WO2011027878A1

WO2011027878A1 - Porous vinylidene fluoride resin membrane and process for producing same

Info

Publication number: WO2011027878A1
Application number: PCT/JP2010/065205
Authority: WO
Inventors: 靖浩多田; 健夫高橋
Original assignee: 株式会社クレハ
Priority date: 2009-09-04
Filing date: 2010-09-06
Publication date: 2011-03-10

Abstract

Disclosed is a porous vinylidene fluoride resin membrane characterized by having two main surfaces, between which a certain thickness is sandwiched, and by having, on the side thereof facing one of the main surfaces, a dense layer that has a small pore diameter and governs the filtration performance, having an asymmetric gradient network structure in which the pore diameter increases continuously from the surface toward the other surface, and satisfying the following requirements (a) to (c): (a) the part of the dense layer which has a thickness of 5 µm and extends continuously from the surface has a porosity (A1) of 60% or higher; (b) the surface has a surface pore diameter (P1) of 0.30 µm or smaller; and (c) the ratio of the amount of water which has passed through in a test length (L) of 200 mm under the conditions of a differential pressure of 100 kPa and a water temperature of 25ºC, the water amount being a converted value (Q (m/day)) calculated for an overall porosity (A2) of 80%, to the fourth power of the surface pore diameter (P1) of the surface (P1⁴ (µm⁴)), Q/P1⁴, is 5×10⁴ (m/day∙µm⁴) or higher.

Description

Vinylidene fluoride resin porous membrane and method for producing the same

The present invention relates to a porous membrane made of vinylidene fluoride resin having performance suitable as a separation porous membrane, particularly a (filter) water treatment membrane, and a method for producing the same.

Since vinylidene fluoride resin is excellent in weather resistance, chemical resistance, and heat resistance, application to a porous membrane for separation is being studied. In particular, with respect to (filter) water treatment applications, in particular, water purification or sewage treatment applications, many proposals have been made including a production method thereof (for example, Patent Document 1). To 6).

In addition, the present inventors also melt-extruded a vinylidene fluoride resin having a specific molecular weight characteristic into a hollow fiber shape together with a plasticizer and a good solvent of the vinylidene fluoride resin, and then perform extraction removal and stretching of the plasticizer. We found that the method of making porous by performing was effective for the formation of a porous vinylidene fluoride resin membrane having fine pores of appropriate size and distribution and excellent mechanical strength. (Patent Documents 7 to 11 and others). However, there is a strong demand for further improvement with respect to the overall performance including the filtration performance and mechanical performance required when the porous membrane is used as a filtration permeation membrane. For example, as a MF (microfiltration) membrane used for the purpose of the production of drinking water or industrial water by turbidity of river water etc., which has become popular in recent years, or the turbidity purification treatment of sewage, a typical harmful To ensure the removal of Cryptosporidium, Escherichia coli, etc. as microorganisms, the average pore size is 0.25 μm or less, and there is little contamination (clogging) with organic substances during continuous filtration operation of turbid water, and a high water permeability is maintained. It is desirable. From this viewpoint, the porous membrane disclosed in the following Patent Document 6 has an excessive average pore diameter, and the hollow fiber porous membrane disclosed in the following Patent Document 8 has a problem in maintaining the amount of water permeation in the continuous filtration operation of muddy water. Remain.

JP-A 63-296939 JP-A 63-296940 Japanese Patent Laid-Open No. 3-215535 JP 7-173323 A WO01 / 28667 Publication WO02 / 070115A WO2005 / 099879A WO2007 / 010932A WO2008 / 117740A WO2010 / 082437A Specification of PCT / JP2010 / 051425

The present invention provides a porous vinylidene fluoride resin that has a surface pore size, water permeability and mechanical strength suitable for separation applications, particularly (filtered) water treatment, and exhibits good water permeability maintenance performance even during continuous filtration of muddy water. An object of the present invention is to provide a film and a method for producing the same.

Means to solve the problem

The vinylidene fluoride resin porous membrane of the present invention has been developed to achieve the above-mentioned object, and more specifically has two main surfaces sandwiching a certain thickness, and the pore diameter is on one surface side. It has a dense layer that is small and governs separation performance, has an asymmetric mesh-like inclined structure in which the pore diameter continuously increases from one surface to the opposite surface, and satisfies the following conditions (a) to (c) Is characterized by:
(A) The porosity A1 of a portion having a thickness of 5 μm continuous from the one surface of the dense layer is 60% or more,
(B) The total surface porosity A2 = 80 of the water permeability at the test length L = 200 mm measured under the condition that the surface pore diameter P1 of the one surface is 0.30 μm or less and (c) the differential pressure is 100 kPa and the water temperature is 25 ° C. The ratio between the converted value Q to% (m / day) and the fourth power value P1 ⁴ (μm ⁴ ) of the surface pore diameter P1 of the one surface, Q / P1 ⁴ is 5 × 10 ⁴ (m / day · μm ⁴ )more than.

As part of the research for achieving the above-mentioned object, the present inventors have made continuous filtration performance of muddy water on various vinylidene fluoride resin hollow fiber porous membranes including those disclosed in Patent Documents 7 to 11 above. As a practical test for determination, continuous filtration test (details will be described later) by the MBR method (membrane separation activated sludge method) is performed, and the differential pressure increase in the 2-hour membrane filtration treatment is 0.133 kPa or less The critical filtration flux determined as the filtration flux (flux) is evaluated as a practical evaluation standard for the ability to maintain water permeability, and the evaluation is correlated with the outer surface and internal pore size distribution, porosity, etc. of the porous membrane. I investigated. As a result, there is a dense layer that governs filtration performance on the treated water side, and a sparse layer that contributes to strength support on the permeated water side, and the pore diameter is continuous from the treated water side surface to the permeated water side surface. In a porous vinylidene fluoride resin membrane having an expanding asymmetric mesh-like gradient structure, a dense layer having a small surface pore diameter on the treated water side and in contact with the treated water side surface for a porous membrane having a large critical filtration flux In view of the fact that it is necessary to increase the porosity of the resin, a vinylidene fluoride resin porous membrane that almost achieves the above object has been proposed (Patent Document 11). However, porous membrane of vinylidene fluoride resin according to the Patent Document 11, the dense layer is relatively thick, therefore, heading is difficulty Q / P1 ⁴ showing the permeability ability in terms of maintaining the fine particle removal performance is degraded (Comparative Examples 1 to 3 described later). In contrast, the present invention is, while maintaining the characteristics of the film in Patent Document 11 described above, to prevent the thickening of the dense layer, in which succeeded in achieving an improvement in Q / P1 ^4.

In order to realize the structural characteristics of the vinylidene fluoride resin porous membrane, it is extremely important to select a plasticizer that forms a melt-kneaded composition before cooling by melt kneading with the vinylidene fluoride resin. In Patent Document 11, it is compatible with the vinylidene fluoride resin under heating (melt kneading composition formation temperature) and is almost equivalent to the crystallization temperature Tc (° C.) of the vinylidene fluoride resin alone in the melt kneading composition. A film-like product formed by melting and kneading with a high molecular weight vinylidene fluoride resin using a relatively large amount of a polyester plasticizer that gives a crystallization temperature Tc ′ (° C.) is cooled and solidified from one side, and then the plasticizer is added. It was considered that it is preferable to form an asymmetric reticulated resin porous membrane by extraction. Moreover, in order to promote uniform mixing of the film raw material resin and the plasticizer, a large amount of a good solvent of vinylidene fluoride resin used in Patent Documents 7 to 10 and the like and compatible with the cooling liquid is melted. This is not preferable because it causes a decrease in the crystallization temperature of the kneaded composition and makes it difficult to control the surface pore diameter. In the above, Tc ′ of the melt-kneaded material almost equivalent to Tc maintains a high difference Tc′−Tq from the coolant temperature Tq, and a relatively large amount of plasticizer is densely placed near the membrane surface by phase separation during cooling. This is based on the idea of forming a dense solidified layer of vinylidene fluoride resin dispersed in the resin. However, it has been found that the cooling effect from the outer surface reaches the inside of the film at the same time, leading to thickening of the dense solidified layer. In this respect, the plasticizer is preferably one that gives a lower Tc 'than Tc. According to further studies by the present inventors, even a melt-kneaded product having a Tc ′ lower than Tc gives the solidified product a large crystal melting enthalpy on the basis of the mass of the vinylidene fluoride resin. Then, it has been found that it is possible to form a dense solidified layer (dense layer) of vinylidene fluoride resin in which a relatively large amount of plasticizer is densely dispersed in the vicinity of the above-described film surface. In addition, the plasticizer further has a porosity of the dense layer finally formed by extruding the plasticizer once dispersed in the dense solidified layer by phase separation to the adjacent inner layer that has not been sufficiently solidified. It has also been found that it is preferable to have a certain degree of viscosity so as not to cause a decrease in the viscosity.

The method for producing a vinylidene fluoride resin porous membrane of the present invention is based on such knowledge, and more specifically, a melt-kneaded product of a vinylidene fluoride resin and a plasticizer is extruded from a die into a film shape, A method of producing a porous film comprising a step of forming a film to be cooled and solidified, and a step of extracting a plasticizer, wherein the plasticizer is compatible with the vinylidene fluoride resin at the formation temperature of the melt-kneaded product, and further It is characterized by satisfying the following conditions (i) to (iii):
(I) A crystallization temperature Tc ′ (° C.) lower by 6 ° C. or lower than the crystallization temperature Tc (° C.) of the vinylidene fluoride resin alone is given to the melt-kneaded product with the vinylidene fluoride resin.
(Ii) 53 J / g or more as crystal melting enthalpy ΔH ′ (J / g) based on the vinylidene fluoride resin mass standard when measured with a differential scanning calorimeter (DSC) on the solidified product obtained by cooling the melt-kneaded product And (iii) the viscosity of the plasticizer alone measured at a temperature of 25 ° C. in accordance with JIS K7117-2 (cone—using a flat plate type viscometer) is 200 mPa · s to 1000 Pa · s. According to a preferred aspect of the present invention, as the plasticizer, a polyester plasticizer in which the end of a (poly) ester composed of an aliphatic dibasic acid and glycol is sealed with a monovalent aromatic carboxylic acid is used.

The schematic explanatory drawing of the apparatus used in order to evaluate the water permeability of the hollow fiber porous membrane obtained by the Example and the comparative example. The schematic explanatory drawing of the apparatus used in order to evaluate the critical filtration flux by the MBR method of the hollow fiber porous membrane obtained by the Example and the comparative example.

The porous membrane of the present invention can be formed on either a flat membrane or a hollow fiber membrane, but it can be formed as a hollow fiber membrane that can easily increase the membrane area per filtration device, particularly in the case of filtered water treatment. preferable.

Hereinafter, such a vinylidene fluoride resin porous membrane mainly having a hollow fiber form will be sequentially described in accordance with the production method of the present invention which is a preferred production method thereof.

(Vinylidene fluoride resin)
In the present invention, the vinylidene fluoride resin as the main film raw material is a homopolymer of vinylidene fluoride, that is, polyvinylidene fluoride, a copolymer with other monomers copolymerizable with vinylidene fluoride, or a mixture thereof. And those having a weight average molecular weight of 600,000 to 1,200,000, more preferably 650,000 to 1,000,000, particularly preferably 700,000 to 900,000 are preferably used. As the monomer copolymerizable with vinylidene fluoride, one or more of ethylene tetrafluoride, hexafluoropropylene, ethylene trifluoride, ethylene trifluoride chloride, vinyl fluoride and the like can be used. The vinylidene fluoride resin preferably contains 70 mol% or more of vinylidene fluoride as a structural unit. Among these, it is preferable to use a homopolymer composed of 100 mol% of vinylidene fluoride because of its high chemical resistance and mechanical strength.
The relatively high molecular weight vinylidene fluoride resin as described above can be obtained by emulsion polymerization or suspension polymerization, particularly preferably suspension polymerization.

As described above, the vinylidene fluoride resin has a relatively large molecular weight of 600,000 or more as well as the resin's original melting point Tm2 (° C) and crystallization temperature Tc (° C) by DSC measurement. The difference Tm2−Tc is preferably 32 ° C. or less, more preferably 30 ° C. or less, still more preferably 28 ° C. or less, and most preferably less than 25 ° C.

Here, the original melting point Tm2 (° C.) of the resin is distinguished from the melting point Tm1 (° C.) measured by subjecting the obtained sample resin or the resin forming the porous film to the temperature rising process by DSC as it is. It is. That is, generally-available vinylidene fluoride resins exhibit a melting point Tm1 (° C.) different from the original melting point Tm2 (° C.) due to the heat and mechanical history received during the manufacturing process or thermoforming process. The original melting point Tm2 (° C.) of the resin is found again in the DSC temperature raising process after the obtained sample resin is once subjected to a predetermined heating and cooling cycle to remove heat and mechanical history. It is defined as the melting point (endothermic peak temperature accompanying crystal melting), and the details of the measurement method will be described prior to the description of Examples described later.

The above-mentioned vinylidene fluoride resins satisfying the condition of Tm2-Tc ≦ 32 ° C. preferably have a weight average molecular weight of 450,000 to 1,000,000, preferably selected from the above-mentioned vinylidene fluoride resin species as a raw material, 490,000 to 900,000, more preferably 600,000 to 800,000 medium high molecular weight vinylidene fluoride resin for matrix (PVDF-I) 25 to 98% by weight, preferably 50 to 95% by weight, more preferably 60 Crystal characteristic modification with ultra high molecular weight of ˜90% by weight and a weight average molecular weight of 1.4 times or more of PVDF-I and less than 1.5 million, preferably less than 1.4 million, more preferably less than 1.3 million Vinylidene fluoride resin (PVDF-II) for use as a mixture with 2 to 75% by weight, preferably 5 to 50% by weight, more preferably 10 to 40% by weight It is. Among them, the medium high molecular weight component functions as a matrix resin component, which keeps the molecular weight level of the entire vinylidene fluoride resin high and gives a hollow fiber porous membrane excellent in strength and water permeability. On the other hand, the ultrahigh molecular weight component is combined with the medium high molecular weight component to increase the crystallization temperature Tc of the raw material resin (generally about 140 ° C. for vinylidene fluoride homopolymer) and has a high plasticizer content. Nevertheless, by increasing the viscosity of the melt-kneaded composition and reinforcing it, stable extrusion in the form of a hollow fiber becomes possible. In the method of the present invention, when the film-like melt-kneaded material is cooled and solidified, a gradient pore size distribution in the film thickness direction is formed by a cooling rate gradient in which the cooling surface is rapidly cooled and the opposite surface from the inside is gradually cooled. It will be. On the premise of this, the use of a plasticizer that lowers the Tc ′ of the melt-kneaded product maintains the cooling temperature necessary for obtaining the desired surface pore diameter on the small pore diameter surface side (without change) while maintaining the film thickness. Thickening of the dense layer is prevented by delaying crystallization in most of the directions. However, spherulites of vinylidene fluoride resin are formed on the opposite surface from the inside of the film that is gradually cooled, which may cause a decrease in mechanical strength, a decrease in water permeability, and a decrease in stretchability. Even under such slow cooling conditions, the formation of spherulites can be effectively suppressed by the addition of the ultrahigh molecular weight component. The ultrahigh molecular weight component is considered to act as a crystal nucleating agent, and the characteristics as the crystal nucleating agent appear as an increase in the crystallization temperature Tc of the vinylidene fluoride resin alone, but the relative relationship between the cooling surface and the inside of the film This is not inconsistent with the use of a plasticizer that lowers the Tc ′ of the melt-kneaded product for the purpose of extending the crystallization delay range. Tc is preferably 143 ° C. or higher, more preferably 145 ° C. or higher and most preferably higher than 148 ° C. In general, the Tc of the vinylidene fluoride resin used does not substantially change during the production process of the hollow fiber membrane. Therefore, the obtained hollow fiber porous membrane can be measured as a sample by the DSC method described later.

