KR20140005489A - High flux reverse osmosis membrane comprising xanthene compound and manufacturing method thereof - Google Patents

Abstract

The present invention relates to: a reverse osmosis membrane which includes a porous supporter including a polysulfone layer, and a polyamide activation layer containing a xanthene compound formed on the porous supporter; and a production method thereof. The production method of the reverse osmosis membrane comprises the following steps: a step of forming the porous supporter; and a step of forming the polyamide activation layer by surface-polymerizing an aqueous solution containing the xanthene compound and a multifunctional acid halide compound solution on the porous supporter.

Description

High flux reverse osmosis membrane comprising xanthene compound and method for preparing same {High Flux Reverse Osmosis Membrane Comprising Xanthene Compound And Manufacturing Method Thereof}

The present invention relates to a high permeate flow rate reverse osmosis membrane comprising a xanthene compound and a method of preparing the same.

In the process of separating the materials using the reverse osmosis phenomenon, the substances that are dissolved in the solution are separated from the solvent by selective membranes such as microfiltration, ultrafiltration and reverse osmosis membranes. The reverse osmosis membrane is a kind of semi-permeable membrane, and when the salt is pressurized in one direction of the aqueous solution in which the salts are dissolved, by using the principle that separation of the solution and the solute occurs in a certain direction, to remove salts such as brackish water and sea water Thus, it has been used for desalination of industrial water, agricultural water, domestic water and the like with a relatively low salt and a large amount of water.

The conventional reverse osmosis membrane comprises a porous support including a polysulfone layer and a polyamide active layer on the porous support, and interfacially polymerizes a polyfunctional amine solution and an acid halogen organic solution on the porous support to form a polyamide active layer. It was prepared by the method.

The semi-saline desalination process and the seawater desalination process using the reverse osmosis membrane, when passing through the reverse osmosis membrane by pressing an aqueous solution in which salt or ions are dissolved, the salt or ions in the aqueous solution is filtered and purified through the membrane Water refers to the process of passing through a membrane. At this time, the applied pressure must be equal to or higher than the osmotic pressure of the aqueous solution, so that the higher the salinity of the aqueous solution, the greater the osmotic pressure and consequently the higher the pressure to be applied to the feed water, the more energy is consumed.

Therefore, the conditions to be provided for the reverse osmosis membrane for desalinating sea water and sea water containing a large amount of salt are not only excellent in the salt removing ability but also have a characteristic that a large amount of purified water can pass through the membrane even at a relatively low pressure, There must be a characteristic of overflow and flow rate.

Korean Laid-Open Patent Publication No. 2006-0065810 (published on June 14, 2006) relates to a method of manufacturing a reverse osmosis membrane of a polyamide-based reverse osmosis membrane having a high salt removal rate characteristic without a large flow rate reduction compared to a conventional reverse osmosis membrane, and is a microporous support on a nonwoven fabric. After immersing the surface of the substrate coated with a polyfunctional amine solution, the water layer on the surface is removed by the compression method, and in the preparation of a crosslinked polyamide reverse osmosis membrane obtained by interfacial polymerization in an organic solution, Disclosed is a method for preparing a reverse osmosis membrane, which comprises adding a step of swelling by dipping for a predetermined time in distilled water containing a base before being immersed in a functional amine solution.

On the other hand, the invention which is characterized by performing a post-treatment process after interfacial polymerization includes the invention of Korean Patent Laid-Open Publication No. 1999-0070132 (published on September 15, 1999), and the invention using a mixed organic solvent is Korea Korean Patent Laid-Open Publication No. 1999-0070134 (published on September 15, 1999), and an invention characterized by adding an additive to an organic solvent include Korean Patent Publication No. 1999-0019008 (published on March 15, 1999). .

As described above, as the prior art, various inventions provide a method for preparing a reverse osmosis membrane having improved salt removal rate and permeate flow rate, and a reverse osmosis membrane using the same, but an additional process is performed before the porous support is immersed in the polyfunctional amine solution. In addition, in the case of the invention for carrying out the post-treatment process after interfacial polymerization, the process is somewhat complicated and the cost increases. In addition, even in the case of the invention using a mixed organic solvent or adding an additive to the organic solvent, there is a limit in improving the permeation rate and the salt removal rate of the prepared reverse osmosis membrane.

Accordingly, the applicant of the present invention has invented the present invention as a result of research to invent a reverse osmosis membrane not only by improving the permeate flow rate but also by increasing the salt removal rate through a more effective and simple method.

