WO2007046226A1 - 蓄電デバイスセパレータ用微多孔フィルムおよびそれを用いた蓄電デバイスセパレータ - Google Patents
蓄電デバイスセパレータ用微多孔フィルムおよびそれを用いた蓄電デバイスセパレータ Download PDFInfo
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- WO2007046226A1 WO2007046226A1 PCT/JP2006/319408 JP2006319408W WO2007046226A1 WO 2007046226 A1 WO2007046226 A1 WO 2007046226A1 JP 2006319408 W JP2006319408 W JP 2006319408W WO 2007046226 A1 WO2007046226 A1 WO 2007046226A1
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- Prior art keywords
- film
- storage device
- polypropylene
- electricity storage
- stretching
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- 238000004080 punching Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- OKUCEQDKBKYEJY-UHFFFAOYSA-N tert-butyl 3-(methylamino)pyrrolidine-1-carboxylate Chemical compound CNC1CCN(C(=O)OC(C)(C)C)C1 OKUCEQDKBKYEJY-UHFFFAOYSA-N 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- DJZKNOVUNYPPEE-UHFFFAOYSA-N tetradecane-1,4,11,14-tetracarboxamide Chemical compound NC(=O)CCCC(C(N)=O)CCCCCCC(C(N)=O)CCCC(N)=O DJZKNOVUNYPPEE-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005590 trimellitic acid group Chemical group 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/02—Diaphragms; Separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/494—Tensile strength
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a microporous film for an electricity storage device separator suitable for various electricity storage devices such as lithium ion batteries. Specifically, compared to conventional microporous films for power storage device separators, the power storage capacity can be increased and the energy density and output density of power storage devices using such films as separators can be increased.
- the present invention relates to a microporous film for a device separator.
- the present invention also relates to a microporous film for an electricity storage device separator that has a high balance between high porosity and longitudinal strength, and has excellent handling properties when the film is processed as an electricity storage device separator. Furthermore, due to its characteristics, the present invention relates to an electricity storage device having a higher energy density and output density than the conventional electricity storage device by using the microporous film as a separator.
- An electricity storage device is one of the extremely important electrical devices that support today's ubiquitous society because it can extract electrical energy whenever and wherever needed.
- portable devices such as video cameras, personal computers, mobile phones, portable music players, and portable game machines
- the need for high-capacity, small-sized and lightweight storage devices is increasing year by year.
- lithium-ion batteries have a large output density with high energy density per unit volume and mass compared to other electricity storage devices, and as a result, there is a great increase in demand as an electricity storage device that satisfies the above needs. .
- EV electric vehicles
- HEV hybrid electric vehicles
- FCV next-generation fuel measures
- main power supply and auxiliary power supply for example, lithium ion batteries, electric double layer capacitors and the like are attracting attention, and their application is being studied rapidly.
- the lithium ion battery generally has a cylindrical shape, a square shape, a coin shape, a laminate shape, or the like.
- the inside of these batteries has a configuration in which a positive electrode and a negative electrode are separated from the separator coil spirally arranged (winding type, spiral type), and whether these are alternately stacked in a single sheet.
- the configuration conforms to that (stacked type, stacked type).
- the required characteristics of the lithium ion battery separator mainly include isolation characteristics, battery assembly characteristics, battery characteristics, and the like.
- the isolation characteristic is the most basic characteristic required for a separator.
- the separator is electrically isolated without short-circuiting the positive electrode and the negative electrode, and has ion permeability when impregnated with an electrolytic solution. It is required to be inert to the liquid or in the electrochemical reaction field (chemical resistance, oxidation resistance / reduction resistance). In particular, it is important for the separator to have no pinholes or cracks in order to prevent a short circuit between the positive electrode and the negative electrode.
- battery assemblability is required particularly when applied to a wound battery.
- electrodes and separators are stacked and wound into a spiral at high speed.
- the electrode has irregularities, and a peeled product may be generated during high-speed cutting.
- the separator wound at a high speed is broken due to the unevenness and peeled material described above, resulting in poor insulation of the battery. It is required not to. That is, it is important that the puncture strength of the separator is high.
- Battery characteristics include excellent current characteristics such as charge / discharge performance at high current (rate characteristics), charge / discharge performance at low temperatures, and the ability to repeat charge / discharge over a long period of time. (Cyclic characteristics), battery capacity can be maintained at high temperatures (heat resistance), and thermal runaway associated with battery temperature increase due to overcharging etc. can be prevented (current interruption) (shutdown) .
- rate characteristics charge / discharge performance at high current
- current interruption current interruption
- shutdown current interruption
- the internal configuration of the battery such as the selection of the active material for the positive and negative electrodes and the improvement of the packing density, are also important.
- the decomposition product of the electrolyte is less likely to clog the surface pores of the separator.
- the liquid retention of the injected electrolyte and the heat resistance of the separator itself are also important.
- Shutdown is one of the battery safety devices. When the temperature rises due to a runaway reaction, the separator melts instantly. * The hole closes and completely shuts off the current. It is important to form a continuous layer that does not break, and to continue interrupting the current.
- a chemically stable polyolefin-based microporous film represented by polyethylene and polypropylene is mainly used as a separator of a lithium ion battery.
- the pore forming method of the microporous polyolefin film is generally roughly classified into a wet method and a dry method.
- a wet method the extractables are added to polyolefin and finely dispersed, and after forming into a sheet, the extractables are extracted with a solvent or the like to form pores, and stretched before extraction and after Z or as necessary.
- an extraction method having a process for processing for example, see Patent Document 1
- an unstretched sheet with a special crystalline lamella structure is produced by using special melt crystallization conditions of low temperature extrusion and high draft during sheet extrusion by melt extrusion, and this is mainly uniaxially stretched.
- a lamella extension method in which a lamellar interface is cleaved to form a hole (see, for example, Patent Document 2 and Non-Patent Document 1).
- an unstretched sheet obtained by adding a large amount of incompatible particles such as inorganic particles to polyolefin is stretched.
- an inorganic particle method in which pores are formed by peeling the interface between different materials (see, for example, Patent Document 3).
- a low crystal density j8 crystal (crystal density: 0.992 gZcm 3 ) was formed during the preparation of an unstretched sheet by melt extrusion of polypropylene, and by stretching this, ⁇ crystal (crystal density: 0.
- ⁇ crystal crystal density: 0.
- a ⁇ -crystal method for example, see Patent Documents 4 to 9 and Non-Patent Document 2 in which crystal transition is performed to 936 g / cm 3 ) and pores are formed by the difference in crystal density between the two.
- the separator using the microporous polyolefin film is, for example, a polyolefin microporous membrane in which the average pore diameter and the average pore diameter of at least one surface are in a specific range, and a lithium ion battery comprising the same It consists of a separator (see Patent Document 13), a polyolefin microporous membrane with a specific range of compressive deformation rate and pin puncture strength, a lithium ion battery separator (see Patent Document 14), and a polyolefin resin.
- Patent Document 1 Japanese Patent No. 1299979 (Claim 1)
- Patent Document 2 Japanese Patent No. 1046436 (Claim 1)
- Patent Document 3 Japanese Patent No. 1638935 (Claims 1-7)
- Patent Document 4 Japanese Patent No. 2509030 (Claims 1 to 8)
- Patent Document 5 Japanese Patent No. 3443934 (Claims 1 to 5)
- Patent Document 6 Japanese Patent Laid-Open No. 7-118429 (Claims 1 to 3, Examples 1 to 9)
- Patent Document 7 Japanese Patent No. 3523404 (Claim 1)
- Patent Document 8 Pamphlet of International Publication No. 02Z66233 (Claims 1 to: L 1)
- Patent Document 9 Japanese Patent Laid-Open No. 2005-171230 (Claims 1 to 18, Examples 1 to 8)
- Patent Document 10 Japanese Patent No. 2055797 (Claims 1 to 8)
- Patent Document 11 Japanese Patent No. 3243835 (Claim 1)
- Patent Document 12 U.S. Pat.No. 6596814 (Claims 1 to 31, second page, first paragraph, lines 18 to 50, Examples 1 to 3, Comparative Example 4)
- Patent Document 13 Japanese Patent Application Laid-Open No. 2000-212323 (Claims 1 to 3, conventional techniques)
- Patent Document 14 Japanese Unexamined Patent Publication No. 2000-212322 (Claims 1 to 3)
- Patent Document 15 Japanese Patent Application Laid-Open No. 2001-2826 (Claims 1 to 8, conventional technology)
- Patent Document 16 Japanese Patent Laid-Open No. 2000-30683 (Claims 1 to 12, Examples 1 to L0)
- Non-patent Document 1 Adachi et al., “Chemical Industry”, 47th, 1997, p. 47-52
- Non-Patent Document 2 M. Xu et al., “Polymers for Advanced Technologies”
- Non-Patent Document 3 Fujiyama
- Polymer Processing Vol. 38, 1989, p. 35-41
- these power storage device separators or microporous films used therefor have to have increased porosity or thin films to improve battery characteristics. Is being sought.
- an electricity storage device manufactured without winding such as a stacked lithium ion battery, does not necessarily require high piercing strength, i.e., low porosity, but rather has high porosity.
- an electricity storage device separator having excellent handling properties is also required.
- the conventional microporous films of Patent Documents 1 to 9 and 12 to 16 described above or the electricity storage device separator using the same are generally excellent in piercing strength. The porosity is about 50 to 60%. Since the transmission performance was not necessarily high, the battery performance was inferior.
- Patent Document 6 discloses a microporous film obtained by the ⁇ crystal method (for example, Example 2), but has poor reproducibility and low strength in the vertical direction, and is inferior in handling properties.
- the non-compatible molten resin added to the film falls off after the processing step into the power storage device, assembly of the power storage device, or dissolves in the electrolytic solution.
- problems such as worsening the yield when manufacturing power storage devices and increasing the internal resistance of power storage devices, which may deteriorate quality.
- An object of the present invention is mainly to solve the above-mentioned problems, and is extremely empty as compared with a conventional microporous film for an electricity storage device separator in which process contamination by components constituting the film is small.
- a microporous film for a power storage device separator that has a high porosity, excellent handling properties, and excellent permeability, and that can enhance the battery characteristics of a power storage device using the film as a separator, and a power storage using the film
- a device separator and an electricity storage device using the separator are provided.
- the microporous film for an electricity storage device separator of the present invention mainly has a porosity of 70% or more, a longitudinal strength of 40 MPa or more, an average pore diameter of 40 to 400 nm, and It has a non-nuclear hole and is biaxially oriented.
- a film having polypropylene as a main component, having ⁇ -crystal activity, and a film in the azimuth direction of (113) plane by X-ray diffraction method In the in-plane intensity distribution profile:
- the Gurley permeability is 00 sec / 100ml or less.
- an electricity storage device separator using the microporous film is also preferred, an electricity storage device comprising a positive electrode, a negative electrode, and an electrolyte, and the electricity storage device is a lithium ion battery It is also preferable to be an electrolytic capacitor or an electric double layer capacitor.
- the microporous film for an electricity storage device separator of the present invention has an extremely high porosity and high permeability as compared with a conventional microporous film. Therefore, an electricity storage device using the film as a separator. Energy density and power density can be improved. In addition, the film stretches, wrinkles, and breaks during the processing of the electricity storage device using the film as a separator, although the film has high porosity in spite of high porosity. Excellent handleability. In addition, the separator itself can be made thin while maintaining the handling properties as necessary, thereby increasing the capacity of the electricity storage device. Thus, the microporous film for an electricity storage device separator of the present invention can be widely used as a film for a high performance separator that can actively contribute to the enhancement of the performance of an electricity storage device rather than an auxiliary material for the electricity storage device.
- the porosity of the microporous film for an electricity storage device separator of the present invention is 70% or more.
- conventional microporous films for power storage device separators it is virtually impossible to achieve such a high porosity, or it is very difficult to maintain other required characteristics and productivity.
- the upper limit of the achievable porosity was around 60%.
- the extremely high porosity corresponds to the fact that the pores are dense and formed in large quantities.
- the microporous film for an electricity storage device separator of the present invention has a porosity in the above range, so that the permeability can be remarkably enhanced, and the electrolyte can be injected instantaneously in the electricity storage device assembly process. At the same time, more electrolyte can be retained. In addition, it is possible to obtain a film excellent in the liquid retention of the electrolytic solution thereafter. Furthermore, for example, when used as a separator for a lithium ion secondary battery, a battery having a high energy density and capacity may be obtained. The internal resistance of the battery can be lowered and the output density can be improved. As described above, the microporous film for an electricity storage device separator of the present invention can be used as a separator that can actively contribute to higher performance of the electricity storage device than the auxiliary material of the electricity storage device because of its high porosity. .
- the addition amount of j8 crystal nucleating agent is an appropriate amount, more preferably the addition amount is 0.05 to 0.2% by weight; HMS— Add PP, more preferably the amount of added calories is 0.5-5% by weight; mVLDPE is added, more preferably the amount of added force is 1-: LO wt% Cast drum temperature should be 110-125 ° C; contact time with cast drum should be 8 seconds or longer; when manufacturing by longitudinal and transverse sequential biaxial stretching method, longitudinal stretch ratio should be 5-10 Double stretching, longitudinal stretching temperature of 95-120 ° C, transverse stretching temperature of 130-150 ° C, transverse stretching speed of 100-10000%, more preferably 1 000% Z It is important to make it less than minutes.
