CN1759142A - Porous membrane of vinylidene fluoride resin and process for producing the same - Google Patents
Porous membrane of vinylidene fluoride resin and process for producing the same Download PDFInfo
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Abstract
A porous membrane of vinylidene fluoride resin having fine pores of appropriate dimension and distribution, excelling in mechanical strength represented by tensile strength and elongation at break and being useful as a precision filter membrane or a battery separator. This porous membrane of vinylidene fluoride resin is characterized in that crystal orientation portions mixed with crystal nonorientation portions are found by X-ray diffractometry. The porous membrane of vinylidene fluoride resin is produced by providing a melt extrudate of a composition obtained by mixing a vinylidene fluoride resin of appropriately wide and totally high molecular weight distribution with a plasticizer and good solvent therefor and subjecting the melt extrudate at its one major surface side to cooling solidification, plasticizer extraction and drawing.
Description
Technical field
The present invention relates to be used as the porous-film of the secondary filter film of medicine or bacterium etc., or as the porous-film of battery separator, in more detail, relate to the physical strength excellence of tensile strength, elongation at break etc. and the based resin porous film of vinylidene fluoride and the manufacture method thereof of narrow pore size distribution range.
Background technology
All the time, the synthetic resins porous-film as the separatory membrane of gas diaphragm separation, gas-liquid separation and solid-liquid separation etc., or as insulating material, lagging material, sound-proof material and thermal insulation material etc., is used in many-side by people.Wherein, particularly under situation about using, require the influential following characteristic of separation function as separatory membrane.At first, be purpose with the porous-film separation efficiency, require to have the porosity of appropriateness, be the pore size distribution that purpose requires homogeneous to improve separation accuracy, require also that in addition the separate object thing is had optimal aperture.In addition, as the character of film constituent material, requiring has chemical resistant properties, weathering resistance, thermotolerance, intensity etc. to the characteristic of separate object thing.And then the physical strength when using as porous-film requires to have sufficient elongation at break and breaking tenacity etc.
In this one side, the polyolefin resin porous-film of exploitation (for example special public clear 46-40119 communique and special public clear 50-2176 communique) still leaves the chemical-resistant problem as back washing after the separatory membrane use and ozonize the time at present.
Because the vinylidene fluoride resinoid is in aspect excellences such as weathering resistance, chemical resistant properties, thermotolerance and intensity, so they are studied to be applied to separate and use porous-film.But the vinylidene fluoride resinoid has above-mentioned excellent specific property on the other hand, because its Abherent and low consistency are reserved so formability differs.In addition, as the exploitation of porous-film, it is the high porosity of purpose and narrow pore size distribution that people pursue to improve separation performance, but does not obtain the porous-film that also should meet the demands aspect physical strength.Therefore in order to replenish physical strength, porous-film is when using as filter membrane, and present situation is that the stack supporting film uses after improving physical strength on porous-film.In addition, under as situations such as battery separator uses because porous-film on being wound up into core after and use, so preferably it has the rerum natura of machineries such as the sufficient elongation at break that can tolerate the coiling operation when making battery, breaking tenacity.In addition, when using as battery diaphragm, the high efficiency saturating machine of the electrolytic solution after expectation has the perforation aperture of the narrow pore size distribution range that can block the active substance fine powder that uses in electrode and is wound on porous-film on the core.In addition, when using, preferably after long-time, can keep very high filterableness as the secondary filter film.
As 1, the manufacture method of the fluoride based resin porous film of 1-, open the spy and to disclose following method in the flat 3-215535 communique: poly-inclined to one side 1, mix organic liquid such as diethyl phthalate in the 1-fluoride based resin and as the hydrophobic silica of inorganic fine powder, extraction organic liquid and hydrophobic silica behind the melt molding.The porous-film that obtains like this has bigger physical strength.But, owing to this method has been used alkali aqueous solution in order to extract hydrophobic silica, so the easy deterioration of the film forming vinylidene fluoride resinoid of structure.
At this point, about the manufacture method of the based resin porous film of vinylidene fluoride that uses as secondary filter film or battery diaphragm, several schemes have also been proposed by study group of the present invention.Comprising: under controlled condition, the vinylidene fluoride resinoid carried out that crystallization-thermal treatment-stretching-thermal treatment makes the method (spy opens clear 54-62273 communique) of its porous membranization under tension force; The vinylidene fluoride resinoid of specified molecular weight behind softening agent system film, from side cooling, is extracted the method (spy opens flat 7-13323 communique) of softening agent then; To 1 of common molecular weight, cooperate the high molecular 1 that is used to improve resistance to heat distorsion in the 1-fluoride based resin, 1-fluoride based resin and organic porous agent or inorganic porousization agent, carry out film forming, the porous agent is removed in extraction then, make the method that the hole occurs on the film and form porous-film thus, perhaps, under the situation that is inorganic porousization agent, make this inorganic porousization agent when stretching stress concentration nuclear and act on, make the method (spy opens 2000-309672) etc. that occurs the hole on the film and form porous-film thus.But, under the situation of the extraction of softening agent or organic porous agent, when for example porous-film being used as filtering membrane, can not obtain necessary strainability (permeable amount) or mechanical properties sometimes.On the other hand, if stretch, then exist film to rupture, can not be stretched to the shortcoming of enough draw ratios easily in order to improve these characteristics.Particularly under situation about using as the secondary filter film, the thickness that can tolerate filter pressure generally should be more than or equal to 50 μ m, but can distinguish the stretching adaptability non-constant of thickness more than or equal to the thicker film of 50 μ m.
Therefore, in fact do not obtain, have size and the distribute suitable micropore and the based resin porous film of vinylidene fluoride that is suitable as accurate via hole filter membrane or battery diaphragm etc. of physical strength excellence.
Disclosure of an invention
Therefore, main purpose of the present invention provides the based resin porous film of a kind of vinylidene fluoride, and it has size and the suitable micropore and be the physical strength excellence of representative with tensile strength, elongation at break of distributing.
Another object of the present invention provides the stable and high efficiency manufacture method of the based resin porous film of vinylidene fluoride as described above.
Present inventors, study with above-mentioned purpose, results verification: with 1 of molecular weight distribution broad, the 1-fluoride based resin is after the solvent of this resin and softening agent melt extrude, under controlled condition, cool off the system film, the extraction softening agent, and then stretch, can obtain thus to have produced and have size and the suitable micropore and kept the porous-film of excellent mechanical intensity of distributing.The based resin porous film of the vinylidene fluoride that obtains like this is characterized in that, utilizes X-ray diffraction method can observe mixing and has crystalline orientation part and the non-alignment portion of crystallization.