When the Mw of the ultra high molecular weight vinylidene fluoride resin (PVDF-II) is less than 1.4 times the Mw of the medium high molecular weight resin (PVDF-I), it is difficult to sufficiently suppress the formation of spherulites. If it is 10,000 or more, it is difficult to uniformly disperse it in the matrix resin.

Any of the above-mentioned medium and ultra high molecular weight vinylidene fluoride resins can be obtained by emulsion polymerization or suspension polymerization, particularly preferably suspension polymerization.

Further, if the amount of the ultra high molecular weight vinylidene fluoride resin is less than 2% by weight, the effect of suppressing spherulite and the effect of thickening and reinforcing the melt-kneaded composition are not sufficient, while if it exceeds 75% by weight, the vinylidene fluoride is added. There is a tendency that the phase separation structure of the base resin and the plasticizer becomes excessively fine, and the water permeability of the resulting porous membrane decreases, and further, stable film formation becomes difficult due to the occurrence of melt fracture during processing. .

In the production method of the present invention, a plasticizer is added to the above-mentioned vinylidene fluoride resin to form a raw material composition for film formation.
(Plasticizer)
The hollow fiber porous membrane of the present invention is mainly formed from the above-mentioned vinylidene fluoride resin, but in addition to the above-mentioned vinylidene fluoride resin, at least the plasticizer is used as a pore-forming agent for the production. It is preferable. As the plasticizer in the present invention, those having compatibility with the vinylidene fluoride resin at the melt kneading temperature and the following characteristics (i) to (iii) are preferably used:

(I) The melt-kneaded product with the vinylidene fluoride resin is 6 ° C. or more lower than the crystallization temperature Tc (° C.) of the vinylidene fluoride resin alone, preferably 9 ° C. or more, more preferably 12 ° C. or more lower. Giving a crystallization temperature Tc ′ (° C.),
(Ii) As the crystal melting enthalpy ΔH ′ (J / g) based on the vinylidene fluoride resin mass standard when measured with a differential scanning calorimeter (DSC), the molded product obtained by cooling and solidifying the melt-kneaded product, Plasticity measured at a temperature of 25 ° C. in accordance with (iii) JIS K7117-2 (cone-using a plate-type rotary viscometer), and more than 53 J / g, preferably 55 J / g, more preferably 58 J / g. The viscosity of the agent alone is 200 mPa · s to 1000 Pa · s, preferably 400 mPa · s to 100 Pa · s, more preferably 500 mPa · s to 10 Pa · s or less.

Preferable examples of plasticizers having the above-described properties include (poly) esters composed of aliphatic dibasic acids and glycols, that is, polyesters or esters (mono- or diglycol esters of aliphatic dibasic acids, preferably A polyester plasticizer having both ends sealed with a monovalent aromatic carboxylic acid is used.

The aliphatic dibasic acid component constituting the (poly) ester at the center of the polyester plasticizer is preferably an aliphatic dibasic acid having 4 to 12 carbon atoms. Examples of such an aliphatic dibasic acid component include succinic acid, maleic acid, fumaric acid, glutamic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. Among these, aliphatic dibasic acids having 6 to 10 carbon atoms are preferable in terms of obtaining a polyester plasticizer having good compatibility with vinylidene fluoride resins, and adipic acid is particularly preferable from the viewpoint of industrial availability. . These aliphatic dibasic acids may be used alone or in combination of two or more.

The glycol component constituting the (poly) ester at the center of the polyester plasticizer is preferably a glycol having 2 to 18 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, and 1,2-butanediol. 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 2,2-diethyl-1, 3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2-butyl-2 -Aliphatic dihydric alcohols such as ethyl-1,5-propanediol, 1,12-octadecanediol, and diethylene glycol, dipropylene glycol And polyalkylene glycols such as In particular, glycols having 3 to 10 carbon atoms are preferably used. These glycols may be used alone or in combination of two or more.

The above-mentioned polyester plasticizer is preferably sealed at its molecular chain end with an aromatic monovalent carboxylic acid. Examples of aromatic monovalent carboxylic acids include benzoic acid, toluic acid, dimethyl aromatic monocarboxylic acid, ethyl aromatic monocarboxylic acid, cumic acid, tetramethyl aromatic monocarboxylic acid, naphthoic acid, biphenyl carboxylic acid, and furic acid. In general, monocyclic or bicyclic aromatic monovalent carboxylic acids are used, and these may be used alone or in combination of two or more. In particular, benzoic acid is preferable because of industrial availability.

In the present invention, in addition to the polyester plasticizer, a monomeric resin as long as the plasticizer (components other than the vinylidene fluoride resin in the melt-kneaded product) satisfies the above characteristics (i) to (iii). A plasticizer or a water-insoluble solvent can be used in combination. A preferred example of such a monomeric plasticizer is a dibenzoate monomeric plasticizer comprising glycol and an aromatic monovalent carboxylic acid. As the glycol and aromatic monovalent carboxylic acid contained, those similar to those contained in the above-mentioned polyester plasticizer are used. As the water-insoluble solvent, for example, a solvent that is immiscible with water such as propylene carbonate and has a solubility of, for example, 0.1 g / ml or more at 200 ° C. with respect to vinylidene fluoride resin.

As to the viscosity of the plasticizer shown in (iii) above, if the viscosity is less than 200 mPa · s, the porosity of the dense layer tends to decrease as described above, and the vinylidene fluoride resin and plastic The melt viscosity of the melt mixture with the agent may decrease, and it may be difficult to stably take out the melt mixture discharged from the die. This tendency is particularly remarkable when it is formed into a hollow fiber shape. Polyester plasticizers are preferred from the standpoint of imparting a moderately high melt viscosity to the molten mixture and stabilizing molding even when a large amount of plasticizer is added to the vinylidene fluoride resin.

The degree of polymerization of the polyester plasticizer is preferably 10,000 or less, more preferably 5000 or less, and most preferably 2000 or less as the number average molecular weight. If the number average molecular weight is more than 10,000, when the molten mixture is cooled and solidified, crystallization of the vinylidene fluoride resin is hindered and ΔH ′ is lowered, and the phase separation property at low temperature may be lowered. In general, as an index for the degree of polymerization of a polyester plasticizer, a viscosity measured at a temperature of 25 ° C. in accordance with JIS K7117-2 (cone-flat plate viscometer used) is often used, preferably 1000 Pa. · S or less, more preferably 100 Pa · s or less, and most preferably 10 Pa · s or less.

By selecting such a preferable plasticizer, it becomes possible to add a large amount of the plasticizer to the vinylidene fluoride resin having the preferable molecular weight characteristics as described above, and the molded product solidified by cooling after melt extrusion is fluorinated. After separating the vinylidene resin phase and the plasticizer phase and removing the plasticizer phase in the subsequent extraction step, a high dense layer porosity is obtained.

The polyester plasticizer used in the present invention is such that a melted mixture can be obtained by melting and kneading with a vinylidene fluoride resin in an extruder so as to obtain a clear (that is, without leaving a dispersion that can be visually recognized with the naked eye). In addition, it is compatible with the vinylidene fluoride resin. However, the formation of the melt-kneaded product in the extruder includes factors other than the properties derived from the raw materials, such as mechanical conditions, and in the sense of eliminating these factors, the compatibility determination method described later in the present invention. To determine compatibility.

(Composition)
In the raw material composition for forming the porous film, the plasticizer is 50 to 80% by weight, preferably 60 to 75% by weight relative to 20 to 50% by weight, preferably 25 to 40% by weight, of the vinylidene fluoride resin. % Is good to mix. The monomeric ester plasticizer, water-insoluble solvent, and the like added as necessary are used in such a manner that a part of the plasticizer is replaced in consideration of the melt viscosity of the raw material composition under melt kneading. (In addition to the plasticizer, the whole of the components other than the vinylidene fluoride resin constituting the melt mixture including these optional components may be referred to as “plasticizer or the like” hereinafter.)

If the amount of the plasticizer is too small, it is difficult to obtain an increase in the porosity of the dense layer that is the object of the present invention.If the amount is too large, the melt viscosity is excessively reduced, and in the case of hollow fibers, the yarn tends to be crushed. Moreover, there exists a possibility that the mechanical strength of the porous film obtained may fall.

The addition amount of the plasticizer is adjusted within the above range so that the Tc ′ of the melt-kneaded product with the vinylidene fluoride resin is 120 to 140 ° C., more preferably 125 to 139 ° C., and further preferably 130 to 138 ° C. Is done. If it is less than 120 ° C., the crystal melting enthalpy ΔH ′ of the melt-kneaded product is lowered, and the porosity A1 of the dense layer is lowered, or in the case of a hollow fiber, solidification in the cooling bath is insufficient and the yarn is crushed. May occur. If it exceeds 140 ° C., the thickening prevention effect of the dense layer is insufficient.

(Mixing / melt extrusion)
A melt-extruded composition melt-kneaded at a barrel temperature of 180 to 250 ° C., preferably 200 to 240 ° C., is generally extruded from a T die or a hollow nozzle at a temperature of 150 to 270 ° C., preferably 170 to 240 ° C. Filmed. Therefore, as long as a homogeneous composition in the above temperature range is finally obtained, the mixing and melting forms of the vinylidene fluoride resin and the plasticizer are arbitrary. According to one preferred embodiment for obtaining such a composition, a biaxial kneading extruder is used, and the vinylidene fluoride resin (preferably comprising a mixture of a main resin and a crystal characteristic modifying resin) is The plasticizer and the like are supplied from the upstream side of the extruder, supplied downstream, and made into a homogeneous mixture before being discharged through the extruder. This twin-screw extruder can be controlled independently by dividing it into a plurality of blocks along its longitudinal axis direction, and appropriate temperature adjustment is made according to the contents of the passing material at each site.

(cooling)
Next, the melt-extruded hollow fiber membrane is converted into a vinylidene fluoride resin having a temperature Tq of 50 to 140 ° C., more preferably 55 to 130 ° C., and even more preferably 60 to 110 ° C., lower than the crystallization temperature Tc ′. On the other hand, it introduce | transduces in the cooling bath which consists of a liquid (preferably water) which is inactive (namely, non-solvent and non-reactive), preferentially cools from the outer surface, and solidifies into a film. When Tc′−Tq is less than 50 ° C., it is difficult to form a porous film having a small pore size distribution with a small pore size on the surface of the water to be treated, which is the object of the present invention. In order to exceed 140 ° C., it is generally necessary to set the cooling liquid temperature to less than 0 ° C., which makes it difficult to use an aqueous medium as a preferable cooling liquid. The cooling bath temperature Tq is preferably 0 to 90 ° C., more preferably 5 to 80 ° C., and further preferably 25 to 70 ° C. At that time, in forming the hollow fiber membrane, a hollow fiber membrane having an enlarged diameter is obtained by cooling while injecting an inert gas such as air or nitrogen into the hollow portion. This is advantageous for obtaining a hollow fiber porous membrane having a small decrease in the amount of water per area (WO 2005 / 03700A). In order to form a flat film, cooling from one side by a chill roll is also used in addition to a cooling bath shower. In order to prevent the melt-extruded hollow fiber membrane from collapsing in the cooling bath, the elapsed time from the melt extrusion until entering the cooling bath (air gap passage time = air gap / melt extrudate take-off speed) Is generally in the range of 0.3 to 10.0 seconds, particularly 0.5 to 5.0 seconds.

(Extraction)
The cooled and solidified film-like material is then introduced into an extraction liquid bath and subjected to extraction and removal of a plasticizer and the like. The extraction liquid is not particularly limited as long as it does not dissolve the polyvinylidene fluoride resin and can dissolve the plasticizer and the like. For example, a solvent having a boiling point of about 30 to 100 ° C. is suitable for alcohols such as methanol and isopropyl alcohol, and for a halogen-based solvent such as dichloromethane and 1,1,1-trichloroethane.

The halogen-based solvent is swellable with respect to the vinylidene fluoride resin and has a large plasticizer extraction effect. However, due to its swelling property, when the extracted film-like material is transferred to the drying process as it is, the pores formed by the extraction of the plasticizer tend to shrink. Therefore, for the solidified film after melt extrusion and cooling, after extracting the plasticizer with a halogen-based solvent, the halogen-based solvent is removed by immersing in a solvent that does not swell with respect to the vinylidene fluoride resin. It is preferable to dry after substitution. Whether the solvent is swellable with respect to the vinylidene fluoride resin can be evaluated as follows. Examples of non-swellable solvents include, for example, isopropyl alcohol, ethanol, hexane and the like, but are not limited thereto as long as the following evaluation criteria are satisfied.

<Swelling evaluation method>
A vinylidene fluoride resin is heated and pressed at a temperature of 230 ° C. for 5 minutes, and then cooled and solidified by a cooling press at a temperature of 20 ° C. to produce a press sheet having a thickness of 0.5 mm. This press sheet is cut into 50 mm squares to form test pieces. After measuring the weight W1 of this test piece, it is immersed in a solvent at room temperature for 120 hours. Thereafter, the test piece is taken out, the solvent adhering to the surface is wiped off with a filter paper, and the weight W2 of the test piece is measured. The swelling rate (%) is measured by the following formula. If the swelling rate is less than 1%, it does not have swelling property, and if it is 1% or more, it is evaluated as having swelling property.
Swell rate (%) = (W2−W1) / W1 × 100.

