plays the role which bind | concludes an inorganic filler (b-2) and a porous base material layer (A) mutually.
The type of the resin binder (b-1) is one that is insoluble in the electrolyte solution of the lithium ion secondary battery when used as a separator and is electrochemically stable within the range of use of the lithium ion secondary battery. It is preferable to use it.

Specific examples of the resin binder (b-1) include the following 1) to 6).
1) Polyolefin: For example, polyethylene, polypropylene, ethylene propylene rubber, and modified products thereof;
2) Conjugated diene polymer: for example, styrene-butadiene copolymer and its hydride, acrylonitrile-butadiene copolymer and its hydride, acrylonitrile-butadiene-styrene copolymer and its hydride;
3) Acrylic polymer: For example, methacrylic acid ester-acrylic acid ester copolymer, styrene-acrylic acid ester copolymer, acrylonitrile-acrylic acid ester copolymer;

4) Polyvinyl alcohol resin: for example, polyvinyl alcohol, polyvinyl acetate;
5) Fluorine-containing resin: For example, polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene Copolymer, hexafluoropropylene-tetrafluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer;
6) A resin having a melting point and / or glass transition temperature of 180 ° C. or higher or a polymer having no melting point but a decomposition temperature of 200 ° C. or higher: for example, polyphenylene ether, polysulfone, polyether sulfone, polyphenylene sulfide, polyetherimide, polyamideimide , Polyamide, polyester. In particular, from the viewpoint of durability, wholly aromatic polyamides, particularly polymetaphenylene isophthalamide, are preferred.
Among these, 2) conjugated diene polymers are preferable from the viewpoint of easy compatibility with electrodes, and 3) acrylic polymers and 5) fluorine-containing resins are preferable from the viewpoint of voltage resistance.

The 2) conjugated diene polymer is a polymer containing a conjugated diene compound as a monomer unit.
Examples of the conjugated diene compound include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, and substituted linear chains. Examples thereof include conjugated pentadienes, substituted and side chain conjugated hexadienes, and these may be used alone or in combination of two or more. Among these, 1,3-butadiene is particularly preferable.

The 3) acrylic polymer is a polymer containing a (meth) acrylic compound as a monomer unit. The (meth) acrylic compound indicates at least one selected from the group consisting of (meth) acrylic acid and (meth) acrylic acid ester.
Examples of (meth) acrylic acid used in the above 3) acrylic polymer include acrylic acid and methacrylic acid.
As the (meth) acrylic acid ester used in the above 3) acrylic polymer, for example,
(Meth) acrylic acid alkyl esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl amethacrylate, phenyl acrylate, phenyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate ;
Epoxy group-containing (meth) acrylic acid esters such as glycidyl acrylate and glycidyl methacrylate may be used, and these may be used alone or in combination of two or more.

The above 2) conjugated diene polymer and 3) acrylic polymer may be obtained by copolymerizing other monomers copolymerizable therewith. Examples of other copolymerizable monomers used include unsaturated carboxylic acid alkyl esters, aromatic vinyl monomers, vinyl cyanide monomers, and unsaturated monomers containing a hydroxyalkyl group. , Unsaturated carboxylic acid amide monomer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid and the like. These may be used alone or in combination of two or more. Good. Among the above, an unsaturated carboxylic acid alkyl ester monomer is particularly preferable. Examples of unsaturated carboxylic acid alkyl ester monomers include dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl itaconate, monomethyl fumarate, monoethyl fumarate, and the like. It may be used alone or in combination of two or more.
The 2) conjugated diene polymer may be obtained by copolymerizing the (meth) acrylic compound as another monomer.

The resin binder (b-1) includes two or more types of resin binders. As such a resin binder (b-1),
A first resin binder (b-1-1) exhibiting a glass transition temperature in a region of 30 ° C. or higher;
A second resin binder (b-1-2) exhibiting a glass transition temperature in a region of less than 30 ° C .;
It is preferable that it is a mixture containing.
The glass transition temperature of the 1st resin binder (b-1-1) which shows a high glass transition temperature is 30 degreeC or more, Preferably it is 45 degreeC or more, More preferably, it is 70 degreeC or more. When glass transition temperature is 30 degreeC or more, it is preferable from the viewpoint of the stickiness of a separator outermost surface, and handling property.
The glass transition temperature of the 2nd resin binder (b-1-2) which shows a low glass transition temperature is less than 30 degreeC, Preferably it is 5 degrees C or less, More preferably, it is -10 degrees C or less. When glass transition temperature is less than 30 degreeC, it is preferable from a viewpoint of adhesiveness with an electrode, adhesive strength with a porous base material layer (A), and binding strength of an inorganic filler (b-2).

  As the first resin binder (b-1-1) and the second resin binder (b-1-2), binders having the above glass transition temperatures are selected, and the resin binders (b) having different glass transition temperatures are used. -1) can be separated and migrated using the specific gravity difference of each resin binder. As a result, in the resulting porous layer (B), the adhesion to the electrode, the adhesive strength with the porous substrate layer (A), the binding strength of the inorganic filler (b-2), and the stickiness of the outermost surface of the separator Performance and handling performance can be made compatible.

It is preferable that the specific gravity of the second resin binder (b-1-2) is larger than the specific gravity of the first resin binder (b-1-1).
The relationship between the glass transition temperature of resin binder (b-1) and specific gravity is demonstrated.
The porous layer (B) in the separator of this embodiment is
The surface on the side in contact with the multilayer base material layer (A) has sufficient adhesiveness,
On the outer surface side (the side opposite to the contact surface with the porous base material layer (A)), it is preferable not to exhibit excessive tackiness (stickiness). Therefore, in the porous layer (B) after formation, the first resin binder (b-1-1) having a high glass transition temperature is formed on the outer surface side.
On the contact surface side with the multilayer base material layer (A), the second resin binder (b-1-2) having a low glass transition temperature is provided.
It is advantageous that there are many of each.

On the other hand, the specific gravity of the resin binder (b-1) is related to migration. In the step of forming the porous layer (B) through the immobilization and drying process of the coating layer after coating the coating liquid containing the resin binder (b-1) to the porous substrate layer (A). The resin binder (b-1) migrates to the outer surface side in the porous layer (B). At this time, since the resin binder having a lower specific gravity migrates more than the resin binder having a higher specific gravity, the resin binder is unevenly distributed near the surface of the formed porous layer (B).
Therefore,
The specific gravity of the first resin binder (b-1-1) having a high glass transition temperature is further reduced,
It is advantageous to increase the specific gravity of the second resin binder (b-1-2) having a low glass transition temperature.

Here, the specific gravity difference [(b-1-2)-(b-1-1)] between the second resin binder (b-1-2) and the first resin binder (b-1-1) is is preferably 0.05 g / cm ³ or more, more preferably 0.10 g / cm ³ or more, further preferably 0.15 g / cm ³ or more. When the specific gravity difference is 0.05 g / cm ³ or more, the first resin binder (b-1-1) and the second resin binder (b-1-2) are separated and migrated, The adhesiveness with an electrode, the stickiness on the surface of the porous layer (B) of the separator, and the handling property can be made compatible, which is preferable.

  When the specific gravity relationship is reversed from the above, the second resin binder (b-1-2) having a low glass transition temperature is placed on the outer surface side of the porous layer (B), and the first resin binder having a high glass transition temperature. Since (b-1-1) has a structure that is unevenly distributed on the porous substrate (A) side of the porous layer (B), the stickiness and handling properties of the outermost surface of the separator, and the adhesion with the electrode deteriorate. It is not preferable.

The specific gravity of the resin binders (b-1-1) and (b-1-2) can be controlled, for example, as follows.
(1) When synthesizing the resin binder (b-1),
Increasing the proportion of one or more selected from acrylic monomers and fluorine monomers tends to increase the specific gravity,
When the ratio of the olefin-based, diene-based monomer, and styrene-based monomer is increased, the specific gravity tends to decrease. Therefore, the first resin binder (b-1-1) is, for example, a styrene / pig diene copolymer, and the second resin binder (b-1-2) is, for example, an acrylic acid copolymer. This is a preferred embodiment.
(2) Solid particles tend to have a higher specific gravity,
Hollow particles tend to have a lower specific gravity. Therefore, it is a preferred embodiment that the first resin binder (b-1-1) is a hollow particle and the second resin binder (b-1-2) is a solid particle.

The glass transition temperature can be arbitrarily set by the selection of the monomer by those skilled in the art. Therefore, by appropriately combining the selection of the monomer and one or more of the above methods,
A first resin binder (b-1-1) having a desired high glass transition temperature and small specific gravity;
The second resin binder (b-1-2) having a desired low glass temperature and large specific gravity can be easily obtained.

  It is preferable that the first resin binder (b-1-1) and the second resin binder (b-1-2) do not exhibit complete compatibility. Since these two types of resin binders do not exhibit complete compatibility, resin binders having different properties are present separately, and each characteristic can be exhibited. Therefore, the adhesiveness with the electrode, the adhesive strength with the porous base material layer (A), the binding strength of the inorganic filler (b-2), the stickiness of the outermost surface of the separator, and the handling properties are at a high level. It can be compatible. Here, when two types of resins exhibit complete compatibility, the resin binders having different properties behave as if they are one type of polymer. As a result, depending on the glass transition temperature as a whole of the mixture shown after the compatibilization, adhesion with the electrode, adhesive strength with the porous base material layer (A), binding of the inorganic filler (b-2) The strength, the stickiness of the outermost surface of the separator, and the handling properties are not preferable because they only show averaged performance.