That is, the based resin porous film of vinylidene fluoride of the present invention is characterized in that, comprise (A) weight-average molecular weight more than or equal to 200,000 and the ratio of weight-average molecular weight/number-average molecular weight more than or equal to the resinoid porous-film of 2.5 vinylidene fluoride; Or the weight-average molecular weight that (B) comprises 2～75 weight % be 400,000～1,200,000 the 1, the weight-average molecular weight of 1-fluoride based resin and 25～98 weight % be 150,000～600,000 the 21, the 1-fluoride based resin, the and the 1, the weight-average molecular weight of 1-fluoride based resin/2 1, the ratio of the weight-average molecular weight of 1-fluoride based resin more than or equal to 1.2 1, the porous-film of 1-fluoride based resin, this film utilize X-ray diffraction method can confirm that mixing exists crystalline orientation part and noncrystalline alignment portion.
In addition, the manufacture method of the based resin porous film of vinylidene fluoride of the present invention, it is characterized in that, with respect to (A) of above-mentioned 100 weight parts or vinylidene fluoride resinoid (B), 1 of the softening agent of interpolation 70～250 weight parts and 5～80 weight parts, the good solvent of 1-fluoride based resin, with the composition that is obtained melt extrude into membranaceous after, from a side preferentially cool off, behind the film-forming, the extraction softening agent, and then, stretch.
Can think, utilize method of the present invention, in order to obtain to have 1 of desired characteristic, the fluoride based resin porous film of 1-, Several Factors is synergistic, in brief, can be interpreted as, owing in the operation before the cooling extraction, formed 1, resulting micropore after 1-fluoride based resin film, this film have controlled crystallization property and have the extraction softening agent, institute is so that relatively more difficult all the time 1, the smooth stretching of 1-fluoride based resin becomes possibility, and then can stably form the porous-film with desired aperture (distribution).Especially, the factor as playing useful effect can be exemplified below.(a) above-mentioned spy opens the technology of 2000-309672 communique record and is, utilization is with to 1 of common molecular weight, add the polymer 1 that is considered to improve the resistance to heat distorsion composition in the 1-fluoride based resin, the 1-fluoride based resin is the method for representative, obtain molecular weight distribution wide 1, the 1-fluoride based resin, by use this 1, the 1-fluoride based resin, when making membranoid substance after cooling melt extrudes, (inhibition) (spherical) crystalline formation speed can be adjusted, the film of the tensile crystallization property that is suitable for subsequently can be obtained to have.(b) form thickness direction demulcent grain size number distribution (the cooling surface side attenuates, and it is more coarse that opposite side becomes) by cooling off from a side that melt extrudes the back membranoid substance that forms, this grain size number distributes and makes the stretching of back become smooth.(c) the disengaging hole by the softening agent that forms of extraction softening agent the film behind cooling curing makes membranoid substance softening, making stretches becomes easy, form tensile stress with some cycles simultaneously and concentrate nuclear, the result makes the film after the stretching form the fiber (fibril) that causes because of stretching is partly tied (node) part with non-stretching, extension alternatively distributed film, and this helps keeping the micropore distribution and the film toughness of whole homogeneous.
The simple declaration of accompanying drawing
Fig. 1 is the X-ray diffraction photo that utilizes the based resin porous macaroni yarn of vinylidene fluoride of embodiment 5 acquisitions.
Fig. 2 is the explanatory view of the X-ray diffraction photo of Fig. 1.
Fig. 3 be according to and the corresponding X-ray diffraction of Fig. 1, in 2 θ=20.1 ± 1 ° with the repeatedly record diagram of the strength distribution curve at ° position angle of locating, 2 θ=23.0 ± 1 (β angle).
Fig. 4 is 5000 times of electron scanning micrographs that utilize the outside surface of the based resin porous macaroni yarn of vinylidene fluoride that embodiment 5 obtains.
Fig. 5 is 5000 times of electron scanning micrographs that utilize the internal surface of the based resin porous macaroni yarn of vinylidene fluoride that embodiment 5 obtains.
Fig. 6 is 5000 times of electron scanning micrographs that utilize near the cross section the outside surface of the based resin porous macaroni yarn of vinylidene fluoride that embodiment 5 obtains.
Fig. 7 is 5000 times of electron scanning micrographs that utilize near the cross section the internal surface of the based resin porous macaroni yarn of vinylidene fluoride that embodiment 5 obtains.
The best mode that carries out an invention
Below, the manufacture method of the present invention according to as preferred manufacture method describes the based resin porous film of vinylidene fluoride of the present invention successively.
(vinylidene fluoride resinoid)
In the present invention, use following resin as main pleurodiaphragmatic in terspace material: (A) a kind of vinylidene fluoride resinoid, its weight-average molecular weight are more than or equal to 200,000, and the ratio of weight-average molecular weight/number-average molecular weight is more than or equal to 2.5 (that is, molecular weight distribution is wide); Or (B) a kind of 1, the 1-fluoride based resin, the weight-average molecular weight that contains 2～75 weight % be 400,000～1,200,000 the 1, the weight-average molecular weight of 1-fluoride based resin and 25～98 weight % be 150,000～600,000 the 21, the 1-fluoride based resin, and the ratio of the resinoid weight-average molecular weight of first vinylidene fluoride/resinoid weight-average molecular weight of second vinylidene fluoride is more than or equal to 1.2.
In the present invention,, use the homopolymer of vinylidene fluoride as the vinylidene fluoride resinoid, that is, poly(vinylidene fluoride), but or the monomeric multipolymer of vinylidene fluoride and other copolymerization, or the mixture of these materials.As can with the monomer of vinylidene fluoride copolymerization, can use: one or more in tetrafluoroethylene, R 1216, trifluoro-ethylene, trifluorochloroethylene or the vinylidene fluoride etc.The vinylidene fluoride resinoid preferably contains more than or equal to the vinylidene fluoride of 70mol% as constituting the unit.Wherein, consider, preferably use 100mol%1, the homopolymer that the 1-difluoroethylene forms from the size of physical strength.
