WO2016052675A1 - 分離膜 - Google Patents
分離膜 Download PDFInfo
- Publication number
- WO2016052675A1 WO2016052675A1 PCT/JP2015/077868 JP2015077868W WO2016052675A1 WO 2016052675 A1 WO2016052675 A1 WO 2016052675A1 JP 2015077868 W JP2015077868 W JP 2015077868W WO 2016052675 A1 WO2016052675 A1 WO 2016052675A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- separation membrane
- membrane
- hollow fiber
- weight
- separation
- Prior art date
Links
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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- B01D71/12—Cellulose derivatives
- B01D71/14—Esters of organic acids
- B01D71/18—Mixed esters, e.g. cellulose acetate-butyrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/002—Forward osmosis or direct osmosis
- B01D61/0022—Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
- B01D69/081—Hollow fibre membranes characterised by the fibre diameter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
- B01D71/14—Esters of organic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/52—Polyethers
- B01D71/521—Aliphatic polyethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/52—Polyethers
- B01D71/521—Aliphatic polyethers
- B01D71/5211—Polyethylene glycol or polyethyleneoxide
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/14—Pressure control
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/34—Molecular weight or degree of polymerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/02—Odour removal or prevention of malodour
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/10—Different kinds of radiation or particles
- G01N2223/108—Different kinds of radiation or particles positrons; electron-positron annihilation
Definitions
- the present invention relates to a separation membrane mainly composed of a cellulose resin having excellent separation performance and permeation performance and high membrane strength.
- Cellulosic resins are widely used as separation membranes including membranes for water treatment because they have water permeability due to their hydrophilicity and chlorine resistance that is strong against chlorine-based disinfectants.
- Patent Document 1 discloses a hollow fiber membrane obtained by mixing cellulose diacetate with a water-soluble polyhydric alcohol having an average molecular weight of 200 to 1000 and melt spinning.
- Patent Document 2 a solution obtained by mixing cellulose triacetate with N-methyl-2-pyrrolidone, ethylene glycol, and benzoic acid is discharged from an arc nozzle, and N-methyl-2-pyrrolidone / ethylene glycol / A hollow fiber membrane obtained by immersing in a coagulation bath made of water, followed by washing with water and heat treatment is disclosed.
- the hollow fiber membrane obtained by the technique of Patent Document 2 is excellent in separation performance and permeation performance, but has low membrane strength.
- the present invention has been made in view of the background of the prior art, and an object thereof is to provide a separation membrane that is excellent in separation performance and permeation performance, has high membrane strength, and is mainly composed of a cellulose resin.
- the present invention provides a separation membrane characterized by containing a cellulose ester and exhibiting a tensile elastic modulus of 1,500 to 6,500 MPa.
- the separation membrane of the present invention provides a separation membrane mainly composed of a cellulose-based resin having excellent separation performance and permeation performance and high membrane strength.
- the separation membrane of the present invention can be preferably used for applications requiring separation performance, permeation performance, and high membrane strength.
- water treatment membranes for producing industrial water, drinking water, etc. from seawater, brine, sewage, wastewater, etc. medical membranes such as artificial kidneys and plasma separation, membranes for food and beverage industries such as fruit juice concentration
- It can be used for gas separation membranes for separating exhaust gas, carbon dioxide gas, etc., and membranes for electronic industries such as fuel cell separators.
- the type of the water treatment membrane can be preferably used for microfiltration, ultrafiltration, nanofiltration, reverse osmosis membrane, forward osmosis membrane and the like.
- the separation membrane of the present invention may contain a liquid such as water in order to maintain its shape.
- these liquids for maintaining the shape are not considered as components of the hollow fiber membrane.
- the separation membrane of the present invention contains a cellulose ester (A).
- a cellulose ester (A) include cellulose acetate, cellulose propionate, cellulose butyrate, and a cellulose mixed ester in which three hydroxyl groups present in the glucose unit of cellulose are blocked by two or more acyl groups. Etc.
- cellulose mixed ester examples include cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate laurate, cellulose acetate oleate, and cellulose acetate stearate.
- Each exemplified cellulose mixed ester has an acetyl group and another acyl group (for example, propionyl group, butyryl group, lauryl group, oleyl group, stearyl group, etc.).
- the average degree of substitution between the acetyl group and other acyl groups in the cellulose mixed ester preferably satisfies the following formula.
- the average degree of substitution refers to the number of chemically bonded acetyl groups and other acyl groups among the three hydroxyl groups present per glucose unit of cellulose.
- the separation membrane of the present invention may contain only one type of cellulose ester (A) or two or more types.
- the separation membrane of the present invention preferably contains at least one of cellulose acetate propionate and cellulose acetate butyrate among the cellulose esters (A) described above as specific examples. By containing these cellulose esters, a separation membrane having high separation performance and high permeation performance is realized.
- the weight average molecular weight (Mw) of the cellulose ester (A) is preferably 50,000 to 255,000.
- Mw is 50,000 or more, thermal decomposition of the cellulose ester (A) during melt spinning is suppressed, and the membrane strength of the separation membrane can reach a practical level.
- Mw is 255,000 or less, the melt viscosity does not become too high, and stable melt spinning becomes possible.
- Mw is more preferably from 60,000 to 22 million, and even more preferably from 80,000 to 200000.
- the weight average molecular weight (Mw) is a value calculated by GPC measurement. The calculation method will be described in detail in Examples.
- the separation membrane of the present invention preferably contains cellulose ester (A) as a main component.
- “Contains as a main component” means that the content of the cellulose ester (A) is 70% by weight or more, 80% by weight or more, or 90% by weight or more.
- Plasticizer (B) The separation membrane of the present invention can contain a plasticizer (B).
- the plasticizer (B) may remain in the separation membrane after the cellulose ester is thermoplasticized during melt spinning, or may be eluted from the separation membrane into water. When the plasticizer (B) is eluted in water, the trace of the plasticizer being removed becomes pores in the membrane, and the permeation performance is improved.
- the plasticizer (B) is not particularly limited as long as it is a compound that thermoplasticizes the cellulose ester (A). Moreover, not only one type of plasticizer but also two or more types of plasticizers may be used in combination.
- the plasticizer (B) is preferably a polyhydric alcohol compound, and specific examples include polyalkylene glycol, glycerin compound, caprolactone compound and the like. Among these, since polyalkylene glycol has good compatibility with cellulose ester, it exhibits thermoplasticity even when added in a small amount. Polyalkylene glycol is preferable because it becomes fine and enables both separation performance and permeation performance.
- polyalkylene glycol examples include polyethylene glycol, polypropylene glycol, and polybutylene glycol having a weight average molecular weight of 400 to 2000.
- glycerin compound examples include glycerin fatty acid esters such as glycerin, glycerin diacetomonostearate, glycerin diacetomonolaurate, and glycerin diacetomonooleate, diglycerin, and diglycerin fatty acid ester.
- the content of the plasticizer (B) at the time of melt spinning is preferably 5 to 26% by weight.
- the content of the plasticizer (B) is 5% by weight or more, the thermoplasticity of the cellulose ester (A) and the permeation performance of the separation membrane are improved.
- the content of the plasticizer (B) is more preferably 10 to 24% by weight, still more preferably 14 to 22% by weight.
- High molecular weight polyalkylene glycol (1-3) High molecular weight polyalkylene glycol (C)
- the separation membrane of the present invention preferably contains a high molecular weight polyalkylene glycol (hereinafter simply referred to as high molecular weight polyalkylene glycol) (C) having a number average molecular weight (Mn) of 2,000 to 1,000,000.
- the high molecular weight polyalkylene glycol (C) in the present invention may remain in the separation membrane after membrane formation or may be eluted from the separation membrane into water.
- the molecular gap between the high molecular weight polyalkylene glycol (C) and the cellulose ester (A) becomes a flow path, which is preferable in terms of good permeability.
- the trace of the removal of the high molecular weight polyalkylene glycol (C) becomes pores in the membrane, which is preferable in terms of good permeability.
- high molecular weight polyalkylene glycol (C) examples include, for example, polyethylene glycol, polypropylene glycol, polybutylene glycol and the like whose Mn is 2,000 to 1,000,000.
- Mn is 1 million or less, the dispersibility in the cellulose ester is improved, and the film-forming property is improved because the composition is uniform.
- Mn is more preferably 500,000 or less, further preferably 300,000 or less, still more preferably 100,000 or less, and particularly preferably 20,000 or less.
- Mn is 2,000 or more, continuous flow paths and / or pores are easily formed, and good permeability is obtained.
- Mn is more preferably 6,000 or more, and even more preferably 8,000 or more.