Korean Unexamined Patent Publication No. 2006-0065810 (Published June 14, 2006) Korean Patent Publication No. 1999-0070132 (published on September 15, 1999) Korean Patent Publication No. 1999-0070134 (published on September 15, 1999) Korean Patent Publication No. 1999-0019008 (published on Mar. 15, 1999)

The present invention is to provide a method for producing a reverse osmosis membrane with improved permeate flow rate and salt removal rate and a reverse osmosis membrane using the same.

One embodiment of the present invention provides a reverse osmosis membrane including a porous support including a polysulfone layer and a polyamide active layer formed on the porous support and including a xanthene compound.

The xanthene-based compound may be represented by Formula 1.

[Formula 1]

In the above formula, R ₁ and R ₂ are each independently amino group, amino aryl oxy group, amino phenyl group, amino phenyl oxy group, amino phenol group, amino phenol oxy group, amino carboxy phenyl group, amino carboxy phenyl oxy group, amino carboxy phenol group , Amino carboxy phenol oxy group, amino sulfo phenyl group, amino sulfo phenyl oxy group, amino sulfo phenol group, amino sulfo phenol oxy group, amino aryl sulfinyl group and amino aryl sulfonyl group, A is flu Fluorene, Azulene, Naphthalene, Naphthalene, 1-Methylnaphthalene, Acenaphthene, Acenaphthylene, Acenaphthylene, Anthracene, Phenal Phenalene, Phenanthrene, Benzo (a) fluorine, Chrysene, Fluoranthene, Pyrene ) And a tetracene group (Tetracene), which may be substituted or unsubstituted with an alkyl group, a carboxy group, a hydroxy group, or a halogen group, respectively.

R ₁ and R ₂ may each independently be a substituted or unsubstituted amino phenoxy group.

The second embodiment of the present invention comprises the steps of forming a porous support and the reverse osmosis membrane manufacturing method comprising the step of interfacial polymerization of an aqueous solution and a multifunctional acid halide compound solution containing xanthene-based compound on the porous support to form a polyamide active layer To provide.

The xanthene-based compound may be represented by Formula 1.

[Formula 1]

In the above formula, R ₁ and R ₂ are each independently amino group, amino aryl oxy group, amino phenyl group, amino phenyl oxy group, amino phenol group, amino phenol oxy group, amino carboxy phenyl group, amino carboxy phenyl oxy group, amino carboxy phenol group , Amino carboxy phenol oxy group, amino sulfo phenyl group, amino sulfo phenyl oxy group, amino sulfo phenol group, amino sulfo phenol oxy group, amino aryl sulfinyl group and amino aryl sulfonyl group, A is flu Fluorene, Azulene, Naphthalene, Naphthalene, 1-Methylnaphthalene, Acenaphthene, Acenaphthylene, Acenaphthylene, Anthracene, Phenal Phenalene, Phenanthrene, Benzo (a) fluorine, Chrysene, Fluoranthene, Pyrene ) And a tetracene group (Tetracene), which may be substituted or unsubstituted with an alkyl group, a carboxy group, a hydroxy group, or a halogen group, respectively.

R ₁ and R ₂ may each independently be a substituted or unsubstituted amino phenoxy group.

The xanthene-based compound may be included in an amount of 0.01 to 10 wt% based on 100 wt% of the aqueous solution containing the xanthene-based compound.

The preparation method of the aqueous solution containing the xanthene compound is m-phenylenediamine, p-phenylenediamine, 1,3,6-benzenetriamine, 4-chloro-1,3-phenylenediamine, 6-chloro It may include one or more selected from the group consisting of -1,3-phenylenediamine, 3-chloro-1,4-phenylenediamine.

The reverse osmosis membrane of the present invention forms a polyamide active layer by interfacially polymerizing an aqueous solution containing a xanthene-based compound and a polyfunctional acid halide compound solution when the polyamide active layer is formed on a porous support, thereby improving both the salt removal rate and the water permeability. It can manufacture. In addition, the reverse osmosis membrane of the present invention including a polyamide active layer containing a xanthene compound may have good performances such as salt removal rate and water permeability.

The high permeation rate reverse osmosis membrane of the present invention provides a reverse osmosis membrane comprising a porous support including a polysulfone layer and a polyamide active layer formed on the porous support and comprising a xanthene compound.