- the porosity of the microporous film for an electricity storage device separator of the present invention is more preferably 72% or more, still more preferably 73% or more, and even more preferably 75% or more. Further, in the present invention, the higher the porosity, the higher the force that tends to obtain the above-mentioned good effect. If the porosity is too high, the film forming process results in many film tears, resulting in poor film forming properties. The film tends to stretch, crack, or break in the subsequent heating process of the electricity storage device due to excessive or poor mechanical properties. If this phenomenon is observed, the film is said to be inferior in process passability, secondary strength or handling properties).
- the longitudinal strength of the microporous film for an electricity storage device separator of the present invention is 40 MPa or more.
- the porosity is remarkably increased, the mechanical properties such as the strength of the film are impaired, and it is very difficult to balance both characteristics at a high level.
- the power storage device using the separator having the microporous film force is used. In the processing process, the film does not stretch, become wrinkled or break, and has excellent handling properties.
- the longitudinal strength of the microporous film for an electricity storage device separator of the present invention is more preferably 45 MPa or more, and still more preferably 50 MPa or more. Further, in the present invention, the higher the strength in the vertical direction, the more the force that tends to be excellent in the above-described nodling property, and if the strength is too high, the power will be excessively shrunk in the lateral direction in the processing step for the power storage device. For example, it is preferably 150 MPa or less because the permeability performance may be inferior.
- the strength of the microporous film for an electricity storage device separator of the present invention is preferably as follows, for example. That is, the crystallinity (corresponding to wrinkles) of polypropylene is high as shown below, and can be controlled by the porosity, orientation state (orientation state in the film plane) of the microporous film obtained.
- the higher the plane orientation the higher the strength, so the control of the orientation state is important.
- the film is produced by stretching in at least one direction in the film forming process
- the plane orientation of the microporous film can be increased as the stretching condition is higher or lower.
- the longitudinal stretching ratio should be increased, more preferably 5 to 10 times; It is effective to lower the temperature, more preferably 95 to 110 ° C.
- the average pore size of the microporous film for an electricity storage device separator of the present invention is 40 to 400 nm.
- the average pore diameter is measured according to the so-called bubble point method of JIS K 3832 (1990).
- the lithium ion conductivity and the separation characteristics between the positive electrode and the negative electrode blocking of the active material, formation of precipitates / growth / prevention of passage, electrical insulation
- the average pore diameter is higher, and the power density can be improved as it becomes higher.
- the average pore diameter is more preferably 43 to 400 nm, and still more preferably 45 to 400 nm. is there.
- the lower limit is particularly preferably 52 nm, more preferably more than 55 nm, and most preferably 60 nm or more.
- the film is a microporous polypropylene film by the ⁇ crystal method
- it is difficult to significantly increase the average pore diameter simply by changing the film forming conditions such as temperature and magnification.
- the resulting film may have an uneven pore structure.
- a uniform and dense pore structure and a nucleus-free pore can be formed.
- it can be achieved by adding the following mVLDPE).
- the resin for example, by finely dispersing in polypropylene, pore formation is promoted by interfacial peeling at the time of stretching without forming coarse pores, and melted during the production process. It is possible to form non-nucleated holes in the resulting film.
- the average pore diameter can be extremely increased by setting the stretching speed in the stretching process in at least one direction to less than 1000% Z as described below.
- the microporous film for an electricity storage device separator of the present invention needs to be biaxially oriented.
- toughness can be imparted to the film and it is difficult to tear in any direction.
- the film can be broken in the processing step to the electricity storage device using the separator having the microporous film force.
- the film does not shrink excessively in the lateral direction during the processing of the electricity storage device.
- Examples of the method for biaxially orienting the microporous film of the present invention include various biaxial stretching methods such as simultaneous biaxial stretching, sequential biaxial stretching, and subsequent re-stretching.
- the microporous film for an electricity storage device separator of the present invention has substantially nucleus-free pores.
- the “nuclear-free hole” in the present invention is a hole in which a nucleus for hole formation is not observed in the inside, such as a resin or particle that induces hole formation by stretching or the like. Defined. As shown below, when these ultra-thin sections of the film are observed under specific conditions using a transmission electron microscope (TEM), nothing is observed inside the holes. This On the other hand, in the above TEM observation image, a hole having a spherical shape, a fibrous shape, an indefinite shape, or other shape is observed in a hole that does not correspond to a non-nucleated hole.
- TEM transmission electron microscope
- “having non-nuclear holes” means that all nuclei in the entire observation visual field area (total area of the film) in the TEM observation image as shown in the following measurement method (4).
- the area ratio (R) is defined as 3% or less, and in this case, the microporous film has non-nucleated pores. At this time, even if there are a few pores with nuclei from a microscopic viewpoint, it may be detected as a film having nuclei-free pores by the above method, but the ratio R calculated by this method is within the above range. If so, the object of the present invention is achieved.
- the microporous film for an electricity storage device separator of the present invention has a non-nucleated hole and does not depend on the formation of a hole using a nucleus, a uniform and dense hole structure can be formed.
- a film having no coarse void formed from the nucleus is difficult to cleave.
- the cleaving of the film means a phenomenon that the film is torn into a plurality of sheets approximately parallel to the surface.
- impurities that can become the internal resistance of the power storage device from the separator are prevented from dropping off and Z or dissolving.
- the film In order for the film to have non-nucleated pores as described above, it is important that the main polymer constituting the film has low compatibility or affinity and that different polymers and particles are not added as much as possible.
- the above-mentioned R is more preferably 2% or less, more preferably 1% or less, and still more preferably substantially 0%.
- the resin constituting the microporous film for the electricity storage device separator of the present invention includes a polyolefin resin, a halogenated resin, a polyester resin, a polyamide resin, and a polyphenylene sulfide. Examples thereof include, but are not limited to, as long as the effects of the present invention are exhibited. Desirable permeability, dimensional stability, rigidity, heat resistance, chemical resistance of the microporous film of the present invention are included. In order to impart oxidation resistance / reduction properties, etc., it may be selected as appropriate. In short, it is used for the microporous film for the electricity storage device separator of the present invention.
- the resin may be composed of two or more kinds of resin if appropriately selected according to the purpose. However, as shown below, it is necessary that the resulting microporous film has a nucleus-free pore.
- Examples of the monomer component constituting the polyolefin-based resin include ethylene, propylene, 1-butene, 1-pentene, 3-methinorepentene, 1, 3-methinole 1-butene, and 1- Xene, 4-methyl 1-pentene, 5 ethyl 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eicosene, butylcyclohexene, styrene, arylbenzene, cyclopentene, norbornene, 5-methyl-2-norbornene, and the like.
- homopolymers and at least two kinds of copolymers selected from the above monomer components are listed. Examples thereof include, but are not limited to, and blends of these homopolymers and copolymers.
- monomer components for example, butyl alcohol, maleic anhydride, acrylic acid compounds and the like may be copolymerized or graft polymerized.
- the present invention is not limited to these.
- Examples of the vinyl halide-based resin include, but are not limited to, powers including, for example, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene, and polytetrafluoroethylene.
- polyester-based resin examples include, but are not limited to, a polyester having a dicarboxylic acid component and a glycol component as main components.
- aromatic dicarboxylic acid As the strong dicarboxylic acid component, aromatic dicarboxylic acid, aliphatic dicarboxylic acid, alicyclic dicarboxylic acid and the like can be used.
- aromatic dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 1,4 naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6 naphthalenedicarboxylic acid, 4,4'-diphenyldicarbon Examples include acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenyl sulfone dicarboxylic acid, 5-sodium sulfoisophthalic acid, and phenylndane dicarboxylic acid.
- Examples of the aliphatic dicarboxylic acid component include succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, and eicosandioic acid. I can get lost.
- Examples of the alicyclic dicarboxylic acid component include 1,4-cyclohexanedicarboxylic acid. These acid components may be used alone or in combination of two or more, or may be partially copolymerized with oxyacids such as hydroxybenzoic acid.
- glycol component examples include ethylene glycol, 1,2 propanediol, 1,3 propanediol, neopentyl glycol, 1,3 butanediol, 1,4 butanediol, 1,5 pentanediol, 1 , 6 hexanediol, 1,2 cyclohexane dimethanol, 1,3 cyclohexane dimethanol, 1,4-cyclohexane dimethanol, spiroglycol, diethylene glycol, triethylene glycol, polyalkylene glycol, 2, 2 ′ bis (4′—j8-hydroxyethoxyphenol) propane or the like can be used.
- ethylene glycol 1,4 butanediol, 1,6 hexanediol, 1,4-cyclohexanedimethanol, spiroglycol and the like are preferably used. These glycol components may be used alone or in combination of two or more.
- the polyester is trimellitic acid, trimesic acid, pentaerythritol, trimethylolpropane.
- polyfunctional compounds such as glycerin and oxydicarboxylic acids such as p-oxybenzoic acid may be copolymerized! /.
- the polyester-based resin is preferably polyethylene terephthalate, a copolymer of ethylene terephthalate and ethylene isophthalate, polyethylene 2, 6 naphthalate, polybutylene terephthalate, a copolymer of butylene terephthalate and ethylene terephthalate.
- the force which can use these blends etc. is not necessarily limited to these.
- polyamide-based resin examples include nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, polyethylene isophthalamide, polymetaxylene azinamide, poly (hexamethylene isophthalamide Z terephthalamide). ), Poly (hexamethylene terephthalamide Z mono) Methinoreterephthalamide), Hexamethyleneisophthalamide, Copolymer of Z-terephthalamide and ⁇ -Force Prolactam, Copolymer of Hexamethyleneterephthalamide and Hexamethyleneadipamide, and these forces However, it is not limited to these.
- Examples of the polyphenylene sulfide-based resin include (co) polymers in which 70 mol% or more, more preferably 85 mol% or more of the repeating units also have thio-1,4-phenylene power.
- the resin can be obtained by reacting an alkali metal sulfate and paradihalobenzene in a polar solvent at a high temperature. More preferably, sodium sulfate and paradichlorobenzene are used in a high boiling point solvent such as ⁇ -methyl monopyrrolidone at 230-280 ° C to adjust the degree of polymerization as necessary. It can be obtained by adding a polymerization aid such as carboxylic acid alkali metal salt and reacting them.
- the polyimide-based resin is exemplified by, for example, one or more compounds selected from aromatic diamine compounds exemplified by 4,4'-diaminodiphenyl ether and pyromellitic dianhydride.
- Aromatic tetracarboxylic acid-compound strength It can be obtained by subjecting a polyamic acid compound obtained by polymerizing one or more selected compounds to cyclization or thermal ring closure and then drying.
- the resin constituting the microporous film for an electricity storage device separator of the present invention includes a flame retardant, a heat stabilizer, a weathering material, an antioxidant, an ultraviolet absorber, a light stabilizer, a foam, depending on the purpose.
- Various additives such as an inhibitor, a copper damage resistance stabilizer, an antistatic agent, a pigment, a plasticizer, a terminal blocker, and an organic lubricant may be added as long as the effects of the present invention are exhibited.
- the resin constituting the microporous film for an electricity storage device separator of the present invention produces the microporous film of the present invention within a range that does not impair the characteristics of the present invention from the viewpoint of economy. It is also possible to use a blend of scrap film generated during the manufacturing process or scrap film generated when other films are manufactured. However, as shown below, it is necessary to have microporous film force-free core pores.
- the resin constituting the microporous film for an electricity storage device separator of the present invention includes heat resistance, shutdown temperature control, moldability, production cost reduction, chemical resistance, oxidation resistance and reduction. From the standpoint of properties, it is preferable to use polyolefin-based resin.
- the microporous film for an electricity storage device separator of the present invention is particularly preferably composed mainly of polypropylene.
- a main component polypropylene, for all of the polymer constituting the film refers to comprising propylene monomer 90 weight 0/0 above.
- polypropylene As the main component, it has excellent productivity and excellent heat resistance, moldability, chemical resistance, and oxidation / reduction resistance when used as an electricity storage device separator.
- the electrolytic solution may be uniformly wet without unevenness on the film, and the subsequent liquid retention may be excellent.
- the ⁇ crystal method if the propylene monomer content is less than 90% by weight, the resulting microporous film has insufficient ⁇ crystal activity, resulting in low porosity.
- the transmission performance may be inferior.
- the content of the propylene monomer is more preferably 95% by weight or more, and still more preferably 97% by weight or more based on the total amount of monomers of all the polymers constituting the film.
- Polypropylene as referred to in the present invention is preferably mainly composed of a homopolymer of propylene, but is a copolymer obtained by copolymerizing propylene and a monomer other than propylene within a range not impairing the object of the present invention.
- the copolymer may be blended! / And the copolymer may be blended with polypropylene.
- it is necessary that the resulting microporous film has a nucleus-free pore.
