KR101557460B1 - Polymer resin composition for preparing hollow fiber membrane, preparation method of hollow fiber membrane, and hollow fiber membrane - Google Patents

Abstract

The present invention relates to a polymer resin composition for producing a hollow fiber membrane containing a vinylidene fluoride polymer resin, a good solvent, a poor solvent and an organic phosphate, a hollow fiber membrane production method using the polymer resin composition, and a hollow fiber membrane obtained therefrom.

Description

TECHNICAL FIELD [0001] The present invention relates to a polymer resin composition for producing a hollow fiber membrane, a method for producing the hollow fiber membrane, and a hollow fiber membrane. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a polymer resin composition for producing a hollow fiber membrane, a method for producing the hollow fiber membrane, and a hollow fiber membrane, and more particularly, to a hollow fiber membrane which has high strength and excellent chemical resistance and realizes a high water permeability, And a method for producing a hollow fiber membrane and a polymer resin composition capable of providing such a hollow fiber membrane.

With the development of the industry and population growth, interest in efficient water use and treatment technologies is increasing. In recent years, membrane technology has been increasingly applied to ensure water quality stability in water treatment, under-wastewater treatment, and seawater desalination. Among the membrane technologies, especially, hollow fiber membranes have a high area per unit volume, have a low membrane contamination, and are being studied because membrane washing is easy.

In general, physical and chemical treatments are carried out to control the contamination of the membrane, which shortens the lifetime of the membrane. Therefore, research on manufacturing technology of PVDF (polyvinylidene fluoride) hollow fiber membrane with excellent strength and chemical resistance is advanced . As a method for producing a PVDF hollow fiber membrane, there is generally used a thermal induced phase separation method in which a polymer is melted at a high temperature and extruded from a nozzle to solidify the polymer into a non-solvent to form a porous structure .

In the heat-induced phase separation method, the inorganic fine particles and the organic liquid body are melt-kneaded in a polyvinylidene fluoride resin, extruded from the neck at a temperature not lower than the melting point of the polyvinylidene fluoride resin, pressed or molded by a press machine, And thereafter the organic liquid material and the inorganic fine particles are extracted to form a porous structure

Such a heat-induced phase separation method can produce a homogeneous and high-strength film without forming relatively macroboids. However, if the dispersibility of the inorganic fine particles is poor, defects such as pinholes may be generated, to be.

In recent years, there has been a growing demand for PVDF hollow fiber membrane manufacturing technology in the industry, which is excellent in strength and chemical resistance and is economical, and it is necessary to develop a method for solving the limitations of the previously known heat-induced phase separation method.

Patent Document 1: Japanese Patent No. 5062798 (Oct. 31, 2012) Patent Document 2: Korean Patent Laid-Open No. 10-2002-0019078 (Mar. Patent Document 3: Korean Patent Laid-Open No. 10-2010-0106025 (2010.10.01.)

The present invention provides a polymer resin composition for producing a hollow fiber membrane capable of providing a hollow fiber membrane having high strength and excellent chemical resistance and realizing a high water permeability and stably and efficiently performing water treatment.

It is another object of the present invention to provide a method for producing a hollow fiber membrane which has high strength and excellent chemical resistance and which realizes high water permeability and enables stable and efficient water treatment.

Another object of the present invention is to provide a hollow fiber membrane which has high strength and excellent chemical resistance and which realizes high water permeability and enables stable and efficient water treatment.

One embodiment of the invention is a hollow fiber membrane comprising 10 to 70% by weight of a vinylidene fluoride polymer resin, 1 to 50% by weight of a good solvent, 1 to 75% by weight of a poor solvent and 0.001 to 5% by weight of an organic phosphate A polymeric resin composition for use in the production thereof is provided.

According to another embodiment of the present invention, there is provided a method for producing a hollow fiber membrane, comprising the steps of: heating the polymer resin composition for producing the hollow fiber membrane at a temperature of from 50 캜 to 175 캜; Mixing the heated polymeric resin composition for producing a hollow fiber membrane with an internal coagulant; And spinning the polymeric resin composition for producing a hollow fiber membrane mixed with the internal coagulating agent into a wet coagulation bath.