The porous support may be formed by casting a polymeric material on a nonwoven fabric. As the nonwoven fabric material, for example, polyester, polycarbonate, microporous polypropylene, polyphenylene ether, polyvinylidene divinyl and the like may be used But is not limited thereto.

The porous support may have a thickness of 100 to 200 μm, 120 to 170 μm, or 140 to 150 μm. This is because if the thickness of the porous support is less than 100 탆, the reverse osmosis membrane is likely to be damaged because it can not withstand the pressure applied during the water treatment reverse osmosis membrane operation. If it is thicker than 200 탆, the surface roughness may become large, The performance of the membrane is likely to deteriorate because the pathway through which the water escapes is prolonged.

In addition, the pore size of the porous support is preferably 5 to 70 nm. This is because it is an effective range for selectively separating suspended substances, polysaccharides, proteins, and polymeric substances, which are generally known as substances capable of being separated from a porous support.

Examples of the polymeric material include polymeric materials such as polysulfone, polyethersulfone, polyethylene oxide, polyimide, polyamide, polyetherimide, polyetheretherketone, polyacrylonitrile, polymethylmethacrylate, polyethylene, poly Propylene, polymethylpentene, polymethyl chloride, and polyvinylidene fluoride may be used. In the present invention, polysulfone was used.

The polyamide active layer is formed on the porous support and performs the function of excluding the salt. In the present invention, the polyamide active layer is characterized in that it comprises a xanthene compound.

The xanthene-based compound may be represented by Formula 1.

[Formula 1]

In the above formula, R ₁ and R ₂ are each independently amino group, amino aryl oxy group, amino phenyl group, amino phenyl oxy group, amino phenol group, amino phenol oxy group, amino carboxy phenyl group, amino carboxy phenyl oxy group, amino carboxy phenol group , Amino carboxy phenol oxy group, amino sulfo phenyl group, amino sulfo phenyl oxy group, amino sulfo phenol group, amino sulfo phenol oxy group, amino aryl sulfinyl group and amino aryl sulfonyl group, A is flu Fluorene, Azulene, Naphthalene, Naphthalene, 1-Methylnaphthalene, Acenaphthene, Acenaphthylene, Acenaphthylene, Anthracene, Phenal Phenalene, Phenanthrene, Benzo (a) fluorine, Chrysene, Fluoranthene, Pyrene ) And a tetracene group (Tetracene), which may be substituted or unsubstituted with an alkyl group, a carboxy group, a hydroxy group, or a halogen group, respectively.

Alternatively, the xanthene compound may be represented by Formula 2.

(2)

In the above formula, the definitions for R ₁ , R _2, and A are the same as above.

Alternatively, the xanthene compound may be represented by Formula 3.

(3)

In the above formula, the definitions for R ₁ and R ₂ are the same as above.

More specifically, R ₁ and R ₂ may each be an independently substituted or unsubstituted amino phenoxy group.

In another aspect, the present invention provides a method for producing a reverse osmosis membrane comprising the step of forming a porous support and interfacial polymerization of an aqueous solution containing a xanthene-based compound and a solution of a polyfunctional acid halogen compound on the porous support to form a polyamide active layer. do.

The step of forming the porous support is a step of casting a polymeric material on the nonwoven fabric, and the thickness, pore size, etc. of the nonwoven fabric, the polymeric material, and the porous support are as described above.

In the present invention, a conventional technique for producing a porous support can be used without limitation. For example, there are a stretching method in which a molten polymer is formed into a sheet, a lamella structure is formed by heat treatment, uniaxial stretching is carried out to separate the crystal interface, a polymer (polymer And a phase separation method in which a solvent is heated and melted to form a sheet, a micro phase is separated, and then the solvent is uniaxially or biaxially stretched while being extracted and removed.

On the other hand, the polyamide active layer is formed on the porous support, and performs a function of excluding salt, polyamide by interfacial polymerization of an aqueous solution containing a xanthene-based compound and a polyfunctional acid halide compound solution on the porous support In the forming of the active layer, specifically, for example, the porous support is immersed in an aqueous solution containing a xanthene-based compound, and then interfacially polymerized by contacting a polyfunctional acid halide compound solution, and the excess aqueous solution on the porous support is By removing and drying, it may be a step of forming an active layer on the porous support.

The xanthene-based compound may be represented by Formula 1.

