Multi-layer, microporous polyolefin membrane, its production method, battery separator, and battery

1. A method for producing the multi-layer, microporous polyolefin membrane comprising first microporous layers constituting at least both surface layers, and at least one second microporous layer disposed between both surface layers, said first microporous layer comprising (a) a first polyethylene resin containing 8% or more by mass of ultra-high-molecular-weight polyethylene having a weight-average molecular weight of 1×10 6 or more, based on the total mass of the polyethylene in the first microporous layer, and (b) 25% or less by mass of polypropylene based on the total mass of the polyethylene and the polypropylene in the first microporous layer, said second microporous layer comprising a second polyethylene resin containing 7% or less by mass of said ultra-high-molecular-weight polyethylene, and having a structure in which a pore diameter distribution curve obtained by mercury intrusion porosimetry has at least two peaks, and the total thickness of said first microporous layers being 15-60% per 100% of the total thickness of said first and second microporous layers, comprising the steps of (1) preparing a first polyolefin solution comprising a first polyethylene resin containing 8% or more by mass of ultra-high-molecular-weight polyethylene having a weight-average molecular weight of 1×10 6 or more based on the total mass of the polyethylene in the first polyethylene resin, 25% or less by mass of polypropylene based on the total mass of the polyethylene and the polypropylene in the first polyethylene resin, and a membrane-forming solvent, and a second polyolefin solution comprising a second polyethylene resin containing 7% or less by mass of said ultra-high-molecular-weight polyethylene and a membrane-forming solvent, (2) simultaneously extruding said first and second polyolefin solutions through a die, such that said first polyolefin solution forms at least both surface layers, while said second polyolefin solution forms at least one layer between both surface layers, (3) cooling the resultant extrudate, (4) stretching the resultant multi-layer, gel-like sheet, (5) removing said membrane-forming solvent from said multi-layer, gel-like sheet, and (6) stretching the resultant multi-layer, microporous membrane to 1.1-1.8 folds in at least one direction.

2. A method for producing the multi-layer, microporous polyolefin membrane comprising first microporous layers constituting at least both surface layers, and at least one second microporous layer disposed between both surface layers, said first microporous layer comprising (a) a first polyethylene resin containing 8% or more by mass of ultra-high-molecular-weight polyethylene having a weight-average molecular weight of 1×10 6 or more, based on the total mass of the polyethylene in the first microporous layer, and (b) 25% or less by mass of polypropylene based on the total mass of the polyethylene and the polypropylene in the first microporous layer, said second microporous layer comprising a second polyethylene resin containing 7% or less by mass of said ultra-high-molecular-weight polyethylene, and having a structure in which a pore diameter distribution curve obtained by mercury intrusion porosimetry has at least two peaks, and the total thickness of said first microporous layers being 15-60% per 100% of the total thickness of said first and second microporous layers, comprising the steps of (1) preparing a first polyolefin solution comprising a first polyethylene resin containing 8% or more by mass of ultra-high-molecular-weight polyethylene having a weight-average molecular weight of 1×10 6 or more based on the total mass of the polyethylene in the first polyethylene resin, 35% or less by mass of a polypropylene based on the total mass of the polyethylene and the polypropylene in the first polyethylene resin, and a membrane-forming solvent, and a second polyolefin solution comprising a second polyethylene resin containing 7% or less by mass of said ultra-high-molecular-weight polyethylene and a membrane-forming solvent, (2) extruding said first and second polyolefin solutions through separate dies and immediately laminating them, such that said first polyolefin solution forms at least both surface layers, while said second polyolefin solution forms at least one layer between both surface layers, (3) cooling the resultant extrudate, (4) stretching the resultant multi-layer, gel-like sheet, (5) removing said membrane-forming solvent from said multi-layer, gel-like sheet, and (6) stretching the resultant multi-layer, microporous membrane to 1.1-1.8 folds in at least one direction.