The vinylidene fluoride resinoid that vinylidene fluoride as described above is more preferably utilizes emulsion polymerization or suspension polymerization to obtain, and especially preferably utilizes suspension polymerization to obtain.By changing polymerizing condition gradually, also can obtain the wide vinylidene fluoride resinoid (A) of above-mentioned molecular weight distribution.But, easier method is: utilize polymerization process separately to obtain 1 of at least two kinds of different molecular weights, the 1-fluoride based resin, they are mixed, thereby the ratio that obtains weight-average molecular weight/number-average molecular weight is preferably more than and equals 2.5 vinylidene fluoride, promptly 1,1-fluoride based resin (B) preferably uses this resin (B).The preferred configuration according to the present invention will contain the above-mentioned first vinylidene fluoride resinoid of 5～75 weight % and the resinoid mixture of second vinylidene fluoride of 25～95 weight % and use as main pleurodiaphragmatic in terspace material.
The vinylidene fluoride resinoid that uses among the present invention becomes easily for making melt extruding of composition described later, is preferably uncrosslinkedly, and in addition, its fusing point is preferably 160～220 ℃, and more preferably 170～180 ℃, more preferably 175～179 ℃.Less than 160 ℃ the time, it is insufficient that the resistance to heat distorsion of the porous-film that is generated becomes easily, if surpass 220 ℃, and then melting mixing reduction, becoming is difficult to form the film of homogeneous.
Fusing point is meant the top temperature of the heat absorption of the crystallization fusion of following resin that utilizes differential scanning calorimeter (DSC) mensuration.
According to the present invention, in above-mentioned vinylidene fluoride resinoid, add resinoid softening agent of vinylidene fluoride and good solvent, form the feedstock composition that film forms usefulness.
(softening agent)
As softening agent, the general aliphatic polyester that generates by diprotic acid and dibasic alcohol that uses, for example, the hexanodioic acid kind polyester of hexanodioic acid propylene glycol ester class, hexanodioic acid-1,3 butylene glycol ester class etc.; Sebacic acid kind polyesters such as sebacic acid propylene glycol ester class; The nonane diacid kind polyester of nonane diacid-propylene glycol ester class, nonane diacid-1,3 butylene glycol ester class etc. etc.
(good solvent)
In addition, as 1, the good solvent of 1-fluoride based resin, use can dissolve 1 in 20～250 ℃ temperature range, the solvent of 1-fluoride based resin, for example, N-Methyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl-sulphoxide, methyl ethyl ketone, acetone, tetrahydrofuran (THF), diox, ethyl acetate, isobutyl carbonate propylene glycol ester, hexanaphthene, methyl iso-butyl ketone (MIBK), dimethyl phthalate, and the mixed solvent of these solvents etc.Wherein, from the angle of high temperatures, preferred N-methylpyridone (NMP).
(composition)
By the vinylidene fluoride resinoid of mixed phase for 100 weight parts, be preferably the softening agent of 70～250 weight parts and the good solvent of 5～80 weight parts, can obtain the feedstock composition that film forms usefulness.
If softening agent is less than 70 weight parts, then because the porosity of film reduces, so in battery diaphragm, the dipping difference of electrolytic solution or resistance increase, in the secondary filter film, strainability (permeable amount) is poor.In addition, if surpass 250 weight parts, then because porosity is excessive, so physical strength reduces.
During less than 5 weight parts, can not mix poly(vinylidene fluoride) resinoid and softening agent at good solvent equably, perhaps need to mix for a long time.In addition, if greater than 80 weight parts, then can not obtain porosity corresponding to the add-on of softening agent.Promptly hindered and utilized removing of softening agent and form emptying aperture effectively.
The total amount of softening agent and good solvent is preferably in 100～250 weight part scope.Both all have the effect that reduces the viscosity melt extrude composition, with alternating action to a certain degree.Wherein, the ratio of good solvent is preferably 5～30 weight %.
(mixed melting is extruded)
Melt extrude composition generally at 140～270 ℃, under preferred 150～200 ℃ temperature, extrude and membranaceousization from hollow nozzle or T-mould.Therefore, as long as finally can obtain the interior homogeneous composition of said temperature scope, the mixing of vinylidene fluoride resinoid, softening agent and good solvent and molten form can be arbitrarily so.One of optimal way that is used to obtain above-mentioned composition is, use twin shaft mixing forcing machine, supply with 1 from the upstream side of this forcing machine, the 1-fluoride based resin is (preferably by the first and second 1, the mixture of 1-fluoride based resin is formed), supply with the mixture of softening agent and good solvent from the downstream, before spuing, form homogeneous composition by forcing machine.Such twin shaft mixing forcing machine is divided into a plurality of treatment zones along its long axis direction, can carry out independently temperature control, carries out suitable temperature regulation according to the thing that passes through at position separately.
(cooling)
The method according to this invention, the membranoid substance after melt extruding carries out cooling curing since a side.The cooling drum of the smooth flap extruded from the T-punch die and adjusted surface temperature or roller are contacted cool off, under situation, flap is cooled off by heat-eliminating mediums such as water for the hollow fiber membrane extruded from nozzle.Though the temperature of cooling drum or heat-eliminating medium can be selected in the temperature range of 5～120 ℃ non-constant width, but preferred in 10～100 ℃ scope, particularly preferably in 30～80 ℃ scope.
(extraction)
Then, the membranoid substance behind the cooling curing is imported in the extraction bath of liquid, softening agent and good solvent are removed in extraction.As extraction liquid, as long as insoluble depolymerization vinylidene fluoride resinoid can dissolve softening agent and good solvent, just there is no particular limitation.Methyl alcohol in preference such as the alcohols, Virahol etc., the polar solvent of boiling points such as the methylene dichloride in the chlorinated hydrocarbon, 1 about 30～100 ℃ etc.
(thermal treatment)
In order to improve ensuing stretched operation, in 80～160 ℃ scope, preferably thermal treatment 1 second～3600 seconds in 100～400 ℃ scope, preferred 3 seconds～900 seconds increases degree of crystallinity with the membranoid substance after the extraction.
(stretching)
Then, the stretching membranoid substance to be increasing porosity and aperture, and improves tensile strength.Stretching, can be for example utilize the tentering method biaxial stretch-formed, and the general preferred different cylinder equity of circumferential speed of utilizing is carried out uniaxial extension to the membranoid substance length direction.We think that this is owing in order to adjust the porosity rate and the tensile strength of the based resin porous film of vinylidene fluoride of the present invention, the microtexture of stretchiness fiber (fibril) part and non-stretching knot (node) part preferably alternately occurs along draw direction.Stretching ratio is preferably 1.2～4.0 times, is preferably especially about 1.4～3.0 times.