- the content of the high molecular weight polyalkylene glycol (C) with respect to the whole composition constituting the separation membrane is preferably 0.01 to 10% by weight.
- the content of the high molecular weight polyalkylene glycol (C) is preferably 0.01% by weight or more, the permeation performance of the separation membrane is improved.
- the content of the high molecular weight polyalkylene glycol (C) is more preferably 0.05 to 8.0% by weight, still more preferably 0.1 to 6.0% by weight.
- the separation membrane of the present invention preferably contains an antioxidant (D), particularly a phosphorus antioxidant, and particularly preferably a pentaerythritol compound.
- an antioxidant particularly a phosphorus antioxidant, and particularly preferably a pentaerythritol compound.
- the pentaerythritol compound include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite.
- the separation membrane of the present invention preferably contains a hydrophilic polymer.
- a hydrophilic polymer is contained, the permeation performance can be improved particularly when used as a water treatment membrane.
- the hydrophilic polymer is a polymer having a high affinity for water, and refers to a polymer that is dissolved in water or has a smaller contact angle with respect to water than the cellulose ester used for the separation membrane.
- the hydrophilic polymer is not particularly limited as long as it has the above-mentioned properties, but preferred examples include polyalkylene glycol and polyvinyl alcohol.
- the shape of the separation membrane of the present invention is not particularly limited, but a hollow fiber-shaped separation membrane (hereinafter also referred to as a hollow fiber membrane) or a planar membrane (hereinafter referred to as a flat membrane).
- a hollow fiber membrane is more preferable because it can be efficiently filled into the module and the effective membrane area per unit volume of the module can be increased.
- a hollow fiber membrane is a filamentous membrane having a hollow.
- the thickness of the separation membrane is preferably 2 to 50 ⁇ m, more preferably 3 to 40 ⁇ m, and further preferably 4 to 30 ⁇ m from the viewpoint of improving the permeation performance.
- the outer diameter of the hollow fiber is preferably 20 ⁇ m or more, more preferably 40 ⁇ m or more, and 100 ⁇ m from the viewpoint of achieving both an effective membrane area when the module is filled and the membrane strength. More preferably, it is more preferably 110 ⁇ m or more.
- the outer diameter of the hollow fiber is preferably 200 ⁇ m or less, more preferably 180 ⁇ m or less, and particularly preferably 160 ⁇ m or less.
- the hollow ratio of the hollow fiber is preferably 20 to 55%, more preferably 25 to 50%, from the relationship between the pressure loss of the fluid flowing through the hollow part and the buckling pressure. Preferably, it is 30 to 45%.
- the method of setting the outer diameter and hollow ratio of the hollow fiber in the hollow fiber membrane in the above range is not particularly limited.
- the shape of the discharge hole of the spinneret for producing the hollow fiber, or the draft ratio that can be calculated by the winding speed / discharge speed It can be adjusted by appropriately changing.
- the separation membrane of the present invention preferably has a homogeneous cross-sectional structure in the thickness direction of the membrane.
- the cross section in the thickness direction of the membrane here refers to a cross section in the direction (width direction) perpendicular to the machine direction (longitudinal direction) and the thickness direction of the membrane, and hollow fiber.
- it refers to a cross section in the direction (fiber diameter direction) perpendicular to the machine direction (longitudinal direction) and the thickness direction of the membrane.
- press film formation or the like in which the machine direction during production is not clearly defined, it refers to a cross section in the thickness direction at an arbitrary position of the film.
- the cross-sectional structure referred to here is homogeneous, with a scanning electron microscope with a magnification of 1,000 times, with respect to the cross-section in the thickness direction of the film, from one surface side of the film toward the other surface side, It means a state in which no structural change can be confirmed when continuously observed in the thickness direction.
- the distortion or the like of the cross-sectional structure affecting the surface shape of the film is not regarded as a structural change.
- a resin composition that does not contain a solvent and is heated and melted is discharged from a slit-shaped base, and then cooled and solidified, a flat membrane or a hollow fiber membrane, a solution obtained by dissolving a resin composition in a solvent, etc. on a glass plate, etc.
- the film in which all of the solvent has been evaporated, and further, the solution in which the resin composition is dissolved in the solvent are discharged from the slit-shaped die, and then solidified uniformly in the thickness direction.
- a uniformly extracted film or the like cannot be confirmed as described above and has a uniform cross-sectional structure.
- a membrane generally called an asymmetric membrane having a dense separation functional layer in a part of the thickness direction of the membrane by a non-solvent phase separation method, a heat-induced phase separation method, or the like becomes a membrane having a heterogeneous cross-sectional structure.
- the separation membrane of the present invention preferably has a heat of crystal melting ( ⁇ Hm) of 4 to 20 J / g in the temperature rise measurement by a differential scanning calorimeter (DSC).
- ⁇ Hm heat of crystal melting
- DSC differential scanning calorimeter
- the method for setting ⁇ Hm to 4 to 20 J / g is not particularly limited, but the temperature condition of the spinning temperature during melt spinning, the distance from the lower surface of the spinneret to the upper end of the cooling device (chimney), the condition of the cooling air of the cooling device , Draft ratio and / or stretching / heat setting conditions may be mentioned as preferable conditions described later.
- ⁇ Hm is more preferably 6 J / g or more, and further preferably 8 J / g or more. Further, ⁇ Hm is more preferably 15 J / g or less, and further preferably 10 J / g or less.
- the separation membrane of the present invention has a membrane permeation flux of 0.5 L / m 2 / m in order to exhibit good permeation performance particularly when used as a water treatment membrane. It is preferably day or more.
- the measurement conditions of the membrane permeation flux will be described in detail in Examples.
- the membrane permeation flux is more preferably 1.0 L / m 2 / day or more, further preferably 1.5 L / m 2 / day or more, and 2.0 L / m 2 / day or more. Even more preferred is 3.0 L / m 2 / day or more.
- a higher membrane permeation flux is preferable, but the upper limit is 300 L / m 2 / day from the balance with the salt rejection.
- the separation membrane of the present invention has a salt rejection rate of 50.0% to 99.5% in order to exhibit good separation performance especially when used as a membrane for water treatment. It is preferable that The measurement conditions for the salt rejection will be described in detail in Examples.
- the salt rejection is more preferably 90.0 to 99.5%, further preferably 93.0 to 99.5%, and particularly preferably 96.0 to 99.5%.
- the separation membrane of the present invention exhibits a tensile elastic modulus of 1,500 to 6,500 MPa.
- the tensile modulus in the longitudinal direction of the separation membrane is preferably within this range.
- the longitudinal direction is the machine direction during production. The measurement conditions of the tensile modulus will be described in detail in the examples.
- the tensile modulus in the longitudinal direction is 1,500 MPa or more, an appropriate film strength can be obtained. Further, when the tensile modulus in the longitudinal direction is 6,500 MPa or less, flexibility suitable for incorporating the separation membrane into the membrane module is realized.
- the method for adjusting the tensile modulus to 1,500 to 6,500 MPa is not particularly limited, but the above-described preferred weight average molecular weight cellulose ester is used, and the draft ratio and / or the stretching / heat setting conditions during melt spinning are as follows: Examples of the preferable conditions are those described later.
- the tensile elastic modulus is preferably 1,800 MPa or more, more preferably 2,000 MPa or more, and further preferably 2,200 MPa or more. Further, the tensile elastic modulus is preferably 6,000 MPa or less, more preferably 5,000 MPa or less, further preferably 4,000 MPa, and particularly preferably 3,000 MPa.
- the separation membrane of the present invention preferably has a tensile strength of 80 MPa or more in order to exhibit membrane strength.
- the conditions for measuring the tensile strength will be described in detail in Examples.
- the tensile strength is more preferably 100 MPa or more, and further preferably 120 MPa or more. Higher tensile strength is preferable, but the practical upper limit is 300 MPa.
- the separation membrane of the present invention preferably has an orientation degree of 1.05 or more and 2.50 or less in the longitudinal direction.
- the longitudinal direction here is the machine direction at the time of manufacture.
- the degree of orientation is 1.05 or more, both high permeability and separability can be achieved.
- the degree of orientation As the degree of orientation increases, the molecular chain spacing of the cellulose ester becomes uniform, so that the hydrogen bonding sites are dispersed at even intervals, promoting water adsorption and permeation, and allowing the entry of substances to be separated such as salts. It is thought that it is for inhibiting. Therefore, a higher effect can be obtained when the degree of orientation is 1.15 or more, 1.30 or more, 1.50 or more, 1.70 or more.