  The amount of the resin binder (b-1) used is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, based on the total amount of the porous layer (B). It is still more preferable to set it as 5-10 mass%. It is preferably 0.5% by mass or more from the viewpoint of adhesion to the electrode, adhesive strength with the porous base material layer (A), and binding strength of the inorganic filler (b-2), and is 30% by mass. The following is preferable from the viewpoints of stickiness on the outermost surface of the separator and handling properties.

  The use ratio of the first resin binder (b-1-1) and the second resin binder (b-1-2) is the first resin binder (b-1) with respect to the total amount of the resin binder (b-1). -1) use ratio {mass ratio of (b-1-1) / (b-1)} is preferably 0.05 to 0.95, more preferably 0.1 to 0.7. More preferably, it is still more preferably 0.15 to 0.5. It is preferably 0.05 or more from the viewpoint of the stickiness of the outermost surface of the separator and handling properties, and 0.95 or less is the adhesion to the electrode and the adhesive strength to the porous substrate layer (A). And from the viewpoint of the binding strength of the inorganic filler (b-2).

[Porous layer (B)]
The layer thickness of the porous layer (B) in the present embodiment is preferably 1 μm or more from the viewpoint of improving heat resistance and insulation, and 50 μm or less from the viewpoint of increasing the capacity and permeability of the electricity storage device. It is preferable that The layer thickness of the porous layer (B) is more preferably 1.5 μm or more and 20 μm or less, further preferably 2 μm or more and 10 μm or less, and particularly preferably 2 μm or more and 7 μm or less.
Layer density of the porous layer (B) is preferably from 0.5 to 2.0 g / cm ^3, more preferably 0.7~1.5g / cm ^3. When the layer density of the porous layer (B) is 0.5 g / cm ³ or more, the thermal contraction rate at a high temperature of the separator tends to be good, and when it is 2.0 g / cm ³ or less, the air permeability is low. It tends to decrease.

The surface softening temperature of the porous layer (B) in this embodiment is 30 to 60 ° C, preferably 30 to 50 ° C, more preferably 30 to 45 ° C, and further preferably 35 to 45 ° C. When the surface softening temperature is 30 ° C. or higher, the separator having the porous layer (B) is wound into a roll shape at the time of manufacture, and when the separator is unwound at the time of use, the separators are not in close contact and wrinkled. Since it can unwind, it is preferable. When the surface softening temperature is 60 ° C. or lower, the press temperature can be set low when the electrode and the separator are pressure-bonded using a high-temperature press. Therefore, even when a polyolefin resin having a low glass transition temperature, which is generally used for the porous base material layer (A) constituting the separator, is used, it is possible to suppress the occurrence of wrinkles in the laminate obtained after pressure bonding, which is preferable. .
Of the resin binder (b-1) present in the thickness range (upper half region) of 0% to 50% from the outer surface in the porous layer (B), the first resin binder (b-1-1) is The occupying ratio is preferably 55% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more and 95% by mass or less, and most preferably 70% by mass or more and 90% by mass or less. It is preferable that this ratio is 55% by mass or more from the viewpoint of the stickiness and handling properties of the separator outermost surface.

Of the resin binder (b-1) present in the thickness range (lower half region) of 50% to 100% from the outer surface in the porous layer (B), the second resin binder (b-1-2) is The proportion occupied is preferably 55% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more and 95% by mass or less, and most preferably 70% by mass or more and 90% by mass or less. It is preferable that it is 55 mass% or more from a viewpoint of adhesiveness with an electrode, adhesiveness with a porous base material layer (A), and binding property with an inorganic filler (b-2).
Each resin binder (b-1) in the region (upper half region) in the thickness range of 0 to 50% from the outer surface in the porous layer (B) and the region (lower half region) in the thickness range of 50 to 100% After the porous layer (B) is separated into an upper half region and a lower half region, each region can be determined by performing, for example, the following analysis.

(1) By measuring the weight reduction rate of each region using TG-DTA (thermogravimetric-differential thermal analysis method), the first resin binder ((b-1-1) and second Next, the total amount of the resin binder (b-1-2) is examined.
(2) By DSC (Differential Scanning Calorimetry) measurement, the peak area ratio of each of the high temperature side peaks in DDSC (DSC differential curve) is the first resin binder and the low temperature side peak is the second resin binder. From the above, the ratio of both resin binders is calculated.

By the above operation, the abundance of the first resin binder ((b-1-1) and the second resin binder (b-1-2) in the upper half region and the lower half region in the porous layer (B) and You can know the existence ratio.
The porous layer (B) in the present embodiment is parallel to the long axis of each hole and the interface between the porous substrate layer (A) and the porous layer (B) in the holes having an area of 0.01 μm ² or more in the cross section. The ratio of holes having an angle θ formed by the shaft of 60 degrees or more and 120 degrees or less is 30% or more. As a result, the separator of this embodiment is excellent in heat resistance and output characteristics.
The pore area can be obtained by binarizing a cross-sectional SEM image obtained by observing the cross section of the porous layer (B) with a scanning electron microscope (SEM) at a photographing magnification of 10,000 times. .

Specifically, the hole area and the angle θ can be measured by the following method.
First, cross section processing is performed on the separator by BIB (broad ion beam). In this processing, in order to suppress thermal damage, a separator as a sample may be cooled until just before processing, if necessary. Specifically, the separator can be left overnight in a -40 ° C cooling device. Thereby, a smooth separator cross section is obtained.

  Next, the obtained separator cross section is subjected to a conductive treatment by C paste and Os coating. Thereafter, using “HITACHI S-4700” (manufactured by Hitachi High-Tech Fielding), imaging is performed with the imaging magnification set to 10,000 times, the acceleration voltage: 1.0 kV, and the detector: secondary electron (upper UPPER). An electronic image of the obtained cross-sectional SEM image is obtained, and the hole angle θ is calculated.

  The angle θ can be calculated by the following method using image processing software “ImageJ” (version 1.46). Open an electronic image of the desired cross-section SEM and measure the length of a known distance in the image using a line selection tool “Stright”. Open “SET SCALE” from the “Analyze” tab, enter the unit of measurement and the known distance, and set the scale. Next, the pores in the porous layer (B) are filled with black using “Paintbrush Tool” as a pretreatment for the binarization process.

Here, the identification of the hole may not necessarily be clear depending on the measurement target. An example will be described with reference to FIG. FIG. 1 is a cross-sectional SEM image of the porous layer (B). For example, when attention is paid to the hole (1) at the left end in FIG. 1, there is a dark part in the rear where the inorganic filler (b-2) cannot be confirmed. A region where the outline is closed centering on such a dark part is recognized as a hole (gap). In this case, although the inorganic filler (b-2) is also observed in the interior certified as a hole, it can be evaluated that this part forms part of the void and contributes to ionic conductivity. There is no problem in accrediting the department. On the other hand, since the inorganic filler (b-2) 2 positioned slightly rearward from the BIB processed cross section cannot be evaluated as contributing to ionic conductivity, it is not recognized as a hole.
In this way, by identifying the hole centered on the dark part of the image captured under the SEM imaging conditions described above, it is possible to recognize the hole that matches the technical significance of the present embodiment in various measurement objects. it can.

  Note that the contour identified with the dark portion as the center may be cut off at the end of the SEM image (for example, the hole (3) at the right end of the image). In such an image edge portion, even if the contour recognized centering on the dark portion is interrupted, it is clear that this portion contributes to ion conductivity by forming a hole portion. Authorize.

After filling the hole (gap) thus identified, binarization processing is performed.
Specifically, first, in order to select an evaluation area, a desired region of the porous layer (B) is selected using “Rectangular selections”. When selecting, the surface layer part of the porous layer (B) is excluded. Subsequently, in order to create the selected area in another file, “Duplicate” is opened from the “Image” tab, and a new electronic image of only the porous layer (B) is created. Next, processing for specifying the hole is performed from the obtained electronic image. Specifically, “Adjust” is selected from “Image”, and “Threshold” is further selected, and processing is performed by setting the range to be painted with a single color out of 256 gradations as “0-100”.

Subsequently, the process proceeds to a process of making the hole filled with a single color oval by the binarization process. Specifically, by selecting “Analyze particles”, entering “0.01 μm ² or more” in the “Size” item, and selecting “Elipse” as the Show item, the pores of 0.01 μm ² or more are selected. An image in which each hole is ovalized is obtained.

  Finally, for each ovalized hole, an angle θ formed by the long axis of the hole and an axis parallel to the interface between the porous substrate layer (A) and the porous layer (B) is calculated (see FIG. 2). ). A histogram is created for the angle θ thus determined, and the ratio of the holes satisfying 60 ° ≦ θ ≦ 120 ° with respect to the entire hole is calculated.

  The separator of the present embodiment has a high ion conductivity and a low membrane resistance by including the above-described hole structure. Therefore, an electricity storage device having high output characteristics can be realized. The reason is not clear, but since the porous layer (B) has the pore structure, the diffusion and movement of lithium ions becomes faster and the low membrane resistance can be maintained, so that it has high output characteristics. Conceivable.

