MICROPOROUS MEMBRANE AND PRODUCTION METHOD THEREFOR

Abstract

Provided is a microporous membrane made of a polypropylene-based resin and having high porosity, being useful as a battery separator. The microporous membrane is composed of a polypropylene-based polymer in which a melt mass flow rate (MFR) measured at 230 C. and a load of 21.18 N in accordance with JIS K6758 is 1.0 g/10 min or less, and has porosity of 50% or more. Provided is also a method for producing the same.

Claims

1. A microporous membrane, comprising a polypropylene-based polymer in which a melt mass flow rate (MFR, measured under conditions in accordance with JIS K6758 (230 C., 21.18 N)) is 1.0 g/10 min or less, and having porosity of 50% or more.

2. The microporous membrane according to claim 1, wherein the porosity is in the range of 50 to 60%.

3. The microporous membrane according to claim 1, wherein air permeability is 200 seconds per 100 milliliters or more.

4. The microporous membrane according to claim 1, wherein the air permeability is in the range of 200 to 300 seconds per 100 milliliters.

5. The microporous membrane according to claim 1, wherein the polypropylene-based polymer is a polymer that mainly contains propylene, in which a melting point is in the range of 150 to 170 C., and a melt mass flow rate (MFR, measured under conditions in accordance with JIS K6758 (230 C., 21.18 N)) is 1.0 g/10 min or less, and may arbitrarily contain at least one kind selected from ethylene and -olefin having 4 to 8 carbons.

6. The microporous membrane according to claim 1, wherein the microporous membrane is used for a separator of an electric storage device.

7. The microporous membrane according to claim 6, wherein the electric storage device is a lithium ion battery.

8. The microporous membrane according to claim 6, wherein the electric storage device is a capacitor.

9. An electric storage device, comprising the microporous membrane according to claim 6.

10. A lithium ion battery, comprising the microporous membrane according to claim 7.

11. A capacitor, comprising the microporous membrane according to claim 8.

12. A method for producing the microporous membrane according to claim 1, comprising: a step of forming an original film by extrusion-molding a polypropylene-based polymer in which a melt mass flow rate (MFR) measured at 230 C. and a load of 21.18 N in accordance with JIS K6758 is 1.0 g/10 min or less (step 1); a step of applying heat treatment to the original film obtained in the step 1 (step 2); a step of stretching the original film after heat treatment as obtained in the step 2 at 5 to 45 C. by 1.0 to 1.1 times in a length direction (step 3); a step of stretching the stretched film obtained by finishing the step 3, at a temperature lower by 5 to 65 C. than a melting point of the polypropylene-based polymer by 1.5 to 4.0 times in the length direction (step 4); and a step of relaxing the film after hot stretching as obtained in the step 4 under heating to be 0.7 to 1.0 time in length (step 5).

Description

DESCRIPTION OF EMBODIMENTS

[0034] A microporous membrane according to the invention is composed of a polypropylene-based polymer in which a melt mass flow rate (MFR, measured in accordance with JIS K6758 (230 C., 21.18 N)) is 1.0 g/10 min or less, and has air permeability of 50% or more.

(Raw Material of Microporous Membrane)

[0035] A raw material of the microporous membrane according to the invention is a polypropylene-based polymer, and a homopolymer of propylene or a copolymer produced by copolymerizing a comonomer with propylene corresponds to the polypropylene-based polymer. The polypropylene-based polymer to be used in the invention is a polymer having a melting point preferably in the range of 150 to 170 C., and further preferably in the range of 155 to 168 C. The comonomer is generally at least one kind selected from ethylene and -olefin having 4 to 8 carbons. Moreover, the polymer may be a polymer produced by copolymerizing, together therewith, branched olefins having 4 to 8 carbons, such as 2-methylpropene, 3-methyl-1-butene and 4-methyl-1-pentene, styrenes, or dienes.

[0036] A content of the comonomer may be in any range as long as the microporous membrane exhibits desired properties. The content is preferably 5 parts by weight or less, and particularly preferably 2 parts by weight, based on 100 parts by weight of the polymer, being the range in which a high-crystalline polypropylene-based polymer is provided.

[0037] Moreover, the melt mass flow rate (MFR, measured in accordance with JIS K6758 (230 C., 21.18 N)) of the polypropylene-based polymer is 1.0 g/10 min or less, and preferably 0.2 to 0.6.

[0038] An additive such as a nucleating agent and a filler can be compounded with the raw material of the microporous membrane according to the invention. A kind and an amount of the additive are not limited as long as porousness is not adversely affected.

(Method for Producing Microporous Membrane)

[0039] The microporous membrane according to the invention is produced by using the raw material described above according to a so-called dry process. The method for producing the microporous membrane according to the invention includes steps 1 to 5 described below.

