CN101495552A - Roll of polyolefin microporous film and production method thereof - Google Patents

Roll of polyolefin microporous film and production method thereof Download PDF

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Publication number
CN101495552A
CN101495552A CNA2007800282326A CN200780028232A CN101495552A CN 101495552 A CN101495552 A CN 101495552A CN A2007800282326 A CNA2007800282326 A CN A2007800282326A CN 200780028232 A CN200780028232 A CN 200780028232A CN 101495552 A CN101495552 A CN 101495552A
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coiling
thing
polyolefin microporous
film
roll
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CN101495552B (en
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西村佳史
高桥晃
新原靖
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Asahi Kasei Corp
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Asahi Kasei Chemicals Corp
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    • 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
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • 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
    • 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
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0404—Machines for assembling batteries
    • H01M10/0409—Machines for assembling batteries for cells with wound electrodes
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H01M50/406—Moulding; Embossing; Cutting
    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Cell Separators (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention provides a roll of polyolefin microporous film and its production method. The roll of polyolefin microporous film consists of a roll having a polyolefin microporous film rolled up around a roll core, characterized in that the absolute value ([mu]m) of difference (film thickness difference) between the film thickness (T, [mu]m) calculated according to the formula (1) and the film thickness (t, [mu]m) evaluated for one sheet is 1.5 [mu]m or less. Further, there is provided a process for producing the same. T([mu]m) = p(D<2>-d<2>)/4L, wherein D is the outer diameter (mm) of roll resulting from rolling up around the roll core including the porous film; d is the outer diameter (mm) of roll core; and L is the rolling length (m) of the roll.

Description

Roll of polyolefin microporous film thing and manufacture method thereof
Technical field
The present invention relates to the employed roll of polyolefin microporous film thing of a kind of battery diaphragm (separator), be about to by polyolefine or contain the micro-porous film that polyolefinic resin combination constitutes be wound on the coiling thing that forms on the core.Be particularly related to and be suitable as lithium-ion secondary cell with membranous roll of polyolefin microporous film thing and manufacture method thereof.
Background technology
Polyolefin microporous film is used as various battery separators.Particularly good with respect to the patience of organic solvent owing to polyolefin resin, and electronic isolation is also good, therefore especially lithium-ion secondary celies that are used for more.
In recent years, be accompanied by portable telephone as the lithium-ion secondary cell main application, PC, the multifunction of other handheld device, lightweight, cost degradation, strong request cell high-capacityization, high-energy-densityization.Wherein, high capacity, high energy quantification with respect to battery require membrane filmization.On the other hand, put in the battery can, more and more require the external diameter precision of electrode-membrane coil around thing for the coiling thing (electrode-membrane coil is around thing) of will reel together barrier film and electrode.
In addition, also worked out recently large-scale lithium-ion secondary cell as automobile with, storage usefulness, this moment, employed membranous wider width, coiling length were longer.In order extensively to popularize so large-scale lithium-ion secondary cell, also need to make accurately the external diameter of coiling thing, thereby can reduce the fraction defective when being inserted into lithium-ion secondary cell in the jar, seek cost degradation.
For example, patent documentation 1 is a purpose to improve making the isochronous operation of battery diaphragm etc., has proposed to make maximum outside diameter and the minimum outer diameter roll of polyolefin microporous film thing in specified range.But the external diameter precision of above-mentioned coiling thing is not enough.
Patent documentation 1: TOHKEMY 2004-99799 communique
Summary of the invention
Problem of the present invention is to provide a kind of and can reduces at the bad roll of polyolefin microporous film thing of the insertion that electrode-membrane coil is taken place when thing is inserted in the jar.And, roll of polyolefin microporous film thing and the manufacture method thereof that can use electrode-membrane coil to carry out the thickness management around the external diameter of thing are provided.
Improving electrode-membrane coil around aspect the external diameter precision of thing, is extremely important as electrode-membrane coil around the management of the external diameter precision of polyolefin microporous film (barrier film) the coiling thing of the material of thing, the inventor is conceived to this situation and concentrates on studies, found that can solution to the problems described above, has proposed the present invention.Particularly, found according to cutting apart the thickness information that the measured external diameter of volume outside diameter measuring machine and coiling length calculate by TOHKEMY 2006-88255 communique is disclosed, can manage the external diameter of the coiling thing of together reeling accurately, thereby propose the present invention with electrode.
In addition, the inventor finds, will be wound on polyolefin microporous film on the parent roll (be cut into desired width before coiling thing) in whole width range, cut into Rack after, each polyolefin microporous film after the cutting of reeling and making under the situation of coiling thing, in order to improve the external diameter precision of coiling thing, can be respectively to each coiling thing control coiling tension.
Promptly, to be wound on polyolefin microporous film on the parent roll cuts into Rack in whole width range after in the past, reel after the cutting each polyolefin microporous film and make under the situation of coiling thing, the coiling tension of each polyolefin microporous film is that a plurality of coiling thing collective that reels is simultaneously controlled, or cooperate specific coiling to control equably, but the inventor judges through research, in such control method, as the coiling thing of non-independent controlled member be not reel tension, it is too loose to reel exactly, thereby can't manage the external diameter of these coiling things.
Promptly, the present invention is as described below.
A kind of coiling thing, it is the coiling thing that the coiling polyolefin microporous film forms on the volume core, it is characterized in that utilizing the absolute value (μ m) of film thickness T (μ m) that following formula (1) calculates and the film thickness t (μ m) that draws with a micro-porous film evaluation poor (film thickness poor) is below the 1.5 μ m.
T(μm)＝π(D 2-d 2)/4L (1)
(in the above-mentioned formula (1), D refers to comprise the external diameter (mm) that is wound on the coiling thing on the core of porous-film, and d refers to roll up the external diameter (mm) of core, L refer to reel the coiling length (m) of thing)
In addition, the present invention is as described below.
A kind of manufacture method of roll of polyolefin microporous film thing, this manufacture method comprises following operation:
The polyolefin microporous film that is wound on the parent roll is cut into Rack in whole width range;
On one side to each coiling thing control coiling tension, reel and be cut into each polyolefin microporous film of this Rack on one side.
Adopt roll of polyolefin microporous film thing of the present invention, play to be manufactured on the such effect of the insertion one-piece type coiling thing of bad less electrode-barrier film that takes place when inserting this coiling thing in the jar.And, adopt the present invention, play the external diameter that can use the one-piece type coiling thing of electrode-barrier film and carry out the such effect of thickness management.In addition, manufacture method of the present invention plays and can make the such effect of said polyolefins microporous film coiling thing expeditiously.If method of the present invention also is applied to can also manage the external diameter of the one-piece type coiling thing of electrode-barrier film more accurately in the electrode etc.
Description of drawings
Fig. 1 is the sketch chart of an example of the expression device that is used to measure coiling beyond the region of objective existence of the present invention footpath.
Fig. 2 is the sketch chart of an example of the device of the expression external diameter that is used to measure coiling thing group of the present invention.
Fig. 3 is a line chart of representing to measure simultaneously the result's who obtains after the size of a plurality of coiling things a example.
Fig. 4 is the sketch chart that batches arm of an example of manufacture method of the present invention.
Fig. 5 is the sketch chart of an example of expression manufacture method of the present invention.
Fig. 6 is the synoptic diagram of basic comprising part of the part of the expression film thickness that is used to measure micro-porous film.
Fig. 7 is the synoptic diagram (front view) of the preferred film thickness measuring apparatus of expression.
Fig. 8 is the synoptic diagram (front view) of the preferred film thickness measuring apparatus of expression.
Fig. 9 is the synoptic diagram of an example of the elasticity measuring apparatus of expression coiling thing.
Description of reference numerals
The luminous machine of 1A, optical profile type dimensional measurement machine; 1B, optical profile type dimensional measurement machine be subjected to ray machine; 2, roll of polyolefin microporous film thing; 3, signal processing part; 5, check result efferent; 6, drive transfer part; 7, be with synchronously; 8, chuck portion; 9, drive shaft; 10, gear; 11, parent roll; 12, roll of polyolefin microporous film thing; 13, independent arm; 14, cutter; 21, supporting station; 22, pillar; 23, test portion platform; 24, measuring junction sub bar; 25, the manual indicator stem up and down of measuring junction sub bar; 26, analog information portion; 27, terminal parallelism adjustment function; 28, surface pressure adjustment part; 29, optical profile type test section fixed part; 30, optical profile type test section; 31, optical profile type test section fixed part height control portion; 32, surface pressure adjustment part fixed part; 37, test portion.