<< Extraction rinse method >>
The above-described extraction rinse method (that is, the vinylidene fluoride resin film-like molded article containing a halogen-based solvent in the pores is once immersed in a solvent that does not swell with respect to the vinylidene fluoride resin. For example, a method of substituting (rinsing) a halogen-based solvent with, for example, and then drying is performed by, for example, a thermally induced phase separation method using a halogenated solvent as an extraction solvent or a non-solvent using a halogenated solvent as a non-solvent If a film-like molded body (b) of vinylidene fluoride resin containing a halogenated solvent is formed in its pores by induced phase separation, it can be applied to both the formation of flat membranes and hollow fiber membranes. Is possible. However, if anything, there is an aspect in which a film-shaped molded article (b) containing a halogenated solvent is formed by a thermally induced phase separation method that requires the use of a halogenated solvent in order to efficiently extract an organic liquid. preferable. Moreover, when considering the use as a filtered water treatment membrane, it is preferably used for forming a hollow fiber membrane in which the membrane area per filtration device can be easily increased.

As will be described later, the stretching is generally performed after extraction of the organic liquid with a halogenated solvent, but can also be performed before extraction of the organic liquid with a halogenated solvent. Although the effect of increasing the water permeability through increasing the porosity and expanding the pore diameter is smaller than the stretching after extraction, there is an advantage that the process from spinning to stretching of the hollow fiber can be continued. In the case of a hollow fiber, the draw ratio is preferably 1.4 to 5.0 times, more preferably 1.6 to 4.0 times, and most preferably about 1.8 to 3.0 times. The stretching temperature is the same as in the case of stretching after extraction.

Thus, the method for producing a vinylidene fluoride resin porous membrane including the generalized “extraction rinsing method” is characterized by the following (1) to (8).
(1) A film-like molded body (a) of a mixture of a vinylidene fluoride resin and an organic liquid is immersed in a halogenated solvent to extract and remove the organic liquid, and the halogenated solvent is left in the voids of the trace. Without forming a film-like molded body (b) containing, and substantially lysing it, immersing it in a solvent that does not swell with respect to the vinylidene fluoride resin to replace the halogenated solvent, Then, it is made to dry, The manufacturing method of the vinylidene fluoride resin porous membrane characterized by the above-mentioned.
(2) The film-shaped molded body (a) causes the vinylidene fluoride resin and the organic liquid to phase separate and solidify by cooling the melt-kneaded product of the vinylidene fluoride resin and the organic liquid. The manufacturing method as described in said (1) which is a film-like molded object.
(3) The said film-shaped molded object (a) has 5 J / g or more as a crystal-melting enthalpy on the basis of vinylidene fluoride resin mass measured by differential operation calorimetry (DSC), as described in (2) above Production method.
(4) The mixing ratio of the organic liquid in the mixture of the vinylidene fluoride resin and the organic liquid forming the film-shaped molded body (a) is 200 parts by volume or more with respect to 100 parts by volume of the vinylidene fluoride resin. The production method according to any one of the above (1) to (3).
(5) The production method according to any one of (1) to (4), wherein the organic liquid is a polyester plasticizer.
(6) The production method according to any one of (1) to (5) above, wherein the swelling ratio of the halogenated solvent to the vinylidene fluoride resin is 2 to 20% by weight.
(7) The pore formation efficiency determined as the porosity in the product porous film with respect to the volume ratio of the organic liquid in the mixture of the vinylidene fluoride resin and the organic liquid forming the film-shaped molded body (a) is 0. The production method according to any one of the above (1) to (6), which is 85 or more.
(8) The above-mentioned (1) to (7) including a stretching step before extraction with a halogenated solvent, or after substitution and drying of a halogenated solvent with a solvent that does not swell to vinylidene fluoride resin The manufacturing method in any one.

(Stretching)
It is preferable that the extracted film-like material is then subjected to stretching to increase the porosity and pore diameter and improve the strength. In particular, prior to stretching, it is possible to selectively wet from the outer surface of the film-like material after extraction (porous membrane) to a certain depth and stretch in this state (hereinafter referred to as “partial wet stretching”). It is preferable for obtaining a high dense layer porosity A1. More specifically, prior to stretching, 5 μm or more from the outer surface of the porous membrane, preferably 7 μm or more, more preferably 10 μm or more, and ½ or less, preferably １／ or less, more preferably 1 / １／ of the film thickness. A depth of 4 or less is selectively wetted. When the wet depth is less than 5 μm, the increase in the dense layer porosity A1 is not sufficient, and when it exceeds 1/2, when the dry heat is relaxed after stretching, the drying of the wetting liquid becomes uneven, and the heat treatment or relaxation Processing may be uneven.

The reason why the dense layer porosity A1 is improved by the partial wet stretching is not clarified, but the present inventors presume as follows. That is, it is considered that compressive stress acts in the film thickness direction when stretching in the longitudinal direction, but by wetting a certain depth from the outer surface, (a) heat transfer in the heating bath is improved. In particular, the temperature gradient of the dense layer is relaxed and the compressive stress in the film thickness direction is reduced. (B) Since the liquid is filled in the voids, the compressive stress in the film thickness direction is increased by stretching. It is presumed that the hole is less likely to collapse even if it works.

<< Partial wet stretching method >>
As understood from the above description, the “partial wet stretching method” basically has a main feature of a stretching step applied to a resin porous membrane that has already been formed in a dry state. Is not subject to essential constraints. The porous membrane is applicable regardless of whether it is a flat membrane or a hollow fiber membrane. The resin forming the porous film can be either a hydrophilic resin or a hydrophobic resin, and either a natural resin or a synthetic resin can be used. However, considering durability such as when the liquid to be treated when used as a separation membrane is an aqueous liquid, it is preferable that the resin be insoluble in water. As typical examples of such water-insoluble resins, polyolefin resins (eg JP46-40119B, JP50-2176B), polyvinylidene fluoride resins (eg JP63-296940A, JP03-215535A, WO99 / 47593A, WO03 / 031038A, WO2004 / 081109A, WO2005 / 099879A, JP2001-179062A, JP2003-210954A), polytetrafluoroethylene resin, polysulfone resin, polyethersulfone resin (WO02 / 058828A1), polyvinyl chloride resin, polyarylene sulfide system Resin, polyacrylonitrile-based resin, cellulose acetate resin (JP2003-31133A), etc. are also used as preferred resin materials in the present invention.

Among them, application to a porous film made of vinylidene fluoride resin having both chemical resistance, weather resistance, and heat resistance is most preferable. Generally, a vinylidene fluoride resin porous membrane is obtained by cooling a mixture of (A) a vinylidene fluoride resin and an organic liquid material that is compatible at least at an elevated temperature, and thereby fluorinating the organic liquid material. A method of obtaining a porous film by causing phase separation from vinylidene resin and removing the organic liquid from the film-like molded body of vinylidene fluoride resin containing the organic liquid separated by phase extraction (thermally induced phase separation method) WO99 / 47593A, WO03 / 031038A, WO2004 / 081109A, WO2005 / 099879A, JP2001-179062A), or (B) a film-like molded body of a mixture of the vinylidene fluoride resin and the organic liquid, and the phase of the organic liquid Contact with a non-solvent of the soluble vinylidene fluoride resin, and replace the organic liquid with the non-solvent. A method of forming a film-like molded body of a vinylidene fluoride resin containing a non-solvent by causing phase separation between the organic liquid and the vinylidene fluoride resin (non-solvent induced phase separation method; JP63-296940A and JP2003) 210954A) or (C) a vinylidene fluoride resin, an organic liquid incompatible with the resin, and a mechanical kneaded product of the inorganic fine powder into a film, and then the organic liquid from the film In many cases, it is manufactured by a method (JP03-215535A) for extracting a body and inorganic fine powder to obtain a porous membrane, but the method of the present invention can be applied to a porous membrane obtained through any of the above methods. is there.

As described above, the partial wet stretching method can be formed on either a flat membrane or a hollow fiber membrane. However, in general, a hollow fiber in which the membrane area per filtration device can be easily increased in drainage treatment. It is preferably formed as a film, and a flat film shape is preferable for electrochemical element separators including batteries. The method for producing a stretched resin porous membrane including the generalized “partial wet stretching method” is characterized by the following (1) to (14):
(1) A stretched resin porous membrane, wherein the resin porous membrane is stretched in a state of being selectively wetted with a wetting liquid to a depth of 5 μm or more and 1/2 or less of the film thickness from the outer surface. Manufacturing method.
(2) The production method according to (1), wherein stretching is performed in a state of being selectively wetted from the outer surface to a depth of 7 μm or more and ½ or less of the film thickness.
(3) The production method according to the above (1) or (2), wherein a resin porous membrane having a porosity of 50% or more is stretched.
(4) The production method according to any one of (1) to (3), wherein the porous resin membrane is an asymmetric structure membrane having different pore diameters on its two main surfaces, and wets only the surface having the smaller pore diameter. .
(5) The production method according to any one of (1) to (4), wherein the draw ratio is 1.5 times or more.
(6) The production method according to any one of (1) to (5) above, wherein the resin porous membrane is made of a hydrophobic resin.
(7) The production method according to any one of (1) to (5) above, wherein the resin porous membrane is made of a vinylidene fluoride resin.
(8) The production method according to the above (6) or (7), wherein the wetting liquid is an aqueous solution.
(9) The production method according to (8), wherein the wetting liquid is an aqueous surfactant solution.
(10) The production method according to (8), wherein the wetting liquid is an aqueous solution of a polyglycerin fatty acid ester.
(11) The production method according to any one of the above (1) to (10), wherein the pore diameter of the resin porous membrane after stretching has a surface pore diameter of 0.5 μm or less.
(12) The production method according to any one of (1) to (11) above, wherein the resin porous membrane after stretching has an average pore diameter of 0.5 μm or less in a half dry method.
(13) The production method according to any one of (1) to (12) above, wherein the stretching temperature is 25 to 90 ° C.
(14) The production method according to any one of (1) to (13), comprising a relaxation step in a liquid or gas that does not wet the resin porous membrane after stretching.

Hereinafter, embodiments in which a vinylidene fluoride resin porous membrane mainly having a hollow fiber form is formed by a heat-induced phase separation method and a partial wet stretching method is applied thereto will be sequentially described. It can be easily understood that the present invention can be applied to various forms and materials of porous resin membranes including a flat membrane formed according to the conventional method by modification.

As a specific method for wetting a certain depth from the outer surface, selective application of a solvent for wetting vinylidene fluoride resin such as methanol or ethanol or its aqueous solution to the outer surface of the porous membrane is also possible. However, in order to give selective coating properties to the outer surface of the vinylidene fluoride resin porous membrane, it is preferable to apply a wettability improving liquid having a surface tension of 25 to 45 mN / m (including the case of immersion). If the surface tension is less than 25 mN / m, it may be difficult to selectively apply the wettability improving liquid to the outer surface because the penetration rate into the PVDF porous membrane is too fast. If the surface tension exceeds 45 mN / m, It may be difficult to apply the wettability improving liquid uniformly on the outer surface because it is repelled on the outer surface (the wettability or permeability to the PVDF porous membrane is insufficient). In particular, it is preferable to use a surfactant solution obtained by adding a surfactant to water (that is, an aqueous solution or an aqueous homogeneous dispersion of a surfactant) as a wettability improving solution. The type of the surfactant is not particularly limited. In the anionic surfactant, a carboxylate type such as an aliphatic monocarboxylate, a sulfonate type such as an alkylbenzene sulfonate, a sulfate ester type such as an alkyl sulfate, Phosphate ester type such as alkyl phosphate salt; amine salt type such as alkylamine salt for cationic surfactant, quaternary ammonium salt type such as alkyltrimethylammonium salt; glycerin fatty acid for nonionic surfactant Ester type such as ester, ether type such as polyoxyethylene alkylphenyl ether, ester ether type such as polyethylene glycol fatty acid ester; for amphoteric surfactant, carboxybetaine type such as N, N-dimethyl-N-alkylaminoacetic acid betaine 2-alkyl-1-hydroxyl Le - such as glycine type and the like, such as carboxymethyl imidazolinium betaine. In particular, polyglycerin fatty acid ester is preferably used as a wettability improving liquid that does not have any sanitary problems even if it finally remains in the porous membrane.

The surfactant preferably has an HLB (hydrophilic / lipophilic balance) of 8 or more. When the HLB is less than 8, the surfactant is not finely dispersed in water, and as a result, uniform wettability improvement becomes difficult. Particularly preferably used surfactants include nonionic surfactants having an HLB of 8 to 20, and further 10 to 18, or ionic (anionic, cationic and amphoteric) surfactants. A surfactant is preferred.

In many cases, it is preferable to apply the wettability improving liquid to the outer surface of the porous membrane by batch or continuous immersion of the porous membrane. This dipping process is a double-sided coating process for flat membranes and a single-sided coating process for hollow fiber membranes. The flat membrane batch dipping treatment is carried out by dipping the hollow fiber membranes bundled by bobbin winding or casserole winding by dipping the layers cut into appropriate sizes. In the case of batch processing, it is preferable to form relatively large emulsion particles using a surfactant having a relatively low HLB within the above range, more specifically 8-13 HLB. In the case of a flat membrane and a hollow fiber membrane, the continuous treatment is performed by continuously immersing a long porous membrane in the treatment liquid. When selectively applying only to one side of the flat film, spraying of the treatment liquid is also preferably used. In the case of continuous processing, a surfactant having a relatively high HLB within the above range, more specifically 8-20, more preferably 10-18, may be used to form relatively small emulsion particles. preferable.

There are no particular restrictions on the viscosity of the wettability improving liquid, but depending on the method of application of the wettability improving liquid, the penetration speed can be lowered moderately by increasing the wettability improving liquid to a high viscosity, or penetrating with a low viscosity. It is possible to increase the speed.

There are no particular restrictions on the temperature of the wettability improving liquid, but depending on the method of application of the wettability improving liquid, the permeation rate can be moderately slowed by lowering the wettability improving liquid or the permeation at a high temperature. It is possible to increase the speed. Thus, the viscosity and temperature of the wettability improving liquid act in opposite directions, and can be complementarily controlled for adjusting the penetration rate of the wettability improving liquid.

The stretching of the hollow fiber membrane is generally preferably performed as uniaxial stretching in the longitudinal direction of the hollow fiber membrane by a pair of rollers having different peripheral speeds. This is because, in order to harmonize the porosity and the strength and elongation of the vinylidene fluoride resin hollow fiber porous membrane of the present invention, the stretched fibril (fiber) portion and the unstretched node (node) portion are arranged along the stretching direction. This is because it has been found that a microstructure that appears alternately is preferable. The draw ratio is about 1.1 to 4.0 times, particularly about 1.2 to 3.0 times, and most preferably about 1.4 to 2.5 times. When the draw ratio is excessive, the tendency of the hollow fiber membrane to break becomes large. The stretching temperature is preferably 25 to 90 ° C, particularly 45 to 80 ° C. If the stretching temperature is too low, the stretching becomes non-uniform and the hollow fiber membrane is easily broken. On the other hand, if the stretching temperature is too high, it is difficult to increase the porosity even if the stretching ratio is increased. In the case of a flat membrane, sequential or simultaneous biaxial stretching is also possible. In order to improve the drawing operability, the crystallinity is increased by heat treatment in advance at a temperature in the range of 80 to 160 ° C., preferably 100 to 140 ° C. for 1 second to 18000 seconds, preferably 3 seconds to 3600 seconds. It is also preferable.

