JP5877855B2 - Multilayer thin film based reverse osmosis separation membrane using cross-linking between organic monomers and method for producing the same - Google Patents

Description

  The present invention relates to a reverse osmosis separation membrane based on a multilayer thin film utilizing cross-linking between organic monomers and a method for producing the same.

  The phenomenon in which the solvent moves through the separation membrane from a solution having a low solute concentration to a solution having a high solute concentration between two solutions separated by a semipermeable membrane is called an osmosis phenomenon. The pressure acting on the solution side where the concentration of solute is high is called osmotic pressure.

  When an external pressure higher than the osmotic pressure is applied, the solvent moves toward a solution having a low solute concentration, which is called reverse osmosis. Various salts and organic substances can be separated through a semipermeable membrane using the principle of reverse osmosis and a pressure gradient as a driving force. Reverse osmosis separation membranes using such reverse osmosis phenomenon are essential for separating substances at the molecular level and removing salt from salt water or sea water and supplying it as household, architectural, or industrial water. Used as a material.

  Commercial separation membranes are generally selected from polyamides through interfacial polymerization between an aqueous MPD (m-phenylene diamine) monomer and an organic solvent-like TMC (trimesoyl chloride) monomer on a porous support. It has been produced in the form of a composite for producing layers.

  Such a polyamide-based separation membrane has been widely used as a reverse osmosis separation membrane for over 30 years because of its excellent salt removal performance. However, a serious decrease in performance due to relatively low water permeability and membrane fouling has been pointed out as problems.

  Therefore, in order to reduce the energy and cost required for the seawater desalination process, it is necessary to develop a new reverse osmosis separation membrane having high water permeability and contamination resistance as well as a high salt removal rate. .

  The conventional selective layer manufacturing method using interfacial polymerization as a reverse osmosis separation membrane technology has a problem that it is difficult to control the thickness of the selective layer, the surface structure, and the structure of the crosslinking density due to the characteristics of bulk synthesis. Therefore, in recent years, in order to overcome this, LbL (Layer-by-Layer) using an electrostatic attractive force between polymer electrolytes in the form of an aqueous solution, that is, a multilayer thin film selective layer based on repeated lamination technology is manufactured. Attempts have been made to try. However, since the physicochemical structure of the thin film that can be manufactured is limited due to the limitation that the material to be laminated must be water-soluble, the salt removal rate and water permeability of the separation membrane are consequently reduced to the conventional commercialization. There is a problem that it does not reach the performance level of reverse osmosis membranes.

  In recent years, there have been reports of methods for producing multilayer thin films having various chemical structures by repeating cross-linking between organic monomers in the form of organic solvents. There is no optimization of the process in terms of solvent, concentration, etc., and pore filling in which the assembly fills the pores of the support, especially when laminating the LbL multilayer thin film on the porous support. There is a problem that an excessive stacking process is required depending on the phenomenon. Such excessive lamination not only increases the cost in the manufacturing process, but also causes the adverse effect of rapidly decreasing the water permeability of the manufactured separation membrane.

Korean Registered Patent Publication No. 10-1076221

Park et al. Journal of Materials Chemistry, 20, 2085-2091 (2010) Johnson et al. Journal of Polymer Science B, 50, 168-173 (2012) Qian et al. Langmuir, 28, 17803-17810 (2012)

  The present invention, when producing a reverse osmosis separation membrane used for desalination of seawater, produces a multilayer thin film-based reverse osmosis separation membrane having various chemical structures using cross-linking between organic monomers, By introducing an intermediate layer on the porous support, the pore filling phenomenon of the support that occurs in the process of laminating the LbL multilayer thin film is prevented, and a high water permeability and contamination resistance are achieved with a minimum number of layers. It is an object of the present invention to provide a reverse osmosis separation membrane and a method for producing the same that achieves the property and the salt removal rate.

  In order to achieve the above object, an embodiment of the present invention includes a porous support and an LbL (Layer-by-Layer) selection layer laminated thereon, An intermediate layer composed of a polymer nano thin film is included between the LbL selection layer, and the LbL selection layer includes a first selection layer including a first organic monomer and a second layer including a second organic monomer. A reverse osmosis separation membrane including a structure in which selective layers are stacked.