- Examples of monomers constituting such copolymer components and blends include ethylene, 1-butene, 1-pentene, 3-methylpentene-1, 1-methylbutene-1, 1-hexene, 4- 1-Methylpentene 1,5-Ethylhexene 1,1-Otaten, 1-decene, 1-dodecene, butylcyclohexene, styrene, aralkylbenzene, cyclopentene, norbornene, 5-methyl-2-norbornene, acrylic acid and the like Forces such as inducers are not limited to these.
- the microporous film for an electricity storage device separator according to the present invention is one of the important points for achieving high porosity and strength when polypropylene is the main component. It is preferable that high melt strength polypropylene (High Melt Strength—PP; HMS—PP) is included.
- HMS-PP high melt strength polypropylene
- the porosity can be increased. Furthermore, even if the porosity is high, the longitudinal orientation of molecular chains in the film can be promoted, and the mechanical properties in the longitudinal direction can be maintained.
- the inclusion of HMS-PP promotes the entanglement of the tie molecules in the amorphous phase that penetrate the microcrystals in the system from the casting stage, and the stretching stress is uniformly distributed throughout the system in the subsequent stretching process. Presumed to be transmitted
- the method for obtaining HMS-PP is not particularly limited, but the following methods are exemplified, and these methods are preferably used.
- the HMS-PP used in the present invention has a great effect of stability of melt extrusion, the effect of the above-described stable high-magnification stretching, the increase in porosity, and the improvement of permeability! / Therefore, polypropylene having a long chain branch in the main chain skeleton is preferred.
- the polypropylene having a long chain branch in the main chain skeleton is a polypropylene having a polypropylene chain having a branched main chain skeleton strength.
- polypropylene having a long chain branch in the main chain skeleton may have a large effect as described above.
- the step force of casting acts as a tie molecule that pseudo-crosslinks between microcrystals. It is presumed that the stretching stress is uniformly transmitted to the entire system in the subsequent stretching step.
- polypropylene having a long-chain branch in a strong main chain skeleton examples include Basell polypropylene (type names: PF-814, PF-633, PF-611, SD-632, etc.), Bore alis Examples include polypropylene (type name: WB130HMS, etc.) and Dow polypropylene (type names: D114, D201, D206, etc.).
- the amount of HMS-PP used in the present invention is not particularly limited, but the effect can be seen even when added in a small amount, preferably 0.1 to 50% by weight, based on the total amount of polypropylene in the film. .
- the mixing amount is less than the above range, the film-forming property, particularly in the case of successive biaxial stretching in the longitudinal and transverse directions, the stretching property in the transverse direction particularly when stretched at a high magnification in the longitudinal direction is deteriorated ( The film may be broken in the transverse stretching step).
- the porosity may be low or the permeability may be poor.
- the film-forming property in the case of longitudinal and transverse sequential biaxial stretching, the stretchability in the longitudinal direction particularly when stretched at a high magnification in the longitudinal direction is deteriorated (the film is stretched in the longitudinal stretching step). May cut).
- the stable discharge property of the molten polymer at the time of melt extrusion and the impact resistance of the film are deteriorated.
- the j8 crystal fraction defined below may decrease more than necessary.
- the melt flow rate (MFR) of the polypropylene is preferably 1 to 30 gZlO from the viewpoint of film forming property. If the MFR is less than the above range, melt extrusion at low temperatures becomes unstable, and it becomes difficult to form a film with a uniform thickness that requires a long time to replace the extrusion raw material. It may cause problems such as bad habits. When the MFR exceeds the above range, the landing point of the molten polymer on the metal drum greatly fluctuates when the molten polymer discharged from the slit die in the casting process is cast into a metal drum and formed into a sheet shape.
- the mesopentad fraction (mmmm) of the polypropylene constituting the film is preferably 90 to 99.5%. If the mesopentad fraction is less than the above range, the heat resistance and dimensional stability may be inferior when used as an electricity storage device separator. On the other hand, if the above range is exceeded, productivity may be deteriorated as a result of many film tears in the production process.
- the mesopentad fraction is more preferably 92 to 99%, still more preferably 93 to 99%.
- Microporous film strength for power storage device separator of the present invention When polypropylene is the main component, the isotactic index ( ⁇ ) of the polypropylene constituting the film is preferably 9 2-99.8%. . If II is less than the above range, problems such as lowering the stiffness of the film and increasing the thermal shrinkage may occur. The higher the wrinkle, the more the rigidity and dimensional stability tend to be improved. However, when the above range is exceeded, the film-forming property itself may deteriorate. II is more preferably 94 to 99.5%, and still more preferably 96 to 99%.
- the microporous film for an electricity storage device separator of the present invention contains polypropylene as a main component, from the viewpoint of assisting the formation of pores due to a peeling phenomenon at the interface between different materials, a force that is incompatible with polypropylene, Since it has high affinity, it may contain one or more polymers selected from the polyolefin-based resins other than polypropylene that are finely dispersed in polypropylene. However, in this case as well, as shown above, it is necessary that the resulting microporous film has a nucleus-free pore.
- the fact that the obtained film has nucleus-free pores despite the fact that it contains substantially non-compatible resin in polypropylene means that, for example, the resin is melted in the production process. This can be achieved.
- the first stretching step vertical stretching step in longitudinal and lateral sequential biaxial stretching
- polypropylene is used as the starting point for the formation of pores, and the formation of pores is promoted. Since the resin melts, it may be possible to prevent the process from being contaminated by the resin falling off during the film forming process. In this case, it is important to appropriately select characteristics such as the melting point of the polyolefin resin. Further, the dispersion diameter of the resin in the unstretched sheet before stretching is controlled to be small. This is a point for promoting hole formation while maintaining a uniform and dense hole structure.
- Examples of the polyolefin-based resin include homopolymers or copolymers mainly composed of olefins such as the above-exemplified monomers other than propylene, but are not limited thereto. Absent.
- the polyolefin resin is incompatible with polypropylene but has high affinity with polypropylene, so it is super finely dispersed in polypropylene in the melt extrusion process, and the film forming property is improved in the subsequent stretching process, and the pores are improved.
- Examples include ultra-low density polyethylene (mVLDPE) produced by the meta-mouth catalyst method because the formation is promoted and the resulting microporous film has nucleus-free pores and excellent permeability. However, it is not limited to this. Specific examples of the mVLDPE include “Engage” (type name: 8411, etc.) manufactured by DuPont Dow Elastomers.
- a resin that is incompatible with polypropylene other than those described above, and when added in an effective amount, most of the pores in the resulting microporous film have nuclei, that is, the obtained film is
- the microporous film for an electricity storage device separator of the present invention contains polypropylene as a main component, it is preferable that the resin not having substantially nucleus-free pores is not substantially added.
- these unfavorable resins include, for example, polymethylpentene (PMP), copolymers of ⁇ -olefin other than methylpentene and methylpentene, homopolymers or copolymers of cycloolefin (COC), and polybutylene terephthalate.
- PMP polymethylpentene
- COC cycloolefin
- ⁇ polycarbonate
- stPS syndiotactic polystyrene
- UHMWPE ultra high molecular weight polyethylene
- PTFE polytetrafluoroethylene
- LCP liquid crystal resin
- PMMA polymethyl methacrylate
- PET polyethylene terephthalate
- rosins retain a dispersed form in polypropylene even in a film forming process in which the dispersion size in polypropylene is large, and thus in the resulting microporous film, coarse voids are formed with the polymer as a core, In some cases, the permeability is poor and the film-forming property is also poor. In particular, when UHMWPE is used, gel-like substances may precipitate during melt extrusion, and PTFE has a concern that hydrofluoric acid is generated due to decomposition of the polymer and corrodes the extruder and the die. Do not use it.
- the microporous film of the present invention is mainly composed of polypropylene, it should be added.
- the fact that fat is incompatible with polypropylene means that the following requirements are satisfied. That is, as shown in the following measurement method, when a sample prepared by melting and compressing a microporous film was observed with a transmission electron microscope (TEM), the dispersion diameter in the thickness direction of the resin dispersed in polypropylene was measured. This means that the average value of is more than lOnm. When the dispersion diameter is less than the above range, pore formation is not promoted, and a large addition effect may not be obtained.
- the dispersion diameter is more preferably 20 nm or more, and further preferably 40 nm or more.
- the dispersion diameter is preferably 400 nm or less, more preferably 300 nm or less.
- the microporous film for an electricity storage device separator of the present invention has It is preferable to have.
- 8 crystal activity it becomes possible to produce
- the microporous film of the present invention does not have ⁇ crystal activity, the ⁇ crystal method unique to polypropylene cannot be used, and in order to achieve high porosity, nuclei are introduced into most of the resulting film. From the viewpoint of productivity and environmental impact, it is necessary to adopt a mode that does not have a nucleus-free pore, it is necessary to use uniaxial orientation, or it is necessary to use an extraction method using a solvent. Or the permeability of the resulting microporous film may be poor.
- “having ⁇ crystal activity” means that ⁇ crystal is generated when polypropylene is crystallized. In the present invention, this can be confirmed as follows. it can. In other words, using a differential scanning calorimeter (DSC), according to JIS ⁇ 7122 (1987), a 5 mg sample was heated to 280 ° C at a rate of 10 ° CZ in a nitrogen atmosphere. After holding for 5 minutes, cool to 30 ° C at a cooling rate of 10 ° CZ and then hold for 5 minutes and then increase the temperature again at a rate of 10 ° CZ. C has a peak of the endothermic peak accompanying the melting of crystal j8, and the heat of fusion calculated for the peak area force of the endothermic peak.
- DSC differential scanning calorimeter
- the amount is more than lOmjZmg.
- the calorific curve obtained at the first temperature rise may be referred to as a first-run calorie curve
- the caloric curve obtained at the second temperature rise may be referred to as a second-run calorie curve.
- the threshold value is 0.3 or more, more preferably 0.5 or more.
- the ⁇ value is an empirical value indicating the ratio of ⁇ crystals.
- the threshold value such as the calculation method of each diffraction peak intensity, see A. Turner Jones et al., “Makromolekulare Chemie”, 75, 13 4 158 (1964). See [rubbing ⁇ yo ⁇ .
- the fraction is preferably 30% or more.
- the / 3 crystal fraction is derived from polypropylene whose peak is observed at 140 ° C or higher and lower than 160 ° C in the second run caloric curve obtained by DSC as explained above.
- the ⁇ crystal fraction is the ratio of ⁇ crystals to all the crystals of polypropylene, and is described in Japanese Patent Application Publication No. 2004-142321, Japanese Patent Application Laid-Open No. 2005-171230, and International Publication No. WO 02/66233.
- the temperature curve is measured using DSC under the temperature conditions of the present invention in accordance with Nonfrez, JP 2000-30683, etc., and the ⁇ crystal fraction of the film is obtained.
- the ⁇ crystal fraction is less than the above range, the porosity of the resulting microporous film may be lowered or the permeability may be poor.
- the ⁇ crystal fraction is more preferably 40% or more, further preferably 50% or more, and most preferably 60% or more.
- a so-called / 3 crystal nucleating agent is added to the polypropylene of the microporous film. If such a j8 crystal nucleating agent is not added, the above high j8 crystal fraction may not be obtained.
- Examples of the ⁇ crystal nucleating agent that can be preferably added to the polypropylene constituting the microporous film of the present invention include, for example, acid scale iron having a nanoscale size; 1,2-hydroxystearate, magnesium benzoate, Alkali or alkaline earth metal salts of carboxylic acids typified by magnesium succinate and magnesium phthalate; Amide compounds typified by ⁇ , N'-dicyclohexyl 2, 6 naphthalene dicarboxamide; sodium benzenesulfonate Aromatic sulfonic acid compounds represented by sodium naphthalene sulfonate; di- or triesters of di- or tribasic carboxylic acids; tetraoxaspiro compounds Imide carboxylic acid derivatives; phthalocyanine-based pigments typified by phthalocyanine blue; quinacridone-based pigments typified by quinacridone, quinacridone quinone, etc .; organic dibasic acid component A and periodic
- R 1 represents a saturated or unsaturated aliphatic dicarboxylic acid residue having 1 to 24 carbon atoms, a saturated or unsaturated alicyclic dicarboxylic acid residue having 4 to 28 carbon atoms, or a carbon number.
- R 2 and R 3 are the same or different cycloalkyl group having 3 to 18 carbon atoms, cycloalkenyl group having 3 to 12 carbon atoms, or a derivative thereof.
- R 4 represents a saturated or unsaturated aliphatic diamine residue having 1 to 24 carbon atoms, a saturated or unsaturated alicyclic diamine residue having 4 to 28 carbon atoms, or 6 to 6 carbon atoms.
- 12 represents a bicyclic diamine residue or an aromatic diamine residue having 6 to 28 carbon atoms, and R 5 and R 6 are the same or different cycloalkyl groups having 3 to 12 carbon atoms, and 3 to 12 carbon atoms.
- the porosity of the resulting microporous film can be increased and the permeability can be improved.