[Formula 1]

In the above formula, R ₁ and R ₂ are each independently amino group, amino aryl oxy group, amino phenyl group, amino phenyl oxy group, amino phenol group, amino phenol oxy group, amino carboxy phenyl group, amino carboxy phenyl oxy group, amino carboxy phenol group , Amino carboxy phenol oxy group, amino sulfo phenyl group, amino sulfo phenyl oxy group, amino sulfo phenol group, amino sulfo phenol oxy group, amino aryl sulfinyl group and amino aryl sulfonyl group, A is flu Fluorene, Azulene, Naphthalene, Naphthalene, 1-Methylnaphthalene, Acenaphthene, Acenaphthylene, Acenaphthylene, Anthracene, Phenal Phenalene, Phenanthrene, Benzo (a) fluorine, Chrysene, Fluoranthene, Pyrene ) And a tetracene group (Tetracene), which may be substituted or unsubstituted with an alkyl group, a carboxy group, a hydroxy group, or a halogen group, respectively.

Alternatively, the xanthene compound may be represented by Formula 2.

(2)

In the above formula, the definitions for R ₁ , R _2, and A are the same as above.

Alternatively, the xanthene compound may be represented by Formula 3.

(3)

In the above formula, the definitions for R ₁ and R ₂ are the same as above.

More specifically, R ₁ and R ₂ may be each independently a substituted or unsubstituted amino phenoxy group.

In addition, the xanthene-based compound may be included in an amount of 0.01 to 10% by weight based on the total weight of the aqueous solution containing the xanthene-based compound. Or, it may be included in 0.05 to 7% by weight, or 0.1 to 5% by weight. If the xanthene-based compound is less than 0.01% by weight relative to the total weight of the aqueous solution containing the xanthene-based compound, it is difficult to see the effect, and if it exceeds 10% by weight, it is difficult to effectively form pores for removing salts. to be.

On the other hand, in the above production method, the aqueous solution containing the xanthene-based compound is not limited thereto, but may further include an amine-based compound. The aqueous solution containing the xanthene-based compound is, for example, m-phenylenediamine, p-phenylenediamine, 1,3,6-benzenetriamine, 4-chloro-1,3-phenylenediamine, 6-chloro It may include one or more selected from the group consisting of -1,3-phenylenediamine, 3-chloro-1,4-phenylenediamine.

When the aqueous solution including the xanthene-based compound further includes the amine-based compound, there may be a difference in the pore size of the formed polyamide active layer, as compared with the other case. Therefore, in order to control the pore size of the polyamide active layer to be obtained, whether or not to add the amine-based compound to the aqueous solution containing the xanthene-based compound, and the type and content of the amine-based compound to be added may be selected. In the present invention, the type and content of the amine compound is not limited.

The polyfunctional acid halide compound solution is prepared by dissolving at least one reactant selected from the group consisting of polyfunctional acyl halides, polyfunctional sulfonyl halides, and polyfunctional isocyanates in an organic solvent. The polyfunctional acyl halides usable in the present invention may be one or more selected from the group consisting of trimezoyl chloride (TMC), isophthaloyl chloride (IPC) and terephthaloyl chloride (TPC).

The organic solvent may be an aliphatic hydrocarbon solvent such as halogenated hydrocarbons such as freons, hexane, cyclohexane, heptane, or n-alkane having 8 to 12 carbon atoms. At this time, it is preferable that the aliphatic hydrocarbon solvent used can dissolve 0.05 weight% or more of polyfunctional acyl halides. For example, n-alkanes having 5 to 12 carbon atoms, mixtures of structural isomers of saturated or unsaturated hydrocarbons having 8 carbon atoms, cyclic hydrocarbons having 5 to 7 carbon atoms, or mixtures of two or more of the above solvents may be used.

In addition, the polyamide active layer forming step may further include a washing step, the washing liquid is preferably water. The washing time is not particularly limited, but is performed from 12 hours to 1 day or less. The polyamide active layer forming step may further include a step of drying in air. The drying time is not particularly limited, but is preferably 1 hour or less.

Hereinafter, the present invention will be described in more detail by way of examples.