  An embodiment of the present invention is a method of manufacturing a reverse osmosis separation membrane as described above, wherein a porous support is dipped in a polymer nano thin film forming solution, and the porous support is formed on the porous support. Forming an intermediate layer on the intermediate layer, immersing the porous support on which the intermediate layer is formed in an organic solvent containing a first organic monomer, and forming a first selective layer on the intermediate layer A first selective layer forming step to be formed, and a porous support on which the first selective layer is formed are immersed in an organic solvent containing a second organic monomer, and the first selective layer is formed on the first selective layer. A reverse osmosis separation membrane manufacturing method comprising a second selective layer forming step of forming a second selective layer is provided.

  According to the reverse osmosis separation membrane based on the multilayer thin film using the organic monomer cross-linking according to the present invention and the manufacturing method thereof, compared with the reverse osmosis separation membrane manufactured by the conventional interfacial polymerization method, a high level of salt removal is achieved. Reverse osmosis separation membranes that achieve not only rates but also significantly improved water permeability and contamination resistance can be produced.

  In addition, according to the present invention, a multilayer thin film-based reverse osmosis separation membrane using organic monomer cross-linking and a method for manufacturing the same are used. By manufacturing and introducing an intermediate layer on the porous support, the effect of preventing the pore filling phenomenon that occurs during the lamination process of the LbL multilayer thin film is achieved, and separation is performed while using the minimum number of layers. A selective layer thin film having excellent performance can be realized.

It is a schematic diagram which shows the structure of the reverse osmosis separation membrane which concerns on one implementation example of this invention. It is a conceptual diagram which shows the process of manufacturing a reverse osmosis separation membrane according to one embodiment of the present invention. It is a figure which shows the surface SEM image of the separation membrane selection layer formed by the covalent self-assembly (LbL) between the organic monomers contained in the reverse osmosis separation membrane which concerns on one implementation example of this invention. It is a figure which shows the surface SEM image of the separation membrane selection layer formed by the interfacial polymerization according to the prior art as a comparative example of the present invention.

  As used herein, the term “self-assembly” or “LbL (Layer-by-Layer)” as used throughout this specification, including the claims and abstract, This means a technology that is extremely structurally stable by being connected by attractive force, hydrogen bond or covalent bond, and can realize a multilayer ultra-thin film regardless of the size or form of the support. In addition, the term “selective layer” in the present specification is used to include a first selective layer and a second selective layer that are repeatedly laminated one or more times. In this specification, the term “porous support” refers to a structure that is located in the lower layer of a thin film composed of multiple layers and maintains the form of the thin film, and includes a plurality of pores that penetrate the interior, the surface, or the structure. It means a structure in which (pore) exists. As used herein, the term “dipping” means that a specific object is immersed in a solution to form a film on the surface of the specific object.

  The present invention relates to a reverse osmosis separation membrane. Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

  FIG. 1 attached herewith is a view showing an exemplary form of a reverse osmosis separation membrane according to the present invention. Referring to FIG. 1, a reverse osmosis separation membrane according to an embodiment of the present invention includes a porous support A and LbL (Layer-by-Layer) selection layers C and D stacked on the porous support A, Between the porous support A and the LbL selective layers C and D, an intermediate layer B made of a polymer nano thin film is included, and the LbL selective layer is a first selective layer containing a first organic monomer. It includes a structure in which a second selective layer D containing C and a second organic monomer is laminated. As an example, the LbL selection layer of the reverse osmosis separation membrane may include one or more structures in which the first selection layer C and the second selection layer D are stacked.

According to an embodiment of the present invention, the component and form of the porous support are not particularly limited, but from the viewpoint of maintaining the separation ability of various salts and organic substances as part of the reverse osmosis separation membrane. Specifically, it may be an ultrafiltration level porous support having strong dissolution resistance to an organic solvent. More specifically, examples of the porous support include polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polysulfone, and the like. In one embodiment, the porous support has an air diameter of 1 to 500 nm.
v According to an embodiment of the present invention, the porous support includes an intermediate layer between the LbL selection layer stacked on the porous support, and the intermediate layer has a surface pore of the porous support. By closing, the number of LbL selection layers stacked thereon is reduced, and the LbL selection layer can be effectively formed. According to an embodiment of the present invention, the intermediate layer is not particularly limited as long as it has a high water permeability and can block pores on the surface of the porous support. Specifically, it may be a polymer nano thin film formed by interfacial polymerization or self-assembly.