- a particularly preferred example of a strong ⁇ / 3 crystal or j8 crystal nucleating agent-added polypropylene is j8 crystal nucleating agent "ENJESTER” (type name: NU-100, etc.) manufactured by Shin Nippon Rika Co., Ltd. SU NOCO j8 crystal nucleating agent polypropylene "BEPOL” (type name: B022—SP, etc.), etc. Is mentioned.
- the amount of the ⁇ crystal nucleating agent added is preferably 0.001 to 1% by weight based on the total amount of all the substances constituting the film. . If the added amount of the
- the addition amount of the j8-crystal nucleating agent is more preferably 0.5 005-0. 5 wt%, further preferred properly is 0.05 to 0.2 wt 0/0.
- the ⁇ crystal nucleating agent described above is dispersed in a needle shape in the unstretched sheet.
- the dispersion form of the nucleating agent is obtained by observing an unstretched sheet from the surface direction of the film with an optical microscope, and confirming the ratio of the major axis to the minor axis of the nucleating agent shape ( If the average value of (major axis ⁇ minor axis) is 10 or more, it is defined as dispersed in a needle shape.
- the j8 crystal nucleating agent dispersed in a needle shape in the microporous film it may be considered that the j8 crystal nucleating agent is dispersed in a needle shape in the unstretched sheet.
- the same observation is made on the microporous film, and if the average value of the ratio of the minor axis to the major axis of the nucleating agent shape confirmed at that time is 10 or more, it can be said that it is dispersed in a needle shape.
- the porosity of the resulting microporous film can be increased or the permeability can be increased.
- the nucleating agent dispersed in a needle shape is more likely to be arranged in the longitudinal direction (the major axis direction of the nucleating agent is easier to be oriented in the longitudinal direction of the unstretched sheet), so that the crystal lamella itself of the unstretched sheet obtained after casting is also more It becomes easier to align. It is presumed that the porosity of the microporous film and the permeability increase due to the synergistic effect of this and the crystal transition from ⁇ crystal to a crystal.
- the microporous film for an electricity storage device separator of the present invention includes, for example, an antioxidant, a heat stabilizer, and the like within a range that does not impair the object of the present invention.
- Various additives such as a chlorine scavenger, an antistatic agent, a lubricant, an antiblocking agent, a viscosity modifier, and a copper damage inhibitor may be mixed.
- a chlorine scavenger an antistatic agent
- a lubricant an antiblocking agent
- a viscosity modifier e.g., a copper damage inhibitor
- the microporous film for an electricity storage device separator of the present invention has, for example, slipperiness prevention and blocking prevention (blocking prevention) as long as the film has substantially nucleus-free pores.
- slipperiness prevention and blocking prevention blocking prevention
- various particles such as inorganic particles and Z or crosslinked organic particles may be added.
- the resulting microporous film needs to have non-nucleated pores.
- the inorganic particles are inorganic particles of a metal or a metal compound.
- zeolite calcium carbonate, magnesium carbonate, alumina, silica, aluminum silicate, kaolin, force olinite, talc, clay, diatomaceous earth, montmorillonite, acid ⁇ Powers including particles such as titanium or a mixture of these, but not limited to these.
- the crosslinked organic particles are particles obtained by crosslinking a polymer compound using a crosslinking agent.
- a crosslinking agent for example, crosslinked particles of a polymethoxysilane compound, crosslinked particles of a polystyrene compound, and crosslinked of an acryl compound.
- examples thereof include, but are not limited to, particles, crosslinked particles of a polyurethane compound, crosslinked particles of a polyester compound, crosslinked particles of a fluorine compound, or a mixture thereof.
- the volume average particle size of the inorganic particles and the crosslinked organic particles is preferably 0.5 to 5 ⁇ m. If the volume average particle size is less than the above range, the resulting microporous film may be inferior in slipperiness, and if it exceeds the above range, the particles may fall off. In addition, when adding pore formation assistance as a main purpose, it is preferably 0.05 to 1 ⁇ m. When the volume average particle size is less than the above range, the effect of addition may not be exhibited. When the volume average particle size exceeds the above range, the dropout of particles may be remarkable.
- the addition amount of inorganic particles and Z or crosslinked organic particles is preferably 0.02-0. 5% by weight, more preferably 0.05, based on all the materials constituting the film. -0. 2% by weight is preferable because it provides excellent anti-blocking property and slipperiness and has a nucleus-free pore. Furthermore, as described above, when the j8 crystal fraction is reduced by adding particles, or when particles tend to fall off and contaminate the process, it is better not to add them substantially. What is necessary is just to select the addition amount suitably.
- the microporous film for an electricity storage device separator of the present invention contains polypropylene as a main component
- the azimuth ( ⁇ ) direction profile of the (—113) plane by the X-ray diffraction method is represented by the following formula (1 Preferred to meet).
- I (MD) Longitudinal integrated intensity
- I (TD) Horizontal integrated intensity
- I (MD) and I (TD) are as described in the following measurement method (6). This is the integrated intensity calculated by the profile dolphin of the intensity distribution obtained when the position is fixed and the sample is rotated in the azimuth (j8) direction in the film plane.
- the intensity distribution profile in the azimuth direction described in (113) above is the orientation distribution of crystal chains in the film plane. It corresponds.
- I (MD) corresponds to the longitudinally oriented component of the crystal chain in the film plane
- I (TD) corresponds to the laterally oriented component.
- the magnitude of I (MD) Zl (TD) can be said to be a measure of how longitudinally the crystal chains in the film plane are oriented. That is, I (MD) Zl (TD) is higher for highly longitudinally oriented films, and I (MD) Zl (TD) is smaller for films that are mainly horizontally oriented.
- I (MD) ⁇ (TD) When I (MD) ⁇ (TD) is less than the above range, the film stretches, becomes wrinkled, or breaks during the process of processing the electricity storage device using the microporous film as a separator. In some cases, the handling property is inferior. On the other hand, the higher the I (MD) Zl (TD), the better the mechanical properties in the vertical direction. When the above range is exceeded, the film tends to tear in the vertical direction, and the productivity deteriorates in the manufacturing process. Or may shrink excessively in the lateral direction in the process of processing the electricity storage device. Therefore, it is more preferable that I (MD) Zl (TD) satisfies, for example, the following equation (3), which preferably satisfies the following equation (2):
- the crystallization conditions metal drum temperature, peripheral speed of the metal drum, thickness of the unstretched sheet obtained, contact time to the metal drum, etc.
- stretching conditions in the process stretching direction (longitudinal or transverse), stretching method (longitudinal or transverse uniaxial stretching, longitudinal, transverse or transverse longitudinal biaxial stretching, simultaneous biaxial stretching, re-stretching after biaxial stretching, etc.), stretching ratio , Stretching speed, stretching temperature, etc.
- stretching direction longitudinal or transverse
- stretching method longitudinal or transverse uniaxial stretching, longitudinal, transverse or transverse longitudinal biaxial stretching, simultaneous biaxial stretching, re-stretching after biaxial stretching, etc.
- stretching ratio stretching speed, stretching temperature, etc.
- the longitudinal stretching ratio is preferably 5 to 10 times, and the longitudinal stretching temperature is preferably 95 to 110 ° C. At this time, as the longitudinal stretching ratio is higher and the longitudinal stretching temperature is lower, the stretchability in the subsequent transverse stretching becomes unstable.
- HMS-PP HMS-PP
- the amount should be 0.1 to 50% by weight, more preferably the amount added should be 0.5 to 20% by weight, and most preferably the amount of added force should be 0.5 to 5% by weight.
- mV LDPE more preferably 1 to LO weight%.
- Various polymers may be appropriately laminated within a range that does not impair the purpose of the present invention, depending on various purposes such as imparting slipperiness, improving the surface open area ratio, imparting surface hydrophilicity, imparting surface heat resistance.
- the film obtained by lamination must be substantially transmissive.
- Powerful polymer lamination methods include, but are not limited to, coextrusion, in-line or off-line extrusion laminating, in-line or off-line coating, physical vapor deposition, chemical vapor deposition, sputtering, and the like. Choose the best method from time to time.
- various lubricants, various particles, various sliding materials are provided on at least one surface of the film of the present invention in order to impart good slipping properties while maintaining high permeability and to improve the handling properties as a separator. It may be preferable to laminate various polymers containing an agent as a skin layer.
- At least one film surface of the microporous film for an electricity storage device separator of the present invention is subjected to corona discharge treatment to control the wettability of the film, thereby improving surface hydrophilicity, antistatic properties, etc., electrolyte solution It can preferably be employed to control the wettability of the.
- corona discharge treatment air, oxygen, nitrogen, carbon dioxide, or a mixed system of nitrogen and carbon dioxide is preferable. It is particularly preferred to treat. Flame (flame) processing and plasma processing are also preferred from the viewpoint of surface wetting tension control.
- the thickness of the microporous film for an electricity storage device separator of the present invention is preferably 5 to 50 ⁇ m. If the thickness is less than the above range, the handling property may be inferior, such as the film is stretched or wrinkled, in the manufacturing process of the film or the subsequent processing process for the power storage device. If the thickness exceeds the above range, the capacity of the electricity storage device may be reduced because the volume of the separator in the electricity storage device becomes larger than necessary.
- the thickness of the microporous film of the present invention is more preferably 7 to 40 m, further preferably 8 to 35 ⁇ m, and most preferably 9 to 30 ⁇ m.
- the Gurley permeability of the microporous film for an electricity storage device separator of the present invention is preferably 400 sec. Z1 OOml or less.
- a measure of the permeability of the resulting microporous film For example, in the case of using the 13-crystal method with polypropylene as the main component, the amount of HMS-PP or
- HMS-PP is added within a range that does not impair productivity due to film breakage, for example!
- the film is stretched at a high magnification in the machine direction, more preferably the amount of applied force is 1 to 10% by weight; mVLDPE is added, more preferably the amount added is 1 ⁇ 10% by weight; Cast drum temperature should be 110 ⁇ 125 ° C; Cast drum contact time should be 8 seconds or more;
- the stretching ratio in the direction is 5-8 times, the longitudinal stretching temperature is 95-120 ° C, the stretching temperature in the transverse direction is 130-150 ° C, and the stretching speed in the transverse direction is 100- : LOOOO%, more preferably less than 1000% Z is particularly effective.
- the Gurley air permeability exceeds the above range, the permeation performance may be insufficient and the porosity may be lowered. Further, in the present invention, the lower the Gurley air permeability, for example, when used as a separator of a lithium ion secondary power storage device, the power density tends to be high, and the power storage device tends to be obtained. If it is too low, the film will be broken in the manufacturing process, resulting in poor film-forming properties, and the film will be stretched, wrinkled or broken in the subsequent processing process for power storage devices. Therefore, since it may be inferior in handling property, for example, it is preferably 10 seconds or more ZlOOml or more.
- the Gurley air permeability is more preferably 10 to 350 seconds ZlOOml, and most preferably 20 to 250 seconds ZlOOml.
- various film forming methods represented by various biaxial stretching methods such as simultaneous biaxial stretching, sequential biaxial stretching, and subsequent re-stretching are used.
- various film forming methods such as simultaneous biaxial stretching, sequential biaxial stretching, and subsequent re-stretching are used.
- the longitudinal-transverse sequential biaxial stretching method is particularly preferable to use the longitudinal-transverse sequential biaxial stretching method.
- the longitudinal and transverse sequential biaxial stretching methods are also suitable in terms of viewpoints such as apparatus expandability.
- a polypropylene containing HMS-PP and soot or mVLDPE and added with a ⁇ -crystal nucleating agent (having ⁇ -crystal activity) is prepared and supplied to an extruder at 200 to 320 ° C. After melting at temperature and passing through a filtration filter, it is extruded into a slit-shaped die force, cast into a cooling metal drum, and cooled and solidified into a sheet to obtain an unstretched sheet.
- a polymer other than the above-described polypropylene may be appropriately added to the prepared polypropylene. However, it is necessary that the resulting microporous film has a nucleus-free pore.
- the melt extrusion temperature is low.
- the melt extrusion temperature is less than the above range, unmelted material is contained in the molten polymer discharged from the die. May occur, which may cause process failure such as tearing in the subsequent stretching process.
- the thermal decomposition of polypropylene becomes severe and the resulting microporous film may be inferior in film properties such as Young's modulus and breaking strength.
- the temperature of the cooling metal drum is preferably 60 to 130 ° C.
- the permeability of the obtained microporous film tends to increase as it approaches the upper limit in the above temperature range, and tends to decrease as it approaches the lower limit, depending on the amount of ⁇ crystals in the unstretched sheet obtained. It is estimated to be.
- the amount of ⁇ crystal in the unstretched sheet corresponds to the 13 crystal fraction in which the uncured sheet is used as a sample and the caloric curve force of the first run obtained using DSC is also obtained.
- cast drum The temperature is preferably 100 to 125 ° C.
- the time during which the unstretched sheet comes into contact with the cast drum is preferably 6 to 60 seconds.
- the total time for which the unstretched sheet has contacted these drums is the contact time for the metal drum. If the contact time to the metal drum is less than the above range, depending on the temperature, it will be at the time of peeling!
- the film has insufficient porosity after biaxial stretching. May be lower.