Example  One

18 wt% polysulfone was added to a N, N-dimethylformamide (N, N-dimethylformamide) solvent, and stirred at 80 ° C. for 12 hours or longer to obtain a uniform liquid phase, and 150 μm polysulfone was cast on the nonwoven fabric. The cast nonwoven fabric was immersed in water to make a porous support including a polysulfone layer. The prepared porous support was 1% by weight of 3 ', 6'-bis (4-aminophenoxy) -spiro (fluorene-9,9'-xanthene) {3', 6'-bis (4-aminophenoxy)- After soaking for 5 minutes in an aqueous solution containing spiro (fluorene-9,9'-xanthene), hereinafter referred to as 36B4AX.}, the excess aqueous solution on the porous support is removed using a compression roller and dried at room temperature for 1 minute. It was. Subsequently, the coated porous support was immersed in a solution of polyfunctional acid halogen compound containing 0.1% of trimesoyl chloride (hereinafter referred to as TMC) in Isol C (SKC Co., Ltd.) solvent. The organic solution was dried for 10 minutes in an oven at 60 ° C. The reverse osmosis membrane obtained by the above method was washed with a 0.2 wt% sodium carbonate aqueous solution at room temperature for 2 hours or more, and then rinsed with distilled water. A reverse osmosis membrane having a thickness of 180 μm was prepared in the same manner as above.

Example  2

A reverse osmosis membrane was prepared in the same manner as in Example 1, except that the concentration of 36B4AX was changed to 2 wt%.

Example  3

A reverse osmosis membrane was prepared in the same manner as in Example 1, except that the concentration of 36B4AX was changed to 3 wt%.

Example  4

A reverse osmosis membrane was prepared in the same manner as in Example 1, except that the concentration of 36B4AX was changed to 4 wt%.

Example  5

A reverse osmosis membrane was prepared in the same manner as in Example 1, except that the concentration of 36B4AX was changed to 5 wt%.

Example  6

A reverse osmosis membrane was prepared in the same manner as in Example 1, except for changing the concentration of 36B4AX to 0.5% by weight and adding 2% by weight of m-phenylenediamine to the aqueous solution.

Example  7

A reverse osmosis membrane was prepared in the same manner as in Example 1, except that the concentration of 36B4AX was changed to 1% by weight and 2% by weight of m-phenylenediamine was added to the aqueous solution.

Example  8

A reverse osmosis membrane was prepared in the same manner as in Example 1, except for changing the concentration of 36B4AX to 2% by weight and adding 2% by weight of m-phenylenediamine to the aqueous solution.

Comparative Example  One

A reverse osmosis membrane was prepared in the same manner as in Example 1, except that 2 wt% of m-phenylenediamine (m-phenylenediamine, hereinafter referred to as MPD) was added instead of 1 wt% of 36B4AX.

Experimental Example  One

The reverse osmosis membrane evaluation device is a GE Osmosis Sepa CF II cell, which includes a flat plate permeation cell, a high pressure pump, a reservoir, and a cooling device, and the structure of the flat plate permeation cell is cross-flowed. , The effective transmission area is 140 cm ² .

The washed membrane was installed in a permeation cell, and then preliminarily operated for about 1 hour using tertiary distilled water to stabilize the evaluation equipment. Subsequently, the instrument was operated for about 1 hour until the pressure and water permeability reached a steady state by replacing with an aqueous 32,000 ppm NaCl solution, and then the water permeated at 25 ° C. at a flow rate of 4500 ml / min at 800 psi for 8 to 10 minutes. The water permeability was calculated by measuring the amount. In addition, under the same conditions as described above, the removal rate was calculated by analyzing the salt concentration before and after the permeation using a conductivity meter. The results of the water permeability and salt removal rate are shown in Table 1 below.

division Salt Removal Rate (%) Water Permeability (GFD) Example 1 (Aqueous Solution Containing 1% by Weight 36B4AX) 97.1 27.5 Example 2 (Aqueous Solution Containing 2% by Weight 36B4AX) 97.7 30.1 Example 3 (Aqueous Solution Containing 3% by Weight 36B4AX) 98.1 31.2 Example 4 (Aqueous Solution Containing 4% by Weight 36B4AX) 97.9 28.2 Example 5 (Aqueous Solution Containing 5% by Weight 36B4AX) 97.9 23.5 Example 6 (Aqueous solution comprising 0.5 wt% 36B4AX and 2 wt% m-phenylenediamine) 98.9 38.5 Example 7 (Aqueous solution comprising 1 wt% 36B4AX and 2 wt% m-phenylenediamine) 99.3 39.8 Example 8 (Aqueous solution comprising 2 wt% 36B4AX and 2 wt% m-phenylenediamine) 99.1 39.6 Comparative Example 1 (Aqueous Solution Containing 2 wt% of m-phenylenediamine) 96.8 20.6

As shown in Table 1, when using the aqueous solution containing xanthene-based compound in the polyamide active layer forming step, the reverse osmosis membrane prepared through this showed an improved performance in terms of both salt removal rate and water permeability. Accordingly, it can be seen that the reverse osmosis membrane according to the present invention is a reverse osmosis membrane including a polyamide active layer containing a xanthene compound, and has good salt removal rate and water permeability.