  For example, the intermediate layer may be a nano thin film formed by interfacial polymerization between a polyfunctional amine and a polyfunctional acid chloride. At this time, the polyfunctional amine and the polyfunctional acid chloride are not particularly limited. , TMC). Alternatively, each may be piperazine (PIP) amine and an aliphatic trifunctional chloride. As another embodiment, the intermediate layer may be a polymer nano thin film formed by self-assembly of an anionic polyelectrolyte and a cationic polyelectrolyte on a surface of a support exhibiting a charge. At this time, the anionic polymer electrolyte is not particularly limited, and may be, for example, polyethylenimine (PEI) or poly (allylamine hydrochloride) (hereinafter, PAH). The cationic polymer electrolyte is not particularly limited, and examples thereof include poly (acrylic acid) (hereinafter referred to as PAA). In one embodiment, the charge-bearing support may include any general porous support (PAN, PVDF, Polysulfone) that may be used in the present invention. This is because the porous support exhibits a weak negative charge on the neutral aqueous solution without any special treatment. Alternatively, the support that exhibits the charge may be a porous support that has been subjected to NaOH aqueous solution treatment, UV-zone, or oxygen plasma surface treatment in order to increase the intensity of negative charge as necessary.

  According to the embodiment of the present invention, the thickness of the intermediate layer is not particularly limited, and the thinner the better, from the viewpoint of securing the water permeability of the finally manufactured reverse osmosis separation membrane. Specific examples of the thickness of the intermediate layer include 0.1 nm to 100 nm.

  According to an embodiment of the present invention, the LbL selection layer is stacked on the intermediate layer, and includes a first selection layer including a first organic monomer and a second organic monomer. The second selection layer including the body is configured to be stacked. The first selection layer and the second selection layer are stacked by a covalent bond between the first organic monomer and the second organic monomer contained in each. As an example, the LbL selection layer may repeatedly include a structure in which the first selection layer and the second selection layer are stacked one or more times, and the number of stacked first and second selection layers and The kind of the selection layer laminated | stacked on the lowest layer and the uppermost layer may be adjusted as needed.

  As an embodiment, the thickness of each of the first or second selective layers is not particularly limited. However, from the viewpoint of ensuring the water permeability of the reverse osmosis separation membrane to be finally produced, The thinner the better. For example, the thickness of one first or second selection layer may be 0.1 nm to 3.0 nm. In addition, the total thickness of the LbL selection layer including a single or a plurality of first selection layers and a second selection layer is not particularly limited, but ensuring the water permeability of the finally manufactured reverse osmosis separation membrane. Therefore, the thinner the better. In one embodiment, the total thickness of the LbL selection layer may have a range of 0.1 nm to 100 nm.

  For example, the first organic monomer included in the first selective layer may be dissolved in an organic solvent to form a covalent bond or a hydrogen bond with the surface of the intermediate layer. If it can be laminated | stacked by mutually covalent-bonding (crosslinking) with the 2nd organic monomer contained in this selective layer, it will not restrict | limit, Specifically, aromatic diamine is mentioned. For example, the first organic monomer may be an aromatic diamine including ortho-, meta-, or para-phenylenediamine (OPD, MPD, PPD).

  As one embodiment, the second organic monomer contained in the second selective layer is dissolved in an organic solvent and covalently bonded (crosslinked) with the first organic monomer in the first selective layer. As long as they can be laminated, there is no particular limitation, and specific examples thereof include multifunctional chloride. For example, the second organic monomer may be a polyfunctional group chloride containing TMC.

  As one embodiment, the first and second organic monomers may each have a size of 1 nm or less, and the reverse reaction can be achieved by controlling the crosslinking reaction in units of such molecular size. There is an effect of enabling structure control at a molecular level smaller than that in the osmosis separation membrane manufacturing method, that is, bulk interfacial polymerization.

  According to an embodiment of the present invention, a method of manufacturing a reverse osmosis separation membrane having the above-described configuration includes dipping a porous support in a polymer nano thin film forming solution, and then on the porous support. Forming an intermediate layer on the intermediate layer; immersing the porous support on which the intermediate layer is formed in an organic solvent containing a first organic monomer; and forming a first selective layer on the intermediate layer. A first selective layer forming step to be formed; and a porous support on which the first selective layer is formed is immersed in an organic solvent containing a second organic monomer, and the first selective layer is formed on the first selective layer. A second selective layer forming step of forming a second selective layer may be included. As one embodiment, the first selective layer forming step and the second selective layer forming step may be repeated one or more times.