Embodiment
Describe the present invention below in detail.
The roll of polyolefin microporous film thing
Roll of polyolefin microporous film thing of the present invention is the coiling thing that the coiling polyolefin microporous film forms on columned volume cores such as pipe, it is characterized in that the absolute value (μ m) of the film thickness T (μ m) that calculates with following formula (1) and the film thickness t (μ m) that obtains with a micro-porous film evaluation poor (film thickness poor) is below the 1.5 μ m.
T(μm)＝π(D 2-d 2)/4L (1)
(in the above-mentioned formula (1), D refers to comprise the external diameter (mm) that is wound on the coiling thing on the core of porous-film, and d refers to roll up the external diameter (mm) of core, L refer to reel the coiling length (m) of thing).
At poor (T-t) of film thickness during greater than 1.5 μ m, because the coiling of coiling thing is loose excessively, therefore use this coiling thing as electrode-membrane coil under the situation of thing, can't carry out electrode-membrane coil around the management of the external diameter of thing, increase unfavorable conditions such as can not inserting of when should the coiling thing being inserted in the jar, taking place.On the other hand, under poor (T-t) of film thickness situation less than-1.5 μ m, because the coiling tension of coiling thing, the perviousness of the thing that therefore causes reeling is bad.The absolute value of the difference of film thickness is preferably below the 1.2 μ m, more preferably below the 1.0 μ m, most preferably is below the 0.5 μ m.
The absolute value of poor (T-t) of film thickness is more little, approach 0 more, the polyolefin microporous film of can not loosely not reeling tightly more, but in the present invention, preferably rolling-in is a little a little with the roll of polyolefin microporous film thing.Particularly, the value (μ m) of preferred T-t is-0.5≤T-t＜0.
In addition, employed core when " the volume core " among the present invention is meant polyolefin microporous film made the coiling thing, this volume core is a cylindrical shape.As preferred object lesson, can enumerate pipes such as paper tube, plastics tubing.
From reduce bad this viewpoint of insertion that electrode-membrane coil is taken place when thing inserts the jar, the present invention preferably adopts the form of roll of polyolefin microporous film thing group, this roll of polyolefin microporous film thing group be by more than 2 to being wound on that polyolefin microporous film on the parent roll cuts and the coiling thing group that the said polyolefins microporous film coiling thing that obtains constitutes, the coiling deviation is in 5mm, and the standard variance of poor (the μ m) of above-mentioned film thickness is below the 0.7 μ m, more preferably below the 0.5 μ m.At this, parent roll is meant the film volume before the width that is cut into user expectation, and width is more than the 350mm usually, also has more than the 600mm.The coiling deviation is meant in volume has been reeled the coiling thing of polyolefin microporous film on the core, in the whole length range of the polyolefin microporous film of being reeled, and the position deviation of the end of the polyolefin microporous film of being reeled.That is, refer to the polyolefin microporous film of being reeled an end, in outermost part of the width of coiling thing and the distance on the width between the most inboard part.And just under the situation with each coiling thing, even under the situation with a plurality of coiling things (coiling thing group) of constituting the whole width of parent roll, also the difference of preferred film thicknesses is less, and this is self-explantory.
In the present invention, the D that " is wound on the external diameter that comprises porous-film of the coiling thing on the core " is meant that hypothesis is the diameter under the situation of cylinder at the roll of polyolefin microporous film thing of the polyolefin microporous film of having reeled on the axle, but under its cross section was not just round situation, D was meant and the minor face of the bounding rectangle of the external area minimum in cross section and the mean value on long limit.Particularly, for being inboard part, use method as follows more than the 3mm of the two ends of coiling thing, the diameter of the equally spaced a plurality of point measurement coiling things on the width of micro-porous film is obtained D by calculating its mean value.
The outer diameter D of roll of polyolefin microporous film thing of the present invention can be utilized the outside diameter measuring device high precision described in the TOHKEMY 2006-88255 communique for example shown in Figure 1 and record effectively.Fig. 1 is the sketch chart of basic comprising part of the part of the expression external diameter that is used to measure the coiling thing.That is,, measure the external diameter of coiling thing by the image of measuring coiling thing 2 with being subjected to ray machine 1B to receive laser or the visible light that sends by luminous machine 1A.Above-mentioned luminous machine, be subjected to ray machine can adopt the product of usually on market, selling as laser size measuring engine or digital dimensional measurement machine etc.
For example, make by 2 groups of luminous machine 1A and move abreast with the turning axle direction of the dimension measuring device that constituted by ray machine 1B along coiling thing 2, thus the external diameter of all positions on a line of turning axle (volume core) direction of measurement coiling thing.As long as dimension measuring device relatively moves with respect to coiling thing 2, dimension measuring device being moved or coiling thing 2 is moved can.In addition, according to the coiling thing that will measure, consider operability, also can make can be with the measuring apparatus of coiling thing traverse etc.Make the speed that moves by luminous machine, the dimension measuring device that constituted by ray machine according to suitably decisions such as the measuring accuracy of the coiling thing of necessity, Measuring Time.In addition, the measurement of external diameter is carried out with growing on corresponding 2 directions in limit at the minor face with bounding rectangle, use their mean value, but utilize the useful range of the coiling thing 2 that the dimensional measurement machine measures usually so long as to measure the external diameter at 1 position of coiling thing continuously just enough.Why like this, to be because the external diameter difference of coiling thing is that measuring the resulting result of external diameter on any position all is identical basically because the thickness difference accumulation of many films produces, and it is just round that its cross section is actually.
Preferred example when in addition, Fig. 2 represents to measure the external diameter of coiling thing group of the present invention.Work accurately in order to make the dimensional measurement machine, preferably coiling thing group is arranged on 2 groups of substantial middle portions that are subjected to ray machine 1A and are subjected to ray machine 1B, for example, can by 2 groups be subjected to ray machine 1A and be subjected to the central authorities of ray machine 1B be provided for fixedly cutting apart volume spool etc. method etc. fix coiling thing group.If change 2 groups of width that are subjected to ray machine 1A and are subjected to ray machine 1B, the coiling thing group that then can one-shot measurement constitutes by the coiling thing of different diameter.Fig. 3 represents to measure simultaneously the result's of the coiling thing group that a plurality of coiling things by different diameter constitute a example.The part of A is the take off data in the gap between the coiling thing among the figure, preferably has continuously to delete the interruption arithmetic processing section partly of respectively reeling between thing the continuously measured data between a plurality of coiling things.Therefore, can adopt the take off data that rises, descends by deletion to obtain the calculation method in a plurality of coiling beyond the region of objective existences footpath, or take off data be carried out differential handle, deletion outside diameter measuring part jumpy is obtained the calculation method in a plurality of coiling beyond the region of objective existences footpath.In addition, under the situation of cutting time-division slivering, because each bar is wound in respectively on 1 wireline reel, therefore, preferably have the film thickness information of the metrical information that can make each bar and winding film thing and position relationship consistency and handling part that the metrical information of each bar is handled as the film thickness information of bar continuously.The display part that also can have take off data in the said apparatus.
In the present invention, " the film thickness t that obtains with a micro-porous film evaluation " is meant the film thickness t of the polyolefin microporous film that constitutes the coiling thing, for example, micro-porous film for the most peripheral of roll of polyolefin microporous film thing, by measuring film thickness on equally spaced a plurality of points on the width, and the mean value of calculating them is obtained film thickness t.
In the present invention, the measuring method of the film thickness of polyolefin microporous film does not limit, for example, except the method shown in the following embodiment, for example also can be on micro-porous film the mounting measurement terminal, read the action of measurement terminal and be converted into film thickness, thereby measure accurately.For example can adopt optical detector to read the action of measurement terminal.In addition, preferably will be applied to the pressure-controlling of the per unit area on the micro-porous film in the constant scope by measurement terminal.And, preferably in thermostatic chamber, measure.
Fig. 6 represents to be used to measure the side-view of basic comprising part of an example of device of the film thickness t of micro-porous film.Mounting terminal portion fixed part 25, optical detector fixed part 29 on the pillar 22 that is arranged on the supporting station 21.