The ratio of the holes where the angle θ is 60 ° ≦ θ ≦ 120 ° is 30% or more, preferably 30% or more and 70% or less, more preferably 35% or more and 70% or less, and further preferably 35% or more and 50%. Hereinafter, it is particularly preferably 40% or more and 50% or less. When the ratio of the angle of 60 ° ≦ θ ≦ 120 ° is 30% or more, the diffusion of the lithium ion battery in the electrolytic solution is fast, and it tends to be more advantageous in increasing the output of the electricity storage device, and 70% or less. Therefore, it is preferable from the viewpoint of suppressing thermal shrinkage of the separator at a high temperature.
The ratio of the holes having the angle θ of 60 ° ≦ θ ≦ 120 ° can be adjusted by controlling the migration of the resin binder (b-1) to the outer surface of the porous layer (B). In particular, the first resin binder (b-1-1) that easily migrates has a great influence when the ratio of the holes is changed. As factors for changing the ratio of the pores, the amount of the resin binder (b-1) and the glass transition temperature (particularly, the first resin binder (b-1-1));
Examples include the shape of the inorganic filler (b-2), the average particle size, and the particle size distribution, the drying temperature of the coating liquid, and the air volume during drying.

[Method for manufacturing separator for power storage device]
As a method for forming the porous layer (B), for example, a coating liquid containing an inorganic filler (b-2) and a resin binder (b-1) is applied to at least one surface of the porous substrate layer (A). And a method of forming the porous layer (B).
As a solvent for the coating liquid, those capable of uniformly and stably dispersing the inorganic filler (b-2) and the resin binder (b-1) are preferable. For example, N-methylpyrrolidone, N, N-dimethyl Examples include formamide, N, N-dimethylacetamide, water, ethanol, toluene, hot xylene, methylene chloride, and hexane.
In order to stabilize dispersion and improve coating properties, the coating liquid includes various types of dispersants such as surfactants; thickeners; wetting agents; antifoaming agents; pH adjusters containing acids and alkalis. Additives may be added. These additives are preferably those that can be removed simultaneously with the removal of the solvent. However, if the additive is electrochemically stable in the range of use of the electricity storage device, does not inhibit the battery reaction, and is stable up to about 200 ° C., the porous layer It may remain in (B).

  About the method of disperse | distributing the said inorganic filler (b-2) and the said resin binder (b-1) to the solvent of a coating liquid, it is a method which can implement | achieve the dispersion | distribution characteristic of a coating liquid required for a coating process. If there is no particular limitation. Examples thereof include a ball mill, a bead mill, a planetary ball mill, a vibrating ball mill, a sand mill, a colloid mill, an attritor, a roll mill, a high-speed impeller dispersion, a disperser, a homogenizer, a high-speed impact mill, ultrasonic dispersion, and mechanical stirring using a stirring blade.

  The method for applying the coating liquid to the porous substrate layer (A) is not particularly limited as long as it can achieve the required porous layer (B) thickness and coating area. For example, gravure coater method, small diameter gravure coater method, reverse roll coater method, transfer roll coater method, kiss coater method, dip coater method, knife coater method, air doctor coater method, blade coater method, rod coater method, squeeze coater method, cast Examples thereof include a coater method, a die coater method, a screen printing method, a spray coating method, a spray coater coating method, and an ink jet coating. Of these, the gravure coater method or the spray coating method is preferable in that the degree of freedom of the coating shape is high and a preferable area ratio can be easily obtained.

Further, by applying a surface treatment to the surface of the porous base material layer (A) prior to the application of the coating liquid, it becomes easier to apply the coating liquid, and the porous layer (B) after coating and the porous substrate Since adhesiveness with the surface of a material layer (A) improves, it is preferable. The surface treatment method is not particularly limited as long as it does not significantly impair the porous structure of the porous base material layer (A). For example, corona discharge treatment method, mechanical surface roughening method, solvent treatment method, acid treatment Method, ultraviolet oxidation method and the like.
The method for removing the solvent from the coating film after coating is not particularly limited as long as it does not adversely affect the porous substrate layer (A). For example, while fixing the porous substrate layer (A), the method Examples thereof include a method of drying at a temperature below the melting point, a method of drying under reduced pressure at a low temperature, and the like. From the viewpoint of controlling the shrinkage stress in the MD direction of the porous substrate layer (A) and the separator, it is preferable to appropriately adjust the drying temperature, the winding tension, and the like.
The drying temperature is preferably 20 to 100 ° C, more preferably 30 to 80 ° C, and further preferably 40 to 70 ° C, from the viewpoint of binder migration.
From the viewpoint of binder migration, the drying time is preferably 10 seconds to 30 minutes, more preferably 30 seconds to 20 minutes, still more preferably 40 seconds to 10 minutes, and most preferably 1 minute to 3 minutes.

<Separator for electricity storage device>
The separator for an electricity storage device according to the present embodiment (hereinafter also simply referred to as “separator”) has the porous layer (B) as described above on one side or both sides of the porous substrate layer (A) as described above. Formed.
The air permeability of the separator in the present embodiment is preferably 10 to 500 seconds / 100 cc, more preferably 20 to 400 seconds / 100 cc, still more preferably 30 to 300 seconds / 100 cc. The air permeability is preferably 10 seconds / 100 cc or more from the viewpoint of suppressing self-discharge of the electricity storage device, and the air permeability is preferably 500 seconds / 100 cc or less from the viewpoint of obtaining good charge / discharge characteristics.

  Peel strength after pressing aluminum foil (positive electrode current collector, etc.) for 3 minutes at a temperature of 25 ° C. and a pressure of 5 MPa on the outermost surface of the electricity storage device separator on which the porous layer (B) is present (Hereinafter also referred to as “room temperature peel strength”) is preferably 8 gf / cm or less, more preferably 7 gf / cm or less, and still more preferably 6 gf / cm or less. When it is 8 gf / cm or less, the stickiness is further suppressed, and the slit property and winding property of the separator tend to be excellent. When the peel strength is within the above range, the adhesion when the separator of this embodiment is hot-pressed on the electrode is improved. The reason why such an effect can be obtained is not clear, but in the separator of this embodiment having a room temperature peel strength within the above range, a large amount of the first resin binder (b-1-1) is present on the outermost surface side of the separator. And it is thought that it shows that many 2nd resin binders (b-1-2) exist in the porous base material layer (A) side of the separator of this embodiment.

That is, the stickiness is suppressed by the presence of a large amount of the first resin binder (b-1-1) having a high glass transition temperature on the outermost surface side of the separator of the present embodiment. Further, the resin binder (b-1) Since -1) is excellent in adhesion to the electrode, it is considered that a separator having low stickiness and excellent adhesion to the electrode was obtained as a result.
In addition, since a large amount of the second resin binder (b-1-2) having a low Tg is present on the porous substrate layer (A) side of the separator of the present embodiment, the porous substrate layer (A) and the porous layer ( As a result of improving the adhesion with B), separation at the interface between the porous base material layer (A) and the porous layer (B) is suppressed, and as a result, a separator having excellent adhesion to the electrode is obtained. Conceivable.

Peel strength after pressing aluminum foil (positive electrode current collector, etc.) for 3 minutes at a temperature of 80 ° C. and a pressure of 10 MPa on the outermost surface of the separator on the porous layer (B) side (hereinafter referred to as “heat peel strength”) Is preferably 10 gf / cm or more, more preferably 15 gf / cm or more, and still more preferably 20 gf / cm or more. A separator having a heat peel strength in the above range is preferable in that the adhesive strength between the electrode and the separator is excellent when the separator is applied to an electricity storage device described later.
In addition, when the separator and the negative electrode are laminated in the presence of the electrolyte and pressed at 80 ° C. and a pressure of 10 MPa for 2 minutes, when the separator and the negative electrode are peeled off, the active material adheres to the separator in an area of 10% or more. It is preferable.

  In the separator according to this embodiment, the 90 ° peel strength between the porous base material layer (A) and the porous layer (B) is preferably 6 gf / mm or more, more preferably 7 gf / mm or more, and still more preferably 8 gf / mm or more. . The 90 ° peel strength between the porous substrate layer (A) and the porous layer (B) is 6 gf / mm or more, indicating that the adhesion between the porous substrate layer (A) and the porous layer (B) (particularly the porous group) It means that the adhesiveness between the material layer (A) and the second resin binder (b-1-2) is more excellent. As a result, the loss of the porous layer (B) is suppressed, or the adhesion between the separator and the electrode is excellent.

The film thickness of the electricity storage device separator is preferably 2 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more as a value including both the porous substrate layer (A) and the porous layer (B). As an upper limit, Preferably it is 100 micrometers or less, More preferably, it is 50 micrometers or less, More preferably, it is 30 micrometers or less. The film thickness of 2 μm or more is preferable from the viewpoint of securing the strength of the electricity storage device separator. On the other hand, it is preferable to set it as 100 micrometers or less from a viewpoint of obtaining favorable charging / discharging characteristics.
The short-circuit temperature, which is an index of heat resistance, of the electricity storage device separator is preferably 140 ° C. or higher, more preferably 150 ° C. or higher, and further preferably 160 ° C. or higher. When the short-circuit temperature is set to 160 ° C. or higher, it is preferable from the viewpoint of the safety of the electricity storage device when the electricity storage device separator is used.

  The separator for an electricity storage device according to the present embodiment is excellent in handling properties at the time of winding and the rate characteristics of the electricity storage device, and further in the adhesion and permeability between the porous substrate layer (A) and the porous layer (B). Also excellent. Therefore, the use of the power storage device separator is not particularly limited, but can be suitably used for, for example, batteries such as non-aqueous electrolyte secondary batteries, power storage device separators such as capacitors and capacitors, and separation of substances.