Yet another embodiment of the present invention provides a hollow fiber membrane comprising a polymer substrate comprising a vinylidene fluoride-based polymer resin and an organic phosphate and having an outer diameter of 0.5 to 6 mm and an inner diameter of 0.3 to 6 mm .

Hereinafter, the polymer resin composition for producing a hollow fiber membrane, the method for producing a hollow fiber membrane, and the hollow fiber membrane according to a specific embodiment of the present invention will be described in detail.

According to an embodiment of the present invention, there is provided a hollow fiber membrane comprising 10 to 70% by weight of a vinylidene fluoride polymer resin, 1 to 70% by weight of a good solvent, 1 to 75% by weight of a poor solvent and 0.001 to 5% A polymeric resin composition for production can be provided.

In the previously known heat-induced phase separation method, it has been common to use inorganic fine particles to form a large number of pores in the hollow fiber membrane. When such inorganic fine particles are used, the dispersibility or compatibility is improved in the polymer solution or spinning solvent, And there is a limit in that it is difficult to uniformly form pores in the produced hollow fiber membrane.

Therefore, the inventors of the present invention conducted a study on the production of a hollow fiber membrane, and found that when a polymer resin composition containing an organic phosphate is used together with a vinylidene fluoride polymer resin, a good solvent, and a poor solvent, the strength and chemical resistance of the hollow fiber membrane But it is possible to realize stable and efficient water treatment by realizing a high water permeability while achieving the invention by the experiment.

By using the organic phosphate, the crystallinity and the crystallization rate of the polymer resin included in the hollow fiber membrane can be promoted and the crystal size can be miniaturized, thereby improving the strength and chemical resistance of the hollow fiber membrane.

The organic phosphate may include an aromatic phosphate metal salt. The aromatic phosphate ester metal salt means a phosphate salt of a phosphoric acid ester having at least one aromatic group having 6 to 20 carbon atoms.

The aromatic phosphoric acid ester metal salt may include a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R _{6 ,} R ₇ and R ₈ may be the same or different and are each a hydrogen or a straight or branched alkyl group having 1 to 10 carbon atoms , X is a straight or branched alkylene group having 1 to 5 carbon atoms, and n is 1 or 2. When n is 1, M is an alkali metal, and when n is 2, M is an alkaline earth metal or hydroxyaluminum.

R ₁ , R ₃ , R _{6 ,} and R ₈ are each a straight or branched alkyl group having 1 to 10 carbon atoms, and R ₂ , R ₄ , R _5, and R ₇ may be hydrogen .

Specific examples of the compound of formula (1) include compounds of the following formulas (2) to (6).

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

Meanwhile, the polymer resin composition for preparing a hollow fiber membrane of the embodiment may contain 0.001 to 5% by weight, or 0.01 to 3% by weight of an organic phosphate. If the content of the organic phosphate is too small, the action or effect of the use of the phosphate may be insignificant. If the content of the organic phosphate is too large, a suspension which does not dissolve in the polymer resin composition for producing a hollow fiber membrane may be generated. Due to such suspension, the hollow fiber membrane may be broken during the spinning process or uneven or large bubbles may be generated in the hollow fiber membrane .

The vinylidene fluoride-based polymer resin means a polymer or copolymer containing repeating units of vinylidene fluoride. Specifically, the vinylidene fluoride-based polymer resin is a vinylidene fluoride homopolymer, a vinylidene fluoride copolymer, or a mixture thereof. .

The vinylidene fluoride copolymer includes a copolymer of a vinylidene fluoride monomer and other monomers such as tetrafluoroethylene, propylene hexafluoride, ethylene trifluoride, or ethylene trifluoride chloride.