3. A method for producing the multi-layer, microporous polyolefin membrane comprising first microporous layers constituting at least both surface layers, and at least one second microporous layer disposed between both surface layers, said first microporous layer comprising (a) a first polyethylene resin containing 8% or more by mass of ultra-high-molecular-weight polyethylene having a weight-average molecular weight of 1×10 6 or more, based on the total mass of the polyethylene in the first microporous layer, and (b) 25% or less by mass of polypropylene based on the total mass of the polyethylene and the polypropylene in the first microporous layer, said second microporous layer comprising a second polyethylene resin containing 7% or less by mass of said ultra-high-molecular-weight polyethylene, and having a structure in which a pore diameter distribution curve obtained by mercury intrusion porosimetry has at least two peaks, and the total thickness of said first microporous layers being 15-60% per 100% of the total thickness of said first and second microporous layers, comprising the steps of (1) preparing a first polyolefin solution comprising a first polyethylene resin containing 8% or more by mass of ultra-high-molecular-weight polyethylene having a weight-average molecular weight of 1×10 6 or more based on the total mass of the polyethylene in the first polyethylene resin, 25% or less by mass of polypropylene based on the total mass of the polyethylene and the polypropylene in the first polyethylene resin, and a membrane-forming solvent, and a second polyolefin solution comprising a second polyethylene resin containing 7% or less by mass of said ultra-high-molecular-weight polyethylene and a membrane-forming solvent, (2) extruding said first and second polyolefin solutions through separate dies, (3) cooling the resultant extrudates to form first and second gel-like sheets, (4) stretching each gel-like sheet, (5) laminating said first and second gel-like sheets, such that said first gel-like sheet forms at least both surface layers, while said second gel-like sheet forms at least one layer between both surface layers, (6) removing said membrane-forming solvent from the resultant multi-layer, gel-like sheet, and (7) stretching the resultant multi-layer, microporous membrane to 1.1-1.8 folds in at least one direction.

4. A method for producing the multi-layer, microporous polyolefin membrane comprising first microporous layers constituting at least both surface layers, and at lest one second microporous layer disposed between both surface layers, said first microporous layer comprising (a) a first polyethylene resin containing 8% or more by mass of ultra-high-molecular-weight polyethylene having a weight-average molecular weight of 1×10 6 or more, based on the total mass of the polyethylene in the first microporous layer, and (b) 25% or less by mass of polypropylene based on the total mass of the polyethylene and the polypropylene in the first microporous layer, said second microporous layer comprising a second polyethylene resin containing 7% or less by mass of said ultra-high-molecular-weight polyethylene, and having a structure in which a pore diameter distribution curve obtained by mercury intrusion porosimetry has at least two peaks, and the total thickness of said first microporous layers being 15-60% per 100% of the total thickness of said first and second microporous layers, comprising the steps of (1) preparing a first polyolefin solution comprising a first polyethylene resin containing 8% or more by mass of ultra-high-molecular-weight polyethylene having a weight-average molecular weight of 1×10 6 or more based on the total mass of the polyethylene in the first polyethylene resin, 25% or less by mass of polypropylene based on the total mass of the polyethylene and the polypropylene in the first polyethylene resin, and a membrane-forming solvent, and a second polyolefin solution comprising a second polyethylene resin containing 7% or less by mass of said ultra-high-molecular-weight polyethylene and a membrane-forming solvent, (2) extruding said first and second polyolefin solutions through separate dies, (3) cooling the resultant extrudates to form first and second gel-like sheets, (4) stretching each gel-like sheet, (5) removing said membrane-forming solvent from each stretched gel-like sheet to form first and second microporous polyolefin membranes, (6) stretching at least said second microporous polyolefin membrane to 1.1-1.8 folds in at least one direction, and (7) laminating said first and second microporous polyolefin membranes, such that said first microporous polyolefin membrane forms at least both surface layers, while said second microporous polyolefin membrane forms at least one layer between both surface layers.