<Laminate>
The laminate according to this embodiment is a laminate of the separator and the electrode. The separator of this embodiment can be used as a laminate by bonding to an electrode. Here, “adhesion” means that the heat peel strength between the separator and the electrode is preferably 10 gf / cm or more, more preferably 15 gf / cm or more, and further preferably 20 gf / cm or more. This heat peeling temperature can be measured in the same manner as described above.
The laminated body of this embodiment is excellent in handling property at the time of winding and rate characteristics of the electricity storage device, and further excellent in adhesion and permeability between the porous base material layer (A) and the porous layer (B). Therefore, the use of the laminate is not particularly limited, but can be suitably used for, for example, batteries such as non-aqueous electrolyte secondary batteries, power storage devices such as capacitors and capacitors, and the like.
As an electrode used for the laminated body of this embodiment, the thing as described in the item of the electrical storage device mentioned later can be used.

The method of manufacturing the laminate using the separator of the present embodiment is not particularly limited. For example, the separator and the electrode of the present embodiment may be stacked and heated and / or pressed as necessary. it can. The heating and / or pressing can be performed at the same time as the electrode and the separator are stacked. Moreover, it can also manufacture by heating and / or pressing with respect to the wound body obtained by winding an electrode and a separator on a circular or flat spiral shape.
The laminate of the present embodiment is produced by laminating in the order of positive electrode-separator-negative electrode-separator, or negative electrode-separator-positive electrode-separator, and heating and / or pressing as necessary. More specifically, the separator of this embodiment is prepared as a vertically long separator having a width of 10 to 500 mm (preferably 80 to 500 mm) and a length of 200 to 4,000 m (preferably 1000 to 4000 m). Can be manufactured by stacking in the order of positive electrode-separator-negative electrode-separator, or negative electrode-separator-positive electrode-separator, and heating and / or pressing as necessary.

  As said heating temperature, 40-120 degreeC is preferable. The heating time is preferably 5 seconds to 30 minutes. As a pressure at the time of the said press, 1-30 Mpa is preferable. The pressing time is preferably 5 seconds to 30 minutes. Moreover, the order of heating and pressing may be performed after heating, or may be performed after pressing, or may be performed simultaneously. Among these, it is preferable to perform pressing and heating simultaneously.

<Power storage device>
The separator of the present embodiment can be used not only for separators in batteries, capacitors, capacitors, etc., but also for substance separation. In particular, when used as a separator for a non-aqueous electrolyte battery (especially a lithium ion secondary battery), it is possible to impart adhesion to an electrode and excellent battery performance, which is preferable.
Hereinafter, a suitable aspect in the case where the electricity storage device is a non-aqueous electrolyte secondary battery will be described.
When manufacturing a non-aqueous electrolyte secondary battery using the separator of this embodiment, there is no limitation in the positive electrode, negative electrode, and non-aqueous electrolyte to be used, and a well-known thing can be used.

As the cathode material is not particularly limited, for _example, LiCoO 2, LiNiO _2, spinel-type LiMnO _4, lithium-containing composite oxides such as olivine type LiFePO ₄ and the like.
The negative electrode material is not particularly limited, and examples thereof include carbon materials such as graphite, non-graphitizable carbonaceous, graphitizable carbonaceous, and composite carbon bodies; silicon, tin, metallic lithium, various alloy materials, and the like.
The nonaqueous electrolytic solution is not particularly limited, but an electrolytic solution in which an electrolyte is dissolved in an organic solvent can be used. Examples of the organic solvent include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. But,;
Examples of the solution include lithium salts such as LiClO ₄ , LiBF ₄ , and LiPF ₆ , respectively.

A method for manufacturing an electricity storage device using the separator according to the present embodiment is not particularly limited, but when the electricity storage device is a secondary battery, for example, the separator according to the present embodiment has a width of 10 to 500 mm (preferably 80 to 500 mm). ), A vertically long separator having a length of 200 to 4,000 m (preferably 1,000 to 4,000 m), and the separator is made of a positive electrode-separator-negative electrode-separator or a negative electrode-separator-positive electrode-separator. It can be manufactured by stacking in order, winding in a circular or flat spiral shape to obtain a wound body, storing the wound body in a battery can, and injecting an electrolyte. At this time, the above-described laminate may be formed by heating and / or pressing the wound body. Moreover, it can also manufacture using what wound the above-mentioned laminated body in the shape of a circle or a flat spiral as said wound body. In addition, the electricity storage device is obtained by laminating a positive electrode-separator-negative electrode-separator, or a negative electrode-separator-positive electrode-separator in the order of a flat plate, or laminating the above laminate with a bag-like film, and injecting an electrolytic solution. It can also be manufactured through a process and optionally a process of heating and / or pressing. The step of performing the above heating and / or pressing can be performed before and / or after the step of injecting the electrolytic solution.
In addition, about the measured value of various parameters mentioned above, unless there is particular notice, it is a value measured according to the measuring method in the Example mentioned later.

<Technical significance of the present invention>
The porous layer (B) in the separator of the present embodiment is a first resin binder (b) having an inorganic filler (b-2) and a glass transition temperature (Tg) of 30 ° C. or higher on the porous substrate layer (A). -1-1) and a coating layer containing a second resin binder (b-1-2) having a glass transition temperature (Tg) of less than 30 ° C., thereby forming a porous layer (B). A separator is preferred.
In the step of forming the porous layer (B) (specifically, the step of forming the porous layer (B) by coating, immobilization, and drying), the first resin binder (b-1-1) and the second resin binder (b-1-1) By selecting a combination of resin binders having a large specific gravity difference as the resin binder (b-1-2), a migration difference between the resin binders can be clearly expressed. That is, since the resin binder having a relatively large specific gravity has a small migration or hardly migrates, it is unevenly distributed on the porous substrate layer (A) side in the porous layer (B). Since the resin binder having a relatively small specific gravity has a large migration, it is unevenly distributed on the inner and outer surface sides of the porous layer (B).

By utilizing this phenomenon, a resin binder having a relatively low specific gravity is selected as the first resin binder (b-1-1) having a high Tg, and the second resin binder (b-1-2) having a low Tg is selected. ), A resin binder having a relatively large specific gravity is selected so that the first resin binder (b-1-1) having a high Tg is unevenly distributed on the outer surface side in the porous layer (B), and the Tg is low. The second resin binder (b-1-2) can be unevenly distributed on the porous substrate layer (A) side in the porous layer (B).
With such a mechanism, the surface softening temperature of the porous layer (B) can be controlled within a specific range while maintaining the binding property of the resin binder (b-1).

  Further, in the step of forming the porous layer (B), the second resin binder having a small specific gravity is relatively less susceptible to the influence of gravity, so that it easily migrates and moves to the outer surface side of the porous layer (B). And frequently collide with the inorganic filler (b-2). Thus, the long axis of the inorganic filler (b-2) is oblique to the interface between the porous base material layer (A) and the porous layer (B) when viewed from the cross section of the porous layer (B). The frequency of arrangement in a standing structure or a standing structure increased. As a result, the hole structure formed in the porous layer (B) also has a higher frequency of becoming a structure in which the long axis of the hole stands diagonally or a vertical hole structure. By having the porous layer (B) having such a pore structure, the ion permeability of the separator can be improved, and the electrical characteristics and cycle characteristics can also be improved.

  The pore structure is, for example, the setting of the drying temperature after applying the liquid containing the inorganic filler (b-2) to the porous substrate layer (A) and the shape of the inorganic filler (b-2) to be used, It can be controlled by the average particle diameter of the inorganic filler (b-2), the layer density of the porous layer (B), and the like. For example, the method of gradually increasing the drying temperature tends to increase the ratio of holes where the angle θ is 60 ° ≦ θ ≦ 120 °, compared to the method of rapidly increasing the drying temperature. Further, the method using the block-shaped inorganic filler (b-2) is compared with the method using the plate-shaped inorganic filler (b-2), and the angle θ is 60 ° ≦ θ ≦ 120 °. Tend to increase the percentage of pores. Furthermore, when the particle size of the inorganic filler (b-2) is increased, the layer density in the porous layer (B) decreases, and the proportion of holes where the angle θ is 60 ° ≦ θ ≦ 120 ° increases. Tend to.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to a following example. The measurement methods and evaluation methods for various physical properties used in the following production examples, examples, and comparative examples are as follows. Unless otherwise stated, various measurements and evaluations were performed under conditions of room temperature 23 ° C., 1 atm, and relative humidity 50%.

[Measuring method]
(1) Porosity (%) of porous substrate layer (A)
A sample of 10 cm × 10 cm square is cut from the porous substrate layer (A), its volume (cm ³ ) and mass (g) are obtained, and the film density is 0.95 (g / cm ³ ) and calculated using the following formula: did.
Porosity = (volume−mass / film density) / volume × 100

(2) Air permeability of the separator (sec / 100cc)
Based on JIS P-8117, the air resistance measured by the Gurley type densometer G-B2 (trademark) manufactured by Toyo Seiki Seisakusho was used as the air permeability.

(3) Puncture strength (g) of porous substrate layer (A)
Using a handy compression tester KES-G5 (trademark) manufactured by Kato Tech, the porous substrate layer (A) was fixed with a sample holder having a diameter of 11.3 mm at the opening. Next, the center portion of the fixed porous substrate layer (A) is subjected to a piercing test in a 25 ° C. atmosphere at a radius of curvature of the needle tip of 0.5 mm and a piercing speed of 2 mm / sec. As a result, a puncture strength (g) was obtained.