(Relaxation treatment)
The hollow fiber porous membrane of vinylidene fluoride resin obtained as described above is subjected to at least one stage, more preferably at least two stages of relaxation or constant length heat treatment in a non-wetting atmosphere (or medium). Is preferred. The non-wetting atmosphere is a non-wetting liquid having a surface tension (JIS K6768) larger than the wetting tension of vinylidene fluoride resin near room temperature, typically water or air. Gas is used. The relaxation treatment of the uniaxially stretched porous membrane such as the hollow fiber is carried out by first performing the above-described non-wetting, preferably heated atmosphere, disposed between the upstream roller and the downstream roller, where the peripheral speed gradually decreases. It is obtained by passing the obtained stretched porous membrane. The relaxation rate determined by (1− (downstream roller peripheral speed / upstream roller peripheral speed)) × 100 (%) is preferably in the range of 0% (constant length heat treatment) to 50%, particularly 1 to 20 % Relaxation heat treatment is preferable. A relaxation rate exceeding 20% depends on the stretching ratio in the previous step, but is not preferable because it is difficult to achieve or even if realized, the effect of improving the water permeability is saturated or decreases.

The first-stage constant length or relaxation heat treatment temperature is preferably 0 to 100 ° C., particularly 50 to 100 ° C. The treatment time may be short or long as long as the desired heat setting effect and relaxation rate are obtained. Generally, it is about 5 seconds to 1 minute, but it is not necessary to be within this range.
The post-stage constant length or relaxation heat treatment temperature is preferably 80 to 170 ° C., more preferably 120 to 160 ° C., so that a relaxation rate of 1 to 20% can be obtained.

The effect of the relaxation treatment described above is a remarkable effect that the substantial membrane fractionation performance is maintained in a sharp state and the water permeability of the obtained porous membrane is increased. Moreover, performing the above-mentioned one-stage and two-stage treatment under a constant length is a heat setting operation after stretching.

(Vinylidene fluoride resin porous membrane)
The porous membrane of the present invention obtained through the above series of steps is substantially a single layer membrane of vinylidene fluoride resin, but has a dense layer that has a small pore size and governs separation performance on one surface side thereof. A vinylidene fluoride resin porous membrane having an asymmetric network-like gradient structure in which the pore diameter continuously increases from one surface to the opposite surface, and (a) a portion having a thickness of 5 μm in contact with the one surface of the dense layer The porosity A1 (%) is 60% or more, preferably 65% or more, more preferably 70% or more (the upper limit is not particularly limited, but generally it is difficult to exceed 85%),
(B) The surface pore diameter P1 of the one surface is 0.30 μm or less, preferably 0.25 μm or less, more preferably 0.20 μm or less, most preferably 0.15 μm or less (the lower limit is not particularly limited, but less than 0.01 μm) And (c) the converted value Q (m) of the water permeability at the test length L = 200 mm measured under the conditions of the differential pressure of 100 kPa and the water temperature of 25 ° C. to the total layer porosity A2 = 80%. / Day) to the fourth power value P1 ⁴ (μm ⁴ ) of the surface pore diameter P1 of the one surface, Q / P1 ⁴ is 5 × 10 ⁴ (m / day · μm ⁴ ) or more, preferably 7 × 10 ⁴ (m / day · μm ⁴ ) or more, more preferably 1 × 10 ⁵ (m / day · μm ⁴ ) or more (the upper limit is not particularly limited, but it exceeds 5 × 10 ⁵ (m / day · μm ⁴ )) Difficult)
More preferably, (d) the ratio A1 / P1 with the surface pore diameter P1 (μm) of the treated water is 400 or more, preferably 550 or more, more preferably 500 or more (the upper limit is not particularly limited). In general, it is difficult to exceed 1000)
(E) The ratio A1 / A2 between A1 and the total layer porosity A2 is 0.80 or more, preferably 0.85 or more, more preferably 0.90 or more (the upper limit is generally difficult to exceed 1.0) ) And
(F) The dense layer thickness is generally 7 μm or more, but 40 μm or less, preferably 30 μm or less, more preferably 20 μm or less, most preferably 15 μm or less,
(G) In addition, in the distribution of the inclined pore diameter of the porous membrane of the present invention, the ratio P2 / P1 of the surface pore diameter P1 (μm) on the one surface and the surface pore diameter P2 (μm) on the opposite surface is preferably 2.0 to 10. It is represented by being 0.

(A) The porosity A1 of the dense layer is 60% or more means that the dense layer that governs the separation performance of the porous membrane of the present invention has a high porosity (b) the one surface The surface pore diameter P1 of 0.30 μm or less means that the porous membrane of the present invention has high particle removal performance, and (c) the coefficient Q / P1 ⁴ is 5 × 10 ⁴ (m / day · μm ⁴ ) The above indicates that both fine particle removal performance and water permeability are compatible.

Other general characteristics when the porous membrane of the present invention is a hollow fiber porous membrane which is a preferred form are measured by the half dry / bubble point method (ASTM F316-86 and ASTM E1294-86). The average pore diameter Pm is generally 0.25 μm or less, preferably 0.20 to 0.01 μm, more preferably 0.15 to 0.05 μm, and the maximum pore diameter Pmax is generally 0.70 to 0.03 μm, preferably 0 .40 to 0.06 μm; Properties with a tensile strength of 7 MPa or more, preferably 8 MPa or more, and a breaking elongation of 70% or more, preferably 100% or more can be obtained. The thickness is usually in the range of about 50 to 800 μm, preferably 50 to 600 μm, particularly preferably 150 to 500 μm. The outer diameter of the hollow fiber is about 0.3 to 3 mm, particularly about 1 to 3 mm. The pure water permeation amount at a test length of 200 mm, a water temperature of 25 ° C., and a differential pressure of 100 kPa is 20 m / day or more, preferably 30 m / day or more, more preferably 40 m / day or more, and the total layer porosity is 80%. The converted water permeability Q is 20 m / day or more, preferably 30 m / day or more, and more preferably 40 m / day or more.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. The characteristic values described in the present specification are based on the measured values obtained by the following method except for those already described the measuring method.

(Crystal melting point Tm1, Tm2 and crystallization temperature Tc, Tc ′)
Using a differential scanning calorimeter “DSC7” manufactured by PerkinElmer Co., Ltd., 10 mg of the sample resin was set in the measurement cell, and the temperature was increased from 30 ° C. to 250 ° C. at a rate of 10 ° C./min in a nitrogen gas atmosphere. Then, after holding at 250 ° C. for 1 minute, the temperature was lowered from 250 ° C. to 30 ° C. at a temperature lowering rate of 10 ° C./min to obtain a DSC curve. In the DSC curve, the endothermic peak speed in the temperature rising process was the melting point Tm1 (° C.), and the exothermic peak temperature in the temperature lowering process was the crystallization temperature Tc (° C.). Subsequently, after maintaining at a temperature of 30 ° C. for 1 minute, the temperature was raised again from 30 ° C. to 250 ° C. at a rate of 10 ° C./min, and the DSC curve was measured. The endothermic peak temperature in this reheated DSC curve was the original resin melting point Tm2 (° C.) that defines the crystal characteristics of the vinylidene fluoride resin of the present invention.

The crystallization temperature Tc ′ (° C.) of the mixture of vinylidene fluoride resin as a film raw material and a plasticizer is 10% of the cooled and solidified product of the melt-kneaded product and subjected to the same heating and cooling cycle as described above. An exothermic peak temperature detected during the temperature lowering process after obtaining a curve.

Further, the crystallization temperature Tc of the vinylidene fluoride-based resin does not substantially change throughout the manufacturing process of the porous film according to the method of the present invention, but in the present specification, typically, the film after film formation, that is, the extraction process, If necessary, the DSC curve is obtained by subjecting 10 mg of the film finally obtained through the stretching process and the relaxation process to the same heating and cooling cycle as described above, and the measured value of the exothermic peak temperature detected in the cooling process is obtained. It is described.

(Crystal melting enthalpy ΔH ′ of the cooled and solidified product of the melt-kneaded product)
The crystal melting enthalpy ΔH ′ of a mixture of vinylidene fluoride resin as a film raw material and a plasticizer was measured as follows:
A DSC curve is obtained by subjecting 10 mg of the cooled and solidified product of the melt-kneaded product to the same temperature raising and lowering cycle as the measurement of the crystallization temperature Tc ′, and the total mass of the cooled and solidified product of the melt-kneaded product from the endothermic peak area at the first temperature increase. The reference crystal melting enthalpy ΔH0 (J / g) was determined. Separately, about 1 g of the cooled and solidified product of the melt-kneaded product was weighed to make it W0 (g), and then the cooled and solidified product of the melt-kneaded product was immersed in dichloromethane at room temperature for 30 minutes. The operation of ultrasonic cleaning was repeated three times to extract the plasticizer, etc., dried in an oven at a temperature of 120 ° C., and weighed again. Using the weight as W (g), the crystal melting enthalpy ΔH ′ (J / g) of the cooled and solidified product of the melt-kneaded product based on the vinylidene fluoride resin mass standard was calculated by the following formula.
ΔH ′ = ΔH0 / (W / W0)
As the cooled and solidified product of the melt-kneaded product, it is convenient to use a cooled and solidified film of the melt-kneaded extrudate produced by an actual method and before extraction processing (first intermediate molded body in the examples described later). .

(Compatibility)
The compatibility of the plasticizer (etc.) with the vinylidene fluoride resin was determined by the following method:
A slurry-like mixture is obtained by mixing 23.73 g of vinylidene fluoride resin and 46.27 g of a plasticizer at room temperature. Next, the barrel of “Lab Plast Mill” (mixer type: “R-60”) manufactured by Toyo Seiki Co., Ltd. is 10 ° C. higher than the melting point of the vinylidene fluoride resin (for example, about 17 to 37 ° C. higher). The temperature is adjusted, and the slurry mixture is charged and preheated for 3 minutes, and then melt-kneaded at a mixer rotation speed of 50 rpm. When a melted and kneaded product that is clear (that is, transparent to the extent that there is no visible turbidity) is obtained within 10 minutes after the start of kneading, the plasticizer is based on vinylidene fluoride resin. Determined to be compatible. In addition, when the viscosity of the melt-kneaded material is high, it may appear cloudy due to entrapment of bubbles, and in that case, it is determined by deaeration appropriately by a method such as hot pressing. Once it has cooled and solidified, it is heated again to be in a molten state, and then it is determined whether or not it is clarified.

(Weight average molecular weight (Mw))
Using a GPC device “GPC-900” manufactured by JASCO Corporation, “Shodex KD-806M” manufactured by Showa Denko Co., Ltd. as a column, “Shodex KD-G” used as a pre-column, NMP as a solvent, temperature 40 ° C., flow rate The molecular weight was measured in terms of polystyrene by gel permeation chromatography (GPC) at 10 mL / min.

(All layer porosity A2)
The apparent volume V (cm ³ ) of the porous membrane including the flat membrane and the hollow fiber membrane was calculated, and the weight W (g) of the porous membrane was measured to determine the total-layer porosity A2 from the following formula:
[Equation 1]
Total layer porosity A2 (%) = (1−W / (V × ρ)) × 100
ρ: Specific gravity of PVDF (= 1.78 g / cm ³ ).
In addition, the porosity A0 (%) of the whole layer of the unstretched film measured by the same method for the film after extraction and before stretching, and the ratio RB (% by weight) of the plasticizer (and solvent) mixture B in the melt extrusion mixture The approximate number of the ratio A0 / RB is considered to indicate the pore formation efficiency of the mixture B.

(Hole formation efficiency)
The volume mixing ratio RL of the organic liquid in the mixture with the vinylidene fluoride resin (specific gravity = 1.78) for forming the film-shaped molded body was calculated from the extrusion supply ratio (% by weight) and the specific gravity of the organic liquid. The hole formation efficiency was determined by the ratio A0 / RL between the total layer porosity A0 and RL.

(Dimension shrinkage)
The first intermediate formed body before extraction in the examples and comparative examples described later is cut out to a length of about 300 mm, the pre-extraction yarn length L0 (mm), the pre-extraction outer diameter OD0 (mm), the pre-extraction inner diameter ID0 (mm), and the extraction The previous film thickness T0 (mm) was measured. Then, predetermined operations of extraction, replacement, and drying are performed, and the thread length L1 (mm) after drying, the outer diameter OD1 (mm) after drying, the inner diameter ID1 (mm) after drying, and the film thickness T1 (mm) after drying are obtained. It was measured. Each dimensional shrinkage (%) was calculated by the following formula:
Longitudinal shrinkage (%) = 100 × (L0−L1) / L0
Outer diameter shrinkage (%) = 100 × (OD0−OD1) / OD0
Inner diameter shrinkage (%) = 100 × (ID0−ID1) / ID0
Film thickness shrinkage (%) = 100 × (T0−T1) / T0

(Average pore diameter)
Based on ASTM F316-86 and ASTM E1294-89, average pore size Pm (μm) was measured by a half dry method using “Palm Porometer CFP-200AEX” manufactured by Porous Materials, Inc. Perfluoropolyester (trade name “Galwick”) was used as a test solution.

(Maximum hole diameter)
Based on ASTM F316-86 and ASTM E1294-89, the maximum pore size Pmax (μm) was measured by a bubble point method using “Palm Porometer CFP-200AEX” manufactured by Porous Materials, Inc. Perfluoropolyester (trade name “Galwick”) was used as a test solution.

(Treatment water side surface hole diameter P1 and permeate water side surface hole diameter P2)
For a flat membrane or hollow fiber-like porous membrane sample, the average pore diameter P1 of the treated water side surface (outer surface in hollow fiber) and the average pore diameter P2 of the permeated water side surface (inner surface in hollow fiber) were determined by SEM method. Measured (SEM average pore diameter). Hereinafter, the measurement method will be described by taking a hollow fiber porous membrane sample as an example. SEM photography is performed on the outer surface and inner surface of the hollow fiber membrane sample at an observation magnification of 15,000 times, respectively. Next, for each SEM photograph, the hole diameter is measured for everything that can be recognized as a hole. The hole diameter is obtained by measuring the long and short diameters of each hole and determining the hole diameter = (long diameter + short diameter) / 2. The arithmetic average of the measured pore diameters is obtained and set as the outer surface average pore diameter P1 and the inner surface average pore diameter P2. In addition, when there are too many holes observed in the photograph, the photograph image may be divided into four equal parts, and the above-mentioned hole diameter measurement may be performed for one area (¼ screen). . When the outer surface of the hollow fiber membrane of the present invention is measured on a ¼ screen, the number of measurement holes is approximately 200 to 300.