- the degree of orientation is 2.50 or less, yarn breakage during film formation is suppressed, so that a decrease in productivity is suppressed and good permeability is obtained.
- the degree of orientation is preferably less than 2.30, less than 2.20, less than 2.00, and more preferably less than 1.80.
- the degree of orientation is measured by FT-IR. Specific measurement methods will be described in Examples.
- the positron annihilation lifetime obtained by the positron annihilation lifetime measurement method is preferably 2.2 ns or more and 3.0 ns or less, and 2.25 ns or more and 2.8 ns. Is more preferably less than or equal to 2.3 ns and less than 2.5 ns.
- the membrane has a low water permeability and a high desalination rate. Conversely, if the positron annihilation lifetime is long, the membrane has a high water permeability and a low desalting rate.
- a membrane having the same positron annihilation lifetime as a conventionally known membrane can be obtained a separation membrane with a high desalination rate by keeping the degree of orientation within a certain range. I understood.
- the positron annihilation lifetime measurement method is a method of measuring the time (in the order of several hundred picoseconds to several tens of nanoseconds) from when a positron is incident on a sample until it disappears. This is a technique for nondestructively evaluating information such as the size of holes of 1 to 10 nm, the number density, and the distribution of the sizes. Details of such a measurement method are described in, for example, “Fourth Edition Experimental Chemistry Course” Vol. 14, page 485, edited by The Chemical Society of Japan, Maruzen Co., Ltd. (1992).
- positron beam method using a positron beam emitted from an electron beam accelerator as a positron beam source, and this method is used for evaluating vacancies on thin films of about several hundreds of nanometers formed on various substrates. Useful. A more specific measuring method will be described in Examples.
- additives may contain additives other than those described above as long as the effects of the present invention are not impaired.
- additives include organic lubricants, crystal nucleating agents, organic particles, inorganic particles, end-capping agents, chain extenders, ultraviolet absorbers, infrared absorbers, anti-coloring agents, matting agents, antibacterial agents, antistatic agents , Deodorants, flame retardants, weathering agents, antistatic agents, antioxidants, ion exchange agents, antifoaming agents, color pigments, fluorescent whitening agents, and dyes.
- the separation membrane of the present invention is a membrane that can be used particularly for water treatment.
- Specific examples of the water treatment membrane include microfiltration membranes, ultrafiltration membranes, nanofiltration membranes, reverse osmosis membranes, and forward osmosis membranes.
- the separation membrane of the present invention is particularly preferably applied to nanofiltration membranes, reverse osmosis membranes and forward osmosis membranes.
- the method for manufacturing the separation membrane of the present invention will be specifically described by taking the case where the separation membrane is a hollow fiber membrane as an example, but is not limited thereto.
- the process of producing three steps of the process of producing a resin composition (pellet), the process of producing a hollow fiber, and the process of producing a hollow fiber membrane is included.
- the charging method may be any method such as a method of mixing and charging in advance or a method of charging using a plurality of feeders each having a discharge amount set. After melt-kneading until they are uniformly mixed, the mixture is discharged into a water tank in a gut shape and cut by a pelletizer to obtain pellets.
- the obtained pellet is made into a hollow fiber by a melt spinning method.
- (A) Step of heating and melting the pellet and supplying it to the spinning pack (b) Step of discharging from the spinneret
- (c) Step of obtaining hollow fibers by cooling the discharged resin composition (d) Hollow A step of winding the yarn.
- the spinning temperature is preferably (Tm + 5 ° C.) to (Tm + 25 ° C.), where Tm is the crystal melting temperature in the temperature rise measurement of the differential scanning calorimeter (DSC) of the resin composition. .
- the DSC measurement conditions will be described in detail in Examples.
- the spinning temperature is more preferably (Tm + 5 ° C.) to (Tm + 20 ° C.), more preferably (Tm + 5 ° C.) to (Tm + 15 ° C.), and particularly preferably (Tm + 5 ° C.) to (Tm + 10 ° C.).
- Tm + 5 ° C. the separation performance of the separation membrane is further improved and the membrane strength is further increased by suppressing the spinning temperature to be lower than usual.
- various spinnerets for producing hollow fibers can be used. Specifically, a plurality of C-slit spinnerets and arc-shaped (arc-shaped) slit portions (2 to 5) are arranged. Thus, it can be manufactured using a spinneret that forms one discharge hole, a tube-in-orifice spinneret, or the like.
- the distance L from the lower surface of the spinneret to the upper end of the cooling device is preferably 0 to 50 mm, more preferably 0 to 40 mm, and even more preferably 0 to 30 mm.
- the cooling air temperature of the cooling device is preferably 5 to 25 ° C.
- the cooling air velocity is preferably 0.8 to 2.0 m / sec, more preferably 1.1 to 2.0 m / sec, and preferably 1.4 to 2.0 m / sec. Is more preferable.
- the hollow fiber cooled by the cooling device is wound up by the winding device.
- the draft ratio that can be calculated by the winding speed / discharge speed is preferably 200 to 1,000, more preferably 300 to 900, and still more preferably 400 to 800.
- the present method may further comprise a step of drawing the hollow fiber after spinning.
- the stretching method is not particularly limited, for example, the temperature is raised to a temperature at which stretching is performed by conveying the hollow fiber membrane before stretching on a heating roll, and one stage or two or more stages using a peripheral speed difference between the heating rolls. Stretching is performed in multiple stages.
- the preferable range of the temperature of the hollow fiber membrane in the stretching step is 60 to 140 ° C, more preferably 70 to 130 ° C, and further preferably 80 to 120 ° C.
- the total draw ratio is preferably 1.05 to 1.50 times, more preferably 1.10 to 1.45 times, and even more preferably 1.15 to 1.40 times. If necessary, heat setting may be performed during or after stretching.
- the heat setting temperature is preferably 100 to 220 ° C.
- a step of eluting polyalkylene glycol from the hollow fiber thus obtained is provided. Thereby, a hollow fiber membrane is obtained. This step is carried out simply by immersing the polyalkylene glycol in water and / or alcohol. Water is inexpensive and alcohol is preferable in that the surface of the membrane can be hydrophilized. Further, since the molecular interval changes when the membrane is dried, it is preferable to store the membrane in a state in which alcohol or water is contained.
- the separation membrane of the present invention obtained as described above can be made into a module by filling the case with a conventionally known method.
- the hollow fiber membrane module includes a plurality of hollow fiber membranes and a cylindrical case. A plurality of hollow fiber membranes are bundled and inserted into a cylindrical case, and then the ends thereof are fixed to the case with a thermosetting resin such as polyurethane or epoxy resin and sealed. An end surface of the hollow fiber membrane cured with the thermosetting resin is cut to obtain an opening surface of the hollow fiber membrane, thereby producing a module.
- the separation membrane of the present invention can be used for water making for the purpose of removing the solute from the solution after the module is formed.
- the operation pressure at that time is preferably 0.1 MPa or more, more preferably 0.3 MPa or more, and further preferably 0.6 MPa or more. In general, the greater the operating pressure, the greater the membrane permeation flux and the desalination rate.
- the operation pressure is preferably 6.0 MPa or less, more preferably less than 3.0 MPa, and more preferably 1.5 MPa, in order to suppress membrane breakage such as radial collapse of the hollow fiber membrane. More preferably, it is less than.
- the temperature of the liquid to be supplied is preferably 45 ° C. or less and more preferably less than 40 ° C. in order to achieve a high desalting rate. Preferably, it is less than 35 degreeC.
- the temperature of the feed water is preferably 5 ° C. or higher, more preferably 10 ° C. or higher.
- Average substitution degree of cellulose mixed ester The calculation method of the average substitution degree of the cellulose mixed ester in which an acetyl group and an acyl group are bonded to cellulose is as follows. After 0.9 g of cellulose ester mixed for 8 hours at 80 ° C. was weighed and dissolved by adding 35 ml of acetone and 15 ml of dimethyl sulfoxide, 50 ml of acetone was further added. While stirring, 30 ml of 0.5N sodium hydroxide aqueous solution was added and saponified for 2 hours. After adding 50 ml of hot water and washing the side of the flask, it was titrated with 0.5 N sulfuric acid using phenolphthalein as an indicator.
- Tensile modulus was measured using a tensile testing machine (Tensilon UCT-100 manufactured by Orientec Co., Ltd.) in an environment of temperature 20 ° C. and humidity 65%. Specifically, under the conditions of a sample length of 100 mm and a tensile speed of 100 mm / min, the others were measured according to the method specified in “JIS L 1013: 2010 Chemical Fiber Filament Yarn Test Method / 8.10 Initial Tensile Resistance”. The apparent Young's modulus calculated from the initial tensile resistance was taken as the tensile elastic modulus (MPa). The number of measurements was 5, and the average value was used.