(4) Mean pore size (μm), curvature, and number of pores It is known that the fluid inside the capillary follows the Knudsen flow when the mean free path of the fluid is larger than the pore size of the capillary, and the Poiseuille flow when it is small. It has been. Therefore, it is assumed that the air flow in the air permeability measurement of the porous base material layer (A) follows the Knudsen flow, and the water flow in the water permeability measurement of the porous base material layer (A) follows the Poiseuille flow.
The average pore diameter d (μm) and the curvature τa (dimensionless) are the air permeation rate constant R _gas (m ³ / (m ² · sec · Pa)) and the water permeation rate constant R _liq (m ³ / ( m ² · sec · Pa)), air molecular velocity ν (m / sec), water viscosity η (Pa · sec), standard pressure Ps (= 101,325 Pa), porosity ε (%), and film thickness From L (μm), it was determined using the following formula.
d = 2ν × (R _liq / R _gas ) × (16η / 3Ps) × 10 ⁶
τa = (d × (ε / 100) × ν / (3L × Ps × P _gas )) ^1/2
Here, R _gas is obtained from the air permeability (sec) using the following equation.
R _gas = 0.0001 / (air permeability × (6.424 × 10 ⁻⁴ ) × (0.01276 × 101,325))

R _liq is obtained from the water permeability (cm ³ / (cm ² · sec · Pa)) using the following equation.
R _liq = water permeability / 100
In addition, water permeability is calculated | required as follows. A porous base material layer (A) previously immersed in ethanol is set in a stainless steel liquid-permeable cell having a diameter of 41 mm, and after the ethanol of the membrane is washed with water, water is supplied at a differential pressure of about 50,000 Pa. The permeation amount per unit time, unit pressure, and unit area was calculated from the permeation amount (cm ³ ) at the time of passing for 120 seconds, and this was taken as the water permeability.
Further, the molecular velocity ν of air is obtained from the gas constant R (= 8.314), the absolute temperature T (K), the circumference ratio π, and the average molecular weight M of air (= 2.896 × 10 ⁻² kg / mol). It is obtained using the following formula.
ν = ((8R × T) / (π × M)) ^1/2
The number of holes B (pieces / μm ² ) can be obtained from the following formula.
B = 4 × (ε / 100) / (π × d ² × τa)

(5) Thickness (μm)
(5) -1 Thickness (μm) of porous substrate layer (A) and separator
A 10 cm x 10 cm sample was cut out from each of the porous base material layer (A) and the separator, nine locations (3 points x 3 points) were selected in a lattice shape, and the film thickness was measured with a microthickness meter (Toyo Seiki Seisakusho Co., Ltd.) ) Measured at room temperature 23 ± 2 ° C. using type KBM). In each case, the average value of the measured values at 9 locations was defined as the porous substrate layer (A) and the film thickness (μm) of the separator.

(5) -2 Thickness (μm) of porous layer (B)
The thickness of the porous layer (B) was measured by observing the cross section of the separator using a scanning electron microscope (SEM) “Model S-4800, manufactured by HITACHI”. A sample separator was cut to about 1.5 mm × 2.0 mm and stained with ruthenium. A stained sample and ethanol were placed in a gelatin capsule, frozen with liquid nitrogen, and then cleaved with a hammer. The sample was subjected to osmium vapor deposition and observed at an acceleration voltage of 1.0 kV and 30000 times to examine the thickness of the porous layer (B).

(6-1) Glass transition temperature (Tg) of resin binder (b-1)
An appropriate amount of the resin binder (b-1) -containing latex (nonvolatile content = 38 to 42%, pH = 9.0) was taken in an aluminum dish and dried in a hot air dryer at 130 ° C. for 30 minutes. About 17 mg of the dried film after drying was packed in an aluminum container for measurement, and a DSC curve and a DDSC (DSC differential) curve in a nitrogen atmosphere were obtained with a DSC measuring apparatus (manufactured by Shimadzu Corporation, DSC 6220). Measurement conditions were as follows.
(First stage temperature rise program)
Start at 70 ° C and heat up at a rate of 15 ° C per minute. Maintained for 5 minutes after reaching 110 ° C.
(Second stage temperature drop program)
The temperature drops from 110 ° C at a rate of 40 ° C per minute. Maintain for 5 minutes after reaching -70 ° C.
(Third-stage temperature rising program)
The temperature was raised from -70 ° C to 400 ° C at a rate of 15 ° C per minute. DSC and DDSC data are acquired at the third stage of temperature rise. The peak top temperature of DDSC was taken as the glass transition temperature.

(6-2) Ratio of first resin binder and second resin binder in porous layer (B) The porous layer (B) was separated from the separator using a knife. About the scraped powder, the DSC curve and the DDSC curve in a nitrogen atmosphere were obtained with the DSC measuring apparatus (Shimadzu Corporation make, DSC6220). Measurement conditions were as follows.
(First stage temperature rise program)
Start at 70 ° C and heat up at a rate of 15 ° C per minute. Maintained for 5 minutes after reaching 110 ° C.
(Second stage temperature drop program)
The temperature drops from 110 ° C at a rate of 40 ° C per minute. Maintain for 5 minutes after reaching -70 ° C.
(Third-stage temperature rising program)
The temperature was raised from -70 ° C to 300 ° C at a rate of 15 ° C per minute. DSC and DDSC data are acquired at the third stage of temperature rise. The peak top temperature on the low temperature side in DDSC was the glass transition temperature of the second resin binder having a low Tg, and the peak top temperature on the high temperature side was the glass transition temperature of the first resin binder having a high Tg. Further, a line was drawn between the start point and the end point of the peak, and the area surrounded by the peak and the line was determined as a peak area by a gravimetric method. The ratio of the two resin binders was determined by taking the peak area on the high temperature side as the amount of the first resin binder having a high Tg and the peak area on the low temperature side as the amount of the second resin binder having a low Tg.

(6-3) Ratio of high Tg resin binder and low Tg resin binder in upper half and lower half of porous layer (B) 0 to 50% thickness range (upper half region) and outer surface from outer surface of porous layer (B) The 50% to 100% thickness range (lower half region) is subjected to the same treatment and measurement as in 6-2 above, and the first resin binder (b-1-1) having a high Tg and Tg in each region are measured. The ratio of the low 2nd resin binder (b-1-2) was calculated | required, respectively.

(6-4) Thickness direction distribution of the inorganic filler (b-2) in the porous layer (B) The position of the inorganic filler (b-2) in the porous layer (B) in the thickness direction is the porous layer ( B) was obtained by a technique (SEM (Scanning Electron Microscope) -EDX (Energy Dispersive X-ray Spectroscopy)) combining the cross-sectional photograph and element mapping.
Specifically, this was performed using a scanning electron microscope (SEM) “model S-4800, manufactured by HITACHI” with an EDX (energy dispersive X-ray spectroscopy) apparatus. In order to see the cross section of the separator, the separator sample was cut to about 1.5 mm × 2.0 mm and stained with ruthenium. A stained sample and ethanol were placed in a gelatin capsule, frozen with liquid nitrogen, and then cleaved with a hammer. The sample was subjected to osmium vapor deposition and observed at an acceleration voltage of 1.0 kV and 30,000 times, and the cross section of the porous layer (B) was observed. At that time, using an EDX (energy dispersive X-ray spectroscopy) apparatus, for the metal constituting the main component of the inorganic filler (b-2), for example, in the case of alumina, boehmite, kaolin, the cross-sectional direction of the Al (aluminum) element From the thickness direction mapping, the position of the inorganic filler (b-2) was calculated. The specific calculation method is to divide the porous layer (B) into 5 thicknesses from the outer surface, that is, 0-20%, 20-40%, 40-60%, 60-80%, 80-100% The fraction was divided into fractions, and the number of element dots per the same area of each fraction was counted.

(7) Specific gravity of resin binder (b-1) About the measurement sample cut out to an appropriate size from the film-like sample obtained in (6) above, using an electronic hydrometer SD-200L manufactured by Alpha Mirage, The specific gravity of the resin binder was measured.

(8-1) Average Particle Size of Resin Binder (b-1) The average particle size of the resin binder was measured using a particle size measuring device (Nikkiso Co., Ltd., Microtrac UPA150). As the measurement conditions, the loading index = 0.15 to 0.3, the measurement time was 300 seconds, and the numerical value of 50% particle diameter was described as the particle diameter in the obtained data.

(8-2) Average particle diameter of inorganic filler (b-2) Inorganic filler (b-2) was added to distilled water, a small amount of sodium hexametaphosphate aqueous solution was added, and then dispersed with an ultrasonic homogenizer for 1 minute. Thereafter, the particle size distribution was measured using a laser type particle size distribution measuring device (Microtrack MT3300EX manufactured by Nikkiso Co., Ltd.), and the particle size (median diameter) at which the cumulative frequency was 50% was defined as the average particle size (μm). .

(9) Surface softening temperature of porous layer (B) of separator The surface of porous layer (B) of separator and black lasha paper are combined, using a calender, under conditions of roll temperature 20 ° C. and linear pressure between calender rolls 10 kgf / cm Then, the two were pulled apart to confirm the presence or absence of transfer to the separator of black lasha paper. In the case of no transfer, the calender roll temperature was increased by 5 ° C. and the same test was performed. Thereafter, the roll temperature was increased in increments of 5 ° C., and the same test was repeated, and the lowest temperature at which the transfer of the black rush paper to the separator was observed was defined as the surface softening temperature of the porous layer (B) of the separator.