(Dense layer thickness)
With respect to a flat membrane or hollow fiber-like porous membrane sample, the thickness of the dense and continuous layer having a substantially uniform pore diameter from the surface to be treated (the outer surface in the case of a hollow fiber) is measured by cross-sectional observation using an SEM. Hereinafter, the measurement method will be described by taking a hollow fiber porous membrane sample as an example. First, the hollow fiber porous membrane material is immersed in isopropyl alcohol (IPA), the pores are impregnated with IPA, then immediately immersed in liquid nitrogen and frozen, and while being frozen, the hollow fiber membrane is folded and broken, A cross section perpendicular to the longitudinal direction is exposed. SEM photography is sequentially performed on the exposed cross section at an observation magnification of 15,000 times from the outer surface side toward the inner surface side. Next, in the SEM photograph on the outermost surface side, the hole diameter is measured for all the 3 μm × 3 μm square regions centered on a point of 1.5 μm from the outer surface that can be recognized as holes. The hole diameter is obtained by measuring the long and short diameters of each hole and determining the hole diameter = (long diameter + short diameter) / 2. The arithmetic average of the measured pore diameter is obtained, and this is defined as the sectional pore diameter X _1.5 (μm) at a depth of _1.5 μm. From the outer surface, the arithmetic average pore diameter is obtained in the same manner as described above for the 3 μm × 3 μm square region centered on the point shifted to the inner surface side sequentially at an interval of about 3 μm. By performing interpolation, the cross-sectional hole diameter X _d (μm) at an arbitrary depth d (μm) is obtained from the outer surface. If the condition of X _d / X _1.5 ≦ 1.2 is satisfied, the hole diameter is assumed to be uniform, and the dense layer thickness having a uniform hole diameter is defined as the maximum depth d (μm) that satisfies the condition.

(Dense layer porosity)
A flat membrane or hollow fiber-like porous membrane sample is impregnated with a porosity A1 (%) (hereinafter referred to as “dense layer porosity A1”) of a portion having a thickness of 5 μm in contact with the surface to be treated of the dense layer. Measure by the method. Hereinafter, the measurement method will be described by taking a hollow fiber porous membrane sample as an example. First, a hollow fiber porous membrane sample is cut into a length L = about 300 mm, both ends of the hollow portion are sealed with thermocompression bonding or an adhesive, and the weight W0 (mg) is measured. Next, a hollow fiber membrane sample sealed at both ends was prepared by adding 0.05% by weight of a dye (“Cation Red” manufactured by Kiwa Chemical Industry Co., Ltd.) and “MO-” produced by fatty acid glycerin ester (Sakamoto Pharmaceutical Co., Ltd.). 7S "; HLB value = 12.9) 1.0% by weight and after being immersed in a test solution made of glycerin (" Purified Glycerin D "manufactured by Lion Corporation), the sample was taken out and wiped off the surface test solution. The weight W (mg) is measured again. Next, the sample after weighing is cut with a razor, and the thickness t (μm) of the portion impregnated with the test solution (= stained portion) is measured using an optical microscope (“VQ-Z50” manufactured by KEYENS). The thickness t is adjusted to t = 5 ± 1 (μm) by adjusting the immersion time in the test solution and the concentration of the aliphatic glycerin ester in the test solution. From the thickness L (mm) and the impregnation thickness t (μm), the volume V (ml) of the portion of the sample impregnated with the test liquid is calculated by the following formula:
V = π × ((OD / 2) ² − (OD / 2−t / 1000) ² ) × L / 1000
From the difference between the weight W0 (mg) of the sample before immersion and the weight W (mg) of the sample after immersion, the volume VL (ml) of the test solution impregnated is calculated by the following formula:
VL = (W−W0) / (ρs × 1000)
Here, ρs is the specific gravity of the test solution and is 1.261 (g / ml).
The dense layer porosity A1 (%) is calculated by the following formula.
A1 = VL / V × 100.

(Water permeability F, converted water permeability Q)
In order to measure the pure water permeation amount F, a sample hollow fiber porous membrane having a test length L (see FIG. 1) = 200 mm was immersed in ethanol for 15 minutes, then immersed in pure water for 15 minutes, and then wetted. Divide the amount of water per day (m ³ / day) measured at a water temperature of 25 ° C. and a differential pressure of 100 kPa by the membrane area (m ² ) of the hollow fiber porous membrane (= calculated as outer diameter × π × test length L). I got it. The measured value is expressed as F (100 kPa, L = 200 mm), and the unit is represented by m / day (= m ³ / m ² / day).
The converted pure water permeation amount Q to the total layer porosity 80% was determined by the formula Q = F × 80 / A2 based on the measured total layer porosity A2 (%).

(Critical filtration flux by MBR method)
Using the test apparatus shown in FIG. 2, continuous filtration of activated sludge water is performed while increasing the filtration flux (m / day) stepwise every two hours for submerged mini modules formed from hollow fiber porous membrane samples. And measure the average differential pressure increase rate in each filtration flux. The maximum filtration flux at which the pressure increase rate does not exceed 0.133 kPa / 2 hours is defined as the critical filtration flux (m / day).

The mini module is formed by vertically fixing two hollow fiber porous membrane samples between the upper header and the lower header so that the effective filtration length per one becomes 500 mm. The upper header is an upper insertion port to be fixed with the upper end of the hollow fiber membrane being opened on the lower side, an internal space (flow path) for filtrate water communicating with the upper insertion port, and suction on the upper side. It has a filtrate outlet for discharging filtrate to the pump. The lower header has a lower insertion port for fixing the hollow fiber membrane on its upper side with its lower end closed, and an aeration nozzle that does not communicate with the lower insertion port (diameter 1 mm × 10) And an internal space (supply path) for supplying air to the aeration nozzle and an air supply port for supplying air from the air pump to the internal space. The upper and lower ends of the two hollow fiber membrane samples are each inserted and fixed to the upper insertion port by epoxy resin so that the upper header is liquid-tightly connected, and the lower header is inserted so that the lower header is closed. It is inserted into the mouth and fixed.

This modularized hollow fiber membrane sample was dipped in ethanol for 15 minutes and then wetted by replacement with pure water. Then, the bottom area was approximately 30 cm ² and the height of the water surface was approximately 600 mm. Soak the hollow fiber vertically. On the other hand, in this test water tank, MLSS (floating substance concentration) accommodated in a raw water tank with an internal volume of 20 L = 8600 mg / L, dissolved organic matter concentration DOC (TOC (total organic concentration) after filtration through a 1 μm glass filter) = 7 to 9 mg / L of activated sludge water is supplied at a rate of 0.2 L / min by a pump, and the overflow is circulated to the raw water tank. Further, air is supplied from the lower header at a rate of 5 L / min, and is constantly bubbled into the activated sludge water in the test water tank.

In this state, by operating the suction pump and sucking from the filtrate outlet of the upper header, from the outside to the inside of the hollow fiber porous membrane, the suction filtration operation is performed for 13 minutes with a constant amount of filtrate, and the filtration is stopped for 2 minutes. While repeating the cycle, the suction filtration is performed for 2 hours, and the change with time of the differential pressure inside and outside the hollow fiber porous membrane is measured. The constant amount of filtered water is initially 0.3 m / day as the filtration flux (m / day) and increases by 0.1 m / day every 2 hours, and the differential pressure increase rate becomes higher than 0.133 kPa / 2 hours. The same filtration test was repeated until the permeation amount before the filtration flux cycle (ie, 0.1 m / day lower) in which the differential pressure increase rate exceeded 0.133 kPa / 2 hours was changed to the critical filtration flux (m / day).

(Surface tension measurement)
The surface tension of the wet treatment solution at a temperature of 25 ° C. was measured by a ring method according to JIS-K3362 using a Dunui surface tension tester.

(Critical surface tension)
Water and ethanol were mixed at different ratios to prepare aqueous solutions with different surface tensions. The relationship between the ethanol concentration and the surface tension was referred to the description in the Chemical Engineering Handbook (Maruzen Co., Ltd., revised fifth edition). In the measurement of the water permeability, pure water permeability F ′ (m / day) (= m ³ / m ² / day) was measured using the above aqueous solution instead of wetting the porous membrane with ethanol. The maximum surface tension at which the ratio F ′ / F to the pure water permeation amount F measured by wetting with ethanol alone is 0.9 or more is defined as the critical surface tension of the porous membrane. Incidentally, the critical surface tension γc of the vinylidene fluoride resin hollow fiber porous membrane formed in Examples A1 to A5 described later was measured to be 38 mN / m.

(Tensile test)
Using a tensile tester (“RTM-100” manufactured by Toyo Baldwin Co., Ltd.), measurement was performed in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50% under conditions of an initial sample length of 100 mm and a crosshead speed of 200 mm / min.

Example 1
Polyvinylidene fluoride (PVDF-I) for matrix having a weight average molecular weight (Mw) of 6.6 × 10 ⁵ (powder) and polyvinylidene fluoride for modifying crystal properties having a Mw of 9.7 × 10 ⁵ (PVDF-II) ) (Powder) at a ratio of 75% by weight and 25% by weight, respectively, using a Henschel mixer, a PVDF mixture (mixture A; crystals after film formation) having an Mw of 7.4 × 10 ⁵ Temperature was obtained (Tc = 148.3 ° C.).

As a plasticizer, a polyester plasticizer (polyester of dibasic acid and glycol whose ends are sealed with benzoic acid; “W-83” manufactured by DIC Corporation, number average molecular weight of about 500, JIS K7117-2 (cone-flat plate) The viscosity measured at 25 ° C. with a mold rotational viscometer (750 mPa · s) was used.

Using a co-rotating meshing type twin screw extruder (“TEM-26SS” manufactured by Toshiba Machine Co., Ltd., screw diameter 26 mm, L / D = 60), the mixture A is supplied from the powder supply unit, and the barrel temperature is 220 ° C. Next, the plasticizer is melted and kneaded in a ratio of mixture A / plasticizer = 27.0 wt% / 73.0 wt% from the liquid supply section provided downstream from the powder supply section of the extruder cylinder. The mixture was fed and kneaded at a barrel temperature of 220 ° C., and the mixture was extruded into a hollow fiber shape from a nozzle (190 ° C.) having a circular slit having an outer diameter of 6 mm and an inner diameter of 4 mm. At this time, the inner diameter was adjusted by injecting air into the hollow portion of the hollow fiber from the vent provided in the center of the nozzle.

The extruded mixture is kept in a molten state, is maintained at a temperature of 50 ° C., and has a water surface at a position 280 mm away from the nozzle (that is, an air gap of 280 mm). (Retention time in cooling bath: about 6 seconds) After taking up at a take-up speed of 3.8 m / min, this was wound around a bobbin to obtain a first intermediate molded body.

Next, the plasticizer was extracted by immersing this first intermediate molded body in dichloromethane at room temperature for 30 minutes. At this time, the extraction was performed while rotating the bobbin so that the dichloromethane was evenly distributed over the yarn. Next, the operation of replacing the dichloromethane with a new one and extracting again under the same conditions was repeated, and extraction was performed three times in total.

Next, the first intermediate molded body containing dichloromethane is immersed in isopropyl alcohol (IPA) at room temperature for 30 minutes without being substantially dried (that is, in a state where no whitening is visually recognized in the first intermediate molded body). Then, the dichloromethane impregnated in the first intermediate molded body was replaced with IPA. At this time, the replacement was performed while rotating the bobbin so that the IPA was evenly distributed over the yarn. Subsequently, the operation of replacing the IPA with a new one and replacing the same under the same conditions was repeated, and the replacement was performed twice in total.

Next, IPA was removed by air drying at room temperature for 24 hours, followed by heating in an oven at a temperature of 120 ° C. for 1 hour to remove IPA and heat treatment to obtain a second intermediate molded body. At this time, the shrinkage stress of the yarn was relaxed so that the diameter of the bobbin was freely contracted.

Next, in a state where the second intermediate molded body is wound around a bobbin, a polyglycerin fatty acid ester (“SY Glyster ML-310” manufactured by Sakamoto Pharmaceutical Co., Ltd., HLB = 1) is used as a surfactant.
0.3) was immersed in an emulsion aqueous solution (surface tension = 32.4 mN / m) dissolved in pure water at a concentration of 0.05% by weight at room temperature for 30 minutes.

Further, while the bobbin is immersed in the emulsion aqueous solution, the second intermediate molded body is pulled out while rotating the bobbin, the first roll speed is set to 20.0 m / min, and the second roll is passed through a 60 ° C. water bath. The film was stretched 1.75 times in the longitudinal direction by setting the speed to 35.0 m / min. Next, it is passed through a hot water bath controlled at a temperature of 90 ° C., the first stage relaxation rate is relaxed at 8%, and further passed through a dry heat tank controlled at a spatial temperature of 140 ° C., and the second stage relaxation rate is 1.5%. And relaxed. This was wound up to obtain a polyvinylidene fluoride hollow fiber porous membrane (third molded body) of the present invention. The time required to stretch all the second intermediate molded body wound around the bobbin was about 200 minutes.
The outline of the above Example 1 and the physical properties of the obtained polyvinylidene fluoride hollow fiber porous membrane are summarized in Tables 1 and 2 below together with the results of the following Examples and Comparative Examples.

(Example 2)
A polyvinylidene fluoride hollow fiber porous membrane of the present invention was obtained in the same manner as in Example 1 except that the cooling water bath temperature Tq after melt extrusion was changed to 70 ° C.

(Example 3)
A PVDF mixture A (crystallization temperature Tc = 147.9 ° C.) is obtained using polyvinylidene fluoride having a Mw of 4.9 × 10 ⁵ as PVDF-I, and the cooling water bath temperature Tq after melt extrusion is changed to 30 ° C. Except for the above, a polyvinylidene fluoride hollow fiber porous membrane of the present invention was obtained in the same manner as in Example 1.