Then, use Fig. 7,8 explanations to measure the method for the film thickness t of micro-porous film accurately.Fig. 7 is illustrated in the figure that has placed the state of micro-porous film on the test portion platform 23, and Fig. 8 is the figure that expression is positioned in measuring junction sub bar 24 state on the micro-porous film.Shown in Fig. 7,8, mounting is as the micro-porous film 37 of measuring test portion between test portion platform 23 and measuring junction sub bar 24, move the manual indicator stem 25 up and down of measuring junction sub bar, micro-porous film 37 is clamped between measuring junction sub bar 24 and the test portion platform 23, for example utilize from the reflected light of surface pressure adjustment part fixed part 32 etc. by optical profile type test section 30 and to read knee-action with measuring junction sub bar 24 direct banded surface pressure adjustment part fixed parts 32, be converted into film thickness, thereby read film thickness.Measuring technology about this optical profile type test section, for example, as the products catalogues such as comprehensive individual of Keyemce (KEYENCE) company are introduced, can use confocal measurement mode, range of triangle mode, sight modes such as mode, light wave distance measuring method etc. automatically.As the example of the best, preferably use the fluorescence detector of range of triangle mode.The range of triangle mode is meant to be utilized sensitive lens that the laser of launching is assembled in the part of the lip-deep diffused reflection light of object and makes its imaging mode on CCD, when object generation displacement, the convergence angle generation displacement of diffused reflection light, image space on the CCD moves, detect and to move, accordingly amount of movement is converted into film thickness, thereby reads out film thickness.The resolving power of the optical profile type test section 30 that use preferred this moment is below 1 μ m, more preferably below 0.1 μ m, further preferably below 0.01 μ m.In addition, preferably after micro-porous film 37 being clipped between measuring junction sub bar 24 and the test portion platform 23, after having passed through specified time, for example 5 seconds～1 minute, preferred 5～30 seconds, measure.As the object lesson of preferred fluorescence detector, can enumerate the LK-G15 of Keyemce corporate system.
For high reproducibility, measure the thickness of micro-porous film accurately, it is very important making test portion platform 23 and measuring junction sub bar 24 parallel.Therefore, as shown in Figure 6, measurement terminal parallelism adjustment function 27 is set preferably, thereby can carries out inching.More preferably utilizing after water level gauge adjusts the horizontality of test portion platform 23, adjusting the parallelism of test portion platform and measuring junction sub bar.The diameter of measuring junction sub bar is not particularly limited, but is preferably 1～20mm, more preferably 1～10mm.In the example of Fig. 6～8, as the measuring junction sub bar, use the measuring junction sub bar of its diameter as 5mm, use the measuring junction sub bar of having checked verticality.
And, when utilizing the optical profile type test section to read the action of measuring junction sub bar, measure film thickness in the preferred thermostatic chamber, to avoid producing difference.
In addition, in order to use many high reproducibilities of measuring apparatus, to measure the thickness of micro-porous film accurately, preferably will be set as constant with the surface pressure of the contacted measuring junction sub bar of micro-porous film.In the example of Fig. 6～8, be provided for the surface pressure adjustment part 28 of mounting counterweight on the top of the analog information portion 26 of measuring junction sub bar 24, this counterweight is used to adjust the surface pressure of measuring junction sub bar 24, the surface pressure of measuring junction sub bar 24 is adjusted into constant, and utilizes surface pressure adjustment part fixed part 32 to fix.In the example of Fig. 6～8, adjust the surface pressure of measuring junction sub bars 24 in order to utilize surface pressure adjustment part 28, as shown in Figure 7, used in the inside of analog information portion 26 and measuring junction sub bar 24 surface pressure adjustment part as one.As being used to make the surface pressure of measuring junction sub bar 24 is other method of specified pressure, for example also employed measuring junction sub bar in a plurality of measuring apparatuss self can be set as same weight.
The manufacture method of roll of polyolefin microporous film thing
Only pine among the present invention but the roll of polyolefin microporous film thing of reeling tightly, the external diameter precision is higher, can in whole width range, cut into each roll of polyolefin microporous film after cut after the Rack on the volume core time by being wound on polyolefin microporous film on the parent roll, each coiling thing is controlled the coiling tension of polyolefin microporous film and made.
Method to each coiling thing control coiling tension is unqualified.For example, can have respectively on the individual volume core of rotary driving part, and utilize separately rotary driving part to make and independently roll up the core rotation, to each coiling thing control coiling tension by each roll of polyolefin microporous film after will cutting.In addition, each roll of polyolefin microporous film that will obtain after will cutting has on the volume core of shared rotary driving part or is being wound under the situation on a plurality of volume cores that are fixed on the turning axle with shared rotary driving part, can tenslator comes each coiling thing control coiling tension by being provided with independently in addition each polyolefin microporous film.
Particularly, can preferably obtain coiling thing of the present invention by utilizing independent drive formula cutting machine cutting polyolefin microporous film and this film being wound on the pipe (volume core).Owing to when independent drive formula cutting machine cuts on the whole width of parent roll, can cut apart each and involve in capable tension control, therefore be applicable to and make roll of polyolefin microporous film thing of the present invention expeditiously.
As the example of independent drive formula cutting machine, the cutting machine with a plurality of driving transfer part 6 is as shown in Figure 4 arranged.Drive transfer part 6 and for example use powder clutch etc., the roller 9 that turns round with utilizing general AC electric motor is connected, and can utilize synchronously and come the driving of self-driven transfer part to be placed in the coiling of the pipe (not shown) in the chuck portion 8 with 7 transmission such as grade.Under the situation of having used powder clutch, can utilize electrical signal to control its output torque.Thereby, carry out the tension force detection by each independently being managed coiling portion, and impose the electricity feedback, can carry out independently managing the corresponding coiling of tension force of coiling portion with each.Fig. 5 represents the sketch chart of such device.Utilize cutter 14 will cut into the width of expectation, and the roll of polyolefin microporous film after will cutting have on the pipe independent arm 13 (each is coiling portion independently), that supported by shared axle (not shown) from the polyolefin microporous film before the cutting that parent roll 11 is emitted.Relative therewith, coaxial drive type cutting machine in the past cuts parent roll in whole width range, when on pipe, reeling with shared coiling portion, cooperate the specific coiling thing ground in adjacent a plurality of coiling things to carry out tension control, therefore the coiling thing that is obtained is not to reel tightly, reel loosely exactly, therefore be difficult to manage external diameter, thereby be difficult to preferably obtain coiling thing of the present invention.In addition, also be easy to produce the coiling deviation.
In addition, in the present invention, independent drive formula cutting machine is the device of reeling after the flap cutting, and each flap after the cutting is wound on the independently volume core that has rotary driving part respectively.
Coiling tension during about the coiling polyolefin microporous film, preferably make parent roll emit tension force be 125 (N/m) following about, what make the coiling tension of the thing of respectively reeling and parent roll emits tension force (preferably in ± 20%) about equally.For example, coiling tension is repeatedly reeled in above-mentioned scope with changing, and measure the coiling elasticity of the coiling thing that is obtained, decide the occurrence of coiling tension according to its result.
In the present invention, the elasticity of preferred polyolefm microporous film coiling thing is being below the 34N apart from volume core 5mm distance.When reeling more tightly, can cause that the roll-shape of coiling thing is bad above this elasticity.
In addition, the elasticity (F (10)) of the distance volume core 10mm distance of preferred polyolefm microporous film coiling thing is 0.05N～2N with poor (F (10)-F (20)) of the elasticity (F (20)) of distance volume core 20mm distance.When the value of F (10)-F (20) was in this scope, it was bad to reduce coiling deviation, layer deviation, depoling etc.
At this, the elasticity of coiling thing is one of the index that is used to estimate the reeling condition of coiling thing, is to be that 0.04～0.07mm, needle point angle are that 25～27 °, needle point R are the needed power of side 1cm (N) that is needled into the coiling thing of 0.04～0.07mm with point diameter.In addition, apart from the volume core distance be meant the side of coiling thing see from the volume wicking surface to the volume core cross section (circle) the vertical direction of tangent line on distance.
For example can utilize the following method of " Smith reel the test of thing elasticity " that in " simple basic technology lecture the 7th backrush of cutting machine/rewinder is around the quality of thing " in December, 1996 number, introduced based on コ Application バ one テ Star Network (convertech) to measure the elasticity of coiling thing.
Fig. 9 represents to be used to measure the sketch chart of device of the elasticity of coiling thing.The elasticity measuring apparatus 101 of coiling thing is the device that pin has been installed on ergometer.The pin front end of measuring apparatus 101 is thrust the measuring position, and vertical depression measuring apparatus 101 is up to inserting the needle into 1cm, the load of measurement peak value at this moment, thereby the elasticity of measurement coiling thing.This device for example can adopt the pin of " model-13 " total length 38mm of the safety pin of intercepting Kokuyo company (kokuyo) system partly to be installed on the device that obtains on the digital force gauge of HF-10 of Japanese measurement system (strain).
