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Wo 2010/147798 A2 (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date 23 December 2010 (23.12.2010) WO 2010/147798 A2 (51) International Patent Classification: hara, Asaka-shi, Saitama-ken, 35 1-0025 (JP). BRANT, BOlD 67/00 (2006.01) C08J 5/18 (2006.01) Patrick [US/US]; 1038 Shorewood Drive, Seabrook, TX BOlD 71/00 (2006.01) HOlM 2/16 (2006.01) 77586 (US). (21) International Application Number: (74) Agents: HUGHES, Gerard J. et al; Exxon Mobil Chem PCT/US2010/037755 ical Company, Law Technology, P.O. Box 2149, Bay- town, TX 77522-2149 (US). (22) International Filing Date: 8 June 2010 (08.06.2010) (81) Designated States (unless otherwise indicated, for every kind of national protection available): AE, AG, AL, AM, English (25) Filing Language: AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, (26) Publication Language: English CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (30) Priority Data: HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, 61/218,720 19 June 2009 (19.06.2009) US KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, 09168193.2 19 August 2009 (19.08.2009) EP ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, 61/298,756 27 January 2010 (27.01 .2010) US NO, NZ, OM, PE, PG, PH, PL, PT, RO, RS, RU, SC, SD, 61/298,752 27 January 2010 (27.01 .2010) US SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, 61/346,675 20 May 2010 (20.05.2010) US TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. 61/35 1,380 4 June 2010 (04.06.2010) US (84) Designated States (unless otherwise indicated, for every (71) Applicant (for all designated States except US): TORAY kind of regional protection available): ARIPO (BW, GH, TONEN SPECIALTY SEPARATOR GODO KAISHA GM, KE, LR, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, [JP/JP]; 8-15 Kohnan, 1-Chome, Minato-ku, Tokyo, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, 108-8005 (JP). TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, (71) Applicant (for GB only): EXXONMOBIL CHEMICAL EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, PATENTS INC. [US/US]; 5200 Bayway Drive, Bay- LV, MC, MK, MT, NL, NO, PL, PT, RO, SE, SI, SK, town, TX 77520-2101 (US). SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, ML, MR, NE, SN, TD, TG). (72) Inventors; and (75) Inventors/Applicants (for US only): ISHIHARA, Published: Takeshi [JP/JP]; 272-16 Namiki, Kawagoe-shi, Saitama- — without international search report and to be republished ken, 350-0023 (JP). MIYAOKA, Satoshi [JP/JP]; 5-91-9 upon receipt of that report (Rule 48.2(g)) A-301, Higashi-Mishima, Nasushiobara-shi, Tochigi-ken, 329-275 1 (JP). KONO, Koichi [JP/JP]; 3-29-10-404, Mi- (54) Title: MICROPOROUS MEMBRANES, METHODS FOR MAKING SUCH MEMBRANES, AND THE USE OF SUCH MEMBRANES AS BATTERY SEPARATOR FILM PMP content (wt.%) Figure 1 (57) Abstract: The present invention relates to microporous membranes comprising polymer and having well-balanced permeabil- ity and heat shrinkage, especially heat shrinkage at elevated temperature. The invention also relates to methods for making such membranes, and the use of such membranes as battery separator film in, e.g., lithium ion secondary batteries. MICROPOROUS MEMBRANES, METHODS FOR MAKING SUCH MEMBRANES, AND THE USE OF SUCH MEMBRANES AS BATTERY SEPARATOR FILM CROSS REFERENCE RELATED TO APPLICATION [0001] The present application claims priority from U.S.S.N. 61/218,720, filed June 19, 2009 and EP 09168193.2, filed August 19, 2009, and claims the benefit of and priority from U.S.S.N. 61/298,752, filed January 27, 2010; U.S.S.N. 61/298,756, filed January 27, 2010; U.S.S.N. 61/346,675, filed May 20, 2010, and U.S.S.N. 61/351,380, filed June 4, 2010, all of which are incorporated by reference in their entirety. FIELD OF THE INVENTION [0002] The present invention relates to microporous membranes comprising polymer and having well-balanced permeability and heat shrinkage, especially heat shrinkage at elevated temperature. The invention also relates to methods for making such membranes, and the use of such membranes as battery separator film in, e.g., lithium ion secondary batteries. BACKGROUND OF THE INVENTION [0003] Microporous membranes are useful as separators for primary and secondary batteries. Such batteries include lithium ion secondary batteries, lithium-polymer secondary batteries, nickel-hydrogen batteries, nickel-cadmium batteries, nickel-zinc batteries, silver-zinc batteries, etc. [0004] It is desirable for a battery separator film to have a relatively low heat shrinkage, especially high temperature, in order to prevent internal short circuits. Microporous membranes having a heat shrinkage in the range of about 1.0% to 10.0% at 105 0C have been made using polyolefin. For