(elutriant processing)
By above-mentioned operation, can obtain the based resin porous film of vinylidene fluoride of the present invention, but especially preferably utilize elutriant to come this porous-film of dip treating.This is because utilize elutriant to handle, and can not damage the characteristic of porous-film of the present invention in essence, can enlarge markedly its permeable amount.As elutriant, use the extraction liquid of alkali lye, acid solution or softening agent.
Though the reason of utilizing above-mentioned elutriant processing that the permeable amount of porous-film is enlarged markedly is very not clear and definite, but can infer may be because, the softening agent that remains on the fine hole wall that expands out because of stretching exposes, and utilizes elutriant to handle and can remove the softening agent that these expose effectively.Can think,,, this resin can be dissolved, thereby have the effect that promotes that its wash-out is removed by decomposing the polyester that uses as the resinoid softening agent of vinylidene fluoride as the alkali and the acid of elutriant.
Therefore, for alkali lye, preferably use the pH value more than or equal to the alkaline aqueous solution or water/alcoholic solutions such as 12 sodium hydroxide, potassium hydroxide, calcium hydroxides, more preferably the pH value is more than or equal to 13 strong alkali aqueous solution or water/alcoholic solution.On the other hand, as acid solution, preferably use the aqueous solution or the water/alcoholic solution of pH value smaller or equal to strong acid such as 4 hydrochloric acid, sulfuric acid, phosphoric acid, more preferably the pH value is smaller or equal to 3, and preferred especially pH value is smaller or equal to the aqueous solution or the water/alcoholic solution of 2 strong acid.
In addition, as the extraction liquid of softening agent, the preceding solution that uses is the same with stretching, if the inclined to one side vinylidene fluoride resinoid of insoluble depolymerization, and can dissolve softening agent, just there is no particular limitation.For example preferably use methyl alcohol in the alcohols, Virahol etc., the methylene dichloride in the chlorinated hydrocarbon, 1,1, the polar solvents of boiling point about 30～100 ℃ such as 1-trichloromethane.
After being used to improve the preceding dipping of lyophily as required,, carrying out elutriant and handle by porous-film was flooded 10 seconds～6 hours in elutriant under the temperature about 5～100 ℃.When under the condition of heating, carrying out the elutriant processing,, preferably under the fixed state, carry out in order not cause the contraction of porous-film.
(the based resin porous film of vinylidene fluoride)
The based resin porous film of vinylidene fluoride of the present invention that utilizes aforesaid operations to obtain can obtain following characteristic: general porosity is 55～90%, is preferably 60～85%, is preferably 65～80% especially; Tensile strength is more than or equal to 5MPa, elongation at break is more than or equal to 5%, tensile yield point stress is more than or equal to 5MPa, be preferably greater than and equal 6MPa, elongation at yield point is more than or equal to 3%, be preferably greater than and equal 5%, under the situation that this porous-film is used as permeable processing film, can obtain more than or equal to 5m
3/ m
2The permeable amount of it 100kPa.In addition, thickness in the scope about 5～800 μ m, is preferably 50～600 μ m usually, is preferably 150～500 μ m especially.Under the situation that is macaroni yarn, its external diameter is preferably about 0.3～3mm, is preferably about 1～3mm especially.
In addition, of the present invention 1, the fluoride based resin porous film of 1-is characterised in that, as its microtexture, utilize X-ray diffraction method can observe crystalline orientation part and the non-alignment portion of crystallization (random orientation part), can think, they be respectively with oriented fibre part and the partly corresponding part of non-stretching knot.
(X-ray diffraction method)
In more detail, the X-ray diffraction characteristic of the membranoid substance of putting down in writing in this specification sheets is based on the measurement result of utilizing following assay method.
Under the situation that is the membranoid substance macaroni yarn, make alongst the length direction of the macaroni yarn after half-and-half cutting become vertical and be installed in like that on the sample table, vertically shine X ray with length direction.X-ray generator uses motor society's system of science " ロ one Off レ ッ Network ス 200RB ", with the CuK alpha-ray that passes through the nickel strainer of 30kV-100mA as the X ray light source.Using imaging plate (Fuji's description Off イ Le system society's system " BAS-SR127 "), is that 60mm takes diffraction image with distance between sample-imaging plate.Fig. 1 shows the diffraction image that the macaroni yarn by aftermentioned embodiment 5 obtains, and Fig. 2 is the explanatory view of Fig. 1.Can know that with reference to figure 2 the β angle is the angle that forms along debye ring, 2 θ are outer angles of mind-set therefrom.Make position angle (β angle) strength distribution curve (curve 2) of position angle (β angle) strength distribution curve (curve 1) of 2 θ=20.1 ± 1 ° and 2 θ=23.0 ± 1 °, repeatedly write down these curves and obtain Fig. 3.The debye ring of 2 θ=20.1 ± 1 ° is equivalent to the diffraction from PVDF α type crystalline (110) face, and the intensity of 2 θ=23.0 ± 1 ° is equivalent to the background intensity of diffraction X ray.
Equally under the situation of the porous-film of non-orientation, under for the situation of typically only utilizing the porous-film that extraction process or phase inversion method produce, curve 1 does not show the peak, perhaps has peak width at half height more than or equal to 90 ° broad peak.In addition because crystallization direction is arbitrarily, so in the curve 1 arbitrarily position angle (β angle) all big than the position angle intensity in the curve 2.
On the other hand, equally under the situation of the porous-film that is orientated sample, under for the typical situation of only utilizing the porous-film that produces of stretching, because crystallization direction has the orientation of selection, so curve 1 has sharp peak near β angle=90 ° or 270 ° (on equators of diffraction image).In addition owing near β angle=0 ° and 180 ° (on meridian of diffraction image), only show very weak diffraction near background intensity, so in β angle=0 ° or 180 ° locate, the strength ratio of curve 1/ curve 2 is less than 1.1.
Because porous-film of the present invention has orientation fibers and non-orientation knot (knot), so diffraction image is the eclipsed form appearance of the diffraction having selected to be orientated with crystal orientation and crystal orientation diffraction at random.That is, come from the curve 1 of orientation fibers, near β angle=90 ° or 270 ° (on equator of diffraction image), have peak width at half height smaller or equal to 80 °, preferably smaller or equal to 60 °, especially preferably smaller or equal to 40 ° peak; And the curve 1 that comes from non-orientation knot locates at position angle (β angle) arbitrarily that all the intensity than curve 2 is big, in β angle=0 ° or 180 ° locate, the strength ratio of curve 1/ curve 2 is more than or equal to 1.1, is preferably greater than to equal 1.2.