- the contact time with the metal drum exceeds the above range, depending on the size of the metal drum, the peripheral speed of the metal drum is unnecessarily low, and the productivity may be significantly deteriorated. Further, the contact time is often not substantially longer than 10 minutes.
- the contact time with the metal drum is more preferably 7 to 45 seconds, and further preferably 8 to 40 seconds.
- an air knife method that has good thickness controllability and can control the cooling rate of the unstretched sheet by the temperature of the blowing air
- the air knife method air is blown from the non-drum surface, and the temperature is preferably 10 to 200 ° C.
- a desired resin is required in addition to the polypropylene described above.
- Prepare these resins according to the requirements supply these resins to different extruders, melt them at the desired temperature, pass through filtration filters, and then merge them in polymer tubes or caps. Extrude with slit-type cap force, cast on cooling drum and sheet It can be cooled and solidified to form a non-laminated stretched sheet.
- the obtained unstretched (laminated) sheet is biaxially stretched using a longitudinal-transverse sequential biaxial stretching method.
- an unstretched film is preheated by passing it through a roll maintained at a predetermined temperature, and then the film is maintained at a predetermined temperature and passed between rolls having a difference in peripheral speed, and stretched in the longitudinal direction. Cool immediately.
- the stretch ratio in the machine direction is important.
- the effective stretching ratio in the longitudinal direction is in the range of 3 to 4.5 times. The film becomes difficult and the film is torn by transverse stretching.
- the effective stretch ratio in the machine direction is 5 to 10 times in order to obtain a microporous film with higher porosity and high permeability.
- the above-described HMS-PP is contained in the microporous polypropylene film of the present invention, which enables stable high-direction stretching in the machine direction.
- the effective draw ratio in the machine direction is less than the above range, the porosity of the resulting microporous film may be low and the permeability may be poor.
- the film formation speed ( line speed) even at the same casting speed because the magnification is low. ) Is slow and productivity may be inferior.
- the effective stretching ratio in the machine direction exceeds the above range, film breakage may occur sporadically by longitudinal stretching or transverse stretching, resulting in poor film forming properties.
- the effective stretch ratio in the machine direction is more preferably 5 to 9 times, still more preferably 5 to 8 times.
- the longitudinal stretching speed is preferably 5000 to 500,000% Z from the viewpoint of productivity and stable film-forming property.
- the longitudinal stretching temperature is preferably from 95 to 120 ° C., for example, from the standpoint of stable film-forming properties, thickness unevenness suppression, porosity improvement, and permeability.
- a desired resin layer may be appropriately placed on the film after longitudinal stretching by extrusion lamination or coating.
- the longitudinally stretched film is guided to a tenter type stretching machine, preheated at a predetermined temperature, and stretched in the transverse direction.
- the effective stretch ratio in the transverse direction is preferably 12 times or less. If the effective stretching ratio in the transverse direction exceeds 12 times, the film forming property may be deteriorated.
- the transverse stretching temperature is preferably 100 to 150 ° C., for example, from the viewpoints of stable film forming property, thickness unevenness suppression, porosity improvement, and permeability. Further, the transverse stretching speed is preferably from 100 to LOOOO% Z from the viewpoint of productivity and stable film-forming property.
- the stretching speed in the present invention is calculated using the following formula when stretching is performed with two roll pairs having a peripheral speed difference in the stretching step.
- This stretching method is used in the longitudinal stretching step in the case of longitudinal and lateral sequential biaxial stretching.
- the roll gap (m) corresponds to a stretching section in the longitudinal stretching step.
- the peripheral speed (mZ) of the high-speed roll By dividing this by the peripheral speed (mZ) of the high-speed roll, the time required for the film to pass through the stretching section of the two roll pairs can be calculated.
- the peripheral speed of the high-speed side roll is the rotational speed of the roll located on the winder side of the two pairs of rolls that perform the stretching.
- Transverse stretching speed (% Z min) ⁇ (Effective transverse stretching ratio) ⁇ ⁇ ⁇ ⁇ (Transverse zone length) ⁇ (Line speed ⁇
- the transverse stretching zone length (unit: m) is the length in the line direction of the zone that is transversely stretched in the tenter.
- the line speed (unit: mZ)
- the line speed is the film transport speed when passing through the transverse stretching zone.
- film formation can be performed by directly inputting a desired stretching speed.
- the permeation performance is improved, and particularly when the average pore diameter is increased, the stretching speed in at least one direction in the stretching step. Is preferably less than 2000% Z minutes, more preferably less than 1000% Z minutes.
- the porosity of the resulting microporous film can be increased, the permeation performance can be improved, and particularly the average pore diameter can be significantly improved.
- the casting speed in the film forming process is lowered (that is, the film forming speed (line speed) is lowered).
- This can be achieved by lengthening the time required to pass through the stretching section, such as lengthening the stretching section.
- the production area of the film per unit time may be low, so the latter method is preferable.
- Increasing the stretching section can be achieved, for example, by increasing the roll gap in the case of the longitudinal stretching step, or by increasing the stretching zone length of the tenter in the case of the lateral stretching step. Of these, it is most easily achievable to increase the length of the laterally elongated zone, and the above effect is also great.
- the stretching speed in the transverse stretching satisfies the above range.
- the stretching speed in at least one direction in the stretching process is more preferably 900% Z min or less, and still more preferably 800 % Z min or less, most preferably 700% Z min or less.
- the stretching speed in at least one direction is more preferably 900% Z min or less, and still more preferably 800 % Z min or less, most preferably 700% Z min or less.
- the stretching speed is preferably 50% Z min or more, for example.
- an electricity storage device is produced using the microporous film of the present invention as a separator.
- the microporous film of the present invention may be used as a separator as it is, or may be used as a force separator by performing various processes such as an antistatic treatment, a hydrophilization treatment, and a metal vapor deposition treatment.
- the antistatic treatment and hydrophilization treatment include various antistatic agents or various surfactants in order to obtain a sufficient treatment effect up to the inside of the film (inner wall portion of the hole) only on the film surface.
- a dipping treatment in which the film is immersed in a solution in which the hydrophilizing agent is dissolved or dispersed is preferred, but it is not limited to this.
- the electricity storage device in the present invention is a device that can store electricity and / or take out electricity from the inside, and has a separator between a positive electrode and a negative electrode.
- a device that is installed and filled with an electrolyte More specifically, manganese dry batteries, alkaline manganese dry batteries, nickel dry batteries, silver oxide batteries, air zinc batteries, lithium graphite fluoride batteries, manganese dioxide lithium batteries, lithium chloride batteries, lithium batteries
- Capacitors such as primary batteries typified by ion batteries, lead-acid batteries, nickel-cadmium batteries, nickel-metal hydride batteries, nickel-zinc batteries, lithium-ion batteries, etc., secondary batteries, electric double layer capacitors, electrolytic capacitors, etc. It is not necessarily limited to these.
- the electricity storage device using the microporous film of the present invention as a separator is preferably a lithium ion battery having high energy density and high output density, but is not particularly limited thereto. Below, the preferable aspect in the case of using the microporous film of this invention as a separator for a lithium ion battery is demonstrated.
- a lithium ion battery is mainly composed of a separator using the microporous film of the present invention, a non-aqueous electrolyte, a positive electrode (a positive electrode during discharge), and a negative electrode cover. Is.
- the non-aqueous electrolyte is preferably prepared by dissolving a lithium salt in a non-aqueous solvent.
- Various ionic liquids may be used.
- the non-aqueous solvent include propylene carbonate, ethylene carbonate, dimethyl carbonate, getinole carbonate, dimethoxyethane, tetrahydrofuran, ⁇ -butinorelatatane, methyl propionate, butyl propionate, ethyl propionate, dimethyl sulfoxide, Examples include, but are not limited to, at least one selected from aprotic electrolyte solutions such as sulfolane.
- Lithium salts include LiBF, LiCIO, LiPF, LiAsF, CF SO Li, (CF SO) N
- Examples of positive electrodes made of lithium compounds include LiCoO, LiNiO, and LiMnO.
- Li MO Li MO (where M is one or more species)
- a transition metal preferably at least one kind of transition metal such as Mn, Co, Ni, etc., where force is also selected, and X is 0.05.ltoreq.X ⁇ 1.10.
- chalcogenides such as S, Se, and Te are preferred.
- These positive electrode active materials and various conductive agents such as carbon black and various binders such as polyvinylidene fluoride and polytetrafluoroethylene are applied to a powerful current collector such as an aluminum foil. It is preferable to produce a positive electrode by drying. At this time, a rolling process may be appropriately performed.
- the negative electrode in addition to lithium metal, lithium alloy, amorphous carbon, non-graphitizable carbon, graphitizable carbon, or graphite, which can be doped and dedoped with lithium ions, is representative. It is preferable to use various carbon materials. It is preferable to prepare a negative electrode by applying a mixture of the negative electrode material and a binder such as an acrylic resin to a force such as a nickel foil or a metal foil such as a copper foil and drying the mixture. . At this time, rolling may be performed as appropriate.
- a binder such as an acrylic resin
- An electricity storage device separator using the microporous film of the present invention as it is or processed as described above is sandwiched between the obtained positive electrode and negative electrode, and wound or laminated. At this time, the separator is inserted such that the innermost and outermost surfaces of the obtained wound body or laminate are the power storage device separator of the present invention.
- a positive electrode terminal such as aluminum, aluminum alloy, copper or nickel and a negative electrode terminal such as nickel, copper, stainless steel or iron are inserted into the obtained wound body or laminate so as to be in contact with the positive electrode and the negative electrode, respectively.
- an in-type electricity storage device can (case) or various film laminates typified by a laminate comprising an aluminum foil and a single-layer or multi-layer filmka. Then, an electrolytic solution is injected, and the electricity storage device can or the laminate is sealed to obtain a lithium ion battery.
- the electricity storage device of the present invention is, for example, a lithium ion battery
- the amount of electrolyte retained can be increased because the porosity of the electricity storage device separator used is extremely high, and the lithium ion battery has a high energy density. It can be. Further, since the electricity storage device separator to be used has high permeability, the internal resistance of the electricity storage device can be lowered, and a lithium ion battery with high output density can be obtained. That is, a battery that can extract a larger current in a shorter time can be obtained.
- the power storage device separator used has high strength in the vertical direction, even if the separator itself is made thin, it can maintain excellent nodling properties, thereby increasing the volume of the electrode active material in the power storage device. For this reason, it is possible to obtain a lithium ion battery with a high storage device capacity.
- the microporous film for an electricity storage device separator of the present invention has less process contamination due to components constituting the film, and has an extremely low porosity compared to conventional microporous films. Because of its high permeability, the energy density and output density of an electricity storage device using the film as a separator can be improved. Furthermore, in the process of forming a power storage device using the film with high porosity in spite of high porosity as a separator, the film stretches, becomes wrinkled, or breaks. Excellent handleability. In addition, the separator itself can be made thin while maintaining handling properties as necessary, and thus the capacity of the electricity storage device can be increased. As described above, the microporous film for an electricity storage device separator of the present invention can be widely used as a high performance separator that can actively contribute to higher performance of the electricity storage device than an auxiliary material for the electricity storage device.
- the sample was sandwiched between 0.5 mm thick aluminum plates, melted and compressed by hot pressing at 280 ° C, and the obtained sheet was immersed in water at 30 ° C together with the aluminum plate. Quenched quickly.
- the obtained sheet was subjected to the same measurement for the same sample five times in the same manner as described above, and the average value of the obtained specific gravity was defined as the specific gravity (dO) after sample preparation. From the obtained dl and dO, the porosity of the film was determined using the following formula (unit:%).
- rupture strength was measured at 25 ° C and 65% RH using Orientec's film strength measuring device (AMFZRTA-100). did. Specifically, the sample was cut into a size of 15 cm in the vertical direction and 1 cm in the horizontal direction, stretched at an original length of 50 mm and a pulling speed of 300 mmZ, and the breaking strength (unit: MPa) was measured. The same measurement was performed five times for the same sample, and the average value of the obtained breaking strengths was defined as the longitudinal strength of the sample.
- the bubble point was measured using an automatic pore size distribution measuring device “PERM-POROMETER” manufactured by POROUS M ATERIALS, Inc. according to the bubble point method (Noffu dry method) of JIS K 3832 (1990). Measurement conditions are as follows.
- Measurement conditions Capillary Flow Porometry-Automatic measurement based on default conditions of wet up and dry down In the bubble point method, the following relational expression holds between the pore diameter (pore diameter) and the test pressure.
- the average pore diameter was calculated from the 1Z2 half-wetting curve using the data analysis software attached to the device. This measurement is also detailed in the manual that comes with the device. The same measurement was performed 5 times for the same sample, and the average value of the obtained average pore diameter was defined as the average pore diameter of the sample (unit: nm).
- An ultra-thin section having a cross section in the transverse direction thickness direction of a microporous film was collected by an embedding method using epoxy resin, using an ultramicrotome. Collected sections of RuO
- the sample was stained with 4 and the cross section was observed using a transmission electron microscope (TEM) under the following conditions. Sample preparation and cross-sectional observation were performed at Toray Research Center.