In addition, utilizing independent drive formula cutting machine and when making the roll of polyolefin microporous film thing to being wound on polyolefin microporous film on the parent roll and cutting, coiling deviation after the whole width range of parent roll cuts 5mm with interior coiling thing group in, can further reduce bad this viewpoint of coiling thing of insertion that takes place when being inserted into the one-piece type coiling thing of electrode-barrier film the jar from providing, preferably making the standard variance of the film thickness T (μ m) that utilizes following formula (1) to calculate and the film thickness t (μ m) that obtains with a micro-porous film evaluation poor (film thickness poor) is below the 0.7 μ m, more preferably below the 0.5 μ m.
T(μm)＝π(D 2-d 2)/4L (1)
(in the above-mentioned formula (1), D refers to comprise the external diameter (mm) that is wound on the coiling thing on the core of porous-film, and d refers to roll up the external diameter (mm) of core, L refer to reel the coiling length (m) of thing).
In the present invention, from the viewpoint of coiling, cost, the volume core size of the polyolefin microporous film that is preferred for reeling is that external diameter is more than the 91.8mm.Usually call employed volume core according to internal diameter.If external diameter is the paper tube of 91.8mm, then internal diameter is 76.2mm usually, and paper thickness can be adjusted according to intensity in the scope of 5～15mm.Employed pipe can use the tolerance of selling on the common market for ± 0.5mm, more preferably ± paper tube of 0.3mm, plastics tubing, preferably use the less pipe of tolerance.
Coiling thing of the present invention plays to provide and can reduce the bad such effect of the one-piece type coiling thing of electrode, barrier film of insertion that takes place when being inserted into the coiling thing in the jar, as the barrier film that has used wider width (for example, 60～160mm), barrier film that coiling length is long (for example 500～3000m, be preferably electrode-membrane coil of 800～2500m) under the situation that thing is used, such particular significant effect.
Adopt roll of polyolefin microporous film thing of the present invention, in volume has been reeled the coiling thing of polyolefin microporous film on the core, also can write down clearly according to the external diameter that comprises porous-film that is wound on the coiling thing on the core, the volume external diameter of core and the film thickness (μ m) that coiling length is calculated, thereby can provide the bad electrode-membrane coil of the insertion that can reduce generation when being inserted into the coiling thing in the jar around thing.
Polyolefin microporous film
The aperture of the polyolefin microporous film among the present invention is preferably 0.001～1 μ m, more preferably 0.01～0.1 μ m.In the present invention, this known fact that utilization flows according to knudsen flow at the fluid of fluidic mean free path kapillary inside during greater than aperture capillaceous, the fluid in fluidic mean free path kapillary inside during less than aperture capillaceous flows according to Poiseuille flow, air flowing during the Gas permeability of supposing micro-porous film is measured flows according to knudsen flow and the permeable degree of micro-porous film the flowing of water in measuring flowed according to Poiseuille flow, represents the aperture r (μ m) of micro-porous film with formula as follows.
r＝2v×(Rliq/Rgas)×(16η/3Ps)×106
At this, Rgas is the penetration speed constant (m of air 3/ (m 2SecPa)), Rliq is the penetration speed constant (m of water 3/ (m 2SecPa)), v is the molecular velocity (m/sec) of air, and η is the viscosity (Pasec) (=0.8950mPasecat25 ℃) of water, Ps be standard pressure (Pa) (=101325Pa), represent with following formula respectively.
Rgas=0.0001/ (Gas permeability * (6.424 * 10-4) * (0.01276 * 101325))
In addition, Gas permeability is tried to achieve according to JIS P-8117.
The permeable degree of Rliq=/100
In addition, permeable degree is following tries to achieve like that.Be placed in the saturating liquid box of stainless steel of diameter 41mm being immersed in micro-porous film in the ethanol in advance, water rinses out after the ethanol of this film, utilizes the differential pressure of about 50000Pa that water is seen through, the permeable amount (cm according to through 120sec the time 3) calculating the permeable amount of time per unit, per unit pressure, per unit area, the result is permeable degree.
v＝((8R×T)/(π×M)) 1/2
In addition, R is gas law constant (=8.314), and T is absolute temperature (K), and π is a pi, and M is the molecular-weight average (=2.896 * 10 of air -2Kg/mol).
The porosity of preferred polyolefm microporous film is 25%～75%.At this, porosity (%) is represented with following formula.
Porosity (%)=[{ V-(M/ ρ) }/V] * 100
In the formula, V is the volume (cm of micro-porous film 3), M is the quality (g) of micro-porous film, ρ constitutes the resin of micro-porous film or the density (g/cm of resin combination 3).
Particularly, for example from micro-porous film, downcut the square test portion of 10cm * 10cm, obtain its volume (cm 3) and quality (g), can be according to the density (g/cm of this volume, quality and the film forming polyolefine resin composition of structure 3) use following formula to calculate porosity.In addition, in the present invention, under the situation that micro-porous film is made of polyethylene, be 0.95 to calculate with poly density.In addition, the film thickness t of preferred polyolefm microporous film is 3 μ m～200 μ m.
Polyolefin microporous film is preferably below 0.6 at the kinetic friction coefficient of TD direction, and more preferably 0.1～0.4.For example for the test portion of width 50mm * direction of measurement 200mm, can use the KES-SE frictional testing machines of カ ト one テ Star Network (Kato Tech) corporate system, at load 50g, contact area 10 * 10=100mm 2(twine 20
Figure A20078002823200211
0.5mm piano wire), measure the kinetic friction coefficient of TD direction under the condition of 25 ℃ of contact translational speed 1mm/sec, tension force 6kPa, temperature.In addition, to be easy to take place coiling deviation etc. bad because the kinetic friction coefficient of TD direction is 0.1～0.4 polyolefin microporous film, therefore, especially preferably utilizes the manufacture method of coiling thing of the present invention to reel.
In addition, suppose under the situation that has involved in foreign matter that the coiling thing of coiling tension damages micro-porous film easily,, increased the ratio of proof voltage substandard products in that this damaged micro-porous film is used as under the situation of battery separator.This tendency is embodied in the tensile strength in length and breadth of only having implemented uniaxial extension especially significantly and differs in the higher micro-porous film of anisotropy more than 10 times.
Therefore, coiling thing and manufacture method thereof that coiling of the present invention is not tight, being particularly suitable for using the endwise tensile strength (MD tensile strength) and the ratio (MD tensile strength/TD tensile strength) of transverse tensile strength (TD tensile strength) is the polyolefin microporous film more than 10.
Polyolefin microporous film used in the present invention for example can followingly be made like that.
Can use the polyolefine separate constituent and more than 2 kinds polyolefin blend as polyolefine.As the polyolefine of main component, can enumerate for example polyethylene, polypropylene, poly--4-methyl-1-pentene etc.As the polyolefine beyond the main component, do not damage the system film and in the scope of not damaging purpose of the present invention, can cooperate various polyolefine.For example, can cooperate with to improve the inaccessible characteristic in hole is the high low-melting-point polyethylene of content purpose, alpha-olefin comonomer, to improve polypropylene that thermotolerance is a purpose and poly--4-methyl-1-pentene etc.In addition, also can not damage performance, not damage the system film and do not damage in the scope of purpose of the present invention and cooperate the polymer materials except polyolefine, other organic and inorganic materials as battery separator.Can be as required in the polyolefin compositions that constitutes micro-porous film mixed phenol system, phosphorus system, sulphur system etc. known additive such as metallic soap class, UV light absorber, photostabilizer, static inhibitor, antifogging agent, tinting pigment such as antioxidant, calcium stearate, Zinic stearas and use.
The manufacture method of polyolefin microporous film of the present invention is not particularly limited, and can adopt so-called drying process, damp process etc.As the manufacture method that adopts so-called damp process, for example, said polyolefins is dissolved in the solvent that is known as softening agent with its temperature more than fusing point, the solution that is obtained is cooled to generate below the Tc high-molecular gel body, use this high-molecular gel body to carry out film forming (film formation process), stretching the film (stretching process) obtained afterwards, remove softening agent (softening agent is removed operation), thereby can make polyolefin microporous film.
Be meant the organic compound that can form uniform solution at its temperature below boiling point and polyolefine at this said softening agent, as its concrete example, can enumerate naphthalane, dimethylbenzene,, the paraffin wet goods.In addition, also can use from softening agent and remove regenerated softening agent the operation.