The result, utilize diffraction angle 2 θ that X-ray diffraction method obtains=20.1 ± 1 ° and diffracted intensity on ° meridian of locating of 2 θ=23.0 ± 1 to compare more than or equal to 1.1, and the peak width at half height Δ β at ° strength distribution curve peak of locating, position angle is smaller or equal to 80 ° in 2 θ=20.1 ± 1, and this has shown that quantitatively mixing exists crystalline orientation part and the non-alignment portion of crystallization in the porous-film of the present invention.
[embodiment]
Below, further specifically describe the present invention by embodiment and comparative example.Comprise be documented in followingly in, the characteristic of putting down in writing in this specification sheets beyond the above-mentioned X-ray diffraction characteristic is based on the measured value that following method obtains.
(weight-average molecular weight (Mw) and number-average molecular weight (Mn))
Use the GPC device " GPC-900 " of Japanese beam split society system, use " Shodex KD-806M " chromatographic column and " Shodex KD=G " pre-column of clear and electrician society system, use nmp solvent, at 40 ℃ of temperature, flow is under the condition of 10ml/ branch, utilizes gel permeation chromatography (GPC) to measure polystyrene calibration molecule amount.
(porosity)
Measure the length of porous-film, wide and thickness (under the situation of macaroni yarn, measuring internal diameter and external diameter), calculate the apparent volume V (cm of porous-film
2), and then the weight W (g) of mensuration porous-film utilizes following formula to obtain porosity.
[mathematical expression 1]
Voidage (%)=(1-W/ (V * ρ)) * 100
The proportion (=1.78g/cm of ρ: PVDF
2)
(permeable amount (flux))
Porous-film was flooded in ethanol 15 minutes, and then dipping made its hydrophilization in 15 minutes in water, measured under 25 ℃ of water temperatures, pressure reduction 100kPa then.When porous-film is the macaroni yarn shape, try to achieve membrane area by following formula according to external diameter.
[mathematical expression 2]
Membrane area (m
2)=external diameter * π * length
(mean pore size)
With ASTM F316-86 and ASTM E1294-89 is benchmark, uses Porous MaterialsInc. society's system " パ one system Port ロ メ one CFP-200AEX ", utilizes semidrying to measure mean pore size.Test solution uses perfluor polyester (trade(brand)name " Galwick ").
(maximum diameter of hole)
With ASTM F316-86 and ASTM E1294-89 is benchmark, uses Porous MaterialsInc society's system " パ one system Port ロ メ one CFP-200AEX ", utilizes the bubbling point method to measure the maximum diameter of hole.Reagent uses aldehyde fluorine polyester (trade(brand)name " Galwick ").
(tensile strength and elongation at break)
Use tension tester (Japan ボ one Le De ウ イ Application society's system " RTM-100 "), under the atmosphere of 23 ℃ of temperature, relative humidity 50%, be 100mm in initial sample length, pinblock speed is to measure under the 200mm/ condition of dividing.
(tensile yield point stress/elongation)
Under the atmosphere of 23 ℃ of temperature, relative humidity 50%, in initial sample length is 100mm, draw speed is under the condition of 200mm/ branch, use tension tester (Japan ボ one Le De ウ イ Application society's system " RTM-100 ") to measure the strain-stress curve of porous macaroni yarn, under the situation that the stress maximum point can occur, with the stress at maximum point place as yield-point.With the stress at yield-point place and elongation respectively as tensile yield point stress and tensile yield point elongation.
In addition, according to this tensile yield point stress, utilize following formula to calculate the yield point stress of fiber.
Fiber yield point stress (MPa)
=yield point stress (MPa) * 100/ (100-voidage (%))
With weight-average molecular weight (Mw) is 6.59 * 10
5The 1st poly(vinylidene fluoride) (PVDF) (powder) and weight-average molecular weight be 2.52 * 10
5The 2nd poly(vinylidene fluoride) (PVDF) (powder) mix with Henschel mixer with the ratio of 12.5 weight % and 87.5 weight % respectively, obtaining Mw is 3.03 * 10
5, Mw/Mn (number-average molecular weight) is than the mixture A that is 2.53.
To mix at normal temperatures as the hexanodioic acid kind polyester softening agent (" PN-150 " of Asahi Denka Kogyo K. K's system) of aliphatic category polyester with as the N-Methyl pyrrolidone (NMP) of solvent ratio, obtain mixture B with 87.5 weight %/12.5 weight %.
Use equidirectional rotation meshing-type two-axis forcing machine (プ ラ ス チ ッ Network engineering institute's society's system " BT-30 ", screw diameter 30mm, L/D=48), supply with mixture A from being set in apart from the powder supply unit of the position of the upstream portion 80mm of cylinder, supply with the mixture B that is heated to 100 ℃ from being set in, and supply with the ratio of mixture A/ mixture B=37.5/62.5 (weight %) apart from the liquid supply unit of the position of the upstream portion 480mm of cylinder.Mixing under 210 ℃ barrel zone temperature, be that 7mm, internal diameter are the nozzle of narrow annular channel of 3.5mm with mixing thing from having external diameter, it is thread to be extruded into hollow with the discharge-amount of 13g/min.
Make the mixture temperature of extruding maintain 60 ℃ with molten state, and, after the pulling speed of be directed in the water-bath of the water surface (being that the clearance is 10mm) apart from nozzle 10mm position, make its cooling curing (residence time in the water-bath: about 10 seconds), dividing with 5m/ is pulled out, it is rolled and formed body in the middle of obtaining the 1st.
Then, for formed body in the middle of preventing the 1st shrinks in the longitudinal direction, the state that its maintenance is fixed, on one side vibration, at room temperature in methylene dichloride, flooded 30 minutes on one side, the methylene dichloride that more renews then, utilize the same terms to flood once more, extraction aliphatic polyester and solvent, keeping the state that is fixed then is that methylene dichloride was removed in heating in 1 hour in 120 ℃ the baking oven in temperature, heat-treat simultaneously, obtained the 2nd middle formed body.
Then, be under 25 ℃ the atmosphere, to stretch with 1.6 times formed body in the middle of the 2nd at length direction in temperature, be that heat setting was carried out in heating in 1 hour in 100 ℃ the baking oven in temperature then, obtain poly-vinylidene fluoride class porous macaroni yarn.
The poly-vinylidene fluoride class porous macaroni yarn that is obtained, show following rerum natura: external diameter is 1.486mm, and internal diameter is 0.702mm, and thickness is 0.392mm, and void content is 72%, permeable amount is 18.01m
3/ m
2It 100kPa, mean pore size is 0.0864 μ m, and the maximum diameter of hole is 0.1839 μ m, and tensile strength is 9.1MPa, and elongation at break is 7%.