example, JP60-242035A discloses a membrane made by a process comprising molding a gel-like sheet made by extruding a solution containing solvent and polyolefin having a weight average molecular weight > 7.0 x 105, removing the solvent from the gel-like sheet, and then stretching the gel-like sheet. [0005] It is also desirable for microporous membranes to have a relatively high meltdown temperature and a relatively low shutdown temperature to improve battery safety margin. Japanese patent applications JP59-196706A and JP61-227804A disclose the use of polymethylpentene (PMP) to increase membrane meltdown temperature. These membranes, however, have a relatively high shutdown temperature. Japanese patent applications JP07-060084A and JP3634397B disclose microporous membrane comprising polyethylene and polymethylpentene, the membrane being produced by mixing polyethylene and polymethylpentene with solvent or third polymer. The film is said to have a relatively low shutdown temperature and a relatively high meltdown temperature. Further, U.S. Patent No. 6096213 discloses a method for making membrane comprising polyethylene and polymethylpentene without using any solvent or third polymer. Japanese patent application JP2004-161899A discloses a microporous membrane comprising polyethylene and polymethylpentene having a relatively high air permeability and a low heat shrinkage at 105°C. Japanese patent application JP2005-145999 discloses a microporous membrane comprising polymethylpentene and alpha-olefm copolymer. While polymethylpentene has been used to improve the properties of microporous membranes, further improvements are desired. SUMMARY OF THE INVENTION [0006] In an embodiment, the invention relates to a microporous membrane having at least one layer, the layer comprising polymethylpentene in an amount in the range of 22.0 wt.% to 40.0 wt.% based on the weight of the layer, the membrane having an air permeability < 1.0 x 103 seconds/100 cm3/20µm, a TD heat shrinkage at 105 0C < 2.1%, and a TD heat shrinkage at 1300C < 25.0%. [0007] In another embodiment, the invention relates to a process for producing a microporous membrane, comprising: (1) extruding a mixture comprising diluent and polymer to produce an extrudate having at least one layer, the layer comprising 22.0 wt.% to 40.0 wt.% of polymethylpentene based on the weight of the polymer in the layer; (2) stretching the extrudate in at least one planar direction; and (3) removing at least a portion of the diluent from the stretched extrudate. [0008] In another embodiment the invention relates to the microporous membrane produced by the preceding process. [0009] In another embodiment, the invention relates to a battery comprising an electrolyte, an anode, a cathode, and a separator situated between the anode and the cathode, wherein the separator comprises a microporous membrane of any preceding embodiment. [0010] In yet another embodiment, the invention relates to the use of such a battery as a power source in, e.g., an electric vehicle, hybrid electric vehicle, power tool, computer, mobile phone, consumer electronics, etc. BRIEF DESCRIPTION OF THE FIGURES [0011] Figures 1-3 illustrate the effect of polymethylpentene content on membrane air permeability (Figure 1), meltdown temperature (Figure 2) and TD heat shrinkage at 105.00C (Figure 3). The figures show that a polymethylpentene content of < 22.0 wt.% results in lower meltdown temperature and increased 105.00C heat shrinkage, but a content of > 40.0 wt.% diminishes air permeability. DETAILED DESCRIPTION OF THE INVENTION [0012] The invention is based on the discovery of microporous membranes comprising polymethylpentene ("PMP") and having desirable air permeability, meltdown temperature, and heat shrink values resulting from the selection of PMP amount. As shown in the Figure 1, membrane air permeability decreases significantly when the PMP content is > 40.0 wt.%. The membrane's meltdown temperature increases significantly when PMP content is > 22.0 wt.%. The membrane's 105.00C heat shrinkage (shown in Figure 3) is relatively high when PMP content is < 22.0 wt.%, but decreases significantly above this value. The PMP used in the membranes exemplified in Figures 1-3 has a Tm of 222.00C and an MFR of 2 1 dg/min. (Mitsui Chemicals, Inc. TPX: MX002). [0013] These test results for these membranes are tabulated in Table A, together with air permeability, meltdown heat shrinkage values (TD) at 130.00C and 170.00C, which are representative of the membrane's thermal stability in batteries at overcharge or short-circuit conditions. Membrane PMP content is in the range of 0 wt.% to 50.0 wt.%, based on the weight of the membrane, with the remainder being polyethylene.
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