Microporous polyethylene film manufactured according to liquid-liquid phase separation and method of producing the same
View Patent ↗Disclosed in the present invention are a microporous polyethylene film and a method of manufacture thereof. The polyethylene microporous film manufactured according to the present invention may contribute to an increased productivity of stable products as its extrusion and stretching may be done readily. And thus manufactured product may be used for battery separators and various filters owing to its high gas permeability, superior puncture strength, and small ratio of shrinkage.
1. A method of manufacturing a microporous polyethylene film, comprising the steps of:
melt-mixing a resin mixture, containing 20-55 weight % of polyethylene (component I) and 80-45 weight % of a diluent (component II) having a liquid-liquid phase separation property from the polyethylene (the component I) at a liquid-liquid separation temperature of 160-280° C., at a temperature higher than the liquid-liquid phase separation temperature to make a molten material of thermodynamic single phase,
carrying out liquid-liquid phase separation by passing the molten material of single phase through a phase separating zone which is maintained at a temperature which is lower than the temperature of liquid-liquid phase separation −10° C. for a residence time of longer than 30 seconds;
molding the liquid-liquid separated molten material in the form of a sheet;
stretching the sheet in the form of a film;
extracting the diluent (component II) from the film to make a microporous polyethylene film and drying the microporous polyethylene film; and
heat-setting the dried microporous polyethylene film by removing residual stress to have a shrinkage percentage of the film of 5% or less.
2. The method of claim 1 , wherein the phase separating zone is provided in an extruder.
3. The method of claim 1 , characterized by that the polyethylene has a average molecular weight in the range of from 2×10 5 to 4.5×10 5 .
4. The method of claim 1 , characterized by that said component II is one or more components selected from phthalic acid esters selected from the group consisting of dibutyl phthalate, dihexyl phthalate and dioctyl phthalate; aromatic ethers selected from the group consisting of diphenyl ether and benzyl ether; aliphatic acids having 10 to 20 carbon atoms selected from the group consisting of palmitic acid, stearic acid, oleic acid, linoleic acid and linolenic acid; aliphatic alcohols having 10 to 20 carbon atoms selected from the group consisting of palmityl alcohol, stearyl alcohol and oleyl alcohol; and among saturated and unsaturated fatty acids having 4 to 26 carbon atoms in the fatty acid group, fatty acid esters in which one or more fatty acids are combined through esterification with alcohols having 1 to 8 hydroxy radicals and 1 to 10 carbon atoms selected from the group consisting of palmitic acid mono-, di-, or triester; stearic acid mono-, di-, or triester; oleic acid mono-, di-, or triester; and linoleic acid mono-, di-, or triester.
5. The method of claim 4 , characterized by that said component II further contains one or more components selected from the group consisting of a paraffin oil, mineral oil, and wax.
6. The method of claim 1 , characterized by that the molding of the liquid-liquid separated molten material is molded in the form of a sheet by extruding through a die or by a casting or calendering method using a water-cooling and air-cooling method.
7. The method claim 1 , characterized by that said heat-setting is done within a temperature range within which 10-30 weight % of the crystalline portion of the extracted and dried film is molten in the tenter method in which the time for heat-setting is for 15 seconds to 2 minutes.
8. The microporous polyethylene film manufactured according to a method in claim 1 .
9. The microporous polyethylene film of claim 8 , characterized by that said microporous polyethylene film has a gas permeability (Darcy's permeability constant) of 2.0×10 −5 or greater, puncture strength of 0.17 N/μm or greater, multiplication of said gas permeability and said puncture strength of 0.45×10 −5 Darcy. N/μm or greater, and ratio of shrinkage in each of machine and traverse directions of 5% or less.
10. The microporous polyethylene film manufactured according to a method in claim 2 .
11. The microporous polyethylene film manufactured according to a method in claim 3 .
12. The microporous polyethylene film manufactured according to a method in claim 4 .
13. The microporous polyethylene film manufactured according to a method in claim 5 .
14. The microporous polyethylene film manufactured according to a method in claim 6 .
15. The microporous polyethylene film manufactured according to a method in claim 7 .