To create conditions and the rerum natura of prepared poly-vinylidene fluoride porous macaroni yarn, the result with following embodiment and comparative example is shown in aftermentioned table 1 and the table 2 in the lump.
Embodiment 2
Except the cooling bath temperature change that cooling is melt extruded thing is 11 ℃, and draw ratio is become beyond 1.8 times, carry out the processing identical and obtained the porous macaroni yarn with embodiment 1.
Embodiment 3
Except the supply ratio with mixture A and mixture B becomes 42.9/57.0 (weight %), carry out the processing identical and obtained the porous macaroni yarn with embodiment 2.
Embodiment 4
Except using mixture ratio to change to 50/50 (weight %) and the mixture A of acquisition with 1PVDF and 2PVDF, and the clearance is extended to 40mm, draw ratio changes to beyond 2.4 times, carries out the processing identical with embodiment 2 and has obtained the porous macaroni yarn.
Embodiment 5
Except draw ratio being changed to 1.8 times, carry out the processing identical and obtained the porous macaroni yarn with embodiment 4.
Fig. 1 illustrates the X-ray diffraction photo of the porous macaroni yarn that is obtained, Fig. 2 is to be the explanation of Fig. 1, Fig. 3 illustrate utilize that X-ray diffraction obtains in 2 θ=20.1 ± 1 ° and the repeatedly record diagram of the strength distribution curve at ° position angle of locating, 2 θ=23.0 ± 1 (β angle).
In addition, Fig. 4～Fig. 7 illustrates near the outer surface, inner surface, outside surface of the porous macaroni yarn that is obtained cross section and near 5000 times of scanning electron microscope photos of the cross section the internal surface respectively.
Embodiment 6
Except respectively the cooling bath temperature is changed to 40 ℃ and from nozzle to cooling surface till the clearance change to the 40mm, carry out the processing identical and obtained the porous macaroni yarn with embodiment 5.
Embodiment 7～9
Except respectively the cooling bath temperature being changed to 60 ℃ (embodiment 7), 80 ℃ (embodiment 8) and 11 ℃ (embodiment 9), carry out the processing identical and obtained the porous macaroni yarn with embodiment 6.
Embodiment 10
Except using mixture ratio to change to 5/95 (weight %) and the mixture A of acquisition, and the clearance is extended to beyond the 5mm, carries out the processing identical and obtained the porous macaroni yarn with embodiment 2 with 1PVD and 2PVD.
Comparative example 1
Replacing mixture A and using weight-average molecular weight separately is 4.92 * 10
5PVDF, make PVDF identical with embodiment 3 with the supply ratio of mixture, be 42.9/57.1 (weight %), making stretching ratio is 2.0 times, in addition, carries out the processing identical with embodiment 5, attempt making the porous macaroni yarn, but fracture of wire has taken place when stretching.
Comparative example 2
Except the pulling speed behind the cooling curing that will melt extrude mixture changes to 10mm/ exceptionally, under the condition identical, made the porous macaroni yarn with comparative example 1.
Comparative example 3
Replace mixture A and only use 1PVDF (Mw=63.59 * 10
5), the supply ratio of PVDF and mixture is changed to 33.3/66.7 (%), the clearance is changed to the 300mm/ branch, in addition, with the identical condition of embodiment 5 under attempt making the porous macaroni yarn, but fracture of wire has taken place when stretching.
Comparative example 4
Except draw ratio being reduced to 1.3 times, under the condition identical, made the porous macaroni yarn with comparative example 3.
Comparative example 5
Except the pulling speed that will melt extrude behind the mixture cooling curing changes to 10mm/ exceptionally, under the condition identical, made the porous macaroni yarn with comparative example 3.
Comparative example 6
Using Mw separately except replacing mixture A is 2.52 * 10
5PVDF (material that in embodiment 2, uses) as 2PVDF outside, carry out the identical processing with comparative example 2, attempt making the porous macaroni yarn, but fracture of wire taken place when stretching.
Comparative example 7
Pulling speed behind the cooling curing that will melt extrude mixture changes to 10mm/ divides, and attempts making the porous macaroni yarn under the condition identical with comparative example 6, but fracture of wire has taken place when stretching.
Comparative example 8
Except the pulling speed behind the cooling curing that will melt extrude mixture changes to 20mm/ exceptionally, under the condition identical, made the porous macaroni yarn with comparative example 6.
In table 2, write down the rerum natura of the porous macaroni yarn that in above-mentioned comparative example, when stretching, fracture of wire does not take place and obtain in the lump.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | |||
| Raw material is formed | Mixture A | The Mw (* 10 of 1PVDF 5) | 6.59 | 6.59 | 6.59 | 6.59 | 6.59 | 6.59 | 6.59 | 6.59 | 6.59 | 6.59 |
| The Mw (* 10 of 2PVDF 5) | 2.52 | 2.52 | 2.52 | 2.52 | 2.52 | 2.52 | 2.52 | 2.52 | 2.52 | 2.52 | ||
| The mixture ratio (weight %) of 1PVDF/ 2PVDF | 12.5/87.5 | 12.5/87.5 | 12.5/87.5 | 50/50 | 50/50 | 50/50 | 50/50 | 50/50 | 50/50 | 5/95 | ||