- Crystal melting temperature (° C) of the resin composition for melt spinning Using a differential scanning calorimeter DSC-6200 manufactured by Seiko Instruments Inc., about 5 mg of a resin composition sample that had been vacuum-dried at 25 ° C. for 8 hours was set in an aluminum pan, and the temperature rising rate from ⁇ 50 ° C. to 20 ° C. / After the temperature was raised to 350 ° C. in minutes, the crystal melting peak observed when the melt was held at 350 ° C. for 5 minutes was taken as the crystal melting temperature (° C.). When a plurality of crystal melting peaks appeared, the crystal melting peak that appeared on the highest temperature side was adopted.
- Membrane permeation flux (L / m 2 / day))
- Membrane filtration was performed by supplying a sodium chloride aqueous solution adjusted to a concentration of 500 ppm, a temperature of 25 ° C., and a pH of 6.5 to a separation membrane immersed in a 10 wt% aqueous solution of isopropyl alcohol for 1 hour for hydrophilization, at an operating pressure of 0.75 MPa.
- the membrane permeation flux was determined by the following formula based on the amount of permeate obtained.
- Membrane permeation flux (L / m 2 / day) permeate per day / membrane area
- the small module was created as follows and the membrane filtration process was performed. After the hollow fiber membranes were bundled and inserted into a plastic pipe, the gap between the membranes and the gap between the pipes were cured with a thermosetting resin at the end of the hollow fiber membrane bundle and sealed. An end surface of the sealed hollow fiber membrane was cut to obtain an opening surface of the hollow fiber membrane, and a small module for evaluation having an outer diameter standard membrane area of about 0.1 m 2 was produced.
- Tensile strength was measured using a tensile testing machine (Tensilon UCT-100 manufactured by Orientec Co., Ltd.) in an environment of temperature 20 ° C. and humidity 65%. Specifically, under the conditions of a sample length of 100 mm and a tensile speed of 100 mm / min, the others are the methods defined in “JIS L 1013: 2010 Chemical Fiber Filament Yarn Test Method / 8.5 Tensile Strength and Elongation”. The tensile strength (breaking strength) (MPa) was calculated from the tensile strength. The number of measurements was 5, and the average value was used.
- a band near 1062 cm ⁇ 1 (pyranose ring (—C—O—C—)) and a band near 1164 cm ⁇ 1 (propiol group (—C—)
- the strength of O-) was measured in the longitudinal direction and the radial direction of the hollow fiber membrane, and the degree of orientation was determined from the following formula.
- Orientation (band intensity near 1164cm -1 in the band intensity / longitudinal around longitudinal 1062 cm -1) / (band intensity near 1164cm -1 in the band intensity / radial near 1062 cm -1 in the radial direction)
- Positron Annihilation Lifetime Measurement Method Using Positron Beam Method Measurement was performed using the positron beam method.
- the separation membrane is dried at room temperature under reduced pressure to obtain a test sample.
- a thin film positron annihilation lifetime measuring device equipped with a positron beam generator (this device is described in detail in Radiation Physics and Chemistry, 58, 603, Pergamon (2000), for example), beam intensity of 3 keV, room temperature Under vacuum, a test sample was measured at a total count of 5 million using a barium difluoride scintillation counter using a photomultiplier tube, and analyzed by POSITRONFIT to obtain an average lifetime ⁇ of the third component.
- Cellulose ester (A) Cellulose ester (A1) To 100 parts by weight of cellulose (cotton linter), 240 parts by weight of acetic acid and 67 parts by weight of propionic acid were added and mixed at 50 ° C. for 30 minutes. After the mixture was cooled to room temperature, 172 parts by weight of acetic anhydride cooled in an ice bath and 168 parts by weight of propionic anhydride were added as an esterifying agent, and 4 parts by weight of sulfuric acid was added as an esterification catalyst, followed by stirring for 150 minutes. An esterification reaction was performed. In the esterification reaction, when it exceeded 40 ° C., it was cooled in a water bath.
- Cellulose ester (A2) 50 g of cellulose (manufactured by Nippon Paper Industries Co., Ltd.) was immersed in 500 ml of deionized water and placed for 10 minutes. This was filtered off with a glass filter, the water was drained, dispersed in 700 ml of acetic acid, and occasionally shaken for 10 minutes. Subsequently, the same operation was repeated again with fresh acetic acid. To the flask, 900 g of acetic acid and 0.9 g of concentrated sulfuric acid were taken and stirred. To this was added 180 g of acetic anhydride, and the mixture was stirred for 60 minutes while cooling with a water bath so that the temperature did not exceed 40 ° C.
- Plasticizer (B) Plasticizer (B1) Polyethylene glycol, weight average molecular weight 600
- Plasticizer (B2) Polyethylene glycol, weight average molecular weight 1000 Plasticizer (B3) Glycerin
- Plasticizer (B4) Glycerin diacetomonostearate Plasticizer (B5) Glycerin diacetate monooleate
- High molecular weight polyalkylene glycol (C) High molecular weight polyalkylene glycol (C1) Polyethylene glycol, number average molecular weight 8300
- High molecular weight polyalkylene glycol (C2) Polyethylene glycol, number average molecular weight 100,000
- High molecular weight polyalkylene glycol (C3) Polyethylene glycol, number average molecular weight 4000
- High molecular weight polyalkylene glycol (C4) Polyethylene glycol, number average molecular weight 20000
- Antioxidant (D) Antioxidant (D1) Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite
- Example 1 Pellets after melt-kneading and homogenizing 74% by weight of cellulose ester (A1), 25.9% by weight of plasticizer (B1) and 0.1% by weight of antioxidant (D1) at 240 ° C. in a twin screw extruder To obtain a resin composition for melt spinning. The pellets were vacuum dried at 80 ° C. for 8 hours. The crystal melting temperature of this resin composition was 220 ° C.
- the dried pellets are supplied to a twin screw extruder, melted at 230 ° C., introduced into a melt spinning pack having a spinning temperature of 230 ° C., and the mouthpiece hole (the arc-shaped slit portion has a discharge amount of 60 g / min).
- the separation membrane of this example had a total amount of polyethylene glycol added as a plasticizer during melt spinning in water from before and after being immersed in a 10 wt% aqueous solution of isopropyl alcohol for 1 hour. It was eluted. Moreover, the cross-sectional structure of the obtained separation membrane was homogeneous.
- Examples 2 to 7, Comparative Example 1 A separation membrane was obtained in the same manner as in Example 1 except that the composition and production conditions of the resin composition for melt spinning were changed as shown in Table 1, respectively.
- Table 1 shows the physical properties of the obtained separation membrane.
- the total amount of polyethylene glycol added as a plasticizer during melt spinning was from the separation membrane because of the change in weight before and after being immersed in a 10 wt% aqueous solution of isopropyl alcohol for 1 hour. It was eluted in water.
- the cross-sectional structure of the obtained separation membrane was homogeneous.
- Comparative Example 1 the melt viscosity was too high, the fluidity was poor, and the spun yarn was not thinned, and could not be wound due to yarn breakage.
- the obtained hollow fiber membrane had a heat of crystal fusion ( ⁇ Hm) of 8 J / g and an orientation degree of 1.14. Further, the membrane permeation flux was 87 L / m 2 / day, the salt rejection was 97.2%, the tensile modulus was 1,435 MPa, and the tensile strength was 72 MPa. Moreover, the cross-sectional structure of the obtained separation membrane was heterogeneous.
- Example 8 A twin screw extruder comprising 82% by weight of cellulose ester (A1), 15.9% by weight of plasticizer (B1), 2.0% by weight of high molecular weight polyalkylene glycol (C1) and 0.1% by weight of antioxidant (D1) The mixture was melt kneaded at 240 ° C., homogenized, and pelletized to obtain a resin composition for melt spinning. The pellets were vacuum dried at 80 ° C. for 8 hours. The crystal melting temperature of this resin composition was 210 ° C.
- the dried pellets are supplied to a twin screw extruder, melted at 235 ° C., introduced into a melt spinning pack having a spinning temperature of 235 ° C., and the mouthpiece hole (the arc-shaped slit portion is at a discharge rate of 60 g / min).
- This spun hollow fiber is guided to the cooling device (length 1 m) so that the distance L from the lower surface of the die to the upper end of the cooling device (chimney) is 30 mm, and the cooling air is 25 ° C.