(10) Adhesiveness between separator and electrode The adhesiveness between the separator and the electrode was evaluated by the following procedure.
(Preparation of positive electrode)
92.2% by mass of lithium cobalt composite oxide (LiCoO ₂ ) as the positive electrode active material, 2.3% by mass of flake graphite and acetylene black as the conductive material, and polyvinylidene fluoride (PVDF) 3.2 as the binder, respectively. Mass% (solid content conversion) was dispersed in N-methylpyrrolidone (NMP) to prepare a slurry. This slurry was applied to one side of a 20 μm thick aluminum foil serving as a positive electrode current collector with a die coater, dried at 130 ° C. for 3 minutes, and then compression molded with a roll press. At this time, the active material coating amount of the positive electrode was 250 g / m ² , and the bulk density of the active material was 3.00 g / cm ³ .

(Preparation of negative electrode)
Artificial graphite 96.9% by weight as the negative electrode active material, and 1.4% by weight ammonium salt of carboxymethylcellulose and styrene-butadiene copolymer latex (average particle size 80 nm, glass transition temperature −40 ° C.) 1.7% by weight (as a negative electrode active material) The solid content was dispersed in purified water to prepare a slurry. This slurry was coated on one side of a 12 μm thick copper foil serving as a negative electrode current collector with a die coater, dried at 120 ° C. for 3 minutes, and then compression molded with a roll press. At this time, the active material coating amount of the negative electrode was 106 g / m ² , and the active material bulk density was 1.35 g / cm ³ .

(Adhesion test)
The negative electrode obtained by the above method was cut into a width of 20 mm and a length of 40 mm. An electrolyte solution (manufactured by Toyama Yakuhin Kogyo Co., Ltd.) in which ethylene carbonate and diethyl carbonate are mixed at a ratio (volume ratio) of 2: 3 is placed on this electrode to such an extent that the negative electrode is immersed, and a separator is stacked thereon to form a laminate. Produced. This laminate was put in an aluminum zip and pressed at 80 ° C. and 10 MPa for 2 minutes, and then the laminate was taken out and the separator was peeled off from the electrode.
○: When the negative electrode active material adheres to 30% or more of the separator.
Δ: When the negative electrode active material adheres to an area of 10% or more and less than 30% of the separator.
X: When a negative electrode active material adheres to the area of less than 10% of a separator.

(11) Stickiness and peeling strength of coating layer)
A separator and a positive electrode current collector (Aji Fushi Paper Co., Ltd. aluminum foil 20 μm) as a adherend were cut out to 30 mm × 150 mm and stacked, and then the Teflon (registered trademark) sheet (Nichias Co., Ltd. Naflon PTFE) was laminated. Sheet TOMBO-No. 9000). By pressing each laminate under the following conditions, two types of test samples with different pressing conditions were obtained.
Condition 1) Pressurization at a temperature of 25 ° C. and a pressure of 5 MPa for 3 minutes Condition 2) Pressurization at a temperature of 80 ° C. and a pressure of 10 MPa for 3 minutes

The peel strength of each of the obtained test samples was measured at a tensile speed of 200 mm / min according to JIS K6854-2 using an autograph AG-IS type (trademark) manufactured by Shimadzu Corporation. Based on the obtained results, the peel strength of the separator was evaluated according to the following evaluation criteria.
[Sticky]
Regarding peel strength after pressing under condition 1)
◎ (very good): When the peel strength is 4 gf / cm or less ○ (Good): When the peel strength is more than 4 gf / cm and 6 gf / cm or less △ (possible): The peel strength is 6 gf / cm When it was more than 8 gf / cm: x (defect): The peel strength was more than 8 gf / cm, and it was used as an index of stickiness and handling properties.
[Coating layer peel strength]
Regarding peel strength after pressing in condition 2)
○ (Good): Peel strength is 10 gf / cm or more x (Poor): Peel strength is less than 10 gf / cm, adhesion to electrode, adhesion strength to porous substrate layer (A), and inorganic filler This was used as an index of the binding strength of (b-2).

(12) Winding property and battery cycle characteristics (12-1) Preparation of sample for evaluation <Electrode>
A positive electrode and a negative electrode were produced in the same manner as in “(10) Adhesiveness between separator and electrode”. The positive electrode was cut to a width of about 57 mm, the negative electrode was cut to a width of about 58 mm, and each was made into a strip shape to produce an evaluation electrode.

(12-2) Adjustment of Nonaqueous Electrolytic Solution The nonaqueous electrolytic solution is a mixed solvent of ethylene carbonate / diethyl carbonate = 2/3 (volume ratio) so that LiPF ₆ as a solute has a concentration of 1.0 mol / L. Prepared by dissolving.

(12-3) Production of Separator A separator for evaluation was produced by slitting the separator obtained in Examples and Comparative Examples into 60 mm strips.

(12-4) Evaluation of winding property Using each member obtained in the above (12-1), the negative electrode, the separator, the positive electrode, and the separator are stacked in this order, and spirally formed with a winding tension of 250 gf. The electrode laminated body was produced by winding several times. About ten electrode laminated bodies produced, the presence or absence of the twist of a separator or wrinkles was observed visually, and the following evaluation criteria evaluated.
-Evaluation criteria-
○ (Good): Appearance defects such as twists and wrinkles did not occur at all.
Δ (possible): A product having one appearance defect such as twist or wrinkle.
X (defect): Two or more appearance defects such as twists and wrinkles occurred.

(12-5) Evaluation of battery cycle characteristics (12-5-1) Battery assembly The negative electrode, separator, positive electrode, and separator obtained in (12-1) above were stacked in this order, and the winding tension was 250 gf. The electrode laminate was manufactured by winding the coil at a winding speed of 45 mm / sec. The electrode laminate is housed in a stainless steel container having an outer diameter of 18 mm and a height of 65 mm, and an aluminum tab derived from the positive electrode current collector is used as a container lid terminal portion, and a nickel tab derived from the negative electrode current collector Were welded to the container wall. Thereafter, drying was performed at 80 ° C. for 12 hours under vacuum. In the argon box, the battery was assembled by injecting the nonaqueous electrolyte solution into the assembled battery container and sealing it.

(12-5-2) Pretreatment The assembled battery was charged with a constant current up to a voltage of 4.2V at a current value of 1 / 3C, then charged with a constant voltage of 4.2V for 8 hours, and then a current of 1 / 3C. The battery was discharged to a final voltage of 3.0V. Next, after constant current charging to a voltage of 4.2 V with a current value of 1 C, 4.2 V constant voltage charging was performed for 3 hours, and then discharging was performed to a final voltage of 3.0 V with a current of 1 C. Finally, after constant current charging to 4.2 V with a current value of 1 C, 4.2 V constant voltage charging was performed for 3 hours as a pretreatment. 1C represents a current value for discharging the reference capacity of the battery in one hour.

(12-5-3) Cycle test The battery subjected to the above pretreatment was discharged at a discharge current of 1 A to a discharge end voltage of 3 V under a temperature of 25 ° C., and then charged at a charge current of 1 A and a charge end voltage of 4. The battery was charged to 2V. Charging / discharging was repeated with this as one cycle, and the cycle characteristics were evaluated according to the following criteria using the capacity retention after 200 cycles with respect to the initial capacity.
(Evaluation criteria)
◎ (Very good): Capacity retention ratio 95% or more and 100% or less ○ (Good): Capacity retention ratio 90% or more and less than 95% × (Poor): Capacity retention ratio less than 90%

(13) Hole structure (ratio of holes where the angle θ is 60 ° ≦ θ ≦ 120 °)
In order to define the angle θ of the pore structure of the porous layer (B), the separator was first subjected to cross-section processing using BIB (broad ion beam). During processing, the separator was cooled to just before as needed to suppress thermal damage. Specifically, the separator was left for a whole day and night in a -40 ° C cooling device. Thereby, a smooth separator cross section was obtained.
Next, the separator cross section obtained was subjected to conduction treatment with C paste and Os coating, and then using “HITACHI S-4700” (manufactured by Hitachi High-Tech Fielding), an imaging magnification of 10,000 times and an acceleration voltage of 1. Photographing was performed at a setting of 0 kV, detector: secondary electron (upper UPPER). An electronic image of the obtained cross-sectional SEM image was obtained, and the hole angle θ was calculated.
The angle θ was calculated by the following method using image processing software “ImageJ” (version 1.46).
An electronic image of the target cross-section SEM was opened, and a known distance in the image was measured using a line selection tool “Stright”. “SET SCALE” was opened from “Analyze”, a measurement unit and a known distance were input, and a scale was set. Next, as a pretreatment for the binarization process, “Paintbrush Tool” was used to fill the holes in the porous layer (B) with black as voids.