| The Mw (* 10 of mixture 5) | 3.03 | 3.03 | 3.03 | 4.56 | 4.56 | 4.56 | 4.56 | 4.56 | 4.56 | 2.83 | ||
| Mw/Mn | 2.53 | 2.53 | 2.53 | 2.94 | 2.94 | 2.94 | 2.94 | 2.94 | 2.94 | 2.53 | ||
| Mixture B | Polyester plasticizer | PN-150 | PN-150 | PN-150 | PN-150 | PN-150 | PN-150 | PN-150 | PN-150 | PN-150 | PN-150 | |
| Solvent | NMP | NMP | NMP | NMP | NMP | NMP | NMP | NMP | NMP | NMP | ||
| The mixture ratio of polyester plasticizer/solvent (weight %) | 87.5/12.5 | 87.5/12.5 | 87.5/12.5 | 87.5/12.5 | 87.5/12.5 | 87.5/12.5 | 87.5/12.5 | 87.5/12.5 | 87.5/12.5 | 87.5/12.5 | ||
| The supply ratio (weight %) of mixture A/ mixture B | 37.5/62.5 | 37.5/62.5 | 42.9/57.1 | 37.5/62.5 | 37.5/62.5 | 37.5/62.5 | 37.5/62.5 | 37.5/62.5 | 37.5/62.5 | 37.5/62.5 | ||
| The spin-drawing condition | Clearance (mm) | 10 | 10 | 10 | 140 | 140 | 40 | 40 | 40 | 40 | 5 | |
| Bath temperature (℃) | 60 | 11 | 11 | 11 | 11 | 40 | 60 | 80 | 11 | 11 | ||
| Pulling speed (m/min) | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | ||
| Draw ratio | 1.6 | 1.8 | 1.8 | 2.4 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | 1.8 | ||
| Rerum natura | External diameter (mm) | 1.486 | 1.549 | 1.527 | 1.469 | 1.62 | 1.51 | 1.488 | 1.455 | 1.500 | 1.581 | |
| Internal diameter (mm) | 0.702 | 0.736 | 0.796 | 0.502 | 0.542 | 0.561 | 0.705 | 0.653 | 0.550 | 0.931 | ||
| Thickness (mm) | 0.392 | 0.407 | 0.366 | 0.484 | 0.539 | 0.475 | 0.392 | 0.401 | 0.475 | 0.325 | ||
| Void content (%) | 72 | 77 | 69 | 78 | 72 | 78 | 72 | 72 | 75 | 72 | ||
| Permeable amount (m 3/m 2It 100kPa) | 18.01 | 13.48 | 7.46 | 5.84 | 5.28 | 12.09 | 8.17 | 10.2 | 5.75 | 11.3 | ||
| Mean pore size (μ m) | 0.0864 | 0.0717 | - | - | 0.0654 | 0.087 | 0.0709 | 0.1067 | - | 0.079 | ||
| Maximum diameter of hole (μ m) | 0.1839 | 0.1454 | - | - | 0.1445 | 0.1513 | 0.1443 | 0.303 | - | 0.150 | ||
| Tensile strength (Mpa) | 9.1 | 8.9 | 16.9 | 17.1 | 13.9 | 10.3 | - | - | 17 | 8.2 | ||
| Elongation at break (%) | 7 | 8.7 | 12 | 47 | 77 | 13 | - | - | 30 | 8.1 | ||
| Yield point stress (Mpa) | 8.9 | 8.9 | 16.9 | 17.2 | 13.1 | 10.3 | - | - | 17.1 | - | ||
| Yield-point extensibility (%) | 5 | 7 | 9 | 11 | 9 | 9 | - | - | 11 | - | ||
| Fiber yield point stress (MPa) | 31.7 | 38.7 | 54.4 | 78 | 46.8 | 46.7 | - | - | 68.2 | - | ||
Table 2
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |||
| Raw material is formed | Mixture A | The Mw (* 10 of 1PVDF 5) | 4.92 | 4.92 | 6.59 | 6.59 | 6.59 | 2.52 | 2.52 | 2.52 |
| The Mw (* 10 of 2PVDF 5) | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | ||
| The mixture ratio (weight %) of 1PVDF and 2PVDF | 100/0 | 100/0 | 100/0 | 100/0 | 100/0 | 100/0 | 100/0 | 100/0 | ||
| The Mw (* 10 of mixture 5) | 4.92 | 4.92 | 6.59 | 6.59 | 6.59 | 2.52 | 2.52 | 2.52 | ||
| Mw/Mn | 2.13 | 2.13 | 2.25 | 2.25 | 2.25 | 2.27 | 2.27 | 2.27 | ||
| Mixture B | Polyester plasticizer | PN-150 | PN-150 | PN-150 | PN-150 | PN-150 | PN-150 | PN-150 | PN-150 | |
| Solvent | NMP | NMP | NMP | NMP | NMP | NMP | NMP | NMP | ||
| The mixture ratio of polyester plasticizer/solvent (weight %) | 87.5/12.5 | 87.5/12.5 | 87.5/12.5 | 87.5/12.5 | 87.5/12.5 | 87.5/12.5 | 87.5/12.5 | 87.5/12.5 | ||
| The supply ratio (weight %) of mixture A/ mixture B | 42.9/57.1 | 42.9/57.1 | 33.3/66.7 | 33.3/66.7 | 33.3/66.7 | 37.5/62.5 | 37.5/62.5 | 37.5/62.5 | ||
| The spin-drawing condition | Clearance (mm) | 140 | 140 | 300 | 300 | 300 | 10 | 10 | 10 | |
| Bath temperature (℃) | 11 | 11 | 11 | 11 | 11 | 11 | 11 | 11 | ||
| Pulling speed (m/min) | 5 | 10 | 5 | 5 | 10 | 5 | 10 | 20 | ||
| Draw ratio | 2 | 2 | 1.8 | 1.3 | 1.8 | 1.8 | 1.8 | 1.8 | ||
| Rerum natura | External diameter (mm) | The stretching fracture of wire | 0.904 | The stretching fracture of wire | 1.66 | 0.929 | The stretching fracture of wire | The stretching fracture of wire | 0.742 | |
| Internal diameter (mm) | - | 0.41 | - | 0.772 | 0.403 | - | - | 0.34 | ||
| Thickness (mm) | - | 0.247 | - | 0.444 | 0.263 | - | - | 0.201 | ||
| Void content (%) | - | 60 | - | 60 | 65 | - | - | 71 | ||
| Permeable amount (m 3/m 2It 100kPa) | - | 1.05 | - | 1.76 | 1.63 | - | - | 3.89 | ||
| Mean pore size (μ m) | - | - | - | - | - | - | - | - | ||
| Maximum diameter of hole (μ m) | - | - | - | - | - | - | - | - | ||
| Tensile strength (MPa) | - | 37.1 | - | - | - | - | - | - | ||
| Elongation at break (%) | - | 44 | - | - | - | - | - | - | ||
Embodiment 11
For the porous macaroni yarn that obtains is shunk and state that it is maintained fixed at length direction, dipping is 15 minutes in methyl alcohol, after then dipping carried out hydrophilization in 15 minutes in pure water, dipping is 1 hour in 20% the caustic soda aqueous solution (pH14) of temperature maintenance at 70 ℃, wash then, temperature maintenance in 60 ℃ hot-air oven dry 1 hour.
Embodiment 12
For the porous macaroni yarn that obtains is shunk and state that it is maintained fixed at length direction, dipping is 15 minutes in methyl alcohol, after then carrying out hydrophilization in 15 minutes with the pure water dipping, in 35% aqueous hydrochloric acid (pH1), flooded 1 hour at normal temperatures, wash then, temperature maintenance in 60 ℃ hot-air oven dry 1 hour.