- TEM transmission electron microscope
- An image obtained by continuously observing from one surface of the film to the other surface is observed in such a manner that one side of the image is parallel to the lateral direction of the film and parallel to the thickness direction. At this time, the size of each image is adjusted so that one side parallel to the horizontal direction is 5 m in actual size of the film.
- an OHP sheet (EPSO manufactured by Seiko Epson Corporation)
- the X-ray diffraction photographic power obtained when X-rays are incident on the film from the three directions shown below is determined as the film orientation.
- Edge incidence Incident perpendicular to the surface formed in the longitudinal direction of the film.
- the sample was cut out by overlapping the film so that the directions were aligned and having a thickness of about 1 mm.
- Imaging plate FUJIFILM BAS -SR 'Photographing conditions: Camera radius (distance between sample and imaging plate) 40mm, exposure time 5 minutes.
- Sample The film was cut out with the direction aligned and piled to a thickness of about lmm, and used for measurement.
- Fig. 3 is a diagram schematically showing the arrangement of the sample and the device when a 2 ⁇ / ⁇ scan X-ray diffraction profile is collected.
- the normal 5 to the film surface of sample 4 is inclined by 0 (°) with respect to the incident X-ray 6.
- a slit (not shown) is arranged at the tip of the diffracted X-ray 7, and further, a scintillator for X-ray measurement There is a sill counter (not shown), and the scintillation counter is tilted by 20 (°).
- the incident X-ray 6 can be obtained by passing through an X-ray source force Ni filter, a pinhole collimator, and a slit.
- a goometer shaft 8 which is a rotatable shaft to adjust the angle between the scintillation counter and the sample.
- the sample rotates under the above conditions along a plane of rotation 9 that is parallel to the film surface, ie perpendicular to the normal 5.
- Fig. 4 schematically shows the geometrical arrangement of the sample in Fig. 3 when observed from the observation point (10 in Fig. 3) in the surface normal direction (5 in Fig. 3). It was. ⁇ is an angle formed by the go-home axis 8 and the longitudinal direction 12 of the sample. In these figures, the sample is drawn long in the vertical direction for convenience, but the reference direction is clear, and if the X-ray irradiation part 11 being measured is constant as shown below, The dimensions of the sample in the horizontal direction are not important.
- the sample is set so that the film surface is parallel to the rotation plane 9 in the ⁇ direction and the goometer axis 8 in order to evaluate the orientation distribution of crystal chains in the film plane.
- ⁇ is fixed at 0 ° or 90 °, and 2 ⁇ / ⁇ scan is performed under the above conditions. Then 2
- the vertical integrated intensity (I (MD)) and the horizontal integrated intensity (I (TD)) are obtained by the following method.
- Integral intensities I (MD) and I (TD) are calculated as the area of the part surrounded by the baseline and X-ray intensity curve in the range of j8 below.
- I (MD) Zl (TD) was calculated, and the obtained value was used as a measure of the orientation balance of crystal chains in the film plane.
- the ⁇ value is an empirical value indicating the ratio of
- the ⁇ value such as the calculation method of each diffraction peak intensity, see Turner Jones; ⁇ , Macro Molecule. (Makromolekulare Chemie), 75, 134—see pages 158 (1964).
- Peak splitting is performed using WINFIT software (Bruker). At that time, the peak splitting is performed from the peak on the high magnetic field side as shown below, soft automatic fitting is performed, the peak splitting is optimized, and mmmm and ss (mmmm spinning sidebands) The sum of the peak fractions of peak) is defined as the mesopentad fraction (mmmm).
- Film polypropylene is extracted with n-heptane at a temperature of 60 ° C for 2 hours. Remove impurities' additives in the process. Then vacuum dry at 130 ° C for 2 hours. A sample of weight W (mg) is taken from this, placed in a Soxhlet extractor and extracted with boiling n-heptane for 12 hours. Next, take out this sample, thoroughly wash with acetone, vacuum dry at 130 ° C for 6 hours, then cool to room temperature, measure the weight W '(mg), and obtain it by the following formula.
- the films were aligned so that the sample thickness after hot press preparation was about lmm.
- This sample was sandwiched between two 0.5 mm thick aluminum plates, melted and compressed by hot pressing at 280 ° C, and the polymer chains were almost non-oriented.
- the obtained sheet was crystallized by being immersed in boiling water at 100 ° C for 5 minutes immediately after taking out the whole aluminum plate. Thereafter, a sample was cut out from the sheet obtained by cooling in an atmosphere at 25 ° C. and subjected to measurement.
- the dispersion diameter of the incompatible resin in the obtained sample was determined as follows.
- the same measurement is performed 5 times on the same sample, and the average value of the ratio of major axis to minor axis obtained is the ratio of major axis to minor axis of the sample.
- those having a ratio of the major axis to the minor axis of 10 or more are judged as the nucleating agent being dispersed in a needle shape.
- the volume average diameter measured using the centrifugal sedimentation method (using CAPA500 manufactured by Horiba Seisakusho) Average particle diameter m).
- the number of tears was counted according to the following criteria. In other words, if a break occurs in the longitudinal stretching process or the transverse stretching process, it is counted as one break at that time, and the film is cut immediately before the process and waits while winding (the break occurs for some reason). If it was difficult to wait in the previous process, the process was waited in the previous process), and the film was introduced again into the process where the break occurred as soon as it was ready. For example, when a film breakage occurs in the transverse stretching process, the film is temporarily cut between the longitudinal stretching machine and the transverse stretching machine (tenter), and the longitudinally stretched film is wound as it is to be in a standby state, and the tenter tear film is removed.
- the film was again introduced into the tenter and stretched laterally to evaluate the film-forming property.
- the 5 hour film formation time is defined as the time including this standby state.
- Similar film-forming experiments for the same level The average value of the number of tears obtained was taken as the number of tears, and the film forming property was judged according to the above criteria.
- the film of the present invention was wound up to a width of lm and a length of 500 m, and the obtained film roll was slit and commercialized using a slitter manufactured by Toray Engineering Co., Ltd.
- the microporous film of the present invention aluminum foil with a thickness of 100 ⁇ m, and copper foil with a thickness of 100 ⁇ m They were rolled up to 100m to form an aluminum foil.
- a lithium ion battery using the microporous film of the present invention as a separator was prepared and evaluated as follows.
- Acetylene black (AB: 75% press product manufactured by Denki Kagaku Kogyo Co., Ltd.) ⁇ ⁇ 4.5 parts by weight
- Polyvinylidene fluoride (PVDF; manufactured by Kureha Chemicals Co., Ltd.) ⁇ ⁇ 6 parts by weight
- the above substances were mixed to prepare a slurry.
- the obtained slurry was applied onto an aluminum foil as a current collector, dried and then punched.
- the above composition was mixed to prepare a slurry.
- the obtained slurry was applied onto a copper foil as a current collector, dried and then punched.
- LiPF was dissolved in a solvent in which propylene carbonate and methylethyl carbonate were mixed at a ratio of 3: 7 so as to have a concentration of ImolZl, and this was used as an electrolytic solution.
- the microporous film was directly sandwiched between the positive electrode and the negative electrode as a separator, and after punching, each terminal of the positive electrode and the negative electrode was taken out and inserted into an aluminum laminate type outer package. After sealing three sides of the outer package, the above electrolyte was injected, and the fourth side was sealed under reduced pressure to obtain a power storage device.
- the internal resistance of the battery was measured with an electric resistance meter (unit: m ⁇ ).
- the battery discharge capacity at the 2C and 3rd cycle was taken as the initial capacity, and the ratio (P) of the discharge capacity at 10C relative to this was determined. The higher P, the better the rate characteristics of the battery.
- the present invention will be described based on examples.
- the extrusion amount of the polymer was adjusted to a predetermined value unless otherwise specified.
- the determination of ⁇ crystal activity, ⁇ crystal fraction, and porosity of the film are values measured for the entire film obtained. Further, unless otherwise specified, it was confirmed that the films that could be collected from the films of Examples and Comparative Examples were biaxially oriented based on the measurement method (5) described above. Furthermore, for all examples, R measured based on the above measurement method (4) is 0%, which is substantially absent. It has a hole in the nucleus, and it is!
- Polypropylene resin A having the following composition was prepared.
- Polypropylene Sumitomo Chemical Co., Ltd. polypropylene WF836DG3 (melt flow rate (M FR): 7gZlO content), 96.8 weight 0/0
- High melt tension polypropylene with long chain branching in the main chain Basell polypropylene PF—814 (MFR: 3 gZlO min) 3% by weight
- N N, monodicyclohexyl 2, 6-naphthalene dicarboxamide (NU-100, manufactured by Nippon Rika Co., Ltd.) ⁇ 0.2 wt%
- IRGANOX1 010 manufactured by Ciba Geigy Co., Ltd. and 0.1 parts by weight of IRGAFOS168 manufactured by Ciba Geigy Co., Ltd. were added as thermal stabilizers to 100 parts by weight of the composition of the resin. This is fed to a twin screw extruder and melted and kneaded at 300 ° C, then extruded into a gut shape, cooled through a 20 ° C water bath, cut into a 3 mm length with a chip cutter, and then 100 ° C. And dried for 2 hours.
- the obtained unstretched sheet was preheated through a group of rolls maintained at 105 ° C, passed between rolls maintained at 105 ° C and provided with a difference in peripheral speed, and quadrupled in the longitudinal direction at 105 ° C. Stretched and cooled to 95 ° C. Subsequently, both ends of this longitudinally stretched film were introduced into a tenter while being held by clips, preheated at 140 ° C., and stretched 8 times in the transverse direction at 140 ° C. Next, heat-fixed at 155 ° C while giving 5% relaxation in the transverse direction in the tenter, uniformly cooled slowly, cooled to room temperature, scraped off, and microporous polypropylene film with a thickness of 20 m Got.
- the longitudinal stretching speed was 18000% Z and the transverse stretching speed was 1400% Z.
- the raw material composition and film property evaluation results of the obtained microporous film are shown in Tables 1 and 2, respectively.
- the obtained microporous film was excellent in film forming property and excellent in permeability with high porosity. Also, the strength in the vertical direction was high and the handling was excellent.
- Example 2 was a microporous polypropylene film having a thickness of 20 ⁇ m produced under the same conditions as in Example 1, except that the longitudinal draw ratio was increased to 5. In this case, the longitudinal stretching speed was 30000% Z and the transverse stretching speed was 1750% Z.
- the results are shown in Tables 1 and 2.
- the obtained microporous film had excellent film forming properties and excellent permeability with a high porosity.
- the strength in the vertical direction was high and the handling was excellent.
- Example 2 a microporous polypropylene film having a thickness of 20 ⁇ m produced under the same conditions except that the stretching ratio in the longitudinal direction was increased to 6 was used as Example 3.
- the longitudinal stretching speed was 45000% Z and the transverse stretching speed was 2100% Z.
- the results are shown in Tables 1 and 2.
- the obtained microporous film had excellent film forming properties and excellent permeability with a high porosity.
- the strength in the vertical direction was high and the handling was excellent.
- Example 2 instead of polypropylene resin A, a resin composition comprising 90% by weight of polypropylene resin A and 10% by weight of polypropylene resin B prepared in the following composition was mixed and uniaxially extruded.
- Example 4 was a microporous polypropylene film with a thickness of 20 ⁇ m produced under the same conditions except that it was stretched at 100 ° C in the longitudinal direction and stretched at 135 ° C in the transverse direction. . At this time, the longitudinal stretching speed was 30000% Z, and the transverse stretching speed was 1750% Z.
- Polypropylene Polypropylene WF836DG3 manufactured by Sumitomo Chemical Co., Ltd. (Melt Flow Rate (MFR): 7gZlO) ⁇ ⁇ 70% by weight
- Polyolefin resin "Engage” 8411 manufactured by DuPonda Welastoma Japan Co., Ltd. (mVLDPEl;. Ethylene Otaten copolymer), 30 weight 0/0
- This resin composition was supplied to a twin screw extruder, melted and kneaded at 250 ° C, extruded into a gut shape, cooled through a 20 ° C water bath, cut into a 3 mm length with a chip cutter, and 100 Dried for 2 hours at ° C.
- the results are shown in Tables 1 and 2.
- the obtained microporous film had excellent film forming properties and excellent permeability with a high porosity.
- the strength in the vertical direction was high and the handling was excellent.
- Example 2 a 20 ⁇ m thick microporous polypropylene produced under the same conditions except that polypropylene resin C prepared in the following composition was supplied to a single screw extruder instead of polypropylene resin A.
- the film was referred to as Example 5.
- the longitudinal stretching speed was 30000% Z and the transverse stretching speed was 1750% Z.