The vinylidene fluoride-based polymer resin may have a weight average molecular weight of 100,000 to 1,000,000, or 250,000 to 800,000, or 300,000 to 600,000. If the weight average molecular weight of the vinylidene fluoride type polymer resin is too small, the mechanical properties and chemical resistance of the hollow fiber membrane to be produced can not be sufficiently secured. If the weight average molecular weight of the vinylidene fluoride-based polymer resin is too large, the viscosity of the polymer resin composition for producing a hollow fiber membrane or the spinning solution prepared therefrom becomes too high, making it difficult to produce a hollow fiber membrane.

The polymer resin composition for producing a hollow fiber membrane of the embodiment may contain 10 to 70% by weight or 25 to 50% by weight of the vinylidene fluoride polymer resin.

If the content of the vinylidene fluoride polymer resin in the polymer resin composition for producing a hollow fiber membrane of the embodiment is too small, it is difficult to secure sufficient mechanical properties and chemical resistance of the produced hollow fiber membrane, It may not be easy. If the content of the vinylidene fluoride polymer resin in the polymer resin composition for producing a hollow fiber membrane of the embodiment is too large, the rate of phase transition may be significantly lowered in the thermally induced phase separation method using the polymer resin composition for producing a hollow fiber membrane, The size of the pores formed in the pores may become very small and water treatment performance may be deteriorated.

The amount of solvent (good-solvent) is an amount having a polyfluorinated vinylidene can be used a known solvent that the dengye resin can be dissolved, and 21 to 27 MPa ^1/2 of the Total solubility parameter and 130 to disconnect point of 230 ℃ It is preferable to select a solvent.

Specific examples of the usable positive solvent include N-methyl-2-pyrrolidone, dimethylformamide, N, N'-dimethylacetamide (N, N'- dimethyl acetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, or a mixture of two or more thereof.

The polymer resin composition for producing a hollow fiber membrane of the embodiment may contain 1 to 70% by weight, or 10 to 60% by weight of a good solvent. If the content of the positive solvent in the polymer resin composition is too low, the flowability of the polymer resin composition or the spinning solution using the polymer resin composition may be lowered and the kneading temperature should be increased accordingly. In addition, if the content of the positive solvent in the polymer resin composition is too high, the phase transition rate is excessively increased in the polymer-resin composition or the heat-induced phase separation method using the spinning solution using the polymer resin composition, The water treatment performance may be deteriorated.

In the poor solvent, the poor solvent has no ability to dissolve in the polymer at room temperature and has the ability to dissolve the polymer at a high temperature. In the thermally induced phase transfer (TIPS) process, the poor solvent forms pores in the polymer separator , The flowability of the spinning solution can be improved, and the function of lowering the melting point of the polymer can be realized.

Specific examples of the poor solvent include dibutyl phthalate, dimethyl phthalate, dioctyl sebacate, dioctyl adipate, gamma-butylolactone, Propylene carbonate, or a mixture of two or more thereof.

The polymer resin composition for producing a hollow fiber membrane of the embodiment may contain 1 to 75% by weight or 10 to 60% by weight of a poor solvent. If the content of the poor solvent in the polymer resin composition is too small, the porosity of the hollow fiber membrane may be lowered or the pore may not be properly formed, thereby reducing the permeate flow rate. Also, if the content of the poor solvent in the polymer resin composition is too large, the flowability of the polymer resin composition or the spinning solution using the polymer resin composition may be lowered and thus the kneading temperature must be increased, or the polymer resin composition or a spinning solution using the polymer resin composition The phase transition speed is excessively high in the heat-induced phase separation method used, or the pore formed in the hollow fiber membrane to be manufactured is very large, so that the water treatment performance may be deteriorated.

Meanwhile, the polymer resin composition for producing a hollow fiber membrane according to one embodiment may further include additives such as a plasticizer, a use agent, or a dispersant.

According to another embodiment of the present invention, there is provided a method for manufacturing a hollow fiber membrane, comprising: heating a polymer resin composition for producing a hollow fiber membrane according to one embodiment; Mixing the heated polymeric resin composition for producing a hollow fiber membrane with an internal coagulant; And spinning the polymer resin composition for producing a hollow fiber membrane mixed with the internal coagulant into a wet coagulation bath.