- the separation membrane of this example had a total amount of polyethylene glycol added as a plasticizer during melt spinning in water from before and after being immersed in a 10 wt% aqueous solution of isopropyl alcohol for 1 hour. It was eluted. Moreover, the cross-sectional structure of the obtained separation membrane was homogeneous.
- Example 9 to 16 A separation membrane was obtained in the same manner as in Example 8 except that the composition and production conditions of the resin composition for melt spinning were changed as shown in Table 2. The physical properties of the obtained separation membrane are shown in Table 2.
- the total amount of polyethylene glycol added as a plasticizer during melt spinning was from the separation membrane because of the change in weight before and after being immersed in a 10 wt% aqueous solution of isopropyl alcohol for 1 hour. It was eluted in water.
- the cross-sectional structure of the obtained separation membrane was homogeneous.
- Example 17 Cellulose ester (A1) 82 wt%, plasticizer (B1) 17.9 wt% and antioxidant (D1) 0.1 wt% were melt-kneaded at 240 ° C. in a twin-screw extruder, homogenized, and then pelletized To obtain pellets for melt spinning. The pellets were vacuum dried at 80 ° C. for 8 hours. The crystal melting temperature of this pellet was 225 ° C.
- the dried pellets were supplied to a twin screw extruder and melted at 230 ° C.
- the melt was introduced into a melt spinning pack having a spinning temperature of 235 ° C. and spun from the die at a speed of 3.0 m / min.
- the base had 72 discharge holes.
- One discharge hole was formed by three arc-shaped slit portions, the discharge hole radius was 0.60 mm, the pitch between slits was 0.10 mm, and the slit width was 0.08 mm.
- the distance L from the lower surface of the base to the upper end of the cooling device (chimney, length 1 m) was adjusted to be 30 mm.
- the melt guided to the cooling device was cooled by cooling air at 25 ° C. and a wind speed of 1.5 m / sec, and an oil agent was applied to converge. Then, the hollow fiber was obtained by winding up with a winder so that the draft ratio might be set to 400 at a speed of 1200 m / min.
- Example 18 A separation membrane (hollow fiber membrane) was obtained in the same manner as in Example 17 except that the composition and production conditions of the resin composition for melt spinning were changed as shown in Table 3. Table 3 shows the physical properties of the obtained separation membrane.
- the separation membranes of Examples 18 to 22 were confirmed to have eluted all of the polyethylene glycol added as a plasticizer during melt spinning from the weight change before and after being immersed in water for 1 hour. Moreover, the cross-sectional structure of the obtained separation membrane was homogeneous.
- Example 23 Cellulose ester (A1) 78% by weight, plasticizer (B1) 17.9% by weight, high molecular weight polyalkylene glycol (C1) 4% by weight and antioxidant (D1) 0.1% by weight in a twin screw extruder The mixture was melt-kneaded at 240 ° C., homogenized and then pelletized to obtain pellets for melt spinning. The pellets were vacuum dried at 80 ° C. for 8 hours. The crystal melting temperature of this pellet was 203 ° C.
- a separation membrane (hollow fiber membrane) was obtained in the same manner as in Example 17.
- the physical properties of the obtained separation membrane are shown in Table 4.
- the polyethylene glycol added as a plasticizer was completely eluted from the hollow fiber membrane of this example due to the weight change of the hollow fiber and the hollow fiber membrane.
- the cross-sectional structure of the obtained separation membrane was homogeneous.
- Examples 24-27, Comparative Examples 3-5 A separation membrane (hollow fiber membrane) was obtained in the same manner as in Example 23 except that the composition and production conditions of the resin composition for melt spinning were changed as shown in Table 4. The physical properties of the obtained separation membrane are shown in Table 4.
- the separation membranes of Examples 24 to 27 and Comparative Examples 3 to 5 had all of the polyethylene glycol added as a plasticizer at the time of melt spinning eluted from the weight change before and after being immersed in water for 1 hour. It was confirmed. Moreover, the cross-sectional structure of the obtained separation membrane was homogeneous.
- Example 28 Pellets after melt-kneading and homogenizing 74% by weight of cellulose ester (A1), 25.9% by weight of plasticizer (B1) and 0.1% by weight of antioxidant (D1) at 240 ° C. in a twin screw extruder To obtain a resin composition for melt spinning. The pellets were vacuum dried at 80 ° C. for 8 hours. The crystal melting temperature of this resin composition was 220 ° C.
- the dried pellets are supplied to a twin screw extruder, melted at 230 ° C., introduced into a melt spinning pack having a spinning temperature of 230 ° C., and the mouthpiece hole (the arc-shaped slit portion has a discharge amount of 26 g / min).
- the separation membrane of this example had a total amount of polyethylene glycol added as a plasticizer during melt spinning in water from before and after being immersed in a 10 wt% aqueous solution of isopropyl alcohol for 1 hour. It was eluted. Moreover, the cross-sectional structure of the obtained separation membrane was homogeneous.
- Examples 29 to 34, Comparative Example 6 A separation membrane (hollow fiber membrane) was obtained in the same manner as in Example 28 except that the composition and production conditions of the resin composition for melt spinning were changed as shown in Table 5. Table 5 shows the physical properties of the obtained separation membrane. In the separation membranes of Examples 29 to 34 and Comparative Example 6, it was confirmed from the change in weight before and after being immersed in water for 1 hour that the total amount of polyethylene glycol added as a plasticizer during melt spinning was eluted. did. Moreover, the cross-sectional structure of the obtained separation membrane was homogeneous.
- the present invention is a separation membrane mainly composed of a cellulose resin having excellent separation performance and permeation performance and high membrane strength.
- the separation membrane of the present invention is a water treatment membrane for producing industrial water, drinking water, etc. from seawater, brine, sewage, drainage, etc., a medical membrane such as an artificial kidney or plasma separation, and a food / beverage such as fruit juice concentrate. It can be used for industrial membranes, gas separation membranes for separating exhaust gas, carbon dioxide gas, etc., and membranes for electronic industries such as fuel cell separators.
- the water treatment membrane can be preferably used for microfiltration membranes, ultrafiltration membranes, nanofiltration membranes, reverse osmosis membranes, forward osmosis membranes and the like.