(Step 1: Membrane Formation Step)

[0040] The step 1 is a step of forming an original film by extrusion-molding the raw material. A polypropylene-based polymer in which a melt mass flow rate (MFR) measured at 230 C. and a load of 21.18 N in accordance with JIS K6758 is 1.0 g/10 min or less is fed to an extruder, and melted and kneaded at a temperature equal to or higher than a melting point thereof, and extruded from dies attached to a tip end of the extruder into a film of the propylene-based polymer. The extruder to be used is not limited. As the extruder, for example, any of a single screw extruder, a twin screw extruder and a tandem extruder can be used. As the dies to be used, any dies can be used as long as such dies are used for film formation. As the dies, for example, various T-dies can be used. A thickness and a shape of the original film are not particularly limited. A ratio (draft ratio) of a dies lip clearance to a thickness of the original film is preferably 100 or more, and further preferably 150 or more. The thickness of the original film is preferably 10 to 200 micrometers, and further preferably 15 to 100 micrometers.

(Step 2: Heat Treatment Step)

[0041] The step 2 is a step of applying heat treatment to the original film obtained by finishing the step 1. Predetermined tension in a length direction is applied to the original film at a temperature lower by 5 to 65 C., and preferably 10 to 25 C. than the melting point of the polypropylene-based polymer. The tension is preferably in magnitude in which a length of the original film becomes over 1.0 time and 1.1 times or less.

(Step 3: Cold Stretching Step)

[0042] The step 3 is a step of stretching the original film after heat treatment as obtained by finishing the step 2, at a comparatively low temperature. A stretching temperature is 5 to 45 C., and preferably 5 to 30 C. A stretch ratio in a length direction is 1.0 time to 1.1 times, preferably 1.00 to 1.08, and further preferably 1.02 or more and less than 1.05. However, the stretch ratio is larger than 1.0 time. A stretching means is not limited. A publicly known method such as a roll stretching process and a tenter stretching process can be applied thereto. The number of steps of stretching can be arbitrarily set. Stretching in one step may be applied thereto, or stretching in two or more steps through a plurality of rolls may be applied thereto. In a cold stretching step, molecules of the polypropylene-based polymer constituting the original film are oriented. As a result, a stretched film having a lamella part in which a molecular chain is dense and a region (craze) in which an inter-lamellar molecular chain is sparse is obtained.

(Step 4: Hot Stretching Step)

[0043] The step 4 is a step of stretching the stretched film obtained by finishing the step 3, at a comparatively high temperature. A stretching temperature is a temperature lower by 5 to 65 C., and preferably 10 to 45 C. than the melting point of the polypropylene-based polymer. A stretch ratio in the length direction is 1.5 to 4.5 times, and preferably 2.0 to 4.0 times. A stretching means is not limited. A publicly known method such as a roll stretching process and a tenter stretching process can be applied thereto. The number of steps of stretching can be arbitrarily set. Stretching in one step may be applied thereto, or stretching in two or more steps through a plurality of rolls may be applied thereto. In a hot stretching step, the craze formed in the step 3 is stretched and voids are formed.

(Step 5: Relaxing Step)

[0044] The step 5 is a step of relaxing the film after the hot stretching as obtained by finishing the step 4 in order to prevent shrinkage of the film. A relaxing temperature is a temperature slightly higher, generally higher by 10 to 20 C. than a temperature of hot stretching. A degree of relaxation is adjusted to be finally 0.7 to 1.0 time in a length of the stretched film obtained by finishing the step 4.

[0045] Porosity and air permeability of the microporous membrane according to the invention are measured under conditions described below.

(Porosity)

[0046] The porosity is expressed in terms of a value calculated according to the calculation formula described below for a microporous membrane piece having a width of 50 millimetersa length of 120 millimeters.

Porosity (%)={1(piece weight)/(piece arearesin densitypiece thickness)}100

(Air Permeability)

[0047] The air permeability is determined by a Gurley test in an atmosphere of room temperature of 23 C.2 C. and humidity of 50%5% in accordance with JIS P8117.

[0048] The porosity of the microporous membrane according to the invention is 50% or more, and preferably in the range of 50 to 60%. The air permeability of the microporous membrane according to the invention is 200 seconds per 100 milliliters or more, and preferably 200 to 300 seconds per 100 milliliters.

EXAMPLES

Example 1

[0049] As a raw material of a microporous membrane, a propylene homopolymer was used in which a melt mass flow rate (MFR) measured in accordance with JIS K6758 (230 C., 21.18 N) was 0.5 g/10 min, and a melting point was 165 C. (raw material). The raw material melted and kneaded by a single screw extruder was extruded from a T-die at a draft ratio of 159 to produce a 22 m-thick original film (step 1). Then, the original film was subjected to heat treatment at 150 C. (step 2). The original film was subjected to cold stretching at 30 C. by 1.03 times in a length direction (step 3). The stretched film obtained was subjected to hot stretching at 145 C. by 3.0 times in the length direction (step 4). The stretched film obtained was relaxed at 150 C. to be 0.88 time in length (step 5). Thus, a microporous membrane having a final thickness of 20 m according to the invention was obtained. Porosity and air permeability of the microporous membrane obtained were measured by the method described above, and the results are shown along with production conditions in Table 1. In addition, for measurement of the air permeability, an air permeability tester (Gurley type Densometer) made by Toyo Seiki Seisaku-Sho, Ltd. was used.