As described above, when the hollow fiber membrane is prepared by the heat-induced phase separation method using the polymer resin composition comprising the organophosphate salt together with the vinylidene fluoride-based polymer resin, the positive solvent and the poor solvent, the strength of the hollow fiber membrane produced, The chemical resistance can be greatly improved, and a high water permeability can be realized, so that a stable and efficient water treatment can be realized. Particularly, by using the organophosphate, the crystallinity and the crystallization rate of the polymer resin included in the hollow fiber membrane substrate can be promoted and the crystal size can be miniaturized, thereby improving the strength and chemical resistance of the hollow fiber membrane.

The specific contents of the polymer resin composition for producing a hollow fiber membrane according to one embodiment include all the above-mentioned contents.

The polymer resin composition for preparing a hollow fiber membrane may be converted into a polymer spinning solution form which can be used for producing a hollow fiber membrane by heating the polymer resin composition for producing the hollow fiber membrane at 50 to 175 ° C or 100 to 171 ° C have.

If the heating temperature of the polymer resin composition for producing a hollow fiber membrane is too low, the viscosity of the polymer resin composition may not be sufficiently lowered and spinning may be difficult. If the spinning solution obtained by applying a low heating temperature is used, Pores having a size that is not sufficiently formed, minute uniform, or not suitable may be formed. If the heating temperature of the polymer resin composition for producing a hollow fiber membrane is too high, components contained in the polymer resin composition for producing the hollow fiber membrane may be decomposed.

The heated polymer resin composition for producing a hollow fiber membrane may be mixed with an internal coagulant before being radiated into a wet coagulation bath. The step of mixing the heated polymer resin composition for producing a hollow fiber membrane with the inner coagulant may be performed in a spinneret serving as an inner coagulant or an inner coagulant.

The mixed weight ratio of the polymer resin composition for preparing a hollow fiber membrane and the internal coagulating agent may vary depending on the properties and physical properties of the hollow fiber membrane to be prepared, and may be mixed at a weight ratio of, for example, 2: 1 to 1:10.

The internal coagulant may be a good solvent, a non-solvent or a mixture of a good solvent and a non-solvent, and preferably a mixture of a good solvent and a non-solvent.

Both of the solvents that can be used as the internal coagulant may use a good solvent contained in the polymer resin composition for producing a hollow fiber membrane according to the embodiment.

The non-solvent which can be used as the internal coagulant may be water, ethylene glycol, an alcohol solvent, a ketone solvent, a polyalkylene glycol, or a mixture of two or more thereof.

The internal coagulant may include both solvents and non-solvent at a weight ratio of 3: 1 to 1: 3.

Meanwhile, the method of the present invention may further include a step of maintaining the polymer resin composition for preparing a hollow fiber membrane mixed with the internal coagulant at a temperature of 5 ° C to 30 ° C. The heated polymer resin composition for producing a hollow fiber membrane and the internal coagulant may be mixed and then allowed to stand in a spinneret serving as an internal coagulant or an internal coagulant. The temperature may be maintained at 5 to 30 ° C.

The polymer resin composition for producing a hollow fiber membrane mixed with the internal coagulant may be radiated into a wet coagulation bath through a spinneret. The hollow fiber membrane described above may be formed through the spinning process to the wet coagulation bath.

The wet coagulation bath is filled with water, and the wet coagulation bath or the water soaking can be maintained at a temperature of -10 ° C to 30 ° C.

The distance between the spinning nozzle and the surface of the water in the wet coagulation bath may be between 0.5 cm and 10 cm. The distance between the spinning nozzle and the surface of the water in the wet coagulation bath may be the distance (air gap) at which the polymer resin composition for producing a hollow fiber membrane mixed with the inner coagulant is exposed to the outside air.

In order to spin the polymer resin composition for producing a hollow fiber membrane mixed with the internal coagulant, the spinning nozzle may be connected to the polymer solution transfer line and the nozzle, or may be connected to a metering pump or nitrogen gas for pushing the polymer solution.