In addition, comparing Examples 6 to 8 with Examples 1 to 5, in the polyamide active layer forming step, when using an aqueous solution containing a xanthene compound and an amine compound, an aqueous solution containing only xanthene compound alone The salt removal rate and water permeability were further increased compared to the case of using. Therefore, even in the case of using not only an aqueous solution containing xanthene-based compounds alone but also an aqueous solution containing both xanthene-based compounds and amine-based compounds, it is possible to obtain an effect of improving both the salt removal rate and the water permeability. It was found out.

Claims (8)

A porous support comprising a polysulfone layer; And
A reverse osmosis membrane formed on the porous support and including a polyamide active layer containing a xanthene compound. The method according to claim 1,
The xanthene compound is a reverse osmosis membrane that is represented by the formula (1).
[Chemical Formula 1]

In the above formula, R ₁ and R ₂ are each independently amino group, amino aryl oxy group, amino phenyl group, amino phenyl oxy group, amino phenol group, amino phenol oxy group, amino carboxy phenyl group, amino carboxy phenyl oxy group, amino carboxy phenol group , Amino carboxy phenol oxy group, amino sulfo phenyl group, amino sulfo phenyl oxy group, amino sulfo phenol group, amino sulfo phenol oxy group, amino aryl sulfinyl group and amino aryl sulfonyl group, A is flu Fluorene, Azulene, Naphthalene, Naphthalene, 1-Methylnaphthalene, Acenaphthene, Acenaphthylene, Acenaphthylene, Anthracene, Phenal Phenalene, Phenanthrene, Benzo (a) fluorine, Chrysene, Fluoranthene, Pyrene ) And a tetracene group (Tetracene), which may be substituted or unsubstituted with an alkyl group, a carboxy group, a hydroxy group, or a halogen group, respectively. The method according to claim 2,
R ₁ and R ₂ are each independently a substituted or unsubstituted amino phenoxy group reverse osmosis membrane. Forming a porous support; And
Method for producing a reverse osmosis membrane comprising the step of interfacial polymerization of an aqueous solution containing a xanthene-based compound and a polyfunctional acid halide compound solution on the porous support. The method of claim 4,
The xanthene compound is a reverse osmosis membrane manufacturing method represented by the formula (1).
[Chemical Formula 1]

In the above formula, R ₁ and R ₂ are each independently amino group, amino aryl oxy group, amino phenyl group, amino phenyl oxy group, amino phenol group, amino phenol oxy group, amino carboxy phenyl group, amino carboxy phenyl oxy group, amino carboxy phenol group , Amino carboxy phenol oxy group, amino sulfo phenyl group, amino sulfo phenyl oxy group, amino sulfo phenol group, amino sulfo phenol oxy group, amino aryl sulfinyl group and amino aryl sulfonyl group, A is flu Fluorene, Azulene, Naphthalene, Naphthalene, 1-Methylnaphthalene, Acenaphthene, Acenaphthylene, Acenaphthylene, Anthracene, Phenal Phenalene, Phenanthrene, Benzo (a) fluorine, Chrysene, Fluoranthene, Pyrene ) And a tetracene group (Tetracene), which may be substituted or unsubstituted with an alkyl group, a carboxy group, a hydroxy group, or a halogen group, respectively. The method according to claim 5,
R ₁ and R ₂ are each independently a substituted or unsubstituted amino phenoxy group reverse osmosis membrane manufacturing method. The method of claim 4,
The xanthene-based compound is 0.01 to 10% by weight relative to 100% by weight of the aqueous solution containing the xanthene-based compound manufacturing method of the reverse osmosis membrane. The method of claim 4,
The aqueous solution containing the xanthene compound is m-phenylenediamine, p-phenylenediamine, 1,3,6-benzenetriamine, 4-chloro-1,3-phenylenediamine, 6-chloro-1,3 -Phenylenediamine, 3-chloro-1,4-phenylenediamine Reverse osmosis membrane production method comprising at least one selected from the group consisting of.