Example 2

[0050] As a raw material of a microporous membrane, a propylene homopolymer was used in which a melt mass flow rate (MFR) measured in accordance with JIS K6758 (230 C., 21.18 N) was 0.5 g/10 min, and a melting point was 165 C. (raw material). The raw material melted and kneaded by a single screw extruder was extruded from a T-die at a draft ratio of 159 to produce a 22 m-thick original film (step 1). Then, the original film was subjected to heat treatment at 150 C. (step 2). The original film was subjected to cold stretching at 30 C. by 1.04 times in a length direction (step 3). The stretched film obtained was subjected to hot stretching at 145 C. by 3.0 times in the length direction (step 4). The stretched film obtained was relaxed at 150 C. to be 0.88 time in length (step 5). Thus, a microporous membrane having a final thickness of 20 m according to the invention was obtained. The evaluation results are shown along with production conditions in Table 1.

Comparative Example 1

[0051] As a raw material of a microporous membrane, a propylene homopolymer was used in which a melt mass flow rate (MFR) measured in accordance with JIS K6758 (230 C., 21.18 N) was 2.0 g/10 min, and a melting point was 165 C. (raw material). The raw material melted and kneaded by a single screw extruder was extruded from a T-die at a draft ratio of 159 to produce a 22 m-thick original film (step 1). Then, the original film was subjected to heat treatment at 150 C. (step 2). The original film was subjected to hot stretching at 30 C. by 1.07 times in a length direction (step 3). The stretched film obtained was subjected to hot stretching at 145 C. by 3.2 times in the length direction (step 4). The stretched film obtained was relaxed at 150 C. to be 0.88 time in length (step 5). Thus, a microporous membrane having a final thickness of 20 m for comparison was obtained. The evaluation results are shown along with production conditions in Table 1.

Comparative Example 2

[0052] As a raw material of a microporous membrane, a propylene-ethylene copolymer was used in which a melt mass flow rate (MFR) measured in accordance with JIS K6758 (230 C., 21.18 N) was 1.5 g/10 min, and a melting point was 158 C. (raw material). The raw material melted and kneaded by a single screw extruder was extruded from a T-die at a draft ratio of 159 to produce a 22 m-thick original film (step 1). Then, the original film was subjected to heat treatment at 150 C. (step 2). The original film was subjected to cold stretching at 30 C. by 1.04 times in a length direction (step 3). The stretched film obtained was subjected to hot stretching at 128 C. by 3.0 times in the length direction (step 4). The stretched film obtained was relaxed at 150 C. to be 0.88 time in length (step 5). Thus, a microporous membrane having a final thickness of 20 m for comparison was obtained. The evaluation results are shown along with production conditions in Table 1.

TABLE-US-00001 TABLE 1 Comparative Example Example Unit 1 2 1 2 Raw Raw material MFR g/10 min 0.50 0.50 2.00 1.50 material polypropylene Melting point C. 165.0 165.0 165.0 158.0 (co)polymer Production Step 1 Original film m 22 22 22 22 method (Film thickness formation) Draft ratio 159 159 159 205 Step 2 Temperature C. 150 150 150 150 (Heat treatment) Step 3 Temperature C. 30 30 30 30 (Cold Total stretch ratio Times 1.03 1.03 1.04 1.07 stretching) Step 4 Temperature C. 145 145 145 128 (Hot Total stretch ratio Times 3.0 3.3 3.0 3.2 stretching) Step 5 Relaxation ratio Times 0.88 0.88 0.88 0.88 (Relaxation) Evaluation Porosity % 54 54 49 46 Air permiability(a) sec/100 mL 200 210 243 417 Air permiability (a)/20 (m) 10.00 10.50 12.15 20.85 per thickness

[0053] The microporous membranes according to the invention obtained in Examples 1 and 3 exhibit the porosity as high as 54%. In contrast, the porosity of the microporous membranes each in Comparative Examples 1 and 2 does not reach 50%, and is poor in practicality as a battery separator. In view of a balance between the porosity and the air permeability, in Examples 1 and 2, micropores having a comparatively smaller pore diameter presumably exist with higher density in comparison with the microporous membranes in Comparative Examples 1 and 2. Such a form of micropores is reflected also on the air permeability per thickness of the microporous membrane. In Examples 1 and 2, comparatively higher ion conductivity is conceivably stably exhibited in comparison with the microporous membranes in Comparative Examples 1 and 2.

INDUSTRIAL APPLICABILITY

[0054] A microporous membrane according to the invention has sufficient porousness, and is composed of a raw material containing no special additive. Such a microporous membrane according to the invention has excellent ion conductivity, and is useful as a material for a battery separator that can be produced at a low cost.