When the polymer resin composition for producing a hollow fiber membrane mixed with the internal coagulant is stabilized, it is pushed by a constant flow rate pump or a valve of nitrogen gas is opened to apply a certain pressure. And the discharge speed can be controlled according to the physical properties and properties of the hollow fiber membrane to be produced, and can be discharged at a speed of, for example, 1 cm to 30 cm per second.

Meanwhile, in the manufacturing method of the hollow fiber membrane of the embodiment, the produced hollow fiber membrane is heated to a temperature of 70 to 100 ° C to remove remaining solvent or the like, or a step of heating the hollow fiber membrane for 3 to 6 hours in a water bath And performing processing.

In addition, the method of the present invention may further include drying the hollow fiber membrane.

According to another embodiment of the present invention, a hollow fiber membrane containing a vinylidene fluoride-based polymer resin and a polymer substrate containing an organic phosphate and having an outer diameter of 0.5 to 5 mm and an inner diameter of 0.1 to 4.5 mm may be provided .

The hollow fiber membrane may have an outer diameter of 0.5 to 5 mm and an inner diameter of 0.1 to 4.5 mm, or an outer diameter of 0.5 to 2 mm and an inner diameter of 0.1 to 1.5 mm.

The hollow fiber membrane manufactured by using the above-described polymer resin composition for producing a hollow fiber membrane and having a high strength and excellent chemical resistance can realize a high water permeability and realize a stable and efficient water treatment. Particularly, the polymer base material included in the hollow fiber membrane of the embodiment may include a polymer resin having a high degree of crystallinity and a relatively small crystal size, thereby improving the strength and chemical resistance of the hollow fiber membrane.

More specifically, the vinylidene fluoride-based polymer resin, the organic phosphate, and the polymer resin composition for producing the hollow fiber membrane include the above-mentioned contents in the polymer resin composition for producing a hollow fiber membrane of one embodiment.

On the polymer substrate, pores having a maximum diameter of 0.001 to 2.0 m can be distributed.

The hollow fiber membrane of this embodiment may have a cut strength of 7.50 N / mm2 or more, or 8.50 N / mm2 to 20 N / mm2. The breaking strength can be measured using an In-Strong machine, and a hollow fiber membrane having a length of about 200 mm is prepared. The hollow fiber membrane is stuck to the upper and lower sample grips of the extruder and is stretched at a rate of 100 mm / min. The tensile strength can be measured by the cutting strength.

The hollow fiber membrane of this embodiment may have a net permeation rate of 250 to 1,500 L / m < 2 > * hr (60 cm Hg).

According to the present invention, there can be provided a hollow fiber membrane that has high strength and excellent chemical resistance, realizes high water permeability and enables stable and efficient water treatment, and such hollow fiber membrane.

1 is a cross-sectional SEM image (50 times) of a cross section of a hollow fiber membrane according to Example 1. Fig.
2 is a SEM enlarged image (2000 times magnification) of the cross section of the hollow fiber membrane of Comparative Example 1. FIG.
3 shows an SEM enlarged image (2000 times) of a cross-section of a hollow fiber membrane according to Example 2. Fig.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Example  And Comparative Example : Manufacture of hollow fiber membrane]

Example 1

A polymer resin composition comprising 40% by weight of a polyvinylidene fluoride resin (PVDF) and an aromatic phosphate ester metal salt of the following formula (2), 10% by weight of N-methyl-2-pyrrolidone and 50% by weight of gamma- And a spinning solution was prepared by mixing at 170 占 폚 for 3 hours. At this time, the content of the phosphoric acid ester metal salt in the polymer resin composition was 1,000 ppmw.

The prepared spinning solution was transferred to a nozzle together with an internal coagulant. The internal coagulant was used in a weight ratio of N-methyl-2-pyrrolidone / polyethyleneglycol (PEG) 1: 1. The coagulation bath was filled with water, and the coagulation bath and the height of the nozzle were 4 cm apart. The coagulation bath temperature was maintained at 5 ° C and the water circulated periodically.