(Comparative Example 1)
A polyvinylidene fluoride-based hollow fiber porous membrane was obtained essentially by the method of Example 1 of Patent Document 11.
PVDF mixture A (crystallization temperature Tc = 150.4 ° C.) was obtained by using polyvinylidene fluoride having a Mw of 4.1 × 10 ⁵ as PVDF-I; an adipic acid polyester plasticizer as a plasticizer (Polyester of adipic acid and 1,2-butanediol whose ends are sealed with isononyl alcohol; “D623N” manufactured by J. Plus Co., Ltd., number average molecular weight of about 1800, JIS K7117-2 (cone-flat plate viscometer) ) And a measured viscosity of 3000 mPa · s at 25 ° C.) and diisononyl adipate (“DINA” manufactured by Jay Plus Co., Ltd.), which is a monomeric ester plasticizer, at a ratio of 88% by weight / 12% by weight, Use of plasticizer mixture B stirred and mixed at normal temperature; mixture A and mixture B were provided at a ratio of 27.9 wt% / 72.1 wt% The take-up speed was 5.0 m / min; the extraction rinse with IPA was not performed after extraction with dichloromethane; and the heat treatment after stretching was passed through a hot water bath controlled at a temperature of 90 ° C. (That is, the first stage relaxation rate is 0%), and heat treatment was performed by passing through a dry heat bath controlled to a space temperature of 80 ° C. (that is, the second stage relaxation rate was 0%); In the same manner as described above, a polyvinylidene fluoride hollow fiber porous membrane was obtained.

(Comparative Example 2)
A polyvinylidene fluoride hollow fiber porous membrane was obtained essentially by the method of Example 7 of Patent Document 11.
PVDF mixture A (crystallization temperature Tc = 149.3 ° C.) was obtained using polyvinylidene fluoride having a Mw of 4.9 × 10 ⁵ as PVDF-I; 27.1% by weight of mixture A and mixture B Supply at a rate of 72.9% by weight; the cooling water bath temperature Tq after melt extrusion was changed to 70 ° C .; the take-up speed was 3.3 m / min; A polyvinylidene fluoride hollow fiber porous membrane of the present invention was obtained in the same manner as in Comparative Example 1 except that 8% relaxation was performed in a water bath and then 2% relaxation treatment was performed in air at 140 ° C.

(Comparative Example 3)
A polyvinylidene fluoride-based hollow fiber porous membrane was obtained essentially by the method of Example 8 of Patent Document 11.
A polyvinylidene fluoride hollow fiber porous membrane of the present invention was obtained in the same manner as in Comparative Example 2 except that the cooling water bath temperature Tq after melt extrusion was changed to 85 ° C.

(Comparative Example 4)
A polyvinylidene fluoride hollow fiber porous membrane was obtained essentially by the method of Patent Document 7 (WO2005 / 099879A).
As PVDF-I, PVDF mixture A in which PVDF-I and PVDF-II were mixed at a ratio of 95% by weight and 5% by weight using polyvinylidene fluoride having Mw of 4.1 × 10 ⁵ was used. Adipic acid polyester plasticizer as a plasticizer (polyester of adipic acid and 1,2-propylene glycol whose ends are sealed with octyl alcohol; “PN150” manufactured by ADEKA Corporation, number average molecular weight of about 1000, viscosity of 500 mPa · s) And N-methylpyrrolidone (NMP) in a proportion of 82.5 wt% / 17.5 wt% with stirring and mixing at room temperature; used plasticizer / solvent mixture B; Supply at a ratio of 4% by weight / 61.6% by weight; water cooling bath temperature at 40 ° C .; no extraction rinse with IPA Except that the draw ratio was 1.85 times; as the heat treatment after stretching, 8% relaxation was performed in a 90 ° C. water bath, and then 3% relaxation treatment was performed in air at 140 ° C .; A polyvinylidene fluoride porous membrane was obtained in the same manner as in Example 1.

(Comparative Example 5)
A polyvinylidene fluoride-based hollow fiber porous membrane was obtained essentially according to the production method of Patent Document 9 (WO2008 / 117740A):
That is, as PVDF-I, PVDF mixture A in which PVDF-I and PVDF-II were mixed at a ratio of 75% by weight and 25% by weight using polyvinylidene fluoride having Mw of 4.1 × 10 ⁵ was used. As a plasticizer, adipic acid-based polyester (polyester of adipic acid and 1,2-propylene glycol whose ends are sealed with octyl alcohol; “PN-150” manufactured by ADEKA Corporation; number average molecular weight = about 1000) 68 A plasticizer / solvent mixture B mixed at a ratio of 0.6 wt% and the solvent N-methylpyrrolidone (NMP) 31.4 wt% was used.

In addition, a co-rotating meshing twin screw extruder (“BT-30” manufactured by Plastics Engineering Laboratory Co., Ltd., screw diameter 30 mm, L / D = 48) was used, and was installed at a position 80 mm from the most upstream part of the cylinder. Mixture A was supplied from the powder supply unit, and the mixture B heated to a temperature of 160 ° C. from the liquid supply unit provided at a position 480 mm from the most upstream part of the cylinder was mixed with mixture A / mixture B = 30.8 / 69. The mixture was fed at a ratio of 2 (weight) and kneaded at a barrel temperature of 220 ° C., and the kneaded product was extruded into a hollow fiber form from a nozzle (temperature 150 ° C.) having a circular slit having an outer diameter of 6 mm and an inner diameter of 4 mm. At this time, air was injected into the air-conditioning section of the hollow fiber from the vent hole provided in the center of the nozzle to adjust the inner diameter.

Thereafter, the extruded molten mixture is cooled at a cooling water bath temperature of 15 ° C., extracted by dichloromethane and then stretched 1.1 times, and further passed through a hot water bath at 90 ° C. and a dry heat bath controlled at a space temperature of 140 ° C. A polyvinylidene fluoride hollow fiber porous membrane was obtained.

(Comparative Example 6)
A polyvinylidene fluoride hollow fiber porous membrane was obtained essentially according to the production method of Patent Document 10.
That is, as PVDF-I, a mixture containing PVDF-I and PVDF-II of 95% by weight and 5% by weight using polyvinylidene fluoride having an Mw of 4.1 × 10 ⁵ was used. Further, as an adipic acid-based polyester plasticizer as a plasticizer, polyester of adipic acid and 1,2-butanediol whose ends are sealed with isononyl alcohol; “D620N” manufactured by J. Plus Co., number average molecular weight of about 800, Plasticizer / solvent mixture B of 82.5% by weight and viscosity of N-methylpyrrolidone (NMP) 17.5% by weight according to JIS K7117-2 (cone-plate type rotational viscometer) measured at 25 ° C. at 200 mPa · s) Was used.

In addition, a co-rotating meshing twin screw extruder (“BT-30” manufactured by Plastics Engineering Laboratory Co., Ltd., screw diameter 30 mm, L / D = 48) was used, and was installed at a position 80 mm from the most upstream part of the cylinder. Mixture A is supplied from the powder supply section, and mixture B is heated to 160 ° C. from the liquid supply section provided at a position 480 mm from the most upstream part of the cylinder. Mixture A / mixture B = 38.4 / 61. The mixture was fed at a ratio of 6 (weight) and kneaded at a barrel temperature of 220 ° C., and the kneaded product was extruded into a hollow fiber shape from a nozzle having a circular slit having an outer diameter of 7 mm and an inner diameter of 5 mm. At this time, air was injected into the air-conditioning section of the hollow fiber from the vent hole provided in the center of the nozzle to adjust the inner diameter.

Thereafter, the extruded molten mixture is cooled at a cooling water bath temperature of 70 ° C., the mixture B is extracted with dichloromethane, dried at 50 ° C. for 1 hour, stretched 2.4 times at 85 ° C., and further heated at a 90 ° C. hot water bath. The polyvinylidene fluoride hollow fiber porous membrane was obtained by relaxing 1% in the solution and further relaxing 1% in a dry heat bath controlled at a space temperature of 140 ° C.

(Comparative Example 7)
Extrusion was performed in the same manner as in Example 1 except that polyvinylidene fluoride having a Mw of 4.1 × 10 ⁵ was used as PVDF-I. However, the yarn could not be formed because the yarn was crushed in the cooling water bath after melt extrusion.

(Comparative Example 8)
Extrusion was carried out in the same manner as in Example 1 except that the cooling water bath temperature Tq after melt extrusion was changed to 85 ° C. However, the yarn could not be formed because the yarn was crushed in the cooling water bath after melt extrusion.

(Comparative Example 9)
A dibenzoate-type monomeric plasticizer (“PB-10” manufactured by DIC Corporation, number average molecular weight of about 300, viscosity of 81 mPa · s) was used as the plasticizer; 26.9 wt% / 73 of the mixture A and the mixture B A polyvinylidene fluoride hollow fiber porous membrane was obtained in the same manner as in Example 1 except that the cooling water bath temperature Tq after melt extrusion was changed to 60 ° C.

The outline of the production conditions of the above Examples and Comparative Examples and the physical properties of the obtained polyvinylidene fluoride hollow fiber porous membrane are summarized in Tables 1 and 2 below. For convenience of comparison between Examples and Comparative Examples, even when only a plasticizer is added to the vinylidene fluoride resin (mixture A), this is indicated under the heading of the mixture B.

<< Example of Partial Wet Stretching Method >>

(Example A1)
Polyvinylidene fluoride (PVDF-I) for matrix having a weight average molecular weight (Mw) of 4.9 × 10 ⁵ (powder) and polyvinylidene fluoride for modifying crystal properties having a Mw of 9.7 × 10 ⁵ (PVDF-II) ) (Powder) at a ratio of 75 wt% and 25 wt%, respectively, was mixed using a Henschel mixer to obtain a PVDF mixture having an Mw of 6.1 × 10 ⁵ .

As an organic liquid, a polyester plasticizer (polyester of adipic acid and 1,2-butanediol whose ends are sealed with isononyl alcohol; “D623N” manufactured by J Plus Co., Ltd., number average molecular weight of about 1800, JIS K7117- 2 (cone-flat-plate rotational viscometer) measured viscosity at 25 ° C. 3000 mPa · s, specific gravity 1.090 g / ml) and monoisonic ester plasticizer diisononyl adipate (“DINA” manufactured by J. Plus) And a plasticizer mixture obtained by stirring and mixing at a normal temperature of 88% / 12% by weight.

Using a co-rotating meshing type twin screw extruder (“TEM-26SS” manufactured by Toshiba Machine Co., Ltd., screw diameter 26 mm, L / D = 60), the mixture A is supplied from the powder supply unit, and the barrel temperature is 220 ° C. Then, the plasticizer is mixed at a ratio of mixture A / plasticizer = 27.9 wt% / 72.1 wt% from the liquid supply section provided downstream from the powder supply section of the extruder cylinder. The mixture was fed and kneaded at a barrel temperature of 220 ° C., and the mixture was extruded into a hollow fiber shape from a nozzle (190 ° C.) having a circular slit having an outer diameter of 6 mm and an inner diameter of 4 mm. At this time, the inner diameter was adjusted by injecting air into the hollow portion of the hollow fiber from the vent provided in the center of the nozzle.

The extruded mixture is kept in a molten state, maintained at a temperature of 45 ° C., and has a water surface at a position 280 mm away from the nozzle (ie, the air gap is 280 mm) and is cooled and solidified in a water cooling bath at a temperature Tq = 45 ° C. (Retention time in the cooling bath: about 6 seconds) After taking up at a take-up speed of 3.8 m / min, this is wound around a bobbin with a length of 500 m, and the first having an outer diameter of 1.80 mm and an inner diameter of 1.20 mm. An intermediate molded body was obtained.

Next, the plasticizer was extracted by immersing the first intermediate molded body in dichloromethane at room temperature for 30 minutes. At this time, the extraction was performed while rotating the bobbin so that the dichloromethane was evenly distributed over the yarn. Next, the operation of replacing the dichloromethane with a new one and extracting again under the same conditions was repeated, and extraction was performed three times in total.

Next, the first intermediate molded body containing dichloromethane is immersed in isopropyl alcohol (IPA) at room temperature for 30 minutes without substantially drying (that is, no whitening is visually recognized in the first intermediate molded body). The dichloromethane impregnated in the first intermediate molded body was replaced with IPA. At this time, the replacement was performed while rotating the bobbin so that the IPA was evenly distributed over the yarn. Subsequently, the operation of replacing the IPA with a new one and replacing the same under the same conditions was repeated, and the replacement was performed twice in total.

Next, IPA was removed by air drying at room temperature for 24 hours, followed by heating in an oven at a temperature of 120 ° C. for 1 hour to remove IPA and heat treatment to obtain a second intermediate molded body. At this time, the bobbin diameter was freely contracted, and drying and heat treatment were performed without restricting the contraction of the yarn.

Next, in a state where the second intermediate molded body is wound around a bobbin, a polyglycerin fatty acid ester (“SY Glyster ML-310” manufactured by Sakamoto Pharmaceutical Co., Ltd., HLB = 1) is used as a surfactant.
0.3) was dissolved in pure water at a concentration of 0.05% by weight (surface tension = 32.4 mN / m) and immersed for 30 minutes at room temperature to perform partial wetting.

Further, while the bobbin is immersed in the emulsion aqueous solution, the second intermediate formed body is pulled out while rotating the bobbin, the first roll speed is set to 20.0 m / min, and the second roll is passed through the 60 ° C. water bath. The film was stretched 1.75 times in the longitudinal direction by setting the speed to 35.0 m / min. Next, it is passed through a hot water bath controlled at a temperature of 90 ° C., the first stage relaxation rate is relaxed at 8%, and further passed through a dry heat tank controlled at a spatial temperature of 140 ° C., and the second stage relaxation rate is 1.5%. And relaxed. This was wound up to obtain a vinylidene fluoride resin hollow fiber porous membrane.

(Example A2)
A vinylidene fluoride resin porous membrane was obtained in the same manner as in Example A1, except that the cooling water bath temperature Tq after melt extrusion was changed to 30 ° C .; the draw ratio was changed to 1.85 times.

(Example A3)
As an organic liquid, a polyester plasticizer (polyester of dibasic acid and glycol whose ends are sealed with benzoic acid; “W-83” manufactured by DIC Corporation, number average molecular weight of about 500, JIS K7117-2 (cone- A viscosity measured at 25 ° C. by a flat plate type viscometer (750 mPa · s, specific gravity 1.155 g / ml); vinylidene fluoride resin / plasticizer = 26.9 wt% / 73.1 wt% A vinylidene fluoride resin porous membrane was obtained in the same manner as in Example A1, except that the cooling water bath temperature Tq after melt extrusion was changed to 50 ° C.

(Example A4)
As an organic liquid, alkylene glycol dibenzoate, a monomeric ester plasticizer (“PB-10” manufactured by DIC Corporation, number average molecular weight of about 300, JIS K7117-2 (cone-flat plate viscometer) at 25 ° C.) Measured viscosity of 81 mPa · s, specific gravity 1.147 g / ml); vinylidene fluoride resin / plasticizer = 26.9 wt% / 73.1 wt% supplied; after melt extrusion A vinylidene fluoride resin porous membrane was obtained in the same manner as in Example A1, except that the cooling water bath temperature Tq was changed to 60 ° C. and the second-stage relaxation rate was changed to 1.5%.