Here, when the identification of the hole was not clear, first, a dark part in which no filler could be confirmed was recognized, and a region where the contour was closed around this dark part was recognized as a hole (gap). On the other hand, since the filler part located slightly behind the BIB processed cross section cannot be evaluated as contributing to the ion conductivity, it was not recognized as a hole part. In addition, at the right end and the left end of the SEM image, even if the contour identified around the dark portion was interrupted at the image end, it was recognized as a hole.
As described above, after filling the hole (void), binarization processing was performed. Specifically, in order to select an evaluation area, a desired region was selected using “Rectangular selections”. When selecting, the surface layer part of B layer was excluded. Subsequently, in order to create a selection area in another file, a new electronic image of only the B layer was created using “Duplicate” in the “Image” tab. Next, a process for specifying a hole was performed from the obtained electronic image. More specifically, “Adjust” is selected from “Image”, and “Threshold” is further selected, and processing is performed by setting the range to be painted with a single color out of 256 gradations as “0-100”. After that, select “Analyze particles”, enter “0.01 μm ² or more” in the “Size” item, and select “Elipse” in the Show item to make each hole elliptical An obtained image was obtained. Finally, the angle θ formed by the major axis of the ovalized hole and the axis parallel to the interface between the porous base material layer (A) and the porous layer (B) is mechanically determined. The angle θ data of holes having a diameter of 01 μm ² or more was made into a histogram, and the ratio of θ satisfying 60 ° ≦ θ ≦ 120 ° was calculated.

<Production of resin binder (b-1)>
(Production Example 1a) Production of acrylic polymer latex In a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, 70.4 parts by mass of ion-exchanged water and “AQUALON KH1025” (registered trademark, first 0.085 parts by mass (in terms of solid content) manufactured by Kogyo Seiyaku Co., Ltd.) and 0.085 parts by mass (in terms of solid content) “Adekaria Soap SR1025” (registered trademark, 25% by mass aqueous solution manufactured by ADEKA Corporation) ), And the temperature inside the reaction vessel was raised to 80 ° C., and while maintaining the temperature at 80 ° C., 0.15 parts by mass (in terms of solid content) of ammonium persulfate (2% by mass aqueous solution) was added.
5 minutes after adding the ammonium persulfate aqueous solution, 85 parts by weight of methyl methacrylate, 5.4 parts by weight of n-butyl acrylate, 2 parts by weight of 2-ethylhexyl acrylate, 0.1 part by weight of methacrylic acid, 0.1 parts of acrylic acid Part by mass, 2 parts by mass of 2-hydroxyethyl methacrylate, 5 parts by mass of acrylamide, 0.4 parts by mass of glycidyl methacrylate, 0.7 parts by mass of trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.) , “AQUALON KH1025” (registered trademark, 25% by mass aqueous solution manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.75 part by mass (in terms of solid content), “ADEKA rear soap SR1025” (registered trademark, 25% by mass aqueous solution manufactured by ADEKA Corporation) 0.75 parts by mass (in terms of solid content), 0.05 parts by mass of sodium p-styrenesulfonate, persulfuric acid A mixture of 0.15 parts by weight of ammonia (2% by weight aqueous solution) (in terms of solid content), 0.3 parts by weight of γ-methacryloxypropyltrimethoxysilane, and 52 parts by weight of ion-exchanged water was mixed for 5 minutes using a homomixer. Thus, an emulsion was prepared. The obtained emulsion was dropped from the dropping tank into the reaction vessel over 150 minutes.

After completion of the dropwise addition of the emulsion, the reaction container was maintained at an internal temperature of 80 ° C. for 90 minutes and then cooled to room temperature to obtain an emulsion. About the obtained emulsion, latex containing acrylic polymer (1a) having a solid content concentration of 40% by mass was obtained by adjusting the pH to 9.0 using an aqueous ammonium hydroxide solution (25% by mass aqueous solution). . The obtained acrylic polymer (1a) had an average particle size of 161 nm, a specific gravity of 1.19 g / cm ³ , and a glass transition temperature of 90 ° C.

(Production Example 1b) Production of acrylic polymer latex In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank, and a thermometer, 70.4 parts by mass of ion-exchanged water, “AQUALON KH1025” (registered trademark, No. 1) 0.15 parts by mass (in terms of solid content) of Ichi Kogyo Seiyaku Co., Ltd.) and 0.15 parts by mass (solid content) of “ADEKA rear soap SR1025” (registered trademark, 25% by mass aqueous solution manufactured by ADEKA Corporation) Conversion), the temperature inside the reaction vessel was raised to 80 ° C., and while maintaining the temperature at 80 ° C., 0.15 parts by mass (in terms of solid content) of ammonium persulfate (2% by mass aqueous solution) was added. .
5 minutes after addition of the aqueous ammonium persulfate solution, 38.5 parts by weight of methyl methacrylate, 19.6 parts by weight of n-butyl acrylate, 31.9 parts by weight of 2-ethylhexyl acrylate, 0.1 part by weight of methacrylic acid, acrylic 0.1 parts by weight of acid, 2 parts by weight of 2-hydroxyethyl methacrylate, 5 parts by weight of acrylamide, 2.8 parts by weight of glycidyl methacrylate, trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0 0.7 parts by mass, 3 parts by mass of “AQUALON KH1025” (registered trademark, 25% by mass aqueous solution manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 3 parts by mass of “ADEKA rear soap SR1025” (registered trademark, 25% by mass aqueous solution manufactured by ADEKA) Parts, 0.05 parts by weight of sodium p-styrenesulfonate, ammonium persulfate (2% by weight aqueous solution) A mixture of 0.15 parts by mass (in terms of solid content), 0.3 parts by mass of γ-methacryloxypropyltrimethoxysilane, and 52 parts by mass of ion-exchanged water was mixed for 5 minutes with a homomixer to prepare an emulsion. . The obtained emulsion was dropped from the dropping tank into the reaction vessel over 150 minutes.

After the dropping of the emulsified liquid was completed, the reaction container was maintained at an internal temperature of 80 ° C. for 90 minutes, and then cooled to room temperature. The resulting emulsion was adjusted to pH = 9.0 using an aqueous ammonium hydroxide solution (25% by mass aqueous solution) to obtain a latex containing an acrylic polymer (1b) having a concentration of 40% by mass. The obtained acrylic polymer (1b) had an average particle diameter of 121 nm, a specific gravity of 1.19 g / cm ³ , and a glass transition temperature of −20 ° C.

(Production Example 1d) Production of Styrene-Butadiene Polymer Latex The inside of a temperature-controllable reactor equipped with a stirrer was previously purged with nitrogen, and then 850 parts by mass of ion-exchanged water and 20 parts by mass of sodium dodecylbenzenesulfonate (solid Minute conversion), sodium hydroxide 0.1 mass part, sodium hydrogen sulfite 0.5 mass part, ferric sulfate 0.0005 mass part, styrene 15 mass parts, methyl methacrylate 30 mass parts, 2-ethylhexyl acrylate 51 After adding a total amount of a monomer mixture consisting of 2 parts by mass, 2 parts by mass of 2-hydroxyethyl acrylate, and 2 parts by mass of itaconic acid and adjusting the internal temperature of the polymerization system to 90 ° C., 1 part by mass of ammonium persulfate (solid content Conversion) and a uniform initiator aqueous solution consisting of 50 parts by mass of ion-exchanged water were added all at once. Thereafter, the temperature in the polymerization system was maintained at 90 ° C. for 2 hours, and then the temperature in the polymerization system was lowered to obtain seed latex A. The solid content concentration of the obtained seed latex A was 10% by mass, the average volume particle diameter of the polymer was 16 nm, the glass transition temperature was 2 ° C., and the mass average molecular weight (Mw) was 70,000.

Next, seed latex A (solid content concentration 10% by mass) 0.05 parts by mass (solid content conversion), sodium dodecylbenzenesulfonate 0.3 mass part (solid content conversion), ion-exchanged water 200 mass parts, After putting into a pressure-resistant reaction vessel equipped with a stirrer and a temperature control jacket, the liquid temperature was adjusted to 60 ° C., and 1.0 part by mass of ammonium persulfate (in terms of solid content) was added. Next, 70 parts by weight of styrene, 15 parts by weight of butadiene, 7 parts by weight of methyl methacrylate, 3 parts by weight of acrylonitrile, 1 part by weight of acrylic acid, 2 parts by weight of glycidyl methacrylate, 2 parts by weight of itaconic acid, and chain A mixed liquid consisting of 0.2 parts by mass of α-methylstyrene dimer and 0.5 parts by mass of t-dodecyl mercaptan as a transfer agent was added over 6 hours while maintaining the liquid temperature at 70 ° C. The final polymerization rate was 98% by mass.
The produced latex was filtered through a 200-mesh wire mesh, an aqueous ammonium hydroxide solution (25% by mass) was added to adjust the pH to 8, and then unreacted monomers were removed. After further concentration, 0.5 parts by weight of ammonium polyacrylate (in terms of solid content) and an aqueous ammonium hydroxide solution were added to finally obtain a styrene-butadiene-based polymer (1d) latex having a solid content concentration of 50% by mass and pH 8. . The average particle diameter of the obtained latex polymer was 200 nm, the specific gravity was 1.07 g / cm ³ , and the glass transition temperature was 70 ° C.