The PVDF hollow fiber membranes phase - inverted in the coagulation bath were passed through a washing tank and wound at the downstream end to produce a PVDF hollow fiber membrane. The prepared hollow fiber membrane was immersed in ethanol for 24 hours, and then the remaining solvent and inner coagulant were removed from the membrane, washed with water, and dried naturally.

(2)

Example 2

A hollow fiber membrane was prepared in the same manner as in Example 1, except that the content of the phosphoric acid ester metal salt in the polymer resin composition was changed to 2,000 ppmw.

Comparative Example 1

A hollow fiber membrane was prepared in the same manner as in Example 1, except that a phosphate ester metal salt was not added to the polymer resin composition.

 [ Experimental Example : Measurement and observation of physical properties of hollow fiber membrane]

Experimental Example 1 : DSC  Measure

In order to completely remove the internal solvent of the hollow fiber membrane sample obtained in the above Examples and Comparative Examples, it was dried in an oven at 120 ° C for 24 hours.

In order to remove the thermal history of the initial specimen, the temperature of the specimen was raised to 210 ° C and the specimen was allowed to stand for 10 minutes. Then, the specimen melted at 210 ° C / Lt; / RTI >

Under these conditions, the crystallization temperature (Tc), heat (J / g) and crystallization time (sec) are measured

DSC  Measurement result DSC Phosphate ester metal salt
Addition amount The crystallization temperature (Tc) Calories (J / g) Crystallization time (sec) Comparative Example 1 0 ppm 120 44.3 77 Example 1 1000 ppm 123 45.4 74 Example 2 2000 ppm 126 47.2 71

When the phosphate ester metal salt is added as in Examples 1 and 2, it can be seen that the crystallization temperature (Tc) and the heat amount increase as the addition amount is increased. This is because the crystallization temperature of the polymer is increased due to the increase of the crystallinity of the polymer due to the phosphate ester metal salt, and the amount of heat released while crystallizing the polymer chain is also increased. It can also be seen that the crystallization time was shortened in Examples 1 and 2 as well.

On the contrary, Comparative Example 1 had lower crystallization temperature and lower heat amount than Examples 1 and 2, and consequently it was confirmed that the phase transition time was longer.

Experimental Example 2 : Cutting strength

About 200 mm of the hollow fiber membrane obtained in the above Examples and Comparative Examples was prepared. The dimensions of the cross section of the hollow fiber membrane were measured by SEM or optical microscope.

Then, using the INSTRON equipment, the hollow fiber membrane was placed on the upper and lower sample grips, and the effective length between the grip and the grip was 100 mm, and the test speed was 100 mm / min. Strength.

Cutting strength measurement result Phosphate ester metal salt
Addition amount Cutting strength (N / mm2) Comparative Example 1 0 ppm 7.30 Example 1 1000 ppm 9.34 Example 2 2000 ppm 12.08

It was confirmed that when the phosphate ester metal salt was added as in Example 1 and Example 2, the breaking strength was improved as the addition amount was increased.

This is because the mechanical properties of the polymer base material of the hollow fiber membrane depend on the degree of crystallinity, so that the crystallinity of the polymer base material is improved by the addition of the phosphate ester metal salt, and the breaking strength is improved. On the other hand, when the nucleating agent was not added (Comparative Example 1), it was confirmed that the breaking strength was relatively weak as compared with the nucleating agent addition.

Experimental Example 3 : SEM Of hollow fiber membranes

The hollow fiber membranes obtained in the above Examples and Comparative Examples were dried and SEM images were measured. Specifically, the specimens of the hollow fiber membranes obtained in the above Examples and Comparative Examples were subjected to liquid nitrogen treatment, and then the specimen was broken, not the knife cutting, to observe the cross section.

OD, outer diameter, and inner diameter were specified through the observed SEM image. The hollow fiber membranes prepared in Examples and Comparative Examples had an OD (OD) of about 1,450 탆 and an ID (ID) of about 1,220 탆.