- Polypropylene Sumitomo Chemical Co., Ltd. polypropylene WF836DG3 (melt flow rate (M FR): 7gZlO min.) ' ⁇ 91.8 weight 0/0
- High melt strength polypropylene having a long chain branch in the main chain skeleton Basell made polypropylene emissions PF- 814 (MFR: 3gZlO min) '- 3 wt 0/0
- j8 nucleating agent ⁇ , N, monodicyclohexyl 2, 6-naphthalene dicarboxamide (NU-100, manufactured by Nippon Rika Co., Ltd.) ⁇ 0.2 wt%
- Polyolefin resin DuPonda Welastoma Japan Japan “engage” 8411 (mVLDPEl) ⁇ ⁇ 5 wt%
- this resin composition To 100 parts by weight of this resin composition, 0.115 parts by weight of IRGANOX 1010 manufactured by Ciba Geigy Co., Ltd. was added as an antioxidant, and 0.1 parts by weight of IRGAFOS168 manufactured by Ciba Geigy Co., Ltd. was added as a heat stabilizer. This was fed to a twin screw extruder and melted and kneaded at 300 ° C, then extruded into a gut shape, cooled through a 20 ° C water tank, cut into a 3 mm length with a chip cutter, and then at 100 ° C. Dried for 2 hours.
- the results are shown in Tables 1 and 2.
- the obtained microporous film had excellent film forming properties and excellent permeability with a high porosity. In addition, the vertical strength is high and the handling is excellent. It was.
- Example 4 50 weight polypropylene ⁇ A 0/0, 40% by weight of polypropylene ⁇ D prepared in the following composition, and the polypropylene ⁇ B combined additive mixed at a ratio of 10 wt% ⁇ Example 6 was a microporous polypropylene film having a thickness of 20 ⁇ m produced under the same conditions except that the composition was supplied to a single screw extruder. In this case, the longitudinal stretching speed was 30000% Z and the transverse stretching speed was 1750% Z.
- Polypropylene Sumitomo Chemical Co., Ltd. polypropylene WF836DG3 (melt flow rate (M FR): 7gZlO content), 99.8 weight 0/0
- j8 nucleating agent ⁇ , N, monodicyclohexyl 2, 6-naphthalene dicarboxamide (NU-100, Nippon Rika Co., Ltd.) ⁇ 0.2 wt%
- this resin composition To 100 parts by weight of this resin composition, 0.115 parts by weight of IRGANOX 1010 manufactured by Ciba Geigy Co., Ltd. was added as an antioxidant, and 0.1 parts by weight of IRGAFOS168 manufactured by Ciba Geigy Co., Ltd. was added as a heat stabilizer. This was fed to a twin screw extruder and melted and kneaded at 300 ° C, then extruded into a gut shape, cooled through a 20 ° C water tank, cut into a 3 mm length with a chip cutter, and then at 100 ° C. Dried for 2 hours.
- the results are shown in Tables 1 and 2.
- the obtained microporous film had excellent film forming properties and excellent permeability with a high porosity.
- the strength in the vertical direction was high and the handling was excellent.
- Example 4 a microporous polypropylene film having a thickness of 20 ⁇ m produced under the same conditions except that the surface temperature of the cast drum was changed to 110 ° C. was used as Example 7.
- the results are shown in Tables 1 and 2.
- the obtained microporous film had excellent film forming properties and excellent permeability with a high porosity.
- the strength in the vertical direction was high and the handling was excellent.
- Example 8 instead of polypropylene resin A, a polyp prepared with the following composition: Example 8 was a microporous polypropylene film having a thickness of 20 m produced under the same conditions except that Lopylene resin E was supplied to a single screw extruder.
- Polypropylene Sumitomo Chemical Co., Ltd. polypropylene WF836DG3 (melt flow rate (M FR): 7gZlO min) - - 96.95 weight 0/0
- j8 crystal nucleating agent ⁇ , N, monodicyclohexyl 2, 6-naphthalene dicarboxamide (Nu Nippon Rika Co., Ltd. NU 100) ⁇ 0.05% by weight
- High melt strength polypropylene having a long chain branch in the main chain skeleton Basell made polypropylene emissions PF- 814 (MFR: 3gZlO min) '- 3 wt 0/0
- this resin composition To 100 parts by weight of this resin composition, 0.115 parts by weight of IRGANOX 1010 manufactured by Ciba Geigy Co., Ltd. was added as an antioxidant, and 0.1 parts by weight of IRGAFOS168 manufactured by Ciba Geigy Co., Ltd. was added as a heat stabilizer. This was fed to a twin screw extruder and melted and kneaded at 300 ° C, then extruded into a gut shape, cooled through a 20 ° C water tank, cut into a 3 mm length with a chip cutter, and then at 100 ° C. Dried for 2 hours.
- the results are shown in Tables 1 and 2.
- the obtained microporous film had excellent film forming properties and excellent permeability with a high porosity.
- the strength in the vertical direction was high and the handling was excellent.
- Example 4 a longitudinally uniaxially stretched film was collected after stretching in the longitudinal direction and cooling.
- the obtained longitudinally uniaxially stretched film was cut into a rectangle having a size of 200 mm in the vertical direction and 85 mm in the horizontal direction.
- the obtained sample was stretched transversely using a film stretcher under the following conditions.
- KARO-IV film stretcher manufactured by Bruckner Maschinenbau GmbH. Temperature conditions:
- Stepl Mode: Heating, Position: Stretching Oven, Time: 15sec
- Step2 Mode: Position, Position: Stretching Oven, MD: 1.00, 15% / sec, TD: 6.00, 15
- Step3 Mode: Position ⁇ Position: Annealing 1 Oven, MD: 1.00, 15% / sec ⁇ TD: 5.70, 15% / sec, Speed Mode: Constant Speed
- Example 9 The above conditions were as follows: the longitudinally uniaxially stretched film was preheated at 135 ° C for 15 seconds, then stretched 6 times at 135 ° C in the horizontal direction at 900% Z, and subsequently given 5% relaxation in the lateral direction. 15 corresponds to the heat treatment at 5 ° C.
- the obtained microporous polypropylene film having a thickness of 25 ⁇ m was defined as Example 9.
- the results are shown in Tables 1 and 2.
- the obtained microporous film was excellent in permeability with a high porosity and a very large pore diameter.
- the vertical strength was high and the handling was excellent.
- Example 4 instead of polypropylene resin A, polypropylene resin F prepared with the following composition was used, and after adjusting the discharge rate of the molten polymer having the extruder power, the longitudinal stretching temperature was set to 110 ° C. A longitudinal uniaxially stretched film was collected at a longitudinal stretching ratio of 4 times. Using the obtained longitudinally uniaxially stretched film, in the same manner as in Example 9, transverse stretching was performed under the following stretching conditions to produce a microporous polypropylene film having a thickness of 25 ⁇ m (Example 10).
- Polypropylene Sumitomo Chemical Co., Ltd. Polypropylene WF836DG3 (melt flow rate (M FR): 7gZlO min). - - 99 8 wt 0/0
- j8 nucleating agent ⁇ , N, monodicyclohexyl 2, 6-naphthalene dicarboxamide (NU-100, manufactured by Nippon Rika Co., Ltd.) ⁇ 0.2 wt%
- IRGANOX1 010 manufactured by Ciba Geigy Co., Ltd. and 0.1 parts by weight of IRGAFOS 168 manufactured by Ciba Geigy Co., Ltd. as a heat stabilizer were added to 100 parts by weight of the resin composition. This is fed to a twin screw extruder and melted and kneaded at 300 ° C, then extruded into a gut shape, cooled through a 20 ° C water tank, cut into a 3 mm length with a chip cutter, and 1 Dried at 00 ° C for 2 hours.
- Stepl Mode: Heating, Position: Stretching Oven, Time: 15sec
- Step2 Mode: Position, Position: Stretching Oven, MD: 1.00, 10% / sec, TD: 6.00, 10
- Step3 Mode: Position ⁇ Position: Annealing 1 Oven, MD: 1.00, 10% / sec ⁇ TD: 5.70, 10% / sec, Speed Mode: Constant Speed
- the above condition is that the longitudinally uniaxially stretched film was preheated at 140 ° C for 15 seconds, then stretched 6 times at 140 ° C in the horizontal direction at 600% Z, and subsequently given 5% relaxation in the lateral direction. , Corresponding to heat treatment at 5 ° C!
- the results are shown in Tables 1 and 2.
- the obtained microporous film was excellent in permeability with a high porosity and a very large pore diameter.
- the vertical strength was high and the handling was excellent.
- Example 5 a longitudinally uniaxially stretched film was collected after stretching in the longitudinal direction and cooling. The obtained longitudinally uniaxially stretched film was subjected to transverse stretching under the following stretching conditions using a film stretcher in the same manner as in Example 9 to produce a microporous polypropylene film having a thickness of 25 m (Examples). 11).
- Stepl Mode: Heating, Position: Stretching Oven, Time: 15sec
- Step2 Mode: Position, Position: Stretching Oven, MD: 1.00, 5% / sec, TD: 6.00, 5% / sec, Speed Mode: Constant Speed
- Step3 Mode: Position, Position: Annealing 1 Oven, MD: 1.00, 5% / sec, TD: 5.70, 5% / sec, Speed Mode: Constant Speed
- MD 1.00, 5% / sec
- TD 5.70, 5% / sec
- Speed Mode Constant Speed
- the results are shown in Tables 1 and 2.
- the obtained microporous film was excellent in permeability with a high porosity and a very large pore diameter.
- the vertical strength was high and the handling was excellent.
- Example 2 a longitudinally uniaxially stretched film was collected after stretching in the longitudinal direction and cooling. Using the obtained longitudinally uniaxially stretched film, a microporous polypropylene film having a thickness of 25 m and produced using a film stretcher under the same conditions as in Example 10 was designated as Example 12.
- the results are shown in Tables 1 and 2.
- the obtained microporous film had a high porosity and an extremely large pore diameter and excellent permeability.
- the vertical strength was high and the handling was excellent.
- Example 5 a longitudinal uniaxially stretched film was collected using a polypropylene resin G prepared with the following composition instead of the polypropylene resin C. Using the obtained longitudinally uniaxially stretched film, transverse stretching was performed under the same conditions as in Example 11 to produce a microporous polypropylene phenolic film having a thickness of 25 m (Example 13).
- Polypropylene Polypropylene manufactured by Sumitomo Chemical Co., Ltd. WF836DG3 (MFR: 7gZlO) ⁇ ⁇ 91.8% by weight
- High melt strength polypropylene having a long chain branch in the main chain skeleton Basell made polypropylene emissions PF- 814 (MFR: 3gZlO min) '- 3 wt 0/0
- j8 nucleating agent ⁇ , N, monodicyclohexyl 2, 6-naphthalene dicarboxamide (NU-100, manufactured by Nippon Rika Co., Ltd.) ⁇ 0.2 wt%
- Polyolefin-based ⁇ DuPont Dow Elastomer one Japan Ltd. "ENGAGE" ENR 7270 (mVLDPE2; ethylene 'butene copolymer), 5 weight 0/0
- the results are shown in Tables 1 and 2.
- the obtained microporous film was excellent in permeability with a high porosity and a very large pore diameter.
- the vertical strength was high and the handling was excellent.
- Example 10 polypropylene ⁇ F100 instead of by weight%, 95 weight polypropylene ⁇ fat F 0/0, with ⁇ set formed was added and mixed polypropylene ⁇ B at a ratio of 5 wt%, an extruder After adjusting the discharge amount of the molten polymer from, a longitudinally uniaxially stretched film was collected. Using the obtained longitudinally uniaxially stretched film, in the same manner as in Example 9, a film stretcher was used for transverse stretching under the following stretching conditions to produce a microporous polypropylene phenolic film having a thickness of 25 m. (Example 14).
- Stepl Mode: Heating, Position: Stretching Oven, Time: 15sec
- Step2 Mode: Position, Position: Stretching Oven, MD: 1.00, 4% / sec, TD: 6.00, 4% / sec, Speed Mode: Constant Speed
- Step3 Mode: Position ⁇ Position: Annealing 1 Oven, MD: 1.00, 4% / sec ⁇ TD: 5.70, 4% / sec, Speed Mode: Constant Speed
- the above condition is that the longitudinally uniaxially stretched film was preheated at 140 ° C for 15 seconds, then stretched 6 times at 140 ° C in the transverse direction at 240% Z, and subsequently given 5% relaxation in the transverse direction. , Corresponding to heat treatment at 5 ° C!
- Example 9 instead of polypropylene-based resin B, polypropylene-based resin H prepared in the following composition was used, and the thickness was 25 ⁇ m, which was produced under the same conditions except that the longitudinal draw ratio was set to 4 times.
- Example 15 was a microporous polypropylene film of m.
- Polypropylene Polypropylene manufactured by Sumitomo Chemical Co., Ltd. WF836DG3 (MFR: 7gZlO) ⁇ ⁇ 70% by weight
- Polyolefin-based ⁇ DuPont Dow Elastomer one Japan Ltd. "ENGAGE" 8100 (. MVLDPE3; ethylene Otaten copolymer), 30 weight 0/0
- This resin composition was supplied to a twin screw extruder, melted and kneaded at 250 ° C, extruded into a gut shape, cooled through a 20 ° C water bath, cut into a 3 mm length with a chip cutter, and 100 Dried for 2 hours at ° C.
- the results are shown in Tables 1 and 2.
- the obtained microporous film was excellent in permeability with a high porosity and a very large pore diameter.
- the vertical strength was high and the handling was excellent.