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Abstract
Description
本発明の分離膜は、形状を保持するために水等の液体をその中に含んでいてもよい。ただし、以下の説明では、形状を保持するためのこれらの液体は中空糸膜の構成要素として考慮しない。
本発明の分離膜は、セルロースエステル(A)を含有する。セルロースエステル(A)の具体例としては、セルロースアセテート、セルロースプロピオネート、セルロースブチレート、及びセルロースのグルコースユニットに存在する3つの水酸基が、2種類以上のアシル基により封鎖された、セルロース混合エステル等が挙げられる。
0.1≦(アセチル基の平均置換度)≦2.6
0.1≦(他のアシル基の平均置換度)≦2.6
本発明の分離膜は、可塑剤(B)を含有することができる。可塑剤(B)は、溶融紡糸時にセルロースエステルが熱可塑化した後は、分離膜の中に残存してもよいし、分離膜の中から水中に溶出させてもよい。可塑剤(B)を水中に溶出させた場合、可塑剤が抜けた跡が膜中における細孔となり、透過性能が良好となる。
グリセリン系化合物の具体的な例としては、例えば、グリセリン、グリセリンジアセトモノステアレート、グリセリンジアセトモノラウレート、グリセリンジアセトモノオレート等のグリセリン脂肪酸エステル、ジグリセリン、ジグリセリン脂肪酸エステル等が挙げられる。
本発明の分離膜は、数平均分子量(Mn)が2,000~100万である高分子量ポリアルキレングリコール(以下、単に高分子量ポリアルキレングリコールと呼ぶ)(C)を含有することが好ましい。本発明における高分子量ポリアルキレングリコール(C)は、製膜を行った後は、分離膜の中に残存してもよいし、分離膜の中から水中に溶出させてもよい。
本発明の分離膜は酸化防止剤(D)、特にリン系酸化防止剤を含有することが好ましく、特にペンタエリスリトール系化合物が好ましい。ペンタエリスリトール系化合物として具体的には、ビス(2,6-ジ-t-ブチル-4-メチルフェニル)ペンタエリスリトールジホスファイト等が挙げられる。リン系酸化防止剤を含有している場合、溶融紡糸時の熱分解が抑制され、その結果、膜強度の向上、膜への着色防止が可能となる。酸化防止剤(D)の含有量は、溶融紡糸する組成物に対して0.005~0.500重量%であることが好ましい。
本発明の分離膜は、親水性ポリマーを含有することが好ましい。親水性ポリマーを含有している場合、特に水処理用膜として使用する際に透過性能の向上が可能となる。ここで親水性ポリマーとは、水と親和性の高いポリマーのことであり、水に溶解するか、または、水に対する接触角が、分離膜に使用するセルロースエステルよりも小さいポリマーを指す。親水性ポリマーとしては、前記した性質を有するものであれば特に限定されないが、ポリアルキレングリコール、ポリビニルアルコール等が好ましい例として挙げられる。
本発明の分離膜の形状は特に限定されないが、中空糸形状の分離膜(以下、中空糸膜ともいう)、または、平面形状の膜(以下、平膜という)が好ましく採用される。このなかでも中空糸膜は、効率良くモジュールに充填することが可能であり、モジュールの単位体積当たりの有効膜面積を大きくとることができるためより好ましい。中空糸膜とは中空を有する糸状の膜である。
本発明の分離膜は、膜の厚み方向の断面構造が均質であることが好ましい。ここでいう膜の厚み方向の断面とは、平膜の場合は、製造時の機械方向(長手方向)と垂直な方向(幅方向)と、膜の厚み方向の断面のことをいい、中空糸膜の場合は、製造時の機械方向(長手方向)と垂直な方向(繊維径方向)と、膜の厚み方向の断面のことをいう。製造時の機械方向が明確には無いプレス製膜等の場合は、膜の任意の場所の厚み方向の断面のことをいう。
本発明の分離膜の物性について以下に説明する。
本発明の分離膜は、示差走査熱量計(DSC)の昇温測定における結晶融解熱量(ΔHm)が、4~20J/gであることが好ましい。DSCの測定条件は実施例にて詳細に説明する。ΔHmを4~20J/gとすることにより、分離性能、膜強度がより良好なものとなる。
本発明の分離膜は、特に水処理用膜として使用する際に良好な透過性能を発現するために、膜透過流束は0.5L/m2/day以上であることが好ましい。膜透過流束の測定条件は実施例にて詳細に説明する。膜透過流束は1.0L/m2/day以上であることがより好ましく、1.5L/m2/day以上であることがさらに好ましく、2.0L/m2/day以上であることがさらにより好ましく、3.0L/m2/day以上であることが特に好ましい。膜透過流束は高い方が好ましいが、塩阻止率とのバランスから上限は300L/m2/dayである。
本発明の分離膜は、特に水処理用膜として使用する際に良好な分離性能を発現するために、塩阻止率は50.0%~99.5%であることが好ましい。塩阻止率の測定条件は実施例にて詳細に説明する。塩阻止率は90.0~99.5%であることがより好ましく、93.0~99.5%であることがさらに好ましく、96.0~99.5%であることが特に好ましい。
本発明の分離膜は、1,500~6,500MPaの引張弾性率を示す。特に、分離膜の長手方向における引張弾性率がこの範囲内にあることが好ましい。ここで長手方向とは、製造時の機械方向のことである。引張弾性率の測定条件は実施例にて詳細に説明する。
本発明の分離膜は、膜強度を発現するために、引張強度は80MPa以上であることが好ましい。引張強度の測定条件は実施例にて詳細に説明する。引張強度は100MPa以上であることがより好ましく、120MPa以上であることがさらに好ましい。引張強度は高い方が好ましいが、実用上の上限は300MPaである。
本発明の分離膜は、長手方向において1.05以上2.50以下の配向度を有することが好ましい。ここでいう長手方向とは、製造時の機械方向である。配向度が1.05以上であることで、高い透過性と分離性を両立することができる。
また、透過性を大きくするためには、配向度は、2.30未満、2.20未満、2.00未満、さらには1.80未満であることが好ましい。
配向度は、FT-IRにより測定される。具体的な測定方法については、実施例で説明する。
本発明の分離膜は、陽電子消滅寿命測定法で得られる陽電子消滅寿命が2.2ns以上3.0ns以下であることが好ましく、2.25ns以上2.8ns未満であることがより好ましく、2.3ns以上2.5ns未満であることがさらに好ましい。
より具体的な測定方法は、実施例で説明する。
本発明の分離膜は、本発明の効果を損なわない範囲で前述した以外の添加剤を含有してもよい。添加剤としては、例えば、有機滑剤、結晶核剤、有機粒子、無機粒子、末端封鎖剤、鎖延長剤、紫外線吸収剤、赤外線吸収剤、着色防止剤、艶消し剤、抗菌剤、制電剤、消臭剤、難燃剤、耐候剤、帯電防止剤、抗酸化剤、イオン交換剤、消泡剤、着色顔料、蛍光増白剤、及び染料等が挙げられる。
本発明の分離膜は、特に水処理に利用可能な膜である。水処理用膜としては、具体的には、精密濾過膜、限外濾過膜、ナノ濾過膜、逆浸透膜、及び正浸透膜等が挙げられる。本発明の分離膜は特に、ナノ濾過膜、逆浸透膜および正浸透膜に好ましく適用される。
次に、本発明の分離膜を製造する方法について、分離膜が中空糸膜の場合を例に具体的に説明するがこれに限定されるものではない。
本発明の分離膜の製造方法の例としては、樹脂組成物(ペレット)を作製する工程、中空糸を作製する工程、中空糸膜を作製する工程の3段階の工程を含む。
セルロースエステルおよび他の材料、例えば、50重量%以上95重量%以下のセルロースエステルと5重量%以上50重量%以下のポリアルキレングリコールを二軸混練押出機に投入し、加熱溶融する。投入方法は事前に混ぜ合わせて投入する方法、またはそれぞれ吐出量が設定された複数台のフィーダーを用いて投入する方法等、どのような方法でも構わない。均一に混ざるまで溶融混練を行った後、ガット状に水槽に吐出して、ペレタイザーによりカットすることによりペレットを得る。
次に、得られたペレットを溶融紡糸法により中空糸化する。具体的には、
(a)ペレットを加熱溶融し、紡糸パックに供給する工程
(b)紡糸口金から吐出する工程
(c)吐出された樹脂組成物を冷却することで、中空糸を得る工程、および
(d)中空糸を巻き取る工程
を有する。
このようにして得られた中空糸から、ポリアルキレングリコールを溶出する工程を備える。これによって、中空糸膜が得られる。
ポリアルキレングリコールは水および/またはアルコールに浸漬するだけで、この工程が実行される。水は安価であり、アルコールは膜の表面を親水化させることができる点で好ましい。また、膜が乾燥すると分子間隔が変化するため、アルコールや水等が入った状態で保管することが好ましい。
上記のようにして得られた本発明の分離膜は、従来公知の方法によりケースに充填することで、モジュールとすることが可能である。例えば、中空糸膜モジュールは、複数の中空糸膜と、筒状のケースと、を備える。複数の中空糸膜は、束ねて、筒状のケースに挿入した後、その端部をポリウレタンやエポキシ樹脂等の熱硬化性樹脂で上記ケースに固定して封止する。熱硬化性樹脂で硬化させた中空糸膜の端部を切断することで中空糸膜の開口面を得て、モジュールを作製する。