(Example A5)
Essentially, an unstretched vinylidene fluoride resin porous membrane was obtained according to the method disclosed in Patent Document 4, and then the unstretched yarn was partially wetted and then stretched.
That is, hydrophobic silica (“Aerosil R-972” manufactured by Nippon Aerosil Co., Ltd., primary particle average diameter 16 nanometer, specific surface area 110 m ^{2 /} g) 14.8% by volume, dioctyl phthalate (DOP) 48.5% by volume %, Dibutyl phthalate (DBP) 4.4% by volume is mixed with a Henschel mixer, and 32.3% by volume of polyvinylidene fluoride (powder) having a weight average molecular weight (Mw) of 2.4 × 10 ⁵ is mixed therewith. Added and mixed again with a Henschel mixer.

This mixture was supplied to a co-rotating meshing twin screw extruder (“TEM-26SS” manufactured by Toshiba Machine Co., Ltd., screw diameter 26 mm, L / D = 60), kneaded at a barrel temperature of 240 ° C., and the mixture was removed. A hollow fiber was extruded from a nozzle (temperature 240 ° C.) having a circular slit with a diameter of 6 mm and an inner diameter of 4 mm. At this time, the inner diameter was adjusted by injecting air into the hollow portion of the hollow fiber from the vent provided in the center of the nozzle.

The extruded mixture is kept in a molten state, maintained at a temperature of 70 ° C., and has a water surface at a position 140 mm away from the nozzle (ie, the air gap is 140 mm). (Residence time in the cooling bath: about 9 seconds) was taken at a take-up speed of 2.5 m / min to obtain a first intermediate molded body having an outer diameter of 2.87 mm and an inner diameter of 1.90 mm.

Next, the plasticizer was extracted by immersing this first intermediate molded body in dichloromethane at room temperature for 30 minutes. Next, the operation of replacing the dichloromethane with a new one and extracting again under the same conditions was repeated, and extraction was performed four times in total. Next, it was dried in a vacuum dryer at a temperature of 30 ° C. for 24 hours to remove dichloromethane.

Next, the hollow fiber was wetted by immersing in 50% ethanol aqueous solution for 30 minutes and further immersing in pure water for 30 minutes. Further, after removing the hydrophobic silica by immersing in a 20% aqueous sodium hydroxide solution at 70 ° C. for 1 hour, it is washed with water to remove the sodium hydroxide, and then dried in a vacuum dryer at a temperature of 30 ° C. for 24 hours. A molded body was obtained. In addition, during a series of operations from extraction to drying, both ends of the hollow fiber were not contracted and were freely contracted.

Next, after sealing both ends of the second intermediate molded body, a polyglycerin fatty acid ester (“SY Glyster ML-310”, HLB = 10.3, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) as a surfactant was added at a concentration of 0. Partial wetting was performed by immersing in an aqueous emulsion (surface tension = 32.4 mN / m) dissolved in pure water at 0.05% by weight at room temperature for 60 minutes. Next, after stretching by hand 1.5 times in the longitudinal direction in a room temperature atmosphere, heat treatment was carried out for 5 minutes in a hot air oven at a temperature of 140 ° C. with the length fixed, thereby forming a vinylidene fluoride resin hollow fiber porous membrane. Obtained.

(Comparative Example A1)
A vinylidene fluoride resin hollow fiber porous membrane was obtained in the same manner as in Example A1, except that partial wetting was not performed prior to stretching.

(Comparative Example A2)
A vinylidene fluoride resin hollow fiber porous membrane was obtained in the same manner as in Example A2 except that partial wetting was not performed prior to stretching.

(Comparative Example A3)
Vinylidene fluoride resin in the same manner as in Example A2, except that an aqueous solution (surface tension = 28.9 mN / m) of sodium alkyl ether sulfate ester dissolved in pure water at a concentration of 0.05% by weight was used as the partial wetting liquid. A hollow fiber porous membrane was obtained.

(Comparative Example A4)
A vinylidene fluoride resin hollow fiber porous membrane was obtained in the same manner as in Example A3 except that partial wetting was not performed prior to stretching.

(Comparative Example A5)
A vinylidene fluoride resin hollow fiber porous membrane was obtained in the same manner as in Example A4 except that partial wetting was not performed prior to stretching.

(Comparative Example A6)
A vinylidene fluoride resin hollow fiber porous membrane was obtained in the same manner as in Example A5 except that partial wetting was not performed prior to stretching.

The outline of the production conditions of Example A and Comparative Example A and the physical properties of the obtained polyvinylidene fluoride hollow fiber porous membrane are summarized in Tables 3 to 4 below.

[Evaluation]
As can be understood by comparing the results of Example A and Comparative Example A shown in Tables 3 to 4 above, according to the partial wet stretching method, the surface of the porous resin membrane once formed is selectively partially in the vicinity of the surface layer. By stretching after wetting, the porosity in the vicinity of the surface layer during stretching is prevented, and as a result, the porosity A1 of the dense layer in the vicinity of the surface layer that governs the separation performance is increased and the entire membrane A porous resin membrane having a high liquid permeability can be obtained. In particular, this result shows that the small hole diameter side surface hole diameter P1 is 0.2 μm or less as compared with the case where the small hole diameter side surface hole diameter P1 governing the separation performance is relatively large as about 1 μm (Example A5, Comparative Example A6). In the case of small size (Examples A1 to A4, Comparative Examples A1 to A5), this is particularly noticeable.

<< Execution Rinse Method Example >>

(Example B1)
Polyvinylidene fluoride (PVDF-I) for matrix having a weight average molecular weight (Mw) of 4.9 × 10 ⁵ (powder) and polyvinylidene fluoride for modifying crystal properties having a Mw of 9.7 × 10 ⁵ (PVDF-II) ) (Powder) at a ratio of 75 wt% and 25 wt%, respectively, was mixed using a Henschel mixer to obtain a PVDF mixture having an Mw of 6.1 × 10 ⁵ .

As an organic liquid, a polyester plasticizer (polyester of dibasic acid and glycol whose ends are sealed with a monohydric alcohol; “W-4010” manufactured by DIC Corporation, number average molecular weight of about 4000, JIS K7117-2 (cone -Viscosity measured at 25 ° C by a flat plate type viscometer), specific gravity 1.113 g / ml), and diisononyl adipate, a monomeric ester plasticizer ("DINA" manufactured by Jay Plus Co., Ltd.) K7117-2 (cone-flat plate viscometer) measured at 25 ° C. with a viscosity of 16 mPa · s and a specific gravity of 0.923 g / ml) was stirred and mixed at a ratio of 80% by weight / 20% by weight at room temperature. A plasticizer mixture was used.

Using a co-rotating meshing type twin screw extruder (“TEM-26SS” manufactured by Toshiba Machine Co., Ltd., screw diameter 26 mm, L / D = 60), the mixture A is supplied from the powder supply unit, and the barrel temperature is 220 ° C. Then, the organic liquid is mixed from the liquid supply unit provided downstream of the powder supply unit of the extruder cylinder, and the mixture A / organic liquid = 27.9 wt% / 72.1 wt% The mixture was fed at a ratio and kneaded at a barrel temperature of 220 ° C., and the mixture was extruded into a hollow fiber shape from a nozzle (190 ° C.) having a circular slit having an outer diameter of 6 mm and an inner diameter of 4 mm. At this time, the inner diameter was adjusted by injecting air into the hollow portion of the hollow fiber from the vent provided in the center of the nozzle.

The extruded mixture is kept in a molten state, maintained at a temperature of 12 ° C., and has a water surface at a position 280 mm away from the nozzle (that is, an air gap of 280 mm). (Retention time in the cooling bath: about 6 seconds) After being taken up at a take-up speed of 3.8 m / min, this was wound up on a bobbin (core diameter: 220 mm) to a length of 500 m to obtain an outer diameter of 1.80 mm, A first intermediate molded body having an inner diameter of 1.20 mm (vinylidene fluoride resin hollow fiber porous membrane containing an organic liquid) was obtained.

Next, this first intermediate molded body was cut out to a length of 300 mm, and the organic liquid was extracted by immersing in dichloromethane as an extraction solvent at room temperature for 30 minutes without fixing both ends. At this time, extraction was carried out while stirring the dichloromethane so that the dichloromethane was evenly distributed over the yarn. Next, the operation of replacing the dichloromethane with a new one and extracting again under the same conditions was repeated, and extraction was performed three times in total.

Next, the first intermediate molded body containing dichloromethane is rinsed without substantially drying (that is, in a state where no whitening is observed in the first intermediate molded body by visual observation) and without fixing both ends. Dichloromethane impregnated in the first intermediate molded body by being immersed in ethanol (swelling ratio of 0.5% relative to the raw material vinylidene fluoride resin) at room temperature for 30 minutes was replaced with ethanol as a rinsing liquid. At this time, the substitution was performed while stirring the ethanol so that the ethanol was evenly distributed over the yarn. Subsequently, the operation of replacing the ethanol with a new one and substituting again under the same conditions was repeated, and the replacement was performed twice in total.

Next, without fixing both ends of the hollow fiber, the ethanol was removed by air drying at room temperature for 24 hours, followed by heating in an oven at a temperature of 120 ° C. for 1 hour to remove the ethanol and a heat treatment, followed by fluorination. A vinylidene resin hollow fiber porous membrane was obtained.

(Example B2)
A vinylidene fluoride resin hollow fiber porous membrane was obtained in the same manner as B1, except that isopropyl alcohol (swelling rate 0.2% with respect to the raw material vinylidene fluoride resin) was used as the rinse liquid.

(Example B3)
A vinylidene fluoride resin hollow fiber porous membrane was obtained in the same manner as in Example B1, except that hexane (swelling ratio of 0.0% relative to the raw material vinylidene fluoride resin) was used as the rinse liquid.

(Example B4)
After substituting with ethanol as the rinsing liquid, the second rinsing liquid, water (swelling ratio 0.0% of the raw material vinylidene fluoride resin) is further obtained without substantially drying the hollow fiber porous membrane containing ethanol. The vinylidene fluoride resin hollow fiber porous membrane was obtained in the same manner as in Example B1 except that it was replaced with a).

(Comparative Example B1)
A vinylidene fluoride resin hollow fiber porous membrane was obtained in the same manner as in Example B1 except that dichloromethane (swelling ratio of 5.7% with respect to the raw material vinylidene fluoride resin) was used as the rinse liquid.

(Comparative Example B2)
A vinylidene fluoride resin hollow fiber porous membrane was obtained in the same manner as in Example B1, except that methanol (swelling ratio of 1.8% relative to the raw material vinylidene fluoride resin) was used as the rinse liquid.

(Comparative Example B3)
A vinylidene fluoride resin hollow fiber porous membrane was obtained in the same manner as in Example B1 except that acetone (swelling ratio of 5.0% with respect to the raw material vinylidene fluoride resin) was used as the rinse liquid.

(Comparative Example B4)
A vinylidene fluoride system was used in the same manner as in Example B1 except that a heptafluorocyclopentane-based solvent (“Zeorolla HTA” manufactured by Nippon Zeon Co., Ltd., a swelling ratio of 3.4% with respect to the raw material vinylidene fluoride resin) was used as the rinse liquid. A resin hollow fiber porous membrane was obtained.

(Example B5)
As an organic liquid, a polyester plasticizer (polyester of adipic acid and 1,2-butanediol whose ends are sealed with isononyl alcohol; “D623N” manufactured by J Plus Co., Ltd., number average molecular weight of about 1800, JIS K7117- 2 (cone-flat-plate rotational viscometer) measured viscosity at 25 ° C. 3000 mPa · s, specific gravity 1.090 g / ml) and monoisonic ester plasticizer diisononyl adipate (“DINA” manufactured by J. Plus) )) Was used at a rate of 88% / 12% by weight at a normal temperature and mixed with a plasticizer mixture; Example B2 except that the cooling water bath temperature Tq after melt extrusion was changed to 45 ° C. In the same manner, a vinylidene fluoride resin hollow fiber porous membrane was obtained.

(Comparative Example B5)
A vinylidene fluoride resin hollow fiber porous membrane was obtained in the same manner as in Example B5, except that dichloromethane (swelling ratio of 5.7% relative to the raw material vinylidene fluoride resin) was used as the rinse liquid.

(Example B6)
Polyvinylidene fluoride resin as a matrix polyvinylidene fluoride (PVDF-I) (powder) with a weight average molecular weight (Mw) of 6.6 × 10 ⁵ and crystal property modification with Mw of 9.7 × 10 ⁵ Polyvinylidene fluoride (PVDF-II) (powder) was mixed at a ratio of 75% by weight and 25% by weight using a Henschel mixer, and a PVDF mixture having an Mw of 7.4 × 10 ⁵ was used. As a plasticizer, a polyester plasticizer (polyester of dibasic acid and glycol whose ends are sealed with benzoic acid; “W-83” manufactured by DIC Corporation, number average molecular weight of about 500, JIS K7117-2 ( (Cone-plate-type rotational viscometer), measured viscosity at 25 ° C. 750 mPa · s, specific gravity 1.155 g / ml); vinylidene fluoride resin / plasticizer = 26. It was fed at a rate of weight% / 73.1 weight%; and except for changing the cooling bath temperature Tq after melt extrusion 50 ° C. in the same manner as in Example B2 obtain a porous membrane of vinylidene fluoride resin.

(Comparative Example B6)
A vinylidene fluoride resin hollow fiber porous membrane was obtained in the same manner as in Example B6 except that dichloromethane (swelling ratio of 5.7% with respect to the raw material vinylidene fluoride resin) was used as the rinse liquid.

(Example B7)
As an organic liquid, alkylene glycol dibenzoate, a monomeric ester plasticizer (“PB-10” manufactured by DIC Corporation, number average molecular weight of about 300, JIS K7117-2 (cone-flat plate viscometer) at 25 ° C.) A measured viscosity of 81 mPa · s and a specific gravity of 1.147 g / ml); a vinylidene fluoride resin porous membrane in the same manner as in Example B6 except that the cooling water bath temperature Tq after melt extrusion was changed to 60 ° C. Got.

(Comparative Example B7)
A vinylidene fluoride resin hollow fiber porous membrane was obtained in the same manner as in Example B7, except that dichloromethane (swelling ratio of 5.7% relative to the raw material vinylidene fluoride resin) was used as the rinse liquid.

The outlines of Examples B1 to B7 and Comparative Examples B1 to B7 and the evaluation results of the obtained hollow fiber porous membrane are summarized in Table 5 below.

In Example B and Comparative Example B described above, extraction (and subsequent rinsing) was performed on the separated single-filamentary first intermediate molded body (vinylidene fluoride hollow fiber membrane containing an organic liquid after phase separation). . On the other hand, in the following Example B and Comparative Example B, extraction of the first intermediate molded body wound around the bobbin (and subsequent rinsing) is performed, and bobbin extraction is performed by reducing the dimensional shrinkage rate according to the method of the present invention. And the film characteristics by subsequent stretching were evaluated.