Embodiment 13
For the porous macaroni yarn that obtains is shunk and state that it is maintained fixed at length direction, in methylene dichloride, flooded 30 minutes while vibrating, the methylene dichloride that more renews then was under the same conditions once more behind the dipping, temperature maintenance in 60 ℃ hot-air oven dry 1 hour.
To the porous macaroni yarn after the elutriant processing of the foregoing description 11～13, porosity, permeable amount, mean pore size, maximum diameter of hole, tensile strength, elongation at break have been measured.In following table 3, show the respective value of measurement result and embodiment 1 in the lump.
Table 3
| Embodiment 11 | Embodiment 12 | Embodiment 13 | | ||
| Elutriant | Alkali lye | Acid solution | Organic solvent | Do not have | |
| Rerum natura | Porosity (%) | 74 | 73 | 75 | 72 |
| Permeable amount (m 3/m 2It 100kPa) | 36.6 | 31.8 | 35.7 | 18.01 | |
| Mean pore size (μ m) | 0.0964 | 0.0914 | 0.0890 | 0.0864 | |
| Maximum diameter of hole (μ m) | 0.1840 | 0.1800 | 0.0810 | 0.1839 | |
| Tensile strength (MPa) | 7.1 | 9.3 | 9.7 | 9.1 | |
| Elongation at break (%) | 6 | 9 | 13 | 7 | |
The industry utilizability
Result in the contrast in table 1 and the table 2 as can be known, according to the present invention, can obtain a kind of 1, the fluoride based resin porous film of 1-, this is 1 years old, the fluoride based resin porous film of 1-has size and the suitable micropore that distributes, and the mechanical strength take tensile strength and elongation at break as representative is excellent, can be used as secondary filter film or battery diaphragm, this film obtains by following operation, that is, make the vinylidene fluoride resinoid and 1 of the distribution that has proper width and have as a whole HMW, the plasticizer of 1-fluoride based resin and good solvent mix and obtain the composition that melt extrudes of composition, from a side this is melt extruded composition cools and solidify, the extraction plasticizer stretches. In addition, as shown in Table 3, process by utilizing alkali, acid or organic solvent that the perforated membrane (embodiment 1) that obtains is carried out eluent, can obtain the effect that permeable amount enlarges markedly.
Claims (13)
1. the based resin porous film of vinylidene fluoride is characterized in that, comprises following porous-film,
(A) weight-average molecular weight more than or equal to 200,000 and the ratio of weight-average molecular weight/number-average molecular weight more than or equal to the resinoid porous-film of 2.5 vinylidene fluoride, or
(B) weight-average molecular weight that comprises 2～75 weight % be 400,000～1,200,000 the 1, the weight-average molecular weight of 1-fluoride based resin and 25～98 weight % be 150,000～600,000 the 21, the 1-fluoride based resin, the and the 1, the weight-average molecular weight of 1-fluoride based resin/2 1, the ratio of the weight-average molecular weight of 1-fluoride based resin is more than or equal to the resinoid porous-film of 1.2 vinylidene fluoride
Described porous-film utilizes X-ray diffraction method to confirm, mixes to have crystalline orientation part and the non-alignment portion of crystallization.
2. porous-film as claimed in claim 1,1, the 1-fluoride based resin is, the weight-average molecular weight that contains 5～75 weight % be 400,000～1,200,000 the 1, the weight-average molecular weight of 1-fluoride based resin and 25～95 weight % is 150,000～600,000 the second vinylidene fluoride resinoid, and the one 1, the ratio of the weight-average molecular weight of 1-fluoride based resin/resinoid weight-average molecular weight of second vinylidene fluoride is more than or equal to 1.2.
3. porous-film as claimed in claim 1 or 2, porosity are 55～90%, and tensile strength is more than or equal to 5MPa, and elongation at break is more than or equal to 5%.
4. as each described porous-film of claim 1～3, tensile yield point stress is more than or equal to 5MPa, and elongation at yield point is more than or equal to 5%.
5. as each described porous-film of claim 1～4, permeable amount is more than or equal to 5m
3/ m
2It 100kPa.
6. as each described porous-film of claim 1～5, forming thickness is 5～800 μ m, and external diameter is that the hollow of 0.3～3mm is thread.
7. one kind 1, the manufacture method of the fluoride based resin porous film of 1-, it is characterized in that, with respect to the resin (A) of 100 weight parts or (B), 1 of the softening agent of interpolation 70～250 weight parts and 5～80 weight parts, the good solvent of 1-fluoride based resin, resultant composition is melt extruded into membranaceous, preferentially cool off, be cured film forming from a side, then, the extraction softening agent, and then stretch, described resin (A) is a kind of 1, the 1-fluoride based resin, its weight-average molecular weight more than or equal to 200,000 and the ratio of weight molecular weight/number-average molecular weight more than or equal to 2.5; Described resin (B) is a kind of 1, the 1-fluoride based resin, the weight-average molecular weight that contains 2～75 weight % be 400,000～1,200,000 the 1, the weight-average molecular weight of 1-fluoride based resin and 25～98 weight % be 150,000～600,000 the 21, the 1-fluoride based resin, and the ratio of the resinoid weight-average molecular weight of first vinylidene fluoride/resinoid weight-average molecular weight of second vinylidene fluoride is more than or equal to 1.2.
8. manufacture method as claimed in claim 7, with respect to the vinylidene fluoride resinoid of 100 weight parts, using total amount is the good solvent and the softening agent of 100～250 weight parts, wherein contains the good solvent of 5～30 weight %, forms above-mentioned composition.
9. as claim 7 or 8 described manufacture method, above-mentioned composition is extruded into macaroni yarn membranaceous after, in 5～120 ℃ heat-eliminating medium,, be cured film forming from outside cooling.
10. as each described manufacture method of claim 7～9, comprise the operation of utilizing elutriant to handle the porous-film after the stretching.
11. manufacture method as claimed in claim 10, elutriant are pH more than or equal to 12 alkali lye.
12. manufacture method as claimed in claim 10, elutriant are pH smaller or equal to 4 acid solution.
13. manufacture method as claimed in claim 10, elutriant are the extraction liquid of softening agent.
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| JP4303355B2 (en) * | 1999-04-26 | 2009-07-29 | 株式会社クレハ | Polyvinylidene fluoride resin, porous membrane comprising the same, and battery using the porous membrane |
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