(Production Example 1e) Production of Hollow Acrylic Polymer Latex After replacing the inside of a temperature-adjustable reactor equipped with a stirrer with nitrogen in advance, 0.05 part by mass of seed latex A prepared in the preceding stage of Production Example 1d (in terms of solid content) ), While maintaining the liquid temperature in the reaction system at 75 ° C., 25.5 parts by weight of methyl methacrylate, 70 parts by weight of butyl acrylate, 0.5 parts by weight of methacrylic acid, 0.5 parts by weight of acrylic acid, An emulsion comprising 1 part by weight of ethylene glycol dimethacrylate, 2.5 parts by weight of glycidyl methacrylate, 0.5 parts by weight of sodium dodecylbenzenesulfonate, and 200 parts by weight of ion-exchanged water, an aqueous solution of ammonium persulfate (solid content concentration) 5 mass%) 1 part by mass (in terms of solid content) was added over 4 hours, and the reaction was continued for 2 hours while maintaining the polymerization system internal temperature of 75 ° C. As a result, latex B having an average particle size of 200 nm was obtained.
After setting the internal temperature of the polymerization system to 75 ° C., 50 parts by mass of methyl methacrylate, 0.2 part by mass of sodium dodecylbenzenesulfonate (in terms of solid content), and 9.6 parts by mass of the latex B (in terms of solid content), and A polymerization system internal temperature 75 is obtained by mixing an emulsion composed of ion-exchanged water and an emulsion 2 composed of 48 parts by mass of styrene, 2 parts by mass of divinylbenzene, 2 parts by mass of sodium dodecylbenzenesulfonate (in terms of solid content), and ion exchange. While maintaining the temperature, gradient addition was carried out over 5 hours each (emulsion 1: 0% to 100% by weight, emulsion 2: 100% to 0% by weight). While maintaining at 75 ° C. for 2 hours, the reaction was continued to obtain Latex C having an average particle diameter of 450 nm and a solid content concentration of 25.6% by mass.

After the temperature in the polymerization system containing latex C was set to 90 ° C., an aqueous solution of ammonium hydroxide (25% by mass aqueous solution) was added so that the pH was 10.8, and the mixture was allowed to swell with alkali for 2 hours, whereby a hollow acrylic polymer (1e ) Containing latex was obtained. The latex obtained had a spherical monodisperse particle size of 500 nm, a hollow diameter of 300 nm, a polymer specific gravity of 0.93 g / cm ³ , and a glass transition temperature of 60 ° C. In addition, the hollow hole diameter of a polymer particle is an average value of the measurement results of 100 particles randomly extracted by observation with an electron microscope.

Example 1
47.5 parts by mass of homopolymer polyethylene having a volume average molecular weight of 700,000, 47.5 parts by mass of homopolymer polyethylene having a volume average molecular weight of 250,000, and 5 parts by mass of polypyrene pyrene having a volume average molecular weight of 400,000 Dry blended using a tumbler-blender. 1 mass of pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) quinone pione] as an antioxidant with respect to 99 parts by mass of the obtained polymer mixture Part of the mixture was added and dry blended again using a tumbler blender to obtain a uniform polymer mixture. The obtained polymer equal mixture was substituted with nitrogen and then fed to the twin-screw extruder with a feeder under a nitrogen atmosphere. Further, liquid paraffin (kinematic viscosity at 37.78 ° C .: 7.59 × 10 ⁻⁵ m ² / s) was injected into the extruder cylinder by a plunger pump. The feeder and the pump were adjusted so that the liquid paraffin content ratio in the total mixture melt-kneaded and extruded was 67 mass% (resin composition concentration was 33 mass%). The melt-kneading conditions were a preset temperature of 200 ° C., a screw rotation of 100 rpm, and a discharge rate of 12 kg / h. Subsequently, the melt-kneaded material was extruded and cast on a cooling roll controlled at a surface temperature of 25 ° C. through a T-die to obtain a gel sheet having a thickness of 1,600 μm. Next, it led to the simultaneous biaxial tenter-stretching machine, and biaxial stretching was performed. The set stretching conditions were an MD magnification of 7/0, a TD magnification of 6.1, and a preset temperature of 121 ° C. Next, the stretched gel sheet was introduced into a methyl ethyl ketone bath and sufficiently immersed in methyl ethyl ketone to extract and remove liquid paraffin, and then methyl ethyl ketone was removed by drying. Subsequently, the gel sheet after removal of the liquid paraffin was guided to a TD tenter and heat fixed. The heat setting temperature was 120 ° C., the TD maximum magnification was 2.0 times, and the relaxation rate was 0.90. As a result, the film thickness was 17 μm, the porosity was 60%, the air permeability was 84 seconds / 100 cc, the average pore diameter calculated by the gas-liquid method was d = 0.057 μm, the curvature τa = 1.45, the number of holes B = 165 / A polyolefin resin porous membrane (A1) having a thickness of μm ² and a pin puncture strength of 5,679 f in terms of 25 μm was obtained.

Next, calcined kaolin (2a) (wet kaolinite (Al ₂ Si ₂ O ₅ (OH) ₄ as a main component) is calcined at a high temperature as the inorganic filler (b-2). 8 μm) is 93.0 parts by mass, the resin binder (b-1) is acrylic polymer (1a) latex (solid content concentration 40% by mass) 2.0 parts by mass (solid content conversion), acrylic polymer (1b) latex (Solid content concentration 40% by mass, average particle size 220 nm, glass transition temperature −15 ° C., minimum film formation temperature 0 ° C. or less) 5.0 parts by mass (in terms of solid content), and ammonium polycarboxylate aqueous solution (Sannopco, SN Dispersan® 5468, solid content concentration 40% by mass) 0.5 parts by mass (in terms of solid content) is uniformly dispersed in 180 parts by mass of water to prepare a coating solution. The separator was coated on the surface of the membrane using a gravure coater, dried at 60 ° C. to remove water, and a porous layer (B) having a thickness of 2 μm formed on one side of the polyolefin resin porous membrane (A1). Obtained.
The evaluation results of this separator are shown in Table 1.

Example 2
A separator was obtained in the same manner as in Example 1 except that the type of the resin binder (b-1) was changed as shown in Table 1 in Example 1.
The evaluation results of this separator are shown in Table 1.

Comparative Example 1
A separator was obtained in the same manner as in Example 1 except that the drying temperature of the coating layer was increased to 80 ° C. in Example 1.
The evaluation results of this separator are shown in Table 1.
This Comparative Example 1 was inferior in electrode adhesion and coating layer peel strength. Both resin binders {first resin binder (b-1-1) and second resin binder (b-1-2)} are not unevenly distributed independently because the drying temperature of the coating layer is increased. It is considered that both resin binders are unevenly distributed on the porous substrate layer (A) side.

Comparative Example 2
A separator was obtained in the same manner as in Example 1 except that the drying temperature of the coating layer was lowered to 45 ° C. in Example 1.
The evaluation results of this separator are shown in Table 1.
Comparative Example 2 was inferior in all of the adhesion to the electrode, the adhesion to the porous substrate layer (A), the stickiness of the outermost surface of the separator, and the handling property. Since the drying temperature of the coating layer was lowered, both resin binders were not unevenly distributed independently, and both resin binders were almost uniformly present in the porous layer (B). It is thought that the surface softening temperature was lowered.

Comparative Example 3
A separator was obtained in the same manner as in Example 1 except that the type of the resin binder (b-1) was changed as shown in Table 1 in Example 1.
The evaluation results of this separator are shown in Table 1.
In Comparative Example 3, none of electrode adhesion, coating layer peel strength, and stickiness was satisfactory. In this comparative example, there is no specific gravity difference [(b-1-2)-(b-1-1)] between the two types of resin binders, and it is considered that both resin binders behaved similarly during migration.

  The separator of the present invention is excellent in both electrode adhesion and roll peelability, has a long battery capacity life, and is excellent in productivity. Accordingly, the separator can be suitably used as a separator for an electricity storage device such as a battery such as a non-aqueous electrolyte secondary battery, a capacitor, or a capacitor.

Claims (9)

A porous substrate layer (A);
An electrical storage device separator having a porous layer (B) containing an inorganic filler (b-2) and a resin binder (b-1),
The resin binder (b-1) contains two or more kinds of resin binders,
The surface of the porous layer (B) has a surface softening temperature in the range of 30 to 60 ° C., and in the holes having an area of 0.01 μm ² or more in the cross section of the porous layer (B), the long axis of each hole and the porous substrate The electrical storage characterized in that the proportion of pores having an angle θ of 60 degrees or more and 120 degrees or less formed by an axis parallel to the interface between the layer (A) and the porous layer (B) is 30% or more Device separator. The resin binder (b-1) is
A first resin binder (b-1-1) having a glass transition temperature of 30 ° C. or higher;
The separator for electrical storage devices of Claim 1 containing the 2nd resin binder (b-1-2) with a glass transition temperature of less than 30 degreeC.   The separator for an electricity storage device according to claim 1, wherein the specific gravity of the second resin binder (b-1-2) is larger than the specific gravity of the first resin binder (b-1-1).   The electrical storage device separator according to any one of claims 1 to 3, wherein the air permeability is in a range of 10 to 500 seconds / 100cc.   The electrical storage device separator according to any one of claims 1 to 4, wherein the first resin binder (b-1-1) is a hollow particle.   Of the resin binder (b-1) present in the thickness range (upper half region) of 0 to 50% from the outer surface of the porous layer (B), the first resin binder (b-1-1) is 60. The separator for an electricity storage device according to any one of claims 1 to 5, wherein the separator is at least% by mass.   Of the resin binder (b-1) present in the thickness range (lower half region) of 50% to 100% from the outer surface of the porous layer (B), the second resin binder (b-1-2) is 60 The separator for an electricity storage device according to any one of claims 1 to 6, wherein the separator is at least mass% and at most 90 mass%.   The laminated body characterized by laminating | stacking the separator for electrical storage devices as described in any one of Claims 1-7, and an electrode.   An electrochemical element comprising the laminate according to claim 8.