(Example B8)
The first intermediate molded body (length: 500 m) wound on the bobbin (core diameter: 220 mm) in Example B5 was immersed in dichloromethane for 30 minutes at room temperature while being wound on the bobbin, and the plasticizer was extracted. At this time, the extraction was performed while rotating the bobbin so that the dichloromethane was evenly distributed over the yarn. Next, the operation of replacing the dichloromethane with a new one and extracting again under the same conditions was repeated, and extraction was performed three times in total.

Next, without substantially drying the first intermediate molded body containing dichloromethane (that is, in a state where no whitening is observed in the first intermediate molded body visually), isopropyl alcohol (IPA), which is a rinse solution, is heated to room temperature. IPA was substituted for dichloromethane impregnated in the first intermediate molded body by immersion for 30 minutes. At this time, the replacement was performed while rotating the bobbin so that the IPA was evenly distributed over the yarn. Subsequently, the operation of replacing the IPA with a new one and replacing the same under the same conditions was repeated, and the replacement was performed twice in total.

Next, in a state where the second intermediate molded body is wound around a bobbin, a polyglycerol fatty acid ester (“SY Glyster ML-310”, HLB = 10.3, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) is used as a surfactant at a concentration of 0.05. It was immersed in an aqueous emulsion solution (surface tension = 32.4 mN / m) dissolved in pure water at a weight percent for 30 minutes at room temperature.

(Example B9)
A vinylidene fluoride resin hollow fiber porous membrane was obtained in the same manner as in Example B8, except that the first intermediate molded body (length: 500 m) wound on a bobbin in Example B6 was used.

(Example B10)
A vinylidene fluoride resin hollow fiber porous membrane was obtained in the same manner as in Example B8, except that the first intermediate molded body (length: 500 m) wound around the bobbin in Example B7 was used.

(Comparative Example B8)
Bobbin extraction was performed in the same manner as in Example B8, except that dichloromethane (swelling ratio of 5.7% with respect to the raw material vinylidene fluoride resin) was used as the rinsing liquid, followed by drying and heat treatment. However, due to the tightness of the yarn, the yarns bite and the yarn was crimped, and could not be used for drawing.

(Comparative Example B9)
Bobbin extraction was performed in the same manner as in Example B9, except that dichloromethane (swelling ratio of 5.7% with respect to the raw material vinylidene fluoride resin) was used as the rinsing liquid, followed by drying and heat treatment. However, due to the tightness of the yarn, the yarns bite and the yarn was crimped, and could not be used for drawing.

(Comparative Example B10)
Bobbin extraction was performed in the same manner as in Example B10, except that dichloromethane (swelling ratio of 5.7% with respect to the raw material vinylidene fluoride resin) was used as the rinsing liquid, followed by drying and heat treatment. However, due to the tightness of the yarn, the yarns bite and the yarn was crimped, and could not be used for drawing.

(Example B11)
The first intermediate molded body (length: 500 m) wound up in Example B6 was pulled out from the bobbin, passed through a 60 ° C. water bath at a first roll speed of 20.0 m / min, and a second roll speed. The film was stretched 2.5 times in the longitudinal direction at a speed of 50 m / min. Next, it is passed through a hot water bath controlled at a temperature of 90 ° C., the first stage relaxation rate is relaxed at 8%, and further passed through a dry heat tank controlled at a spatial temperature of 140 ° C., and the second stage relaxation rate is 1.5%. Was relaxed and wound on a bobbin to obtain a drawn yarn.

Next, the drawn liquid was wound around a bobbin and immersed in dichloromethane at room temperature for 30 minutes to extract an organic liquid. At this time, the extraction was performed while rotating the bobbin so that the dichloromethane was evenly distributed over the yarn. Next, the operation of replacing the dichloromethane with a new one and extracting again under the same conditions was repeated, and extraction was performed three times in total.

Next, without substantially drying the drawn yarn containing dichloromethane (that is, no whitening is visually observed in the drawn yarn), the drawn yarn is immersed in isopropyl alcohol (IPA), which is a rinse solution, at room temperature for 30 minutes for drawing. Dichloromethane impregnated in the yarn was replaced with IPA. At this time, the replacement was performed while rotating the bobbin so that the IPA was evenly distributed over the yarn. Subsequently, the operation of replacing the IPA with a new one and replacing the same under the same conditions was repeated, and the replacement was performed twice in total.

Next, IPA was removed by air drying at room temperature for 24 hours, followed by heating in an oven at 120 ° C. for 1 hour to remove IPA and heat treatment to obtain a vinylidene fluoride resin hollow fiber porous membrane. At this time, the bobbin diameter was freely contracted, and drying and heat treatment were performed without restricting the contraction of the yarn.

(Comparative Example B11)
Bobbin extraction was performed in the same manner as in Example B11, except that dichloromethane (swelling ratio of 5.7% with respect to the raw vinylidene fluoride resin) was used as the rinsing liquid, followed by drying and heat treatment. However, the yarn was bitten and the yarn was crimped due to the tightening of the yarn, and could not be recovered as a hollow fiber porous membrane having a uniform shape.

(Example B12)
After using the first intermediate molded body (length: 500 m) wound around the bobbin in Example B1 and substituting with ethanol as the rinsing liquid, the hollow fiber porous membrane containing ethanol is substantially dried. In addition, a vinylidene fluoride resin hollow fiber porous membrane was prepared in the same manner as in Example B8, except that substitution was used for water (the swelling rate of 0.0% relative to the raw material vinylidene fluoride resin) as the second rinse liquid. Obtained.

(Comparative Example B12)
Bobbin extraction was performed in the same manner as in Example B12 except that dichloromethane (swelling ratio of 5.7% with respect to the raw material vinylidene fluoride resin) was used as the rinsing liquid, followed by drying and heat treatment. However, due to the tightness of the yarn, the yarns bite and the yarn was crimped, and could not be used for drawing.

The summary of Examples B8 to B12 and Comparative Examples B8 to B12 and the evaluation results of the obtained hollow fiber porous membrane are shown in Table 6 below.

[Evaluation]
According to Table 5 above, when removing the halogenated solvent from the vinylidene fluoride resin porous membrane containing the halogenated solvent to form a vinylidene fluoride resin porous membrane, the resin is not directly dried but is fluorinated. By inserting a step of replacing the halogenated solvent of the vinylidene resin with a non-swellable solvent, it is understood that pore shrinkage is suppressed and a vinylidene fluoride resin porous film can be obtained with high hole formation efficiency. . In addition, the results in Table 6 are obtained by bobbing a long hollow fiber membrane-like vinylidene fluoride resin porous membrane for effective extraction, and then substituting with a non-swelling solvent after extraction with a halogenated solvent. The deformation of the hollow fiber membrane due to tightening is suppressed, the removal of the hollow fiber membrane is facilitated, and the vinylidene fluoride resin hollow fiber porous membrane having good water permeability despite the small pore diameter is formed. Show. Thus, the highly permeable vinylidene fluoride resin porous membrane formed by the method of the present invention is not only suitable for drainage treatment, but also for concentrating bacteria and proteins, and collecting chemically aggregated particles of heavy metals. It can also be suitably used as a usable separation membrane, a separation membrane for oil-water separation or gas-liquid separation, a battery membrane such as a lithium ion secondary battery, and a solid electrolyte support. In particular, the vinylidene fluoride resin porous membrane obtained by the thermally induced phase separation method as a preferred embodiment has a pore diameter continuously expanding in the film thickness direction, and a porosity is uniformly distributed in the film thickness direction. In addition to improving the porosity of the dense layer that contributes to separation characteristics or selective permeation characteristics in particular, it has excellent separation characteristics or selective permeation characteristics while maintaining fluid separation or movement of ions, etc. The characteristic that there is little resistance is given. Such characteristics are particularly suitable for the separation applications described above in general.

As can be seen from Tables 1 and 2 above, according to the present invention, (filtration) has a surface pore diameter, water permeability and mechanical strength suitable for water treatment, and is represented by a large critical filtration flux. Thus, there is provided a vinylidene fluoride resin porous membrane that exhibits good water permeability maintaining performance even during continuous filtration of turbid water and has a large water permeability despite the small surface pore diameter of the water to be treated. The vinylidene fluoride resin porous membrane of the present invention is suitable for (filtered) water treatment as described above, but the pore diameter is continuously increased in the film thickness direction and the porosity is the film thickness. It has a characteristic of being uniformly distributed in the vertical direction. In particular, since the porosity of the dense layer contributing to the separation characteristic or the selective permeation characteristic is improved, the resistance to the permeation of fluid or the movement of ions and the like is small while having an excellent separation characteristic or selective permeation characteristic. Therefore, the porous membrane of the present invention is not limited to (filtered) water treatment, but can be used for concentration of bacteria, proteins, etc., recovery of chemically aggregated particles of heavy metals, separation membrane for oil-water separation and gas-liquid separation Also, it can be suitably used as a battery diaphragm such as a lithium ion secondary battery and a solid electrolyte support.

Claims

An asymmetrical network with two main surfaces sandwiching a certain thickness, a dense layer that has a small pore size and governs separation performance on one surface side, and the pore diameter continuously increases from one surface to the opposite surface. A vinylidene fluoride resin porous membrane having an inclined structure and satisfying the following conditions (a) to (c):
(A) The porosity A1 of a portion having a thickness of 5 μm continuous from the one surface of the dense layer is 60% or more,
(B) The total surface porosity A2 = 80 of the water permeability at the test length L = 200 mm measured under the condition that the surface pore diameter P1 of the one surface is 0.30 μm or less and (c) the differential pressure is 100 kPa and the water temperature is 25 ° C. The ratio between the converted value Q to% (m / day) and the fourth power value P1 4 (μm 4 ) of the surface pore diameter P1 of the one surface, Q / P1 4 is 5 × 10 4 (m / day · μm 4 )more than.
The porous film according to claim 1, wherein the vinylidene fluoride resin has a weight average molecular weight of 600,000 to 1,200,000.
The vinylidene fluoride resin is 25 to 98% by weight of vinylidene fluoride resin (PVDF-I) having a weight average molecular weight of 450,000 to 1,000,000, and the weight average molecular weight is 1.4 times or more and less than 1.5 million of PVDF-I. The porous membrane according to claim 2, comprising a mixture of 2 to 75 parts by weight of a vinylidene fluoride resin (PVDF-II) which is
The porous membrane according to any one of claims 1 to 3, wherein A1 / P1 is 400 or more, and a ratio P2 / P1 of the surface pore diameter P2 (µm) to P1 on the opposite surface is 2.0 to 10.0.
The porous membrane according to any one of claims 1 to 4, wherein A1 / A2 is 0.80 or more.
6. The porous membrane according to claim 1, wherein the dense layer has a thickness of 40 μm or less.
7. The vinylidene fluoride resin according to claim 1, wherein a difference Tm2−Tc between a resin original melting point Tm2 (° C.) and a crystallization temperature Tc (° C.) by DSC measurement is 32 ° C. or less. Porous membrane.
The porous film according to any one of claims 1 to 7, wherein the crystallization temperature Tc is 143 ° C or higher.
The porous membrane according to any one of claims 1 to 8, wherein the vinylidene fluoride resin as a whole is made of a homopolymer of vinylidene fluoride.
The porous membrane according to any one of claims 1 to 9, wherein the overall shape is a hollow fiber shape, the outer surface is the one surface, and the inner surface is the opposite surface.
The porous membrane according to any one of claims 1 to 10, which has a tensile strength of 7 MPa or more.
The porous membrane according to any one of claims 1 to 11, which is stretched.
A drainage treatment membrane having the one surface of the porous membrane according to any one of claims 1 to 12 as a surface to be treated water and the reverse surface as a permeate surface.
A method for producing a porous film comprising a step of extruding a melt-kneaded product of a vinylidene fluoride resin and a plasticizer from a die into a film, cooling and solidifying the film, and a step of extracting the plasticizer, the plasticizer Has a compatibility with the vinylidene fluoride resin at the formation temperature of the melt-kneaded product, and further satisfies the following conditions (i) to (iii):
(I) A crystallization temperature Tc ′ (° C.) lower by 6 ° C. or lower than the crystallization temperature Tc (° C.) of the vinylidene fluoride resin alone is given to the melt-kneaded product with the vinylidene fluoride resin.
(Ii) 53 J / g or more as crystal melting enthalpy ΔH ′ (J / g) based on the vinylidene fluoride resin mass standard when measured with a differential scanning calorimeter (DSC) on the solidified product obtained by cooling the melt-kneaded product And (iii) the viscosity of the plasticizer alone measured at a temperature of 25 ° C. in accordance with JIS K7117-2 (cone—using a flat plate type viscometer) is 200 mPa · s to 1000 Pa · s.
The manufacturing method according to claim 14, wherein the plasticizer comprises a polyester plasticizer in which a terminal of a (poly) ester composed of an aliphatic dibasic acid and glycol is sealed with an aromatic monovalent carboxylic acid.
The vinylidene fluoride resin is 25 to 98% by weight of vinylidene fluoride resin (PVDF-I) having a weight average molecular weight of 450,000 to 1,000,000, and the weight average molecular weight is 1.4 times or more and less than 1.5 million of PVDF-I. The production method according to claim 14 or 15, comprising a mixture of 2 to 75 parts by weight of a vinylidene fluoride resin (PVDF-II) which is
The production method according to any one of claims 14 to 16, wherein the melt-kneaded film-like extrudate is preferentially cooled and solidified with an inert liquid from one surface side thereof.
The process according to any one of claims 14 to 16, wherein the hollow fiber membrane extrudate of the melt-kneaded product is cooled and solidified with an inert liquid preferentially from the outside thereof.
The production method according to claim 17 or 18, wherein a difference Tc'-Tq between Tc '(° C) of the melt-kneaded product and temperature Tq (° C) of the cooling inert liquid is 50 to 140 ° C.
The method according to any one of claims 14 to 19, wherein Tc '(° C) of the melt-kneaded product is 120 to 140 ° C.
The vinylidene fluoride-based resin is obtained without substantially drying the film-shaped solidified molded body containing the halogen-based solvent after the film-shaped solidified molded body of the melt-kneaded product is immersed in the halogen-based solvent to extract the plasticizer. The production method according to any one of claims 14 to 20, wherein the halogen-based solvent is substituted by immersion in a solvent that does not swell, and then dried.
The method according to any one of claims 14 to 21, further comprising a step of stretching the porous film after extraction of the plasticizer in a state of being selectively wetted from the outer surface to a depth of 5 µm or more and 1/2 or less of the film thickness. The manufacturing method of crab.