  According to one embodiment, the intermediate layer forming step includes immersing the porous support in an aqueous polyfunctional amine solution, and then interfacially polymerizing the porous support in an aqueous solution of a polyfunctional acid chloride. It may include forming an intermediate layer on top. Alternatively, in one embodiment, the intermediate layer forming step may be performed by immersing the porous support in an anionic polymer electrolyte aqueous solution and then in a cationic polymer electrolyte aqueous solution for self-assembly, It may include forming an intermediate layer on top.

  According to an embodiment of the present invention, the manufacturing method further includes a washing step of washing the porous support on which the selective layer is formed with an organic solvent after the first and second selective layer forming steps. You can leave. In addition, the cleaning step may further include a step of cleaning with a cleaning solution.

  In more detail, the first selective layer is formed by fixing the porous support on which the intermediate layer is formed in an organic solvent in which the first organic monomer is dissolved. It can be manufactured by dipping for a period of time. The dip coating method is advantageous in terms of commercialization as compared with conventional spin-casting. On the intermediate layer of the porous support immersed in the organic solvent, a first selection is made by a covalent bond or a hydrogen bond between the first organic monomer dissolved in the organic solvent and the surface of the intermediate layer. A layer is formed.

  In one embodiment, the manufacturing method further includes a cleaning step of cleaning the porous support on which the first selective layer is formed with an organic solvent after the first selective layer is formed. May be. In the cleaning step, the cleaning may further include a cleaning liquid. That is, in the washing step after the first selective layer forming step, the porous support on which the selective layer is formed is immersed in an organic solvent in order to remove the unreacted first organic monomer. In this case, a cleaning liquid may be further included. At this time, the cleaning liquid is not particularly limited as long as it can clean the first organic monomer. The higher the solubility in the solvent, the better. Examples of the cleaning liquid include acetone, alcohol, tetrahydrofuran (THF), and water.

  In one embodiment, the second selective layer includes immersing the porous support in which the first selective layer is formed in an organic solvent in which the second organic monomer is dissolved for a certain period of time. Can be manufactured. On the first selective layer of the porous support immersed in the organic solvent, the second organic monomer dissolved in the organic solvent and the first organic monolayer on the first selective layer. A second selective layer is formed by covalent (cross-linking) bonding between the monomers.

  As an example, the manufacturing method may further include a cleaning step of cleaning the porous support on which the second selective layer is formed with an organic solvent after the second selective layer is formed. . In the cleaning step, the cleaning may further include a cleaning liquid. That is, in the washing step after the second selective layer forming step, the porous support on which the selective layer is formed is immersed in an organic solvent in order to remove the unreacted second organic monomer, At this time, a cleaning liquid may be further included. At this time, the cleaning liquid is not particularly limited as long as it can clean the second organic monomer, but a solvent having higher solubility in the second organic monomer is better. For example, toluene and tetrahydrofuran (THF) may be used as the cleaning liquid.

  As an embodiment, the organic solvent is not particularly limited as long as it does not dissolve the porous support and can dissolve the first organic monomer and the second organic monomer. In an exemplary embodiment, the organic solvent may be toluene, tetrahydrofuran (THF), or the like.

  As an embodiment of the present invention, the physicochemical structure of the first and second selective layers formed in the manufacturing process of the reverse osmosis separation membrane including the series of steps described above, and the reverse osmosis separation membrane finally produced The separation performance is controlled by the intermediate layer, the first organic monomer, the second organic monomer, the rinsing solution, or the organic solvent. Further, the separation performance of the reverse osmosis separation membrane to be finally produced can be determined by the number and thickness of the first and second selective layers, and the initial and final lamination stages.

  The reverse osmosis separation membrane manufacturing technology described above is a self-assembly (LbL) technology that utilizes cross-linking between organic monomers, compared to conventional technologies such as a selective layer manufacturing technology by interfacial polymerization. Therefore, it is possible to control the structure at a smaller molecular level, and as a result, it becomes easy to control the thickness, physicochemical structure, crosslink density or surface roughness of the manufactured reverse osmosis separation membrane. In addition, when forming the selective layer by self-assembly as described above, a multilayer thin film layer having a high crosslink density while having the minimum number of layers (thickness) can be manufactured, so that an excellent salt removal rate is obtained. The water permeability can be maximized by securing the diffusion resistance of the water molecules as well as ensuring it. Furthermore, since the surface roughness of the formed multilayer thin film layer can be minimized, the contamination of the reverse osmosis separation membrane is improved. Therefore, when the reverse osmosis separation membrane produced according to the present invention is applied to the seawater desalination process, it is possible to obtain an effect that contributes to energy and cost reduction required for the seawater desalination process. Also, in the reverse osmosis separation membrane manufacturing process, by introducing an intermediate layer on the porous support, the pore filling phenomenon that occurs in the subsequent laminating process of the selective layer (LbL multilayer thin film) can be prevented in advance. Thus, at the time of forming the selection layer, not only unnecessary excessive lamination can be prevented, but also the production efficiency can be improved.

  Hereinafter, the present invention will be described in more detail with reference to examples. These examples are merely for the purpose of illustrating the present invention and have ordinary knowledge in the art that the scope of the present invention should not be construed as being limited by these examples. It is obvious to the person.

Example 1
A reverse osmosis separation membrane according to an embodiment of the present invention was manufactured by the following method.

  First, polyacrylonitrile (PAN) was prepared as a porous support, washed with purified water, and then immersed in a 1 wt% PIP aqueous solution for 5 minutes. Subsequently, after removing an excessive amount of PIP solution adhering to the surface using a roller, a 0.05 wt% TMC hexane solution was poured onto the surface of the support and allowed to react for 3 minutes. Thereafter, the surface was washed with an excessive amount of hexane and then dried in an oven at 70 ° C. for 2 minutes.

  The support on which the intermediate layer was formed through the above process was first immersed in toluene for 20 minutes to fully soak the support in a medium, and then the support was immersed in a 1 wt% MPD toluene solution for 40 seconds. After the reaction, the sample was washed and immersed in acetone and toluene sequentially for 1 minute, and the sample was immersed in a 1 wt% TMC toluene solution for 40 seconds. Thereafter, washing was performed twice with toluene for 1 minute. At this time, the above-described series of processes was defined as the number of stacked layers. A multi-layer thin film was manufactured by repeating such a stacking process, and a multi-layer thin film having 10 layers was manufactured (Example 1).

Examples 2 and 3
A reverse osmosis separation membrane according to an embodiment of the present invention was manufactured in the same manner as in Example 1 except for the intermediate layer forming step.

  First, a PAN support as a porous support was immersed in a 2M NaOH aqueous solution at 40 ° C. for 2 hours. After washing the support with an excessive amount of purified water, the substrate was immersed in an aqueous 0.2 wt% PAH solution (pH 7.5) for 10 minutes, and the sample was washed twice with an excessive amount of purified water (pH 7.5) for 1 minute. Thereafter, the sample was immersed in a 0.2 wt% PAA aqueous solution (pH 3.5) for 10 minutes, and then the sample was washed twice with an excessive amount of purified water (pH 3.5) to form an intermediate layer. The subsequent LbL selective layer formation steps in Example 2 and Example 3 were performed in the same manner as in Example 1. Note that the cleaning liquid used in the cleaning step after the first selective layer lamination was different for toluene (Example 2) and acetone (Example 3).

Example 4
A reverse osmosis separation membrane according to an embodiment of the present invention was manufactured as follows.

  First, the PAN support was immersed in a 2M NaOH aqueous solution at 40 ° C. for 2 hours. After washing the support with an excessive amount of purified water, the substrate was immersed in 0.1 wt% PEI / 0.5 wt% NaCl aqueous solution (pH 7.0) for 30 minutes, and then an excessive amount of purified water (pH 7.0) for 2 minutes. The sample was washed multiple times. Subsequently, it was immersed in a 0.1 wt% TMC toluene solution for 3 minutes and then washed with an excessive amount of toluene to form an intermediate layer. The subsequent LbL selective layer formation step in Example 4 was performed in the same manner as in Example 1. The final number of layers to be stacked is 0, 2, 5, 10 layers (Examples 4a, 4b, 4c, 4d, respectively), which are different from each other.

Comparative Example 1
According to the prior art, polyacrylonitrile (PAN) as a porous support was prepared, and a selective layer was manufactured on the porous support using interfacial polymerization between MPD and TMC. Thus, the separation performance of the separation membrane produced by the interfacial polymerization method, which is a conventional separation membrane production method, and the LbL production method using a cross-linked laminate will be compared.

  Specifically, polyacrylonitrile (PAN) was prepared as a porous support, washed with purified water, and then immersed in a 1 wt% MPD aqueous solution for 5 minutes. After removing the excessive amount of MPD solution adhering to the surface using a roller, a 0.1 wt% TMC hexane solution was poured onto the surface of the support and allowed to react for 3 minutes. Thereafter, the surface was washed with an excessive amount of hexane and then dried in an oven at 70 ° C. for 2 minutes to produce a reverse osmosis separation membrane.

Experimental example 1
Separation performance in seawater desalination was measured for reverse osmosis separation membranes manufactured according to Examples 1 to 4 and Comparative Example 1.

Specifically, the reverse osmosis separation membranes manufactured according to Examples 1 to 4 and Comparative Example 1 were cut out as a sample having a diameter of 4.9 cm and attached to a cross-flow cell. At this time, the feed water was a 2,000 ppm NaCl aqueous solution, and the process pressure was set to 15.5 bar. The water permeability (L / m ² h) and salt (NaCl,%) removal rate were measured by measuring the amount of the solution filtered through the separation membrane and the concentration of NaCl contained in the solution after stabilization for 2 hours. Table 1 below shows the results measured by the experiment.

  Looking at the separation performance of the reverse osmosis separation membrane shown in the above table, in the case of Example 3, the salt removal rate (98. 9) superior to the reverse osmosis separation membrane of Comparative Example 1 according to the prior art. 2%) can be confirmed. In addition, it was confirmed that all the examples other than Example 3 showed improved water permeability as compared with Comparative Example 1.

  In particular, in the case of Example 1, the salt removal rate was slightly lower than that of Comparative Example 1, but the water permeability increased by 3 times or more. In addition, in the case of Example 4d, the water permeability increased by about 67% while showing the same level of salt removal rate as compared with Comparative Example 1.

  Therefore, referring to the experimental results, commercialization can be achieved by further optimizing the manufacturing process conditions of the reverse osmosis separation membrane (organic monomer concentration, solvent, washing liquid, intermediate layer, number of layers, etc.) according to the present invention. It is judged that a reverse osmosis separation membrane having a further improved water permeability while exhibiting a salt removal rate equal to or higher than that of the separation membrane can be obtained.

  In addition, a smooth surface in a reverse osmosis separation membrane is known to have higher fouling resistance than a rough surface, and thus the results shown in FIGS. 3a and 3b of the present invention are obtained. When referred to, it is expected that the contamination stability of the separation membrane by the LbL manufacturing method is superior to the separation membrane by the conventional manufacturing method.

  As described above, specific portions of the present invention have been described in detail, and such specific techniques are merely preferred embodiments for those having ordinary knowledge in the art, and the scope of the present invention is thereby limited. It will be clear that it is not limited. Thus, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.

A porous support B intermediate layer C first selective layer D second selective layer E organic solvent F washing solution (rinsing solution)

Claims (14)

A porous support and an LbL (Layer-by-Layer) selective layer laminated on top of the porous support;
Including an intermediate layer composed of a polymer nano thin film between the porous support and the LbL selective layer;
The LbL selection layer is seen containing a second selected layer are stacked structure including a first selective layer and the second organic monomer containing a first organic monomer,
The intermediate layer may be formed by interfacial polymerization between a polyfunctional amine and a polyfunctional acid chloride, or an anionic polyelectrolyte and a cationic polyelectrolyte may be formed on a surface of a support having a charge. A polymer nano thin film with a thickness of 100 nm or less formed by self-assembly,
The first organic monomer includes an aromatic diamine;
The reverse osmosis separation membrane , wherein the second organic monomer includes a multi-functional group chloride .   The reverse osmosis separation membrane according to claim 1, wherein the LbL selection layer includes one or more structures in which the first selection layer and the second selection layer are stacked. The reverse osmosis separation membrane according to claim 1 or 2 , wherein the porous support includes polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), or polysulfone. The reverse osmosis separation membrane according to any one of claims 1 to 3, wherein the aromatic diamine contains ortho-, meta-, or para-phenