JP5532430B2 - Composite porous membrane, method for producing composite porous membrane, and battery separator using the same - Google Patents

Description

  The present invention relates to a composite porous membrane in which a porous membrane containing a fluorine-based resin is laminated on a porous membrane containing a polypropylene resin as the outermost layer, and in particular, a porous membrane excellent in ion permeability and containing a polypropylene resin. The present invention relates to a composite porous membrane useful as a separator for a lithium ion battery, which is excellent in adhesiveness between the resin and the fluorine-based resin membrane.

  A porous membrane made of a thermoplastic resin is widely used as a material for separating, selectively permeating and isolating substances. For example, various filters such as battery separators for lithium secondary batteries, nickel-hydrogen batteries, nickel-cadmium batteries, polymer batteries, separators for electric double layer capacitors, reverse osmosis filtration membranes, ultrafiltration membranes, microfiltration membranes, etc. It is used in breathable and waterproof clothing, medical materials, and the like. In particular, polyethylene porous membranes and polypropylene porous membranes are suitably used or developed as separators for lithium ion secondary batteries, because of their excellent electrical insulation and electrolyte impregnation. Not only has the characteristics of having excellent ion resistance and electrolyte resistance and oxidation resistance, but also has a hole plugging that cuts off the current and suppresses excessive temperature rise at a temperature of about 120 to 150 ° C. during abnormal battery temperature rise. This is because it also has an effect. However, if the temperature continues to rise even after the pores are closed for some reason, a film breakage may occur at a certain temperature due to a decrease in viscosity of the melted polyethylene or polypropylene constituting the film and a contraction of the film. Further, when left at a constant high temperature, there is a possibility that a film breakage may occur after a certain period of time due to a decrease in viscosity of the melted polyethylene or polypropylene and a contraction of the film. This phenomenon is not limited to polyethylene or polypropylene, and even when other thermoplastic resins are used, the phenomenon cannot be avoided beyond the melting point of the resin constituting the porous film.

  In particular, lithium-ion battery separators are deeply involved in battery characteristics, battery productivity, and battery safety. Excellent mechanical characteristics, heat resistance, permeability, dimensional stability, pore clogging characteristics (shutdown characteristics), melting damage Film prevention characteristics (meltdown prevention characteristics) are required. As for batteries for electric vehicles and hybrid vehicles, while lithium ion batteries that can be expected to have higher capacities are being developed in the future, severe mechanical strength, compression resistance, and heat resistance are required. Various heat resistance improvement studies have been made, such as laminating a heat-resistant resin on a polyolefin porous membrane. As the heat resistant resin, a fluorine-based resin having both heat resistance and oxidation resistance is suitably used. However, in general, when a heat resistant resin is laminated on a polyolefin porous membrane, the heat resistant resin layer may be peeled off during the processing of the composite porous membrane, in the slitting process, or in the battery assembly process. It becomes difficult to secure.

  In order to reduce costs, the battery assembly process is expected to increase the speed, and the present inventors have not only ensured the safety of the battery but also the heat-resistant resin layer not only in such high-speed processing. It is expected that there are few troubles such as peeling, and for that purpose, it is assumed that higher adhesion is required.

Patent Document 1 exemplifies a separator obtained by directly applying an aromatic polyamide (poly (phenylene terephthalamide)) containing Al (OH) ₃ to a polypropylene (PP) microporous film subjected to corona discharge treatment. Yes. Patent Document 2 exemplifies a separator for a lithium ion secondary battery obtained by directly applying a polyamideimide resin to a polyolefin porous film so that the film thickness becomes 1 μm, immersing it in water at 25 ° C., and drying it. doing.

  As in the case of Patent Document 1 and Patent Document 2, the roll coating method, die coating method, bar coating method, blade coating method, etc. that are generally used when the coating solution is directly applied to the polyolefin porous membrane, Infiltration of the resin component into the polyolefin-based porous membrane is unavoidable, and a significant increase in the air permeability resistance and a decrease in the pore blocking function are unavoidable, and the resin component easily fills the porous interior. This leads to an extreme increase in resistance. In addition, such a method also has a problem that the film thickness unevenness of the polyolefin-based porous film is likely to be related to the film thickness unevenness of the heat resistant resin layer, and the air resistance is likely to vary.

  Patent Document 3 exemplifies an electrolyte-supported polymer film obtained by immersing a nonwoven fabric made of aramid fibers in a dope containing a vinylidene fluoride copolymer that is a heat-resistant resin and drying it.

  Patent Document 4 exemplifies a composite porous film obtained by immersing a polypropylene porous film in a dope mainly composed of polyvinylidene fluoride, which is a heat-resistant resin, and through a solidification, water washing, and drying process.

  When a non-woven fabric made of aramid fibers is immersed in a heat-resistant resin solution as in Patent Document 3, a heat-resistant porous layer is formed on the inside and both surfaces of the non-woven fabric, so that the communication holes inside the non-woven fabric are mostly covered. In other words, a significant increase in the air permeability resistance cannot be avoided, and a hole closing function that determines the safety of the separator cannot be obtained.

  In Patent Document 4, heat resistant porous layers are still formed inside and on both sides of the polypropylene porous membrane, and a significant increase in air resistance cannot be avoided as in Patent Document 3, and It is difficult to obtain an occlusion function.

  In Patent Document 5, when applying a para-aramid resin solution, which is a heat-resistant resin, directly to a polyethylene porous film, a polar organic used in advance in the heat-resistant resin solution in order to avoid a significant increase in air resistance. After impregnating a porous film made of polyethylene with a solvent, and applying a heat-resistant resin solution, it is formed into a cloudy film in a constant temperature and humidity chamber set at a temperature of 30 ° C. and a relative humidity of 65%, and then washed and dried. A separator having a heat-resistant porous layer made of the obtained para-aramid is disclosed.

  In Patent Document 5, there is no significant increase in the air resistance, but the adhesion between the polyethylene porous film and the heat-resistant resin is extremely small, making it difficult to ensure safety.

  In Patent Document 6, a polyamide-imide resin solution is applied to a polyethylene film and passed through an atmosphere of 25 ° C. and 80% RH over 30 seconds to obtain a semi-gel porous film, and then a polyethylene having a thickness of 20 μm or 10 μm. A composite porous membrane obtained by laminating a porous film on the semi-gel porous membrane, immersing it in an aqueous solution containing N-methyl-2-pyrrolidone (NMP), washing with water and drying is disclosed. .

  In Patent Document 6, there is no significant increase in air permeability resistance, but the adhesion between the polyethylene porous film and the heat-resistant resin is insufficient, and the polyethylene porous film is a polypropylene resin porous film. It was softer and inferior in mechanical strength and compression resistance.

  Thus, in a composite porous membrane in which a heat-resistant resin layer is laminated on a polyolefin-based porous membrane as a base material, the heat-resistant resin is infiltrated into the porous membrane as a base material and the heat-resistant resin layer is closely attached If the improvement is made, the increase in the air resistance increases, and if the permeation of the heat resistant resin is reduced, the increase in the air resistance can be suppressed, but the adhesion of the heat resistant resin layer is small. Therefore, in view of speeding up in the battery assembly process, it becomes difficult to ensure safety, which is becoming increasingly demanding. In particular, when a polypropylene resin porous membrane obtained by the stretch-opening method is used as a porous membrane substrate, generally it is very difficult to obtain close contact with the heat resistant resin layer, and the adhesion of the heat resistant resin layer and the air resistance increase. There were no composite porous membranes with compatible widths.

JP 2010-21033 A JP 2005-281668 A JP 2001-266842 A JP 2003-171495 A Japanese Patent Laid-Open No. 2001-23602 JP 2007-125821 A

  The present invention provides a composite porous membrane in which a porous membrane including a heat-resistant resin layer is laminated on a porous membrane having a polypropylene resin layer as the outermost layer, and has excellent adhesion to a heat-resistant resin layer and a small increase in air resistance. The present invention aims to provide a composite porous membrane that is suitable for battery separators.

The present invention has the following configurations (1) to (8).
(1) A composite porous membrane in which a porous membrane B containing a fluororesin is laminated on the surface of the outermost polypropylene resin of the porous membrane A comprising three layers and at least one of the outermost layers made of polypropylene resin In the case where the porous membrane A satisfies the following formulas (A) and (B), the composite porous membrane satisfies the following formulas (C) and (D), and the porous membrane A is polypropylene / A composite porous membrane, wherein three layers of polyethylene / polypropylene are laminated.
0.01 μm ≦ average pore diameter of porous membrane A ≦ 1.0 μm Formula (A)
30% ≦ Porosity of porous membrane A ≦ 70% Formula (B)
Peel strength at the interface between porous membrane A and porous membrane B ≧ 1.0 N / 25 mm Formula (C)
20 ≦ Y−X ≦ 100 Formula (D)
(X is the air permeability resistance of the porous membrane A (second / 100 cc Air), Y is the air resistance of the entire composite porous membrane (second / 100 cc Air))
(2) The composite porous membrane according to (1), wherein the fluororesin is a fluororesin having a logarithmic viscosity of 0.5 dl / g or more.
(3) The method for producing a composite porous membrane according to (1) or (2), comprising the following steps (i) to (iii):
Step (i): After applying the fluororesin solution on the base film, it is passed through a low-humidity zone having an absolute humidity of less than 6 g / m ³ , and then high in an absolute humidity of 6 g / m ³ or more and 25 g / m ³ or less. Forming a fluororesin film on the base film by passing through the humidity zone;
Step (ii): Step of preparing a porous membrane A comprising three layers and at least one of the outermost layers comprising a polypropylene resin, and Step (iii): Polypropylene resin of the outermost layer of the porous membrane A in Step (ii) After the fluororesin film formed in step (i) is bonded to the surface of the film, it is immersed in a coagulation bath to convert the fluororesin film into a porous film B, washed and dried, and composite porous A step of obtaining a film.
(4) The method for producing a composite porous membrane according to (3), wherein the base film is peeled after obtaining the composite porous membrane in step (iii).
(5) The method for producing a composite porous membrane according to (3) or (4), wherein the base film is a polyester film or a polyolefin film having a thickness of 25 to 100 μm.
(6) The amount of the linear oligomer on the surface of the base film is 20 μg / m ² or more and 100 μg / m ² or less, wherein the composite porous membrane according to any one of (3) to (5) Production method.
(7) In the step (i), the passage time in the low humidity zone is 3 seconds or more and 20 seconds or less, and the passage time in the high humidity zone is 3 seconds or more and 10 seconds or less (3) to (6) The method for producing a composite porous membrane according to any one of the above.
(8) A battery separator comprising the composite porous membrane according to (1) or (2).

  The composite porous membrane of the present invention is based on a porous membrane having a polypropylene resin layer having an excellent shutdown function and mechanical strength and compression resistance as an outermost layer, and further comprising a fluorine resin layer. Since it has a laminated structure and has both excellent adhesion of the fluororesin layer and a small increase in air permeability resistance, it can be suitably used particularly for a battery separator.

The composite porous membrane of the present invention comprises a porous membrane B containing a fluororesin with respect to the surface of the outermost polypropylene resin of the porous membrane A consisting of three layers and at least one of the outermost layers made of polypropylene resin. It is a laminate, and it has achieved excellent adhesion of the fluororesin layer without causing a significant increase in the air resistance due to the lamination by an advanced processing technique.

  Here, the significant increase in the air resistance is that the difference between the air resistance (X) of the porous membrane as the base material and the air resistance (Y) of the composite porous membrane exceeds 100 seconds / 100 cc Air. Means that. The excellent adhesion of the fluororesin layer means that the peel strength is 1.0 N / 25 mm or more, preferably 1.5 N / 25 mm or more, more preferably 2.0 N / 25 mm or more. If it is less than 1.0 N / 25 mm, the fluororesin layer may be peeled off during processing in the battery assembly process. There is no particular upper limit to the peel strength, but 30 N / 25 mm is sufficient for adhesion.

First, the porous membrane A used in the present invention will be described.
The porous membrane A is composed of three layers and at least one of the outermost layers is composed of a polypropylene resin. Such a porous membrane A can be generally produced by a production method such as a stretched hole method or a phase separation method.
The layer structure of the porous membrane A is polypropylene / polyethylene / polypropylene, but the thickness of the polypropylene layer is preferably 3 μm or more on one side. If it is less than 3 μm, sufficient mechanical strength may not be obtained.

  Further, the polypropylene resin in the porous membrane A is preferably from the viewpoint of process workability and mechanical strength that can withstand various external pressures generated during winding with the electrode, such as tensile strength, elastic modulus, elongation, and piercing strength. The mass average molecular weight is 300,000 or more, more preferably 400,000 or more, and most preferably 500,000 or more.

The layer structure of the porous membrane A differs depending on the production method. As long as the above various characteristics are satisfied, the phase structure according to the purpose can be freely given by the production method. There are foaming methods, phase separation methods, dissolution recrystallization methods, stretched pore opening methods, powder sintering methods, etc., among these porous membrane production methods, among these, phase separation in terms of uniform micropores and cost The method is preferred.

  The porous film A needs to have a function of closing the pores when the charge / discharge reaction is abnormal (pore closing function). Therefore, the melting point (softening point) of the constituent resin is preferably 70 to 150 ° C, more preferably 80 to 140 ° C, and most preferably 100 to 130 ° C. If the temperature is lower than 70 ° C, the pore blocking function may be exhibited during normal use and the battery may become unusable. Therefore, if the temperature exceeds 150 ° C, the abnormal reaction proceeds sufficiently and the hole blocking function appears. Therefore, safety may not be ensured.

  The upper limit of the thickness of the porous membrane A is preferably 40 μm, more preferably 35 μm. The lower limit is preferably 10 μm, more preferably 15 μm. If the thickness is less than 10 μm, the battery used in severe environments such as electric vehicles may not have a practical membrane strength and hole blocking function. If the thickness is greater than 40 μm, the unit volume of the battery case The area per contact is greatly restricted, and is not suitable for increasing the capacity of batteries that will be advanced in the future.

  The upper limit of the air permeability resistance (JIS-P8117) of the porous membrane A is preferably 1000 seconds / 100 cc Air, more preferably 800 seconds / 100 cc Air, most preferably 500 seconds / 100 cc Air, and the lower limit is preferably 50 seconds / 100 cc Air. More preferably, it is 70 seconds / 100 cc Air, and most preferably 100 seconds / 100 cc Air.

  The upper limit of the porosity of the porous membrane A is 70%, preferably 60%, more preferably 55%. The lower limit is 30%, preferably 35%, more preferably 40%. Whether the air resistance is higher than 1000 seconds / 100 cc Air or the porosity is lower than 30%, sufficient charge / discharge characteristics of the battery, particularly ion permeability (charge / discharge operating voltage), battery life (electrolysis) (It is closely related to the amount of liquid retained), and if these ranges are exceeded, the battery function may not be fully exhibited. On the other hand, even if the air permeability resistance is lower than 50 seconds / 100 cc Air or the porosity is higher than 70%, sufficient mechanical strength and insulation cannot be obtained, and a short circuit may occur during charging and discharging. Increases nature.

  Since the average pore diameter of the porous membrane A greatly affects the pore closing speed, it is 0.01 to 1.0 μm, preferably 0.05 to 0.5 μm, and more preferably 0.1 to 0.3 μm. If it is smaller than 0.01 μm, the anchor effect of the fluororesin is difficult to obtain, and sufficient adhesiveness of the fluororesin may not be obtained. The possibility increases. When it is larger than 1.0 μm, there is a possibility that a phenomenon such as a slow response to the temperature of the hole closing phenomenon or a phenomenon that the hole closing temperature due to the heating rate shifts to a higher temperature side may occur. When the porous film A is a multilayer film having two or more layers (for example, polypropylene / polyethylene / polypropylene), the average pore diameter of the porous film A only needs to satisfy at least the average pore diameter of the outermost layer polypropylene resin. Good.

  Furthermore, regarding the surface state of the porous membrane A, when the surface roughness (arithmetic average roughness) is in the range of 0.01 to 0.5 μm, the adhesion with the porous membrane B tends to be stronger. . When the surface roughness is lower than 0.01 μm, the effect of improving the adhesion is not observed. When the surface roughness is higher than 0.5 μm, the mechanical strength of the porous film A is reduced or the unevenness is transferred to the surface of the porous film B. Sometimes.

Next, the porous membrane B used in the present invention will be described.
The porous membrane B contains a fluorine-based resin and plays a role of supporting and reinforcing the porous membrane A due to its heat resistance. Therefore, the melting point of the fluororesin constituting the porous membrane B is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, most preferably 210 ° C. or higher, and the upper limit is not particularly limited. When the melting point is higher than the decomposition temperature, the decomposition temperature may be in the above range. When the melting point is lower than 150 ° C., a sufficient heat-resistant film breaking temperature cannot be obtained, and high safety may not be ensured.

Hereinafter, the fluororesin used for the porous membrane B will be described.
The fluororesin is at least one selected from the group consisting of vinylidene fluoride homopolymers, vinylidene fluoride / fluorinated olefin copolymers, vinyl fluoride homopolymers, and vinyl fluoride / fluorinated olefin copolymers. Is preferably used. Particularly preferred is polytetrafluoroethylene. These polymers have high affinity with non-aqueous electrolytes, are suitable for heat resistance, and have high chemical and physical stability against non-aqueous electrolytes. The affinity of can be maintained sufficiently.

  The fluororesin used in the present invention preferably has a logarithmic viscosity of 0.5 dl / g or more. When the logarithmic viscosity is less than 0.5 dl / g, sufficient meltdown characteristics may not be obtained due to a decrease in melting temperature, and the porous film becomes brittle due to low molecular weight, and the anchor effect is reduced, resulting in reduced adhesion. It is to do. On the other hand, the upper limit of the logarithmic viscosity is preferably less than 2.0 dl / g in consideration of processability and solvent solubility.

  The porous membrane B is a fluorine-based resin solution (varnish) which is soluble in a fluorine-based resin and dissolved in a solvent miscible with water, and is applied to a predetermined substrate film, It is obtained by phase-separating a solvent miscible with water and further putting it in a water bath (coagulation bath) to coagulate the fluororesin.

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

  The solid content concentration of the varnish is not particularly limited as long as it can be uniformly applied, but is preferably 2% by weight or more and 50% by weight or less, more preferably 4% by weight or more and 40% by weight or less. When the solid content concentration is less than 2% by weight, the obtained porous membrane B may become brittle. On the other hand, if it exceeds 50% by weight, it may be difficult to control the thickness of the porous membrane B.

  Moreover, in order to reduce the heat shrinkage rate of the porous layer B and to impart slipperiness, inorganic particles or heat-resistant polymer particles may be added to the varnish. When adding particles, the upper limit of the amount added is preferably 95% by mass. When the addition amount exceeds 95% by mass, the ratio of the fluororesin to the total volume of the porous membrane B becomes small, and sufficient adhesion of the fluororesin to the porous membrane A may not be obtained.

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

  It is important that the moisture content of the varnish is 0.5% by weight or less, preferably 0.3% by weight or less. If it exceeds 0.5% by weight, the fluororesin component is likely to coagulate during storage of varnish or immediately after coating, so that the porous film A may not be able to soak the necessary amount of fluororesin. Examples of the method of setting the moisture content of the varnish to 0.5% by weight or less include a method of setting the moisture content of additives such as fluorine resins and solvents, and inorganic particles to 0.5% by weight or less. For this, it is preferable to use each raw material after dehydration or drying. In addition, it is desirable to store the varnish so that it is not exposed to outside air as much as possible from the preparation to the coating. The moisture content of the varnish can be measured using the Karl Fischer method.

  The film thickness of the porous membrane B is preferably 1 to 5 μm, more preferably 1 to 4 μm, and most preferably 1 to 3 μm. If the film thickness is less than 1 μm, there is a possibility that the membrane breaking strength and insulation properties cannot be secured when the porous film A is melted or shrunk at a melting point or higher, and if it is thicker than 5 μm, the porosity in the composite porous film The ratio occupied by the membrane A is small, a sufficient pore blocking function cannot be obtained, and abnormal reactions may not be suppressed. Moreover, there is a possibility that the volume of winding becomes large and it is not suitable for increasing the capacity of a battery that will be advanced in the future.

  The porosity of the porous membrane B is preferably 30 to 90%, more preferably 40 to 70%. If the porosity is less than 30%, the electrical resistance of the film increases and it becomes difficult to pass a large current. On the other hand, if it exceeds 90%, the film strength tends to be weak. Moreover, it is preferable that the value measured by the method based on JIS-P8117 is the air permeability resistance of the porous membrane B is 1-1000 second / 100ccAir. More preferably, it is 50-800 second / 100ccAir, More preferably, it is 100-700 second / 100ccAir. When the air resistance is less than 1 second / 100 cc Air, the film strength becomes weak, and when it exceeds 1000 seconds / 100 cc Air, the cycle characteristics may be deteriorated.

  In the composite porous membrane of the present invention, the difference (Y−X) between the air permeability resistance (X seconds / 100 cc Air) of the porous membrane A and the air permeability resistance (Y seconds / 100 cc Air) of the entire composite porous membrane is 20 Second / 100 cc Air ≦ Y−X ≦ 100 seconds / 100 cc Air If Y-X is less than 20 seconds / 100 cc Air, sufficient adhesion of the fluororesin layer cannot be obtained. On the other hand, if it exceeds 100 seconds / 100 cc Air, the air permeability resistance is significantly increased. As a result, the ion permeability is lowered when the battery is incorporated in the battery, so that the separator is not suitable for a high-performance battery.

  Further, the air resistance of the composite porous membrane is preferably 70 to 1100 seconds / 100 cc Air, more preferably 200 to 800 seconds / 100 cc Air, and most preferably 300 to 700 seconds / 100 cc Air. If the value of air permeability resistance is lower than 70 seconds / 100 cc Air, sufficient insulation cannot be obtained, which may cause clogging of foreign matter, short circuit, and film breakage. If the value is higher than 1100 seconds / 100 cc Air, In some cases, the membrane resistance is high, and charge / discharge characteristics and life characteristics in a practically usable range cannot be obtained.

Next, the manufacturing method of the composite porous membrane of this invention is demonstrated.
In the method for producing a composite porous membrane of the present invention, first, a varnish (fluorine resin solution) is applied on a base film such as a polyester film or a polyolefin film, and then passed through a low humidity zone. During this period, the fluororesin in the varnish and the solvent in which the resin is dissolved are phase-separated.

  Examples of the method for applying the varnish include reverse roll coating, gravure coating, kiss coating, roll brushing, spray coating, air knife coating, wire barber coating, pipe doctor method, blade coating method, and die coating method. These methods can be carried out alone or in combination.

The low humidity zone in the present invention is a zone whose absolute humidity is adjusted to less than 6 g / m ³ . The upper limit of absolute humidity is preferably 4 g / m ³ , more preferably 3 g / m ³ , and the lower limit is preferably 0.5 g / m ³ , more preferably 0.8 g / m ³ . If the absolute humidity is less than 0.5 g / m ³ , phase separation is not sufficiently performed, so that it is difficult to finally become a porous membrane, and the increase in air resistance may be increased. In addition, when the absolute humidity is 6 g / m ³ or more, the solidification of the fluororesin starts in parallel with the phase separation, and when the porous membrane A is pasted, the permeation of the fluororesin into the porous membrane A is not sufficiently performed. Sufficient adhesion of fluororesin cannot be obtained. The passage time in the low humidity zone is preferably 3 seconds or more and 20 seconds or less. If it is less than 3 seconds, the phase separation may not be sufficiently performed. On the other hand, if it exceeds 20 seconds, the solidification of the fluororesin may proceed excessively.

Next, the coated film is passed through a high-humidity zone to form a semi-gel fluorinated resin film on the base film. The high humidity zone referred to in the present invention has a lower limit of absolute humidity of 6 g / m ³ , preferably 7 g / m ³ , more preferably 8 g / m ³ , an upper limit of 25 g / m ³ , preferably 17 g / m ³ , The zone is preferably adjusted to 15 g / m ³ . When the absolute humidity is less than 6 g / m ³ , gelation (non-fluidization) is not sufficiently performed. Therefore, when the porous membrane A is pasted, penetration of the fluororesin into the porous membrane A proceeds too much, Increase in air resistance increases. If the absolute humidity exceeds 25 g / m ³ , the solidification of the fluororesin proceeds too much, the penetration of the fluororesin into the porous film A becomes too small, and sufficient adhesion may not be obtained. The passage time in the high humidity zone is preferably 3 seconds or more and 10 seconds or less. In less than 3 seconds, gelation (non-fluidization) is not sufficiently performed. Therefore, when the porous membrane A is pasted, the penetration of the fluororesin into the porous membrane A proceeds too much, and the air permeability resistance increases. On the other hand, if the width exceeds 10 seconds, the solidification of the fluororesin proceeds too much, the penetration of the fluororesin into the porous film A becomes too small, and sufficient adhesion may not be obtained. is there.

  The temperature condition for both the low humidity zone and the high humidity zone is not particularly limited as long as the absolute humidity is within the above range, but is preferably 20 ° C. or more and 50 ° C. or less from the viewpoint of energy saving. The thickness of the film substrate is not particularly limited as long as it can maintain the flatness, but a thickness of 25 μm to 100 μm is preferable. If it is less than 25 μm, sufficient planarity may not be obtained. Moreover, even if it exceeds 100 micrometers, planarity does not improve.

On the other hand, a porous membrane A comprising three layers and at least one of the outermost layers comprising a polypropylene resin is prepared, and then formed on the surface of the outermost polypropylene resin of the porous membrane A as described above. The semi-gel-like fluororesin film thus formed is bonded so as not to contain bubbles. As a method of laminating, a method of laminating a film coming from two directions on the surface of one metal roll is preferable because it causes less damage to the film. Here, the semi-gel form means a state in which a gelled region and a region holding the solution state are mixed in the process of gelation of the fluororesin solution due to absorption of moisture in the atmosphere. .

  The porous film A is preferably laminated on the semi-gelled fluorine-based resin film within at least 10 seconds immediately after passing through the high humidity zone. If it exceeds 10 seconds, solidification of the fluororesin film proceeds and sufficient adhesion of the porous film B may not be obtained.

  After the formation of the fluororesin film, the base film may be peeled off. However, in the method of the present invention, it is preferable to attach the porous film A to the fluororesin film without peeling off the base film. When this method is used, a composite porous membrane can be produced even when a soft porous membrane A that has a low elastic modulus and is necked by the tension during processing is used. Specifically, it can be expected that the composite porous membrane does not wrinkle or bend when passing through the guide roll, and curling during drying can be reduced. At this time, the base material and the composite porous membrane may be wound up at the same time, or after passing through the drying step, the base material and the composite porous membrane may be wound up on separate winding rolls. Is preferable because there is little risk of winding deviation.

  Next, the bonded porous film A and fluororesin film are immersed in a coagulation bath, and the fluororesin film is phase-converted to be converted into a porous film B. The composition of the coagulation bath is not particularly limited. For example, the coagulation bath may be an aqueous solution containing 1 to 20% by weight, more preferably 5 to 15% by weight of a good solvent for the fluororesin constituting the porous membrane B. By immersion in the coagulation bath, the porous membrane B is transferred to the porous membrane A over the entire surface, and an unwashed composite porous membrane is obtained. This is because a part of the porous membrane B appropriately bites into the pores of the porous membrane A and the anchor effect is expressed.

  Furthermore, the above-mentioned unwashed porous membrane can be subjected to a washing step using pure water or the like and a drying step using hot air at 100 ° C. or lower, and the final composite porous membrane can be obtained.

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

The amount of linear oligomers of the side of the substrate film surface for applying at least varnish, 20 [mu] g / ^m is preferably ² or more 100 [mu] g / ^{m 2} or less, more preferably 30 [mu] g / ^{m 2} or more 80 [mu] g / ^{m 2} It is as follows. When the amount of the linear oligomer on the surface of the base film is less than 20 μg / m ² , when the composite porous film of the porous film A and the porous film B in a bonded state is peeled from the base film, the porous film In some cases, B may remain on the base film. On the other hand, if it exceeds 100 μg / m ² , not only coating spots are likely to be generated when the porous film B is applied, but also a linear oligomer on the base film surface. May cause process contamination such as a transport roll, which is not preferable. In other words, if the amount of the linear oligomer on the surface of the base film on the side on which the varnish is applied is within the above range, the uniformity when the porous film B is applied and the porous film A in a bonded state And good transferability when the composite porous membrane of the porous membrane B is peeled from the substrate film.

  The amount of the linear oligomer referred to here means the total amount of the linear dimer, linear trimer, and linear tetramer derived from the polyester resin used as the raw material for the base film. For example, in the case of a polyester having ethylene terephthalate as the main repeating unit and starting from terephthalic acid and ethylene glycol, the linear dimer has two terephthalic acid units in one molecule and has a carboxylic acid terminal or a hydroxyl terminal. Means an oligomer having Similarly, the linear trimer has three terephthalic acid units in one molecule, and the linear tetramer has the same end group as the linear dimer except that it has four. Means things.

  The surface treatment method for imparting the linear oligomer is not particularly limited, and examples thereof include corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, and ozone treatment. Among these, the corona discharge treatment is particularly preferable because it can be relatively easily performed.

  According to the method of the present invention, even when the outermost layer of the porous membrane A is made of a polypropylene resin having a relatively low porosity, a composite porous membrane having an excellent balance between adhesion and air resistance can be obtained. .

  The composite porous membrane of the present invention can be prepared using a polypropylene-based porous membrane slit to a desired width as the porous membrane A, but can also be processed on-line at the time of producing the polypropylene porous membrane. It is. Here, “online” means that after the production process of the polypropylene porous membrane (specifically, the drying step after washing), the porous membrane B is continuously laminated, followed by the solidification, washing, and slitting steps. Means for obtaining a composite porous membrane. By performing the above-mentioned online coating, mass production becomes possible, which is very advantageous in terms of cost.

  Although it is desirable to store the composite porous membrane of the present invention in a dry state, if it is difficult to store in a completely dry state, it is preferable to perform a vacuum drying treatment at 100 ° C. or lower immediately before use.

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

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

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

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

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

  Hereinafter, although an example is shown and explained concretely, the present invention is not restrict | limited at all by these examples. In addition, the measured value in an Example was measured with the following method.

(1) Film thickness It measured using the contact-type film thickness meter (Sony Manufacturing Co., Ltd. digital micrometer M-30).

(2) Peel strength at the interface between porous membrane A and porous membrane B Adhesive tape (Nichiban Co., Ltd., No. 405; 24 mm width) is applied to the porous membrane B surface of the separator obtained in the examples and comparative examples, and the width It cut | judged to 24 mm and length 150mm, and produced the sample for a test.

  Porous film A using a tensile tester [“Tensilon RTM-100” manufactured by A & D Co., Ltd.] under the conditions of 23 ° C. and 50% RH by a peel method (peeling speed 500 mm / min, T-type peeling). And the peel strength at the interface of the porous membrane B were measured. The measurement was performed over time during 100 mm from the start of measurement to the end of measurement, the average value of the measured values was calculated, and converted to a value per 25 mm width to obtain the peel strength. In addition, although the porous membrane B surface may remain on the porous membrane A side at the peeling interface, the peeling strength at the interface between the porous membrane A and the porous membrane B is also calculated in this case.

(3) Average pore diameter The average pore diameter of the porous membrane A was measured by the following method. The test piece was fixed to the measuring cell using double-sided tape, platinum or gold was vacuum-deposited for several minutes, and the measurement was performed at an appropriate magnification. Arbitrary 10 places observed most foremost on the image obtained by SEM measurement were selected, and the average value of the pore diameters at these 10 places was defined as the average pore diameter of the test piece. In addition, when the hole was not substantially circular, the value obtained by adding the major axis and the minor axis and dividing by 2 was defined as the hole diameter.

(4) Air permeability resistance Using a Gurley-type densometer type B manufactured by Tester Sangyo Co., Ltd., the composite porous membrane is fixed so that no wrinkles are formed between the clamping plate and the adapter plate. Measured according to P-8117. Two samples of 10 cm square were prepared as samples, and for each sample, a total of 10 points were measured with the central part and four corners of the sample as measurement points, and the average value of 10 points was measured for air resistance [seconds / second] 100 cc Air]. When the length of one side of the sample is less than 10 cm, a value obtained by measuring 10 points at intervals of 5 cm may be used.

(5) Logarithmic viscosity A solution of 0.5 g of fluororesin dissolved in 100 ml of NMP was measured at 25 ° C. using an Ubbelohde viscosity tube.

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

(7) Porosity A 10 cm square sample was prepared, its sample volume (cm ³ ) and mass (g) were measured, and the porosity (%) was calculated from the obtained result using the following formula. Note that the sample volume (cm ³ ) of the 10 cm square sample can be obtained by 10 (cm) × 10 (cm) × the thickness (cm) of the porous film A.
Porosity = (1−mass / (resin density × sample volume)) × 100

(8) Amount of linear oligomer on the surface of the base film The faces of the two films to be extracted face each other and fixed to a frame with a spacer so that an area of 25.2 cm × 12.4 cm can be extracted per sheet. 30 ml of ethanol was injected between the extraction surfaces, and linear oligomers on the film surface were extracted at 25 ° C. for 3 minutes. After evaporating the extract to dryness, the dry residue of the resulting extract was made up to 200 μl of dimethylformamide. Subsequently, the linear oligomer was quantified from the analytical curve previously calculated | required by the method shown below using the high performance liquid chromatography. In addition, the quantity of the linear oligomer was taken as the total value of a dimer, a trimer, and a tetramer.

(Measurement condition)
Apparatus: ACQUITY UPLC (manufactured by Waters)
Column: BEH-C18 2.1 × 150 mm (manufactured by Waters)
Mobile phase: Eluent A: 0.1% formic acid (v / v)
Eluent B: Acetonitrile
Gradient B%: 10 → 98 → 98% (0 → 25 → 30 minutes)
Flow rate: 0.2 ml / min Column temperature: 40 ° C
Detector: UV-258nm

Reference example 1
Polyvinylidene fluoride (melting point: 175 ° C., Kureha Chemical Industry Co., Ltd., trade name: KF polymer # 1120 (polyvinylidene fluoride 12% N-methylpyrrolidone solution) diluted with N-methyl-2-pyrrolidone as fluorine resin Then, varnish (a-1) (solid content concentration 5.8% by weight) was prepared, and a series of operations were performed in a dry air flow with a humidity of 10% or less to prevent moisture absorption as much as possible. The varnish (a-1) was applied to the surface of a polyethylene terephthalate resin film having a thickness of 50 μm and a surface linear oligomer amount of 68 μg / m ² by a blade coating method, and the temperature was 25 ° C. A semi-gel-like fluororesin is passed through a low-humidity zone with an absolute humidity of 1.8 g / m ³ for 8 seconds, followed by a high-humidity zone with a temperature of 25 ° C. and an absolute humidity of 12 g / m ³ for 5 seconds. A membrane was formed, and after 1.7 seconds, porous membrane A (made of polypropylene, thickness 20 μm, porosity 40%, average pore diameter 0.10 μm, air resistance 600 seconds / 100 cc Air) Overlaid on a resin film, it was allowed to enter an aqueous solution containing 5% by weight of N-methyl-2-pyrrolidone, then washed with pure water, and then dried by passing through a hot air drying oven at 70 ° C. to obtain a final thickness. A 22.9 μm composite porous membrane was obtained.

Reference example 2
A composite porous membrane was obtained in the same manner as in Reference Example 1 except that the absolute humidity of the low humidity zone was 4.0 g / m ³ .

Reference example 3
A composite porous membrane was obtained in the same manner as in Reference Example 1 except that the absolute humidity in the low humidity zone was 5.5 g / m ³ .

Reference example 4
A composite porous membrane was obtained in the same manner as in Reference Example 1 except that the absolute humidity of the high humidity zone was 7.0 g / m ³ .

Reference Example 5
A composite porous membrane was obtained in the same manner as in Reference Example 1 except that the absolute humidity of the high-humidity zone was 16.0 g / m ³ .

Reference Example 6
Reference Example 1 except that the passage times of the low-humidity zone and the high-humidity zone were 5.3 seconds and 3.0 seconds, respectively, and the time from the exit of the high-humidity zone to the bonding of the porous membrane A was 1.1 seconds. In the same manner, a composite porous membrane was obtained.

Reference Example 7
Reference Example 1 except that the passage times of the low humidity zone and the high humidity zone were 16.0 seconds and 10.0 seconds, respectively, and the time from the exit of the high humidity zone to the bonding of the porous membrane A was 3.4 seconds. In the same manner, a composite porous membrane was obtained.

Example 1
Porous film A having a three-layer structure of polypropylene / polyethylene / polypropylene (thickness 25 μm (polypropylene / polyethylene / polypropylene = 8 μm / 9 μm / 8 μm), porosity 40%, average pore diameter 0.10 μm, air permeability A composite porous membrane was obtained in the same manner as in Reference Example 1 except that the resistivity was 620 seconds / 100 cc Air).

Example 2
The porous film A has a three-layer structure of polypropylene / polyethylene / polypropylene (thickness 20.5 μm (polypropylene / polyethylene / polypropylene = 6 μm / 8.5 μm / 6 μm), porosity 50%, average pore size 0. A composite porous membrane was obtained in the same manner as in Reference Example 1 except that 10 μm and air resistance of 320 seconds / 100 cc Air) were used.

Reference Example 8
Fluorine-based resin as the poly - except for using (vinylidene fluoride hexafluoropropylene) copolymer (Elf Atochem Japan Co. KYNAR2800) in place of the varnish (b) (solid concentration 5.3 wt%) Reference A composite porous membrane was obtained in the same manner as in Example 1.

Reference Example 9
Polyvinylidene fluoride (melting point: 175 ° C., manufactured by Kureha Chemical Industries, Ltd., trade name: KF polymer # 1120 (polyvinylidene fluoride 12% N-methylpyrrolidone solution) 32.6 parts by mass and average particle size 0 10.5 parts by mass of 0.5 μm alumina particles were diluted with 48.4 parts by mass of N-methyl-2-pyrrolidone, and 8.5 parts by mass of ethylene glycol was further added. Together with “Traceram beads” (diameter: 0.5 mm), the mixture was placed in a polypropylene container and dispersed for 6 hours with a paint shaker (manufactured by Toyo Seiki Seisakusho), followed by filtration with a filter having a filtration limit of 5 μm, and varnish (c) ( A solid porosity of 31.0% by weight was prepared in the same manner as in Reference Example 1 except that varnish (a-1) was replaced with varnish (c). A membrane was obtained.

Reference Example 10
Reference was made except that the varnish (d) (solid content concentration 31.0% by weight) in which the alumina particles were replaced with titanium oxide particles (manufactured by Titanium Industry Co., Ltd., trade name “KR-380”, average particle size 0.38 μm). A composite porous membrane was obtained in the same manner as in Example 9 .

Reference Example 11
A composite porous membrane was obtained in the same manner as in Reference Example 1 except that the coating amount of the porous membrane B was adjusted to a final thickness of 21.9 μm.

Reference Example 12
The fluororesin solution (a-1) obtained in Reference Example 1 was put into a water bath 10 times the volume ratio of the resin solution to precipitate the resin component. Next, the resin solid was sufficiently washed with water to remove NMP, and then dried using a vacuum dryer at 180 ° C. for 24 hours. Then, it diluted with N-methyl-2-pyrrolidone so that solid content concentration might be 14 weight%, and varnish (a-2) was prepared. The moisture content of the varnish (a-2) was 0.05% by weight. A composite porous membrane was obtained in the same manner as in Reference Example 1 except that the varnish (a-1) was replaced with the varnish (a-2).

Reference Example 13
A composite porous membrane was obtained in the same manner as in Reference Example 1 except that the absolute humidity of the low-humidity zone was 1.2 g / m ³ .

Reference Example 14
A composite porous membrane was obtained in the same manner as in Reference Example 1 except that the coating amount of the porous membrane B was adjusted and the final thickness was 25.0 μm.

Reference Example 15
Except for using a polyethylene terephthalate resin film of the surface linear oligomers amount 25 [mu] g / m ² in place of the polyethylene terephthalate resin film of the surface linear oligomers amount 68μg / m ² in the same manner as in Reference Example 1 to obtain a composite porous membrane .

Comparative Example 1
A composite porous membrane was obtained in the same manner as in Reference Example 1 except that the low humidity zone was set at a temperature of 25 ° C. and an absolute humidity of 7.0 g / m ³ .

Comparative Example 2
A composite porous membrane was obtained in the same manner as in Reference Example 1 except that the high humidity zone was set to a temperature of 25 ° C. and an absolute humidity of 5.0 g / m ³ .

Comparative Example 3
Varnish (a-1) was applied to the porous membrane A used in Reference Example 1 by a blade coating method, a low humidity zone having a temperature of 25 ° C. and an absolute humidity of 1.8 g / m ³ was applied for 8 seconds, and subsequently a temperature of 25 ° C. After passing through a high humidity zone with an absolute humidity of 12 g / m ³ for 5 seconds, and then 2 seconds later, it was allowed to enter an aqueous solution containing 5% by weight of N-methyl-2-pyrrolidone and then washed with pure water. Then, it was dried by passing it through a hot air drying oven at 70 ° C. to obtain a composite porous membrane having a final thickness of 22.9 μm.

Comparative Example 4
The composite was made in the same manner as in Comparative Example 3 except that the porous film A used in Reference Example 1 was previously immersed in N-methyl-2-pyrrolidone and the pores were filled with N-methyl-2-pyrrolidone. A porous membrane was obtained.
Comparative Example 5
Except for using the surface linear oligomer content 3 [mu] g / m ² polyethylene terephthalate resin film in place of the polyethylene terephthalate resin film of the surface linear oligomers amount 68μg / m ² as a base film in the same manner as in Reference Example 1 composite porous membrane However, when the composite porous film of the porous film A and the porous film B in a bonded state is peeled from the base film, the porous film B remains on the film base material, A porous membrane was not obtained.

Comparative Example 6
A composite porous membrane was obtained in the same manner as in Reference Example 1 except that the absolute humidity of the high humidity zone was 25.5 g / m ³ .

Table 1 shows the production conditions of the composite porous membranes of Reference Examples 1 to 15, Examples 1 to 2 and Comparative Examples 1 to 6, and the characteristics of the porous membrane A and the composite porous membrane.

  The composite porous membrane of the present invention has both excellent adhesion of the fluorine-based resin layer and a small increase in air permeability resistance, and has high battery capacity, high ion permeability, and battery assembly processing steps. It is a composite porous membrane suitable for high-speed processability and particularly suitable for battery separators.

Claims (8)

A composite porous membrane in which a porous membrane B containing a fluororesin is laminated on the surface of the outermost polypropylene resin of the porous membrane A composed of three layers and at least one of the outermost layers is made of polypropylene resin. The porous membrane A satisfies the following formulas (A) and (B), the composite porous membrane satisfies the following formulas (C) and (D), and the porous membrane A is polypropylene / polyethylene / A composite porous membrane characterized in that three layers of polypropylene are laminated.
0.01 μm ≦ average pore diameter of porous membrane A ≦ 1.0 μm Formula (A)
30% ≦ Porosity of porous membrane A ≦ 70% Formula (B)
Peel strength at the interface between porous membrane A and porous membrane B ≧ 1.0 N / 25 mm Formula (C)
20 ≦ Y−X ≦ 100 Formula (D)
(X is the air permeability resistance of the porous membrane A (second / 100 cc Air), Y is the air resistance of the entire composite porous membrane (second / 100 cc Air))   The composite porous membrane according to claim 1, wherein the fluororesin is a fluororesin having a logarithmic viscosity of 0.5 dl / g or more. The method for producing a composite porous membrane according to claim 1, comprising the following steps (i) to (iii).
Step (i): After applying the fluororesin solution on the base film, it is passed through a low-humidity zone having an absolute humidity of less than 6 g / m ³ , and then high in an absolute humidity of 6 g / m ³ or more and 25 g / m ³ or less. Forming a fluororesin film on the base film by passing through the humidity zone;
Step (ii): Step of preparing a porous membrane A comprising three layers and at least one of the outermost layers comprising a polypropylene resin, and Step (iii): Polypropylene resin of the outermost layer of the porous membrane A in Step (ii) After the fluororesin film formed in step (i) is bonded to the surface of the film, it is immersed in a coagulation bath to convert the fluororesin film into a porous film B, washed and dried, and composite porous A step of obtaining a film.   The method for producing a composite porous membrane according to claim 3, wherein the base film is peeled after obtaining the composite porous membrane in the step (iii).   The method for producing a composite porous membrane according to claim 3 or 4, wherein the base film is a polyester film or a polyolefin film having a thickness of 25 to 100 µm. The method for producing a composite porous membrane according to any one of claims 3 to 5, wherein the amount of the linear oligomer on the surface of the substrate film is 20 µg / m ² or more and 100 µg / m ² or less.   The passage time in the low humidity zone is 3 seconds or more and 20 seconds or less in the step (i), and the passage time in the high humidity zone is 3 seconds or more and 10 seconds or less. The manufacturing method of the composite porous membrane as described.   A battery separator comprising the composite porous membrane according to claim 1.