本発明の分離膜は、前記モジュールの形態としたのち、溶液から溶質を除去することを目的とする造水に用いることができる。その際の操作圧力は0.1MPa以上であると好ましく、0.3MPa以上であるとより好ましく、0.6MPa以上であるとさらに好ましい。一般に、操作圧力が大きいほど膜透過流束、脱塩率ともに大きくなる。
以上に記した数値範囲の上限及び下限は、任意に組み合わせることができる。
実施例中の各特性値は次の方法で求めたものである。
なお、以下の(3)~(8)、(11)~(13)においては、分離膜を25℃で8時間、真空乾燥させた状態で測定および評価した。
セルロースにアセチル基およびアシル基が結合したセルロース混合エステルの平均置換度の算出方法については下記の通りである。
80℃で8時間の乾燥したセルロース混合エステル0.9gを秤量し、アセトン35mlとジメチルスルホキシド15mlを加え溶解した後、さらにアセトン50mlを加えた。撹拌しながら0.5N-水酸化ナトリウム水溶液30mlを加え、2時間ケン化した。熱水50mlを加え、フラスコ側面を洗浄した後、フェノールフタレインを指示薬として0.5N-硫酸で滴定した。別に試料と同じ方法で空試験を行った。滴定が終了した溶液の上澄み液を100倍に希釈し、イオンクロマトグラフを用いて、有機酸の組成を測定した。測定結果とイオンクロマトグラフによる酸組成分析結果から、下記式により置換度を計算した。
DSace=(162.14×TA)/[{1-(Mwace-(16.00+1.01))×TA}+{1-(Mwacy-(16.00+1.01))×TA}×(Acy/Ace)]
DSacy=DSace×(Acy/Ace)
TA:全有機酸量(ml)
A:試料滴定量(ml)
B:空試験滴定量(ml)
F:硫酸の力価
W:試料重量(g)
DSace:アセチル基の平均置換度
DSacy:アシル基の平均置換度
Mwace:酢酸の分子量
Mwacy:他の有機酸の分子量
Acy/Ace:酢酸(Ace)と他の有機酸(Acy)とのモル比
162.14:セルロースの繰り返し単位の分子量
16.00:酸素の原子量
1.01:水素の原子量
セルロースエステルの濃度が0.15重量%となるようにテトラヒドロフランに完全に溶解させ、GPC測定用試料とした。この試料を用い、以下の条件のもと、Waters2690でGPC測定を行い、ポリスチレン換算により重量平均分子量(Mw)を求めた。
検出器 :Waters2410 示差屈折計RI
移動層溶媒:テトラヒドロフラン
流速 :1.0ml/分
注入量 :200μl
膜の長手方向と垂直な方向(幅方向)と、膜の厚み方向の断面を光学顕微鏡により観察、撮影し、膜の厚み(μm)を算出した。なお、膜の厚みは、任意の10箇所を観察して算出し、その平均値とした。
中空糸の長手方向と垂直な方向(繊維径方向)と、膜の厚み方向の断面を光学顕微鏡により観察、撮影し、中空糸の外径(μm)を算出した。なお、中空糸の外径は、中空糸10本を用いて算出し、その平均値とした。
中空糸の長手方向と垂直な方向(繊維径方向)と、膜の厚み方向の断面を光学顕微鏡により観察、撮影し、断面の中空部を合わせた全面積Saと中空部の面積Sbを測定し、下式を用いて算出した。なお、中空率は中空糸10本を用いて算出し、その平均値とした。
中空率(%)=(Sb/Sa)×100
温度20℃、湿度65%の環境下において、引張試験機(オリエンテック社製テンシロン UCT-100)を用いて引張弾性率を測定した。具体的には、試料長100mm、引張速度100mm/minの条件にて、その他は、「JIS L 1013:2010化学繊維フィラメント糸試験方法・8.10初期引張抵抗度」に規定された方法に従って測定を行い、初期引張抵抗度から算出した見掛ヤング率を引張弾性率(MPa)とした。なお測定回数は5回とし、その平均値とした。
セイコーインスツルメンツ(株)製示差走査熱量計DSC-6200を用い、25℃、8時間真空乾燥を行った分離膜試料約5mgをアルミニウム製受皿にセットし、-50℃から昇温速度20℃/分で350℃まで昇温後、350℃のまま5分間溶融保持した際に観測される結晶融解ピークをもとに、結晶融解熱量を、JIS K 7121(1987)に規定された方法に従って求めた。なお、120℃以下の範囲に存在する吸熱ピークは、脱水によるものと考えられるため結晶融解熱量には含めない。また、結晶融解ピークが複数現れる場合は、全ての結晶融解熱量を合計することで求めた。
セイコーインスツルメンツ(株)製示差走査熱量計DSC-6200を用い、25℃、8時間真空乾燥を行った樹脂組成物試料約5mgをアルミニウム製受皿にセットし、-50℃から昇温速度20℃/分で350℃まで昇温後、350℃のまま5分間溶融保持した際に観測される結晶融解ピークを結晶融解温度(℃)とした。なお、結晶融解ピークが複数現れる場合は、最も高温側に現れる結晶融解ピークを採用した。
イソプロピルアルコールの10wt%水溶液に1時間浸漬して親水化を行った分離膜に、濃度500ppm、温度25℃、pH6.5に調整した塩化ナトリウム水溶液を操作圧力0.75MPaで供給して、膜ろ過処理を行い、得られた透過水量に基づいて、下記式により膜透過流束を求めた。
膜透過流束(L/m2/day)=1日あたりの透過水量/膜面積
膜透過流束と同条件で膜ろ過処理を行い、得られた透過水の塩濃度を測定した。得られた透過水の塩濃度および供給水の塩濃度から、下記式に基づいて塩阻止率を求めた。なお、透過水の塩濃度は、電気伝導度の測定値より求めた。
塩阻止率(%)=100×{1-(透過水中の塩化ナトリウム濃度/供給水中の塩化ナトリウム濃度)}
中空糸膜を束ねて、プラスチック製パイプに挿入した後、中空糸膜束の端部において、膜間の隙間と、パイプとの隙間を、熱硬化性樹脂によって硬化させて封止した。封止させた中空糸膜の端部を切断することで中空糸膜の開口面を得て、外径基準の膜面積が約0.1m2の評価用小型モジュールを作製した。
温度20℃、湿度65%の環境下において、引張試験機(オリエンテック社製テンシロン UCT-100)を用いて引張強度を測定した。具体的には、試料長100mm、引張速度100mm/minの条件にて、その他は、「JIS L 1013:2010化学繊維フィラメント糸試験方法・8.5引張強さ及び伸び率」に規定された方法に従って測定を行い、引張強さから引張強度(破断強度)(MPa)を算出した。なお測定回数は5回とし、その平均値とした。
1回反射ATR付属装置を付けたBioRad DIGILAB社製FTIR(FTS-55A)を用い、25℃、8時間真空乾燥を行った分離膜試料を用い、長手方向と、長手方向と垂直な方向(幅方向あるいは径方向)について、S偏光ATRスペクトル測定を行った。なお、ATR結晶にはGeプリズムを用い、入射角45°、積算回数256回、偏光子にはワイヤーグリッドを用い、S偏光にて実施した。得られたATRスペクトルから長手方向と、長手方向と垂直な方向(幅方向あるいは径方向)で、バンド強度が変化する2つのバンドを用いて、そのバンド強度比を配向パラメータとして算出した。例えば、セルロースアセテートプロピオネートの中空糸膜の場合は、1062cm-1付近のバンド(ピラノース環(―C―O―C―))、および、1164cm-1付近のバンド(プロピオル基(―C―O―))の強度を、中空糸膜の長手方向および径方向でそれぞれ測定し、以下の式から配向度を求めた。
配向度=(長手方向の1062cm-1付近のバンド強度/長手方向の1164cm-1付近のバンド強度)/(径方向の1062cm-1付近のバンド強度/径方向の1164cm-1付近のバンド強度)
陽電子ビーム法を用いて測定を行った。減圧下室温で分離膜を乾燥させ、検査試料とする。陽電子ビーム発生装置を装備した薄膜対応陽電子消滅寿命測定装置(この装置は、例えば、Radiation Physics and Chemistry,58,603,Pergamon(2000)で詳細に説明されている)にて、ビーム強度3keV、室温、真空下で、光電子増倍管を使用して二フッ化バリウム製シンチレーションカウンターにより総カウント数500万で検査試料を測定し、POSITRONFITにより解析を行って第3成分の平均寿命τを得た。
セルロースエステル(A1)
セルロース(コットンリンター)100重量部に、酢酸240重量部とプロピオン酸67重量部を加え、50℃で30分間混合した。混合物を室温まで冷却した後、氷浴中で冷却した無水酢酸172重量部と無水プロピオン酸168重量部をエステル化剤として、硫酸4重量部をエステル化触媒として加えて、150分間撹拌を行い、エステル化反応を行った。エステル化反応において、40℃を越える時は、水浴で冷却した。
セルロース(日本製紙株式会社製溶解パルプ)50gを500mlの脱イオン水に浸して10分間おいた。これをガラスフィルターで濾別して水を切り、700mlの酢酸に分散させ、時々振り混ぜて10分間おいた。続いて、新しい酢酸を用いて同じ操作を再び繰り返した。フラスコに900gの酢酸と0.9gの濃硫酸をとり、撹拌した。これに180gの無水酢酸を加え、温度が40℃をこえないように水浴で冷却しながら60分撹拌した。反応終了後、炭酸ナトリウム2g含む水溶液を加えて析出したセルロースエステルを濾別、続いて水で洗浄した後、60℃で4時間乾燥した。得られたセルロースアセテートは85.3gであり、セルロースアセテートの平均置換度は2.9であった。