- Example 3 a longitudinally uniaxially stretched film was collected after stretching in the longitudinal direction and cooling. The resulting longitudinally uniaxially stretched film was subjected to transverse stretching under the following stretching conditions using a film stretcher in the same manner as in Example 9, to produce a microporous polypropylene film having a thickness of 25 m (Example 16).
- Stepl Mode: Heating, Position: Stretching Oven, Time: 15sec
- Step2 Mode: Position, Position: Stretching Oven, MD: 1.00, 2% / sec, TD: 6.00, 2% / sec, Speed Mode: Constant Speed
- Step3 Mode: Position, Position: Annealing 1 Oven, MD: 1.00, 2% / sec, TD: 5.70, 2% / sec, Speed Mode: Constant Speed
- MD 1.00, 2% / sec
- TD 5.70, 2% / sec
- Speed Mode Constant Speed
- the results are shown in Tables 1 and 2.
- the obtained microporous film was excellent in permeability with a high porosity and a very large pore diameter.
- the vertical strength was high and the handling was excellent.
- Example 7 longitudinal stretching was performed at a longitudinal stretching ratio of 4 times, and a longitudinally uniaxially stretched film was collected after cooling. Using the obtained longitudinally uniaxially stretched film, in the same manner as in Example 9, transverse stretching was performed under the following stretching conditions to produce a microporous polypropylene film having a thickness of 25 m (Example 17).
- Stepl Mode: Heating, Position: Stretching Oven, Time: 15sec
- Step2 Mode: Position, Position: Stretching Oven, MD: 1.00, 15% / sec, TD: 6.00, 15
- Step3 Mode: Position ⁇ Position: Annealing 1 Oven, MD: 1.00, 15% / sec ⁇ TD: 5.70, 15% / sec, Speed Mode: Constant Speed
- Example 1 instead of polypropylene resin A, film formation was attempted under the same conditions except that polypropylene resin D was supplied to a single screw extruder (Comparative Example 1). [0190] Raw material properties and film property evaluation results of the obtained microporous film are shown in Tables 1 and 2, respectively. Since tearing occurred frequently during transverse stretching, a completely satisfactory film could not be obtained, and the film could not be manufactured industrially.
- Comparative Example 1 a microporous polypropylene film having a thickness of 20 ⁇ m was prepared as Comparative Example 2 except that the film was stretched at 120 ° C. in the longitudinal direction and stretched at 135 ° C. in the transverse direction.
- the results are shown in Tables 1 and 2.
- the obtained microporous film had a low porosity and insufficient permeation performance and a small pore diameter compared to the microporous film obtained in the above Examples.
- Comparative Example 2 film formation was attempted under the same conditions except that the draw ratio in the machine direction was increased to 5 times (Comparative Example 3).
- Comparative Example 2 a 20 ⁇ m thick microporous polypropylene film prepared under the same conditions except that polypropylene resin I prepared in the following composition was supplied to a single screw extruder instead of polypropylene resin D was compared.
- Example 5 was used.
- Polypropylene Polypropylene manufactured by Sumitomo Chemical Co., Ltd. WF836DG3 (Melt Flow Rate (MFR): 7gZlO) ⁇ ⁇ 99. 95 wt%
- j8 crystal nucleating agent ⁇ , N, monodicyclohexyl 2, 6-naphthalene dicarboxamide (Nu Nippon Rika Co., Ltd. NU 100) ⁇ 0.05% by weight
- IRGANOX 1010 manufactured by Ciba Geigy Co., Ltd. was added as an antioxidant
- IRGAFOS168 manufactured by Ciba Geigy Co., Ltd. was added as a heat stabilizer.
- the results are shown in Tables 1 and 2.
- the obtained microporous film had a low porosity and insufficient permeation performance and a small pore diameter compared to the microporous film obtained in the above Examples.
- Comparative Example 2 the surface temperature of the cast drum was set to 125 ° C, and it was produced under the same conditions except that it was stretched 4 times at 90 ° C in the longitudinal direction and 4 times at 120 ° C in the transverse direction.
- a microporous polypropylene film having a thickness of 20 m was designated as Comparative Example 6.
- Comparative Example 1 instead of polypropylene resin D, polypropylene resin J prepared with the following yarn was supplied to a single screw extruder, and an attempt was made to contact the metal drum for 10 minutes. Force that lowers the casting speed to the minimum condition Cap force The point where the extruded sheet lands on the cast drum (landing point) vibrates without stability, and force that could not form an unstretched sheet substantially . Holding the unstretched sheet for 10 minutes on the drum was not practical at all, even if the casting speed was low, and it was necessary to use a cast drum with a diameter of 5 m or larger.
- Polypropylene Polypropylene manufactured by Sumitomo Chemical Co., Ltd. WF836DG3 (Melt Flow Rate (MFR): 7gZlO) ⁇ ⁇ 99. 96 wt%
- j8 nucleating agent ⁇ , N, 1-dicyclohexyl 2, 6-naphthalene dicarboxamide (NU 100, manufactured by Nippon Ryhi Co., Ltd.) ⁇ 0.04% by weight
- IRGANOX 1010 manufactured by Ciba Geigy Co., Ltd.
- IRGAFOS168 manufactured by Ciba Geigy Co., Ltd.
- Comparative Example 1 the polypropylene resin J was supplied to the single screw extruder instead of the polypropylene resin D, and the contact time with the metal drum was set to 40 seconds. Were collected. Immediately after that, the unstretched sheet was heat-treated in a hot air oven heated and maintained at 120 ° C for 10 minutes, and then the roll was again introduced into the longitudinal stretching machine, and stretched 6 times at 105 ° C in the longitudinal direction. An attempt was made to stretch 8 times at 155 ° C in the direction (Comparative Example 7).
- Comparative Example 7 film formation was attempted under the same conditions except that the longitudinal draw ratio was lowered to 4 times (Comparative Example 8).
- Polypropylene resin K having the following composition was prepared.
- Polypropylene Polypropylene WF836DG3 (melt flow rate ( ⁇ FR): 7gZlO min) manufactured by Sumitomo Chemical Co., Ltd. ⁇ 94. 95% by weight
- j8 crystal nucleating agent ⁇ , N, monodicyclohexyl 2, 6-naphthalene dicarboxamide (Nu Nippon Rika Co., Ltd. NU 100) ⁇ 0.05% by weight
- Polymethylpentene Mitsui Chemicals Co., Ltd. polymethylpentene "TPX" RT—18 ⁇ ⁇ 5 wt%
- This resin composition is fed to a twin-screw extruder, melted and kneaded at 280 ° C, and then extruded into a gut shape.
- the sample was cooled by passing through a 30 ° C water bath, cut to a length of 3 mm with a tip cutter, and then dried at 100 ° C for 2 hours.
- the obtained unstretched sheet was preheated through a group of rolls maintained at 120 ° C, passed between rolls maintained at 120 ° C and provided with a difference in peripheral speed, and quadrupled in the longitudinal direction at 120 ° C. Stretched and cooled to 30 ° C. Subsequently, both ends of this longitudinally stretched film were introduced into a tenter while being held by clips, preheated at 135 ° C, and stretched 8 times in the transverse direction at 135 ° C. Next, the film was heat-set at 150 ° C. while giving 5% relaxation in the transverse direction in the tenter, uniformly cooled, and then cooled to room temperature. Furthermore, the both surfaces were subjected to corona discharge treatment in the air and wound up to obtain a microporous polypropylene phenol having a thickness of 25 m.
- Celgard “Celguard” 2500 was designated as Comparative Example 10.
- “Celguard” 2500 is a microporous polypropylene film using a lamellar stretching method.
- the results are shown in Tables 1 and 2.
- the obtained microporous film is a uniaxially oriented film and has a lower porosity than the microporous film of the above-mentioned Examples. Further, since the vertical orientation of the crystal chain was too high, it had the property of being easily broken in the vertical direction.
- Example 3 instead of polypropylene resin A, a polyp prepared with the following composition: Film formation was attempted under the same conditions except that Lopylene-based resin L was supplied to a single screw extruder (Comparative Example 11).
- Polypropylene Sumitomo Chemical Co., Ltd. polypropylene WF836DG3 (melt flow rate (M FR): 7gZlO minutes). ⁇ ⁇ 94 8 weight 0/0
- j8 nucleating agent ⁇ , N, monodicyclohexyl 2, 6-naphthalene dicarboxamide (NU-100, Nippon Rika Co., Ltd.) ⁇ 0.2 wt%
- Acrylic modified high molecular weight polytetrafluoroethylene full O b Ethylene Mitsui Rayon Co., Ltd.
- Metalpuren A type (A- 3000) ⁇ ⁇ 5 weight 0/0
- This resin composition was supplied to a twin screw extruder, melted and kneaded at 250 ° C, extruded into a gut shape, cooled through a 20 ° C water bath, cut into a 3 mm length with a chip cutter, and 100 Dried for 2 hours at ° C.
- I (D) X-ray intensity in the vertical direction of the film
- I (TD) X-ray intensity in the horizontal direction of the film
- Example 3 Using the microporous film obtained in Example 3 as it is as the separator of the present invention, a lithium ion battery, which is the electricity storage device of the present invention, was produced by the method described in (20) above.
- the average pore diameter of the resulting film could be significantly increased.
- the above-described battery characteristics internal resistance, rate characteristics, cycle characteristics
- the microporous film for an electricity storage device separator of the present invention is not limited to the lithium ion battery exemplified above, but also other primary batteries, secondary batteries, and capacitors such as electric double layer capacitors and electrolytic capacitors. Thus, it is preferably used as a high-performance separator exhibiting good ion conductivity while maintaining basic isolation performance.
- FIG. 1 schematically shows a calorimetric curve obtained when the ⁇ crystal fraction described in the above measurement method (13) is obtained using a differential scanning calorimeter (DSC).
- DSC differential scanning calorimeter
- Figure 2 shows the heat of fusion ( ⁇ ⁇
- FIG. 6 is a diagram schematically showing the heat of fusion ( ⁇ H a) obtained from the area of an endothermic peak accompanying melting of a polypropylene-derived crystal other than ⁇ crystal.
- Fig. 3 is a schematic illustration of the arrangement of the sample and the device when the 2 ⁇ , ⁇ scan X-ray diffraction profile described in the measurement method (6) above is collected using the wide-angle X-ray diffraction method. It is a diagram shown in FIG.
- FIG. 4 schematically shows the arrangement of samples when the intensity distribution profile in the azimuth (13) direction described in the measurement method (6) above is collected using the wide-angle X-ray diffraction method. It is a figure.
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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EP06810814A EP1950821B1 (en) | 2005-10-18 | 2006-09-29 | Microporous film for power storage device separator and power storage device separator making use of the same |
CA2625083A CA2625083C (en) | 2005-10-18 | 2006-09-29 | Microporous film for electric storage device separator and electric storage device separator using the same |
CN2006800389738A CN101292378B (zh) | 2005-10-18 | 2006-09-29 | 蓄电装置隔离物用微多孔膜以及使用该膜的蓄电装置隔离物 |
JP2006549738A JP5145712B2 (ja) | 2005-10-18 | 2006-09-29 | 蓄電デバイスセパレータ用微多孔フィルムおよびそれを用いた蓄電デバイスセパレータ |
KR1020087011827A KR101401833B1 (ko) | 2005-10-18 | 2006-09-29 | 축전 디바이스 세퍼레이터용 미다공 필름 및 그것을 이용한축전 디바이스 세퍼레이터 |
US12/083,729 US8089746B2 (en) | 2005-10-18 | 2006-09-29 | Microporous film for electric storage device separator and electric storage device separator using the same |
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JP2005302718 | 2005-10-18 | ||
JP2005-302718 | 2005-10-18 |
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WO2007046226A1 true WO2007046226A1 (ja) | 2007-04-26 |
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PCT/JP2006/319408 WO2007046226A1 (ja) | 2005-10-18 | 2006-09-29 | 蓄電デバイスセパレータ用微多孔フィルムおよびそれを用いた蓄電デバイスセパレータ |
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US (1) | US8089746B2 (ja) |
EP (1) | EP1950821B1 (ja) |
JP (1) | JP5145712B2 (ja) |
KR (1) | KR101401833B1 (ja) |
CN (1) | CN101292378B (ja) |
CA (1) | CA2625083C (ja) |
TW (1) | TWI387145B (ja) |
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EP1950821A1 (en) | 2008-07-30 |
KR101401833B1 (ko) | 2014-05-29 |
CN101292378A (zh) | 2008-10-22 |
TW200740011A (en) | 2007-10-16 |
JPWO2007046226A1 (ja) | 2009-04-23 |
CA2625083A1 (en) | 2007-04-26 |
CA2625083C (en) | 2013-06-18 |
JP5145712B2 (ja) | 2013-02-20 |
EP1950821A4 (en) | 2010-03-03 |
US20090219672A1 (en) | 2009-09-03 |
TWI387145B (zh) | 2013-02-21 |
KR20080070664A (ko) | 2008-07-30 |
EP1950821B1 (en) | 2013-01-16 |
CN101292378B (zh) | 2010-11-03 |
US8089746B2 (en) | 2012-01-03 |
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