1 to 3, it was confirmed that polymer beads of a small size were formed in Examples 1 and 2 using a phosphate ester metal salt as compared with Comparative Example 1. [ As a result, many small beads are grown to improve the crystallinity and the crystallization temperature as a whole. Accordingly, the hollow fiber membranes of Examples 1 and 2 show relatively higher crystallinity of the polymer base material and higher breaking strength.

Claims (16)

10 to 70% by weight of a vinylidene fluoride-based polymer resin,
1 to 70% by weight of both solvents,
1 to 75% by weight of a poor solvent, and
0.001 wt% to 5 wt% of an aromatic phosphate ester metal salt represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R _6, R ₇ and R ₈ may be the same or different and each is hydrogen or a straight- Branched alkyl group,
X is a linear alkylene group having 1 to 2 carbon atoms or a linear or branched alkylene group having 3 to 5 carbon atoms,
n is 1 or 2,
When n is 1, M is an alkali metal, and when n is 2, M is an alkaline earth metal or hydroxy aluminum.
The method according to claim 1,
Wherein the vinylidene fluoride-based polymer resin comprises at least one member selected from the group consisting of a vinylidene fluoride homopolymer and a vinylidene fluoride copolymer.
The method according to claim 1,
Wherein the vinylidene fluoride-based polymer resin has a weight average molecular weight of 100,000 to 1,000,000.
The method according to claim 1,
The two solvents may be selected from N-methyl-2-pyrrolidone, dimethylformamide, N, N'-dimethyl acetamide, (Dimethylsulfoxide), and hexamethylphosphoric triamide. The spinning solution for manufacturing a hollow fiber membrane according to claim 1,
The method according to claim 1,
The poor solvent may be at least one selected from the group consisting of dibutyl phthalate, dimethyl phthalate, dioctyl sebacate, dioctyl adipate, gamma-butylolactone and propylene carbonate propylene carbonate, and the like.
delete delete Heating the spinning solution for manufacturing a hollow fiber membrane of claim 1 to 50 占 폚 to 175 占 폚;
Mixing the heated spinning solution for making a hollow fiber membrane with an internal coagulant; And
And spinning the spinning solution for preparing a hollow fiber membrane mixed with the internal coagulating agent into a wet coagulation bath.
9. The method of claim 8,
Wherein the internal coagulant comprises at least one selected from the group consisting of a good solvent and a non-solvent.
10. The method of claim 9,
Wherein the non-solvent comprises at least one member selected from the group consisting of water, ethylene glycol, alcohol solvents, ketone solvents, and polyalkylene glycols.
9. The method of claim 8,
Further comprising the step of maintaining the spinning solution for preparing a hollow fiber membrane mixed with the internal coagulating agent at a temperature of from 5 캜 to 30 캜.
9. The method of claim 8,
Wherein said wet coagulation bath is filled with water and is maintained at a temperature of from -10 占 폚 to 30 占 폚.
A vinylidene fluoride-based polymer resin, and a polymer base including an aromatic phosphate ester metal salt represented by the following formula (1)
A hollow fiber membrane having an outer diameter of 0.5 to 5 mm and an inner diameter of 0.1 to 4.5 mm;
[Chemical Formula 1]

In Formula 1,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R _6, R ₇ and R ₈ may be the same or different and each is hydrogen or a straight- Branched alkyl group,
X is a linear alkylene group having 1 to 2 carbon atoms or a linear or branched alkylene group having 3 to 5 carbon atoms,
n is 1 or 2,
When n is 1, M is an alkali metal, and when n is 2, M is an alkaline earth metal or hydroxy aluminum.
14. The method of claim 13,
Wherein voids having a maximum diameter of 0.01 탆 to 5.0 탆 are distributed on the polymer substrate.
14. The method of claim 13,
A hollow fiber membrane having a cutting strength of at least 7.50 N / mm 2.
14. The method of claim 13,
A hollow fiber membrane having a net permeation rate of 250 to 1,500 L / m 2 * hr (60 cm Hg).

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