株式会社ダイセル製セルロースアセテート(LT35)、置換度2.90
株式会社ダイセル製セルロースジアセテート(L30)、置換度2.45
可塑剤(B1)
ポリエチレングリコール、重量平均分子量600
ポリエチレングリコール、重量平均分子量1000
可塑剤(B3)
グリセリン
グリセリンジアセトモノステアレート
可塑剤(B5)
グリセリンジアセトモノオレート
高分子量ポリアルキレングリコール(C1)
ポリエチレングリコール、数平均分子量8300
ポリエチレングリコール、数平均分子量10万
ポリエチレングリコール、数平均分子量4000
ポリエチレングリコール、数平均分子量20000
酸化防止剤(D1)
ビス(2,6-ジ-t-ブチル-4-メチルフェニル)ペンタエリスリトールジホスファイト
(実施例1)
セルロースエステル(A1)74重量%と可塑剤(B1)25.9重量%および酸化防止剤(D1)0.1重量%を二軸押出機にて240℃で溶融混練し、均質化した後にペレット化して、溶融紡糸用の樹脂組成物を得た。このペレットを80℃、8時間真空乾燥を行った。この樹脂組成物の結晶融解温度は、220℃であった。
溶融紡糸用樹脂組成物の組成、製造条件をそれぞれ表1のように変更した以外は、実施例1と同様にして分離膜を得た。得られた分離膜の物性を表1に示した。
なお、実施例2~7の分離膜は、イソプロピルアルコールの10wt%水溶液に1時間浸漬する前後における重量変化から、溶融紡糸する際に可塑剤として添加したポリエチレングリコールは、全量が分離膜の中から水中に溶出していた。また、得られた分離膜の断面構造は均質であった。
また、比較例1では、溶融粘度が高すぎて流動性が悪く紡出糸の細化が起こらず、糸切れにより巻き取ることができなかった。
セルロースエステル(A3)41重量%、N-メチル-2-ピロリドン49.9重量%、エチレングリコール8.8重量%、安息香酸0.3重量%を180℃で溶解した。得られた溶液を減圧下で脱泡した後、口金孔(弧状のスリット部が3個配置されて1個の吐出孔を形成するタイプ)から160℃で下方に紡出し、空間時間0.03秒を経て、N-メチル-2-ピロリドン/エチレングリコール/水=4.25重量%/0.75重量%/95重量%からなる12℃の浴中で固化させ、続いて水中で洗浄した。その後、60℃の水中で40分間熱処理し、外径が167μm、中空率が25%の中空糸膜を得た。
セルロースエステル(A1)82重量%と可塑剤(B1)15.9重量%、高分子量ポリアルキレングリコール(C1)2.0重量%および酸化防止剤(D1)0.1重量%を二軸押出機にて240℃で溶融混練し、均質化した後にペレット化して、溶融紡糸用の樹脂組成物を得た。このペレットを80℃、8時間真空乾燥を行った。この樹脂組成物の結晶融解温度は、210℃であった。
溶融紡糸用樹脂組成物の組成、製造条件をそれぞれ表2のように変更した以外は、実施例8と同様にして分離膜を得た。得られた分離膜の物性を表2に示した。なお、実施例9~16の分離膜は、イソプロピルアルコールの10wt%水溶液に1時間浸漬する前後における重量変化から、溶融紡糸する際に可塑剤として添加したポリエチレングリコールは、全量が分離膜の中から水中に溶出していた。また、得られた分離膜の断面構造は均質であった。
セルロースエステル(A1)82重量%と可塑剤(B1)17.9重量%および酸化防止剤(D1)0.1重量%を二軸押出機にて240℃で溶融混練し、均質化した後にペレット化して、溶融紡糸用のペレットを得た。このペレットを80℃、8時間真空乾燥を行った。このペレットの結晶融解温度は225℃であった。
冷却装置へ導かれた溶融物を、25℃、風速1.5m/秒の冷却風によって冷却し、油剤を付与して収束させた。その後、1200m/分の速さで、ドラフト比が400となるようにワインダーで巻き取ることで中空糸を得た。
溶融紡糸用樹脂組成物の組成、製造条件をそれぞれ表3のように変更した以外は、実施例17と同様にして分離膜(中空糸膜)を得た。得られた分離膜の物性を表3に示した。なお、実施例18~22の分離膜は、水に1時間浸漬する前後における重量変化から、溶融紡糸する際に可塑剤として添加したポリエチレングリコールは、全量溶出していることを確認した。また、得られた分離膜の断面構造は均質であった。
セルロースエステル(A1)78重量%と可塑剤(B1)17.9重量%、高分子量ポリアルキレングリコール(C1)4重量%および酸化防止剤(D1)0.1重量%を二軸押出機にて240℃で溶融混練し、均質化した後にペレット化して、溶融紡糸用のペレットを得た。このペレットを80℃、8時間真空乾燥を行った。このペレットの結晶融解温度は203℃であった。
溶融紡糸用樹脂組成物の組成、製造条件をそれぞれ表4のように変更した以外は、実施例23と同様にして分離膜(中空糸膜)を得た。得られた分離膜の物性を表4に示した。なお、実施例24~27、比較例3~5の分離膜は、水に1時間浸漬する前後における重量変化から、溶融紡糸する際に可塑剤として添加したポリエチレングリコールは、全量溶出していることを確認した。また、得られた分離膜の断面構造は均質であった。
セルロースエステル(A1)74重量%と可塑剤(B1)25.9重量%および酸化防止剤(D1)0.1重量%を二軸押出機にて240℃で溶融混練し、均質化した後にペレット化して、溶融紡糸用の樹脂組成物を得た。このペレットを80℃、8時間真空乾燥を行った。この樹脂組成物の結晶融解温度は、220℃であった。
溶融紡糸用樹脂組成物の組成、製造条件をそれぞれ表5のように変更した以外は、実施例28と同様にして分離膜(中空糸膜)を得た。得られた分離膜の物性を表5に示した。なお、実施例29~34、比較例6の分離膜は、水に1時間浸漬する前後における重量変化から、溶融紡糸する際に可塑剤として添加したポリエチレングリコールは、全量溶出していることを確認した。また、得られた分離膜の断面構造は均質であった。
Claims (13)
- セルロースエステルを含有し、1,500~6,500MPaの引張弾性率を示す、分離膜。
- 前記分離膜が中空糸形状であり、長手方向における引張弾性率が1,500~6,500MPaである、請求項1に記載の分離膜。
- 前記中空糸の外径が20~200μmである、請求項2に記載の分離膜。
- 前記分離膜が長手方向において1.05以上2.50以下の配向度を有する、請求項1~3のいずれか1項に記載の分離膜。
- 示差走査熱量計(DSC)の昇温測定における結晶融解熱量(ΔHm)が、4~20J/gである、請求項1~4のいずれか1項に記載の分離膜。
- 陽電子消滅寿命が2.2ns以上3.0ns以下である、請求項1~5のいずれか1項に記載の分離膜。
- 前記セルロースエステルが、セルロースアセテートプロピオネート及びセルロースアセテートブチレートの少なくとも一方である、請求項1~6のいずれか1項に記載の分離膜。
- 数平均分子量(Mn)が2,000~100万であるポリアルキレングリコールを含む、請求項1~7のいずれか1項に記載の分離膜。
- 前記分離膜が、ナノ濾過膜、逆浸透膜、正浸透膜から選ばれるいずれか一つである、請求項1~8のいずれか1項に記載の分離膜。
- 紡糸口金から少なくとも50重量%以上95重量%以下のセルロースエステルと5重量%以上50重量%以下のポリアルキレングリコールが混練されたポリマーを吐出し、冷却風で冷却しながらドラフト比200以上で巻き取ることを特徴とする、中空糸の製造方法。
- セルロースエステルを50重量%以上95重量%以下の割合で含有し、ポリアルキレングリコールを5重量%以上50重量%以下の割合で含有する中空糸から、ポリアルキレングリコールを溶出させることを特徴とする、中空糸膜の製造方法。
- ケースと、
前記ケースに充填された請求項2~9のいずれか1項に記載の分離膜と、
を備える、中空糸膜モジュール。 - 請求項1~9のいずれか1項に記載の分離膜に、0.3MPa以上6.0MPa以下の圧力で水を含む混合液体を供給する工程を含む、造水方法。
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WO2016175308A1 (ja) * | 2015-04-28 | 2016-11-03 | 東レ株式会社 | 複合中空糸膜およびその製造方法 |
WO2018021545A1 (ja) * | 2016-07-29 | 2018-02-01 | 東レ株式会社 | 分離膜およびその製造方法 |
WO2018159642A1 (ja) | 2017-02-28 | 2018-09-07 | 東レ株式会社 | 複合中空糸膜およびその製造方法 |
WO2018182028A1 (ja) | 2017-03-30 | 2018-10-04 | 東レ株式会社 | 分離膜及びその製造方法 |
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EP3278867B1 (en) * | 2015-03-31 | 2021-09-08 | Toray Industries, Inc. | Separation membrane |
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