The ratio of the softening agent in the high-molecular gel body is not particularly limited, and is preferably 20 weight %～90 weight %, more preferably 50 weight %～80 weight %.If the ratio of softening agent below 20 weight %, has the tendency that is difficult to obtain have the micro-porous film of suitable porosity,, the ratio of softening agent is difficult to the tendency of continuous molding film if more than 90 weight %, having the viscosity of hot solution to reduce.
Below, an example of the manufacture method of polyolefin microporous film is divided into above-mentioned film making process, stretching process and softening agent removes operation and be illustrated.
Film formation process
Film is not particularly limited, for example in extrusion machine, supply with and mix polyolefin powder and softening agent, temperature fusion mixing about with 200 ℃ is after both, from common suspension type nozzle to the cooling roller top casting, thereby the sheet of the tens of μ m～number mm thickness that can be shaped continuously.
Stretching process
Then, the film that is obtained is stretched along the single shaft direction at least, thereby form stretched film.Drawing process is not particularly limited, and can use tentering method, roll method, rolling process etc.Wherein, it is biaxial stretch-formed preferably to utilize horizontal sheet process to carry out the while.Draft temperature is the temperature of the fusing point from normal temperature to the high-molecular gel body, is preferably 80～140 ℃, more preferably 100～130 ℃.Stretching ratio is preferably 4～400 times with the dynameter of area, and more preferably 8～200 times, more preferably 16～100 times.If stretching ratio is below 4 times, then as membranous insufficient strength,, then just is not difficult to stretch, and has the tendency of drawbacks such as the porosity that makes the micro-porous film that is obtained easily is lower if stretching ratio is more than 400 times.
Softening agent is removed operation
Next, by being removed, softening agent obtains micro-porous film from stretched film.The method of removing of softening agent is not particularly limited.For example using under paraffin oil, the situation of dioctyl phthalate (DOP) as softening agent, organic solvents such as available methylene dichloride, methylethylketone extract paraffin oil, dioctyl phthalate (DOP), also the micro-porous film that is obtained can be carried out heat drying and removes softening agent more fully with its temperature below melting temperature.In addition, for example using under the situation of low-boiling compound as softening agent such as naphthalane, only the temperature below the melting temperature of micro-porous film is carried out heat drying and just can be removed.In order to realize low cost, also can reclaim used organic solvent and be used to remove softening agent once more.In order to improve perviousness or to improve dimensional stability, the polyolefin microporous film enforcement thermal treatment that also preferred temperature below melting temperature as required obtains utilizing above-mentioned method for making.
Embodiment
Below, utilize embodiment and comparative example to specify the present invention, but this does not limit the scope of the invention.The various rerum naturas of using among the present invention are according to following test method measuring.
(1) the film thickness t that obtains with a micro-porous film evaluation (μ m)
Micro-porous film after cutting cuts out the film of 25cm, uses the small thickness measuring device (KBM formula) of the smart mechanism of Japan to measure 10 places down for 23 ℃ in room temperature, and averaging is t.
(2) according to the external diameter that comprises porous-film that is wound on the coiling thing on the pipe, the external diameter of volume core and the film thickness T (μ m) that coiling length is calculated
Utilize the described outside diameter measuring measurement device of TOHKEMY 2006-88255 communique to comprise the outer diameter D (mm) that is wound onto the polyolefin microporous film on the volume core d (mm) that has measured external diameter in advance after the cutting.If coiling length is L (m), by T (μ m)=π (D 2-d 2)/4L obtains T.
When measurement comprises the outer diameter D of the polyolefin microporous film of being reeled in the cutting back, for the crect ear (part that coiling thing both sides of the edge form to the foreign side's perk of coiling thing cross-section radial) of removing two ends, from the inward at both ends side part broad ways apart from two ends 3mm measuring external diameter every 1mm, averaging is D.
(3) electrode-membrane coil is around the making of thing
Anodal is made: with the lithium cobalt composite oxide LiCoO as active substance of 92.2 weight % 2, the polyvinylidene difluoride (PVDF) as tackiness agent (PVDF) as the flaky graphite of conductive agent and acetylene black, 3.2 weight % that is respectively 2.3 weight % is distributed to preparation slurry in the N-Methyl pyrrolidone (NMP).Utilize die coating machine this slurry of coating on as the single face of the aluminium foil of the thick 20 μ m of positive electrode collector, and after 3 minutes, utilize the roll-type pressing machine to carry out compression molding 130 ℃ of dryings.At this moment, anodal active substance coating amount is 250g/m 2, the active substance volume density is 3.00g/m 3This positive pole is cut into about wide 60mm and becomes band shape.
The making of negative pole: with 96.9 weight % as the synthetic graphite of active substance, 1.4 weight % as the ammonium salt of the carboxymethyl cellulose of tackiness agent and 1.7 weight % styrene-butadiene copolymer latex be distributed to purify waste water in the preparation slurry.Utilize die coating machine this slurry of coating on as the single face of the Copper Foil of the thick 12 μ m of negative electrode collector, and after 3 minutes, utilize the roll-type pressing machine to carry out compression molding 120 ℃ of dryings.At this moment, the active substance coating amount of negative pole is 106g/m 2, the active substance volume density is 1.35g/m 3This negative pole is cut into about wide 60mm and becomes band shape.
Electrode-membrane coil is around the making of thing: with above-mentioned micro-porous film barrier film, banded positive pole and banded negative pole according to banded negative pole, barrier film, banded positive pole, membranous order is overlapping and be vortex shape ground and reel repeatedly, thereby produce electrode-membrane coil around thing.
(4) electrode-membrane coil is around the jar property inserted of thing
Prepare above-mentioned coiling thing, use the coiling thing made from the chuck clamping, the jar insertion machine of inserting automatically that above-mentioned coiling thing is inserted into 18mm
Figure A20078002823200251
The jar in estimate.
Jar insert bad: in 100 volumes 0 volume following be best, 2 is well below rolling up, and in addition is bad.
(5) viscosity-average molecular weight Mv
For the polyethylene that uses in embodiment, the comparative example, try to achieve 135 ℃ limiting viscosity [η] in the naphthalane solvent according to ASTM-D 4020, utilize following formula to calculate viscosity-average molecular weight Mv.
[η]＝6.77×10 -4Mv 0.67
(6) elasticity of coiling thing
The pin part of " model-13 " total length 38mm of the safety pin of intercepting Kokuyo system is installed in it on digital force gauge of HF-10 of Japanese measurement system (strain), makes measuring apparatus.With the side that this measuring apparatus thrusts the coiling thing, vertical depression is measured the load of peak value up to inserting the needle into 1cm.In addition, the front end of the pin of " model-13 " total length 38mm of the safety pin of Kokuyo system part is shaped as, and the needle point angle is 26 °, and needle point R is 0.04～0.07mm, and the diameter in needle point cross section is 0.047mm.
(7) Gas permeability (sec/100cc)
According to JI S P-8117, utilize lattice profit (Gurley) formula Gas permeability meter (the smart device of Japan (strain) system, G-B2 (trade mark)) to measure.
(8) (MD tensile strength/TD tensile strength) ratio
According to JIS K7127, use the tensile testing machine of Shimadzu Seisakusho Ltd.'s system, autoplotter AG-A type (trade mark) measurement MD tensile strength to measure with sample and TD tensile strength and measure with sample (shape: tensile strength wide 10mm * long 100mm).Make between chuck and on the single face at the both ends of sample (each wide 25mm), be pasted with scotch tape (Scotch tape, day eastern electrician's packaging system (strain) system, trade(brand)name: sample N.29) apart from being 50mm, using.And, in order to prevent that sample slides in the test, at the inboard viton of pasting thick 1mm of the chuck of tensile testing machine.
By with the sample in cross section before the test long-pending during divided by sample breakage suffered pulling force obtain tensile strength (MPa), calculate the ratio of MD tensile strength and the value of TD tensile strength.In addition, measuring in temperature is that 23 ± 2 ℃, chuck pressure are that 0.30MPa, draw speed are to carry out under the condition of 200mm/ minute (when sample can not guarantee that distance between chuck is 50mm, rate of straining was 400%/minute).
Embodiment 1
The making of polyolefin microporous film
The poly mixture of the polyethylene of the Mv27 ten thousand of use drum tumbler dry mixed 35 weight %, the Mv95 ten thousand of 65 weight % obtains polyolefin compositions.Utilize the biaxial extruder composition that is obtained of fusion mixing 30 weight % and the whiteruss of 70 weight % equably, obtain polyethylene fusion homomixture.The fusion mixing is to be that 200 ℃, propeller speed are that 170rpm, output are to carry out under the condition of 15kg/hr at design temperature.Next, use and the fusion homomixture to be remained 220 ℃ T pattern (wide 250mm) the fusion homomixture is squeezed into sheet.
Utilize surface temperature to be controlled as 60 ℃ metallic roll compacting, cooling fusion homomixture, thereby obtain the good gel film of thickness stability of thick 1000 μ m.
Then, using biaxial stretch-formed machine simultaneously, is to be stretched to 7 * 7 times under 125 ℃ the condition at draft temperature, next, imports in the methylethylketone groove, fully soaks in methylethylketone and extracts and remove whiteruss, and drying is removed methylethylketone then.
Then, utilize tenter machine under 120 ℃ of conditions, laterally to carry out 1.5 times of stretchings, under 125 ℃ of conditions, carry out heat setting, obtain the micro-porous film of horizontal wide 1.2m, film thickness 18 μ m, porosity 40%, aperture 0.05 μ m.In addition, the kinetic friction coefficient of the TD direction of micro-porous film is 0.4.
The making of roll of polyolefin microporous film thing
For continuous cutting-off is become many roll of polyolefin microporous film many volume cores on the time, can carry out tension control respectively independently, can independently make tension detector in the coiling portion at each, detect the tension force of the polyolefin microporous film that respectively cuts off out respectively independently, thereby control the output torque of each drive source according to its detected value.
Utilize the independent drive cutting machine that the polyolefin microporous film of making is cut into wide 60mm, and be wound on pipe made of paper (size grades: 3B), thereby obtain the roll of polyolefin microporous film thing.D, L are respectively 102mm, 1000m.
Find that the coiling thing that has produced the coiling deviation more than the 5mm has only 1 volume after cutting 8 parent rolls and making 160 volume roll of polyolefin microporous film things.From central extraction 150 volume coiling deviations at 5mm with interior coiling cut substrate, measure and calculate D, T, t, draw D and be 181.2～182.9mm, T and be 17.6～18.1 μ m, t and be 17～19 μ m, | the maximum value of T-t| is that 1.2 μ m, standard variance are 0.4 μ m.In addition, the mean value of F (5) is that the mean value of 25N, F (10)-F (20) is 1N.
In addition, the tension force of emitting of cutting machine is to be the tension force of emitting that the parent roll of 1.2m applies 100N to total width, and the tension force of the thing of respectively reeling of wide 60mm all is controlled to be 5N.
Electrode-membrane coil is around making, the evaluation of thing
Make electrode-membrane coil around thing according to " (3) electrode-membrane coil is around the making of thing ", next estimate according to " (4) electrode-membrane coil is around the evaluation of the jar property inserted of thing ", finding bad is 0, as a result the best.
Comparative example 1
The polyolefin microporous film that utilizes coaxial cutting machine to make in embodiment 1 cuts into wide 60mm, and is wound on pipe (size grades: 3B), thereby obtain the roll of polyolefin microporous film thing.D, L are respectively 102mm, 1000m.
Find that the coiling thing that has produced the coiling deviation more than the 5mm has 12 volumes after cutting 9 parent rolls and making 180 volume roll of polyolefin microporous film things.Extract out 150 volume coiling deviations at 5mm with interior coiling cut substrate, measure and calculate D, T, t, draw D and be 180.2～183.9mm, T and be 17.2～18.5 μ m, t and be 17～19 μ m, | the maximum value of T-t| is that 1.6 μ m, standard variance are 0.8 μ m.
In addition, employed coaxial cutting machine is meant the flap alternate allocation after the cutting and one is wound on and is fixed in 2 devices on a plurality of volume cores on the turning axle with rotary driving part in this comparative example.The tension force of emitting of cutting machine is to be the tension force of emitting that the parent roll of 1.2m applies 100N to total width, and the coiling tension of coiling thing is each turning axle to be applied the coiling tension of 50N, and each coiling thing is not carried out Coiling Tension Control.
Estimated the jar property inserted of coiling thing similarly to Example 1, found to have 3 volumes bad, the result is bad.
Embodiment 2
The making of polyolefin microporous film
The poly mixture of the polyethylene of the Mv27 ten thousand of use drum tumbler dry mixed 35 weight %, the Mv95 ten thousand of 65 weight % obtains polyolefin compositions.Utilize the biaxial extruder composition that is obtained of fusion mixing 30 weight % and the whiteruss of 70 weight % equably, obtain polyolefine fusion homomixture.The fusion mixing is to be that 200 ℃, propeller speed are that 170rpm, output are to carry out under the condition of 15kg/hr at design temperature.Next, use and the fusion homomixture to be remained 220 ℃ T pattern (wide 250mm) the fusion homomixture is squeezed into sheet.
Utilize surface temperature to be controlled so as to 60 ℃ metallic roll compacting, cooling fusion homomixture, thereby obtain the good gel film of thickness stability of thick 1100 μ m.
Then, using biaxial stretch-formed machine simultaneously, is to be stretched to 7 * 7 times under 125 ℃ the condition at draft temperature, next, gel film is imported in the methylethylketone groove, fully soaks in methylethylketone and extracts and remove whiteruss, and drying is removed methylethylketone then.
Then, utilize tenter machine under 120 ℃ condition, laterally to carry out 1.5 times of stretchings, under 125 ℃ condition, carry out heat setting, obtain the micro-porous film of horizontal wide 1.2m, film thickness 20 μ m, porosity 40%, aperture 0.05 μ m.In addition, the kinetic friction coefficient of the TD direction of micro-porous film is 0.4.
The making of roll of polyolefin microporous film thing
The polyolefin microporous film that utilizes the independent drive cutting machine will utilize aforesaid method to make cuts into wide 60mm, and is wound on plastic pipe (size grades: 6B), thereby obtain the roll of polyolefin microporous film thing.D, L are respectively 150mm, 1000m.
Find that the coiling thing that the coiling deviation more than the 5mm has taken place has 2 volumes after cutting 8 parent rolls and making 160 volume roll of polyolefin microporous film things.Extract out 150 volume coiling deviations at 5mm with interior coiling cut substrate, measure and calculate D, T, t, draw D and be 216.2～219.3mm, T and be 19.0～20.1 μ m, t and be 19.7～21 μ m, | the maximum value of T-t| is that 1.4 μ m, standard variance are 0.3 μ m.In addition, the mean value of F (5) is that the mean value of 24N, F (10)-F (20) is 0.9N.
In addition, the tension force of emitting of cutting machine is the tension force of emitting that the parent roll of total width 1.2m is applied 100N, and the tension force of the thing of respectively reeling of wide 60mm all is controlled to be 5N.
Electrode-membrane coil is around making, the evaluation of thing
Make electrode-membrane coil around thing according to " (3) electrode-membrane coil is around the making of thing ", next estimate according to " (4) electrode-membrane coil is around the evaluation of the jar property inserted of thing ", find to have 1 volume bad, the result is good.
Comparative example 2
The polyolefin microporous film that utilizes coaxial cutting machine to make in embodiment 2 cuts into wide 60mm, and is wound on pipe (size grades: 6B), thereby obtain the roll of polyolefin microporous film thing.D, L are respectively 150mm, 1000m.
Find that the coiling thing that has produced the coiling deviation more than the 5mm has 8 volumes after cutting 9 parent rolls and making 180 volume roll of polyolefin microporous film things.Extract out 150 volume coiling deviations at 5mm with interior coiling cut substrate, measure and calculate D, T, t, draw D and be 215.5～220.1mm, T and be 18.2～20.7 μ m, t and be 19.7～21 μ m, | the maximum value of T-t| is that 1.9 μ m, standard variance are 0.8 μ m.
In addition, the tension force of emitting of cutting machine is the tension force of emitting that the parent roll of total width 1.2m is applied 100N, and the coiling tension of coiling thing is each turning axle to be applied the coiling tension of 50N, and each coiling thing is not carried out Coiling Tension Control.
Estimated the jar property inserted of coiling thing similarly to Example 1, found to have 3 volumes bad, the result is bad.
Embodiment 3
After the silica flour (finely divided silica) to the dioctyl phthalate (DOP) (DOP) of the ultrahigh molecular weight polyethylene(UHMWPE) of the Mv95 ten thousand of the polyethylene of the Mv27 ten thousand of 12.8 weight %, 19.2 weight %, 48 weight %, 20 weight % carries out mixing granulation, utilization is pushed after front end is equipped with the biaxial extruder fusion mixing of T pattern, roller with heating rolls from both sides, thereby is configured as the sheet of thick 110 μ m.From this forming composition, extract and remove DOP, silica flour, make micro-porous film.Overlapping 2 these micro-porous films, longitudinal stretching is 4.5 times under 110 ℃ condition, and 1.7 times of cross directional stretchs under 133 ℃ condition are heat-treated under 135 ℃ condition at last then.Obtain the micro-porous film of horizontal wide 1.2m, film thickness 18 μ m, porosity 50%, aperture 0.1 μ m.In addition, the kinetic friction coefficient of the TD direction of micro-porous film is 0.2.
The making of roll of polyolefin microporous film thing
The polyolefin microporous film that utilizes the independent drive cutting machine will utilize aforesaid method to make cuts into wide 60mm, and is wound on plastic pipe (size grades: 3B), thereby obtain the roll of polyolefin microporous film thing.D, L are respectively 102mm, 1000m.
Find that the coiling thing that has produced the coiling deviation more than the 5mm has 2 volumes after cutting 8 parent rolls and making 160 volume roll of polyolefin microporous film things.Extract out 150 volume coiling deviations at 5mm with interior coiling cut substrate, measure and calculate D, T, t, draw D and be 181.2～183.2mm, T and be 17.6～18.2 μ m, t and be 17～19 μ m, | the maximum value of T-t| is that 1.3 μ m, standard variance are 0.5 μ m.In addition, the mean value of F (5) is that the mean value of 25N, F (10)-F (20) is 2N.
In addition, the tension force of emitting of cutting machine is the tension force of emitting that the parent roll of total width 1.2m is applied 100N, and the tension force of the thing of respectively reeling of wide 60mm all is controlled to be 5N.
Electrode-membrane coil is around making, the evaluation of thing
Make electrode-membrane coil around thing according to " (3) electrode-membrane coil is around the making of thing ", next estimate according to " (4) electrode-membrane coil is around the evaluation of the jar property inserted of thing ", find to have 1 volume bad, the result is good.
Comparative example 3
After the silica flour to the dioctyl phthalate (DOP) (DOP) of the straight-chain low density polyethylene of the Mv 150,000 of the high density polyethylene(HDPE) of the Mv 150,000 of the ultrahigh molecular weight polyethylene(UHMWPE) of the Mv200 ten thousand of 12 weight %, 12 weight %, 16 weight %, 42.4 weight %, 17.6 weight % carries out mixing granulation, the biaxial extruder that utilization is equipped with the T pattern carries out fusion, extruding, is configured as the sheet of thick 90 μ m.From this forming composition, extract and remove DOP and silica flour, make micro-porous film.Overlapping 2 these micro-porous films are heated to 118 ℃ with them, 5.3 times of longitudinal stretchings (draw speed 1000%/second) on this basis, 1.8 times of cross directional stretchs (draw speed 2%/second) then.Obtain the micro-porous film of horizontal wide 0.96m, film thickness 22 μ m.In addition, the kinetic friction coefficient of the TD direction of micro-porous film is 0.7.
Utilize coaxial cutting machine that the polyolefin microporous film that obtains is cut into wide 60mm.D, L are respectively 102mm, 1000m.
Find that the coiling thing that has produced the coiling deviation more than the 5mm has 4 volumes after cutting 11 parent rolls and making 176 volume roll of polyolefin microporous film things.Extract out 150 volume coiling deviations at 5mm with interior coiling cut substrate, measure and calculate D, T, t, draw D and be 193～200mm, T and be 21.1～23.2 μ m, t and be 21.5～23.8 μ m, | the maximum value of T-t| is that 1.6 μ m, standard variance are 0.8 μ m.
In addition, the tension force of emitting of cutting machine is the tension force of emitting that the parent roll of total width 0.96m is applied 80N, and the coiling tension of coiling thing is each turning axle to be applied the coiling tension of 40N, and each coiling thing is not carried out Coiling Tension Control.
Estimated the jar property inserted of coiling thing similarly to Example 1, found to have 5 volumes bad, the result is bad.
Embodiment 4
After the silica flour to the dioctyl phthalate (DOP) (DOP) of the ultrahigh molecular weight polyethylene(UHMWPE) of the Mv300 ten thousand of the polyethylene of the Mv27 ten thousand of 14.4 weight %, 9.6 weight %, 56 weight %, 20 weight % carries out mixing granulation, utilization is pushed after front end is equipped with the biaxial extruder fusion mixing of T pattern, utilize the roller of heating to roll, be configured as the sheet of thickness 110 μ m from both sides.From this forming composition, extract and remove DOP, silica flour, make micro-porous film.Under 115 ℃ the condition with 5.5 times of this micro-porous film longitudinal stretchings after, under 120 ℃ condition, heat-treat at last.Obtain the micro-porous film of horizontal wide 0.96m, film thickness 30 μ m, porosity 70%, aperture 0.1 μ m.The tensile strength of MD is that the tensile strength of 190MPa, TD is 18MPa, and (MD tensile strength/TD tensile strength) is than being 10.6.In addition, the kinetic friction coefficient of the TD direction of micro-porous film is 0.5.
The making of roll of polyolefin microporous film thing
The polyolefin microporous film that utilizes the independent drive cutting machine will utilize aforesaid method to make cuts into wide 60mm, and is wound on plastic pipe (size grades: 3B), thereby obtain the roll of polyolefin microporous film thing.D, L are respectively 102mm, 1000m.
Find that the coiling thing that has produced the coiling deviation more than the 5mm has 2 volumes after cutting 11 parent rolls and making 176 volume roll of polyolefin microporous film things.Extract out 150 volume coiling deviations at 5mm with interior coiling cut substrate, measure and calculate D, T, t, draw D and be 214.2～224mm, T and be 27.9～31.2 μ m, t and be 28.2～32.5 μ m, | the maximum value of T-t| is that 1.4 μ m, standard variance are 0.5 μ m.In addition, the mean value of F (5) is that the mean value of 25N, F (10)-F (20) is 2N.
In addition, the tension force of emitting of cutting machine is the tension force of emitting that the parent roll of total width 0.96m is applied 96N, and the tension force of the thing of respectively reeling of wide 60mm all is controlled to be 6N.
Electrode-membrane coil is around making, the evaluation of thing
Make electrode-membrane coil around thing according to " (3) electrode-membrane coil is around the making of thing ", next estimate according to " (4) electrode-membrane coil is around the evaluation of the jar property inserted of thing ", find to have 1 volume bad, the result is good.
The evaluation of the foreign matter vulnerability of roll of polyolefin microporous film thing
Prepare 1 parent roll, use outside diameter measuring device as shown in Figure 2 to measure its external diameter, near external diameter value maximum, put signs on along the width of parent roll.Next similarly cut this parent roll with above-mentioned " making of roll of polyolefin microporous film thing ", each polyolefin microporous film after coiling is cut, when having reeled 100m, being wound with the square aluminum oxide section of the pre-prepd 0.1mm of insertion in the coiling thing that has marked near the polyolefin microporous film of emitting the position of mark, continue cutting.After the 1000m that reeled, take the coiling thing apart, check the perforate situation that polyolefin microporous film produces because of the aluminum oxide section, finding 2 layers has perforate.
Comparative example 4
The polyolefin microporous film that utilizes coaxial cutting machine to make in embodiment 4 cuts into wide 60mm.D, L are respectively 102mm, 1000m.
Find that the coiling thing that has produced the coiling deviation more than the 5mm has 8 volumes after cutting 11 parent rolls and making 176 volume roll of polyolefin microporous film things.Extract out 150 volume coiling deviations at 5mm with interior coiling cut substrate, measure and calculate D, T, t, draw D and be 214.5～223.5mm, T and be 28.0～31.0 μ m, t and be 28.2～32.5 μ m, | the maximum value of T-t| is that 1.9 μ m, standard variance are 0.5 μ m.
In addition, the tension force of emitting of cutting machine is the tension force of emitting that the parent roll of total width 0.96m is applied 80N, and the coiling tension of coiling thing is each turning axle to be applied the coiling tension of 40N, and each coiling thing is not carried out Coiling Tension Control.
The jar that use method has similarly to Example 4 been estimated the coiling thing inserts property, finds to have 10 volumes bad, and the result is bad.In addition, use method has similarly to Example 4 been estimated the foreign matter vulnerability of roll of polyolefin microporous film thing, finds to be of five storeys perforate.
Industrial utilizability
Adopt roll of polyolefin microporous film thing of the present invention and manufacture method thereof, energy Enough provide reduced when being inserted into the coiling thing in the tank the bad electrode of the insertion that takes place, Barrier film one build coiling thing is therefore as battery separator, particularly as large-scale It is useful that the lithium ion secondary cell is used.

Claims (31)

1. roll of polyolefin microporous film thing, this roll of polyolefin microporous film thing are the coiling things that the coiling polyolefin microporous film forms on the volume core, it is characterized in that,
Utilizing the absolute value (μ m) of film thickness T (μ m) that following formula (1) calculates and the film thickness t (μ m) that obtains with a micro-porous film evaluation poor (film thickness poor) is below the 1.5 μ m,
T(μm)＝π(D 2-d 2)/4L (1)
(in the above-mentioned formula (1), D refers to comprise the external diameter (mm) that is wound on the coiling thing on the core of porous-film, and d refers to roll up the external diameter (mm) of core, L refer to reel the coiling length (m) of thing).
2. coiling thing according to claim 1, wherein,
This coiling thing is by will being wound on polyolefin microporous film on the parent roll cuts into Rack in whole width range after, on one side each coiling thing is carried out coiling tension control each polyolefin microporous film that is cut into this Rack of reeling on one side make.
3. coiling thing according to claim 1, wherein,
Utilize independent drive formula cutting machine to cut this coiling thing.
4. according to each described coiling thing in the claim 1～3, wherein,
The elasticity of distance volume core 5mm distance is below 34N.
5. coiling thing according to claim 4, wherein,
Poor (F (10)-F (20)) that roll up the elasticity (F (20)) of core 20mm distance apart from the elasticity (F (10)) and the distance of volume core 10mm distance is 0.05N～2N.
6. according to each described coiling thing in the claim 1～3, wherein,
The coiling length of this coiling thing is more than the 500m.
7. according to each described coiling thing in the claim 1～3, wherein,
The aperture of polyolefin microporous film is 0.001 μ m～1 μ m; Porosity is 25%～75%; Film thickness is 3 μ m～200 μ m.
8. according to each described coiling thing in the claim 1～3, wherein,
The kinetic friction coefficient of the width of polyolefin microporous film is below 0.6.
9. according to each described coiling thing in the claim 1～3, wherein,
The endwise tensile strength of polyolefin microporous film (MD tensile strength) is more than 10 with the ratio (MD tensile strength/TD tensile strength) of the tensile strength (TD tensile strength) of width.
10. according to each described coiling thing in the claim 1～3, wherein,
This coiling thing is used for battery separator.
11. according to each described coiling thing in the claim 1～3, this coiling thing is a battery separator usefulness, wherein,
The aperture of polyolefin microporous film is 0.001 μ m～1 μ m; Porosity is 25%～75%; Film thickness is 3 μ m～200 μ m.
12. a roll of polyolefin microporous film thing group, this roll of polyolefin microporous film thing group be described by 2 above claims 1, will be wound on the coiling thing group that the coiling thing that obtains after the polyolefin microporous film cutting on the parent roll constitutes, wherein,
The coiling deviation is in 5mm, and the standard variance of poor (the μ m) of the described film thickness of claim 1 is below the 0.7 μ m.
13. coiling thing group, be by will be wound on polyolefin microporous film on the parent roll in whole width range, cut into Rack after, the control of each coiling thing being carried out coiling tension on one side each polyolefin microporous film that is cut into Rack of reeling on one side makes, it is characterized in that
The coiling deviation of each thing of reeling is in 5mm, and the standard variance of the film thickness T (μ m) that calculates of the following formula of utilizing of thing (1) of respectively reeling and the film thickness t (μ m) that obtains with a micro-porous film evaluation poor (film thickness poor) is below the 0.7 μ m,
T(μm)＝π(D 2-d 2)/4L (1)
(in the above-mentioned formula (1), D refers to comprise the external diameter (mm) that is wound on the coiling thing on the core of porous-film, and d refers to roll up the external diameter (mm) of core, L refer to reel the coiling length (m) of thing).
14. coiling thing group according to claim 12, wherein,
Utilize independent drive formula cutting machine to cut apart the coiling thing.
15. according to each described coiling thing group in the claim 12～14, wherein,
The coiling length of each roll of polyolefin microporous film thing is more than the 500m.
16. according to each described coiling thing group in the claim 12～14, wherein,
The aperture of polyolefin microporous film is 0.001 μ m～1 μ m; Porosity is 25%～75%; Film thickness is 3 μ m～200 μ m.
17. according to each described coiling thing group in the claim 12～14, wherein,
This coiling thing group is used for battery separator.
18. according to each described coiling thing group in the claim 12～14, this coiling thing group is used for battery separator, wherein,
The aperture of polyolefin microporous film is 0.001 μ m～1 μ m; Porosity is 25%～75%; Film thickness is 3 μ m～200 μ m.
19. the manufacture method of the described coiling thing of claim 1, this method utilize independent drive formula cutting machine to being wound on polyolefin microporous film on the parent roll and cutting and making the roll of polyolefin microporous film thing, wherein,
Coiling deviation after the whole width range of parent roll cuts 5mm with interior coiling thing group in, utilizing the standard variance of film thickness T (μ m) that following formula (1) calculates and the film thickness t (μ m) that obtains with a micro-porous film evaluation poor (film thickness poor) is below the 0.7 μ m
T(μm)＝π(D 2-d 2)/4L (1)
(in the above-mentioned formula (1), D refers to comprise the external diameter (mm) that is wound on the coiling thing on the core of porous-film, and d refers to roll up the external diameter (mm) of core, L refer to reel the coiling length (m) of thing).
20. the manufacture method of a roll of polyolefin microporous film thing, wherein, this method comprises following operation:
The polyolefin microporous film that is wound on the parent roll is cut into Rack in whole width range;
On one side to each coiling thing control coiling tension, reel and be cut into each polyolefin microporous film of this Rack on one side.
21. the manufacture method of a roll of polyolefin microporous film thing, wherein, this method comprises following operation:
In whole width range, cut and block into Rack being wound on polyolefin microporous film on the parent roll;
On one side to each coiling thing control coiling tension, reel and be cut into each polyolefin microporous film of this Rack on one side;
The coiling deviation is in 5mm, and to utilize the standard variance of film thickness T (μ m) that following formula (1) calculates and the film thickness t (μ m) that obtains with a micro-porous film evaluation poor (film thickness poor) be below the 0.7 μ m,
T(μm)＝π(D 2-d 2)/4L (1)
(in the above-mentioned formula (1), D refers to comprise the external diameter (mm) that is wound on the coiling thing on the core of porous-film, and d refers to roll up the external diameter (mm) of core, L refer to reel the coiling length (m) of thing).
22. manufacture method according to claim 20, wherein,
Utilize independent drive formula cutting machine to cut.
23. manufacture method according to claim 20, wherein,
The absolute value (μ m) of poor (film thickness poor) that utilize film thickness T (μ m) that following formula (1) calculates and the film thickness t (μ m) that obtains with a micro-porous film evaluation of roll of polyolefin microporous film thing is below the 1.5 μ m,
T(μm)＝π(D 2-d 2)/4L (1)
(in the above-mentioned formula (1), D refers to comprise the external diameter (mm) that is wound on the coiling thing on the core of porous-film, and d refers to roll up the external diameter (mm) of core, L refer to reel the coiling length (m) of thing).
24. according to each described manufacture method in the claim 19～23, wherein,
The elasticity apart from volume core 5mm distance of roll of polyolefin microporous film thing is below the 34N.
25. according to each described manufacture method in the claim 19～23, wherein,
Poor (F (10)-F (20)) that roll up the elasticity (F (20)) of core 20mm distance apart from the elasticity (F (10)) and the distance of volume core 10mm distance is 0.05N～2N.
26. according to each described manufacture method in the claim 19～23, wherein,
The coiling length of roll of polyolefin microporous film thing is more than the 500m.
27. according to each described manufacture method in the claim 19～23, wherein,
The aperture of polyolefin microporous film is 0.001 μ m～1 μ m; Porosity is 25%～75%; Film thickness is 3 μ m～200 μ m.
28. according to each described manufacture method in the claim 19～23, wherein,
The kinetic friction coefficient of the width of polyolefin microporous film is below 0.6.
29. according to each described manufacture method in the claim 19～23, wherein,
The endwise tensile strength of polyolefin microporous film (MD tensile strength) is more than 10 with the ratio (MD tensile strength/TD tensile strength) of the tensile strength (TD tensile strength) of width.
30. according to each described manufacture method in the claim 19～23, wherein,
Polyolefin microporous film is a battery separator.
31. according to each described manufacture method in the claim 19～23, wherein,
Polyolefin microporous film is a battery separator,
The aperture of polyolefin microporous film is 0.001 μ m～1 μ m; Porosity is 25%～75%; Film thickness is 3 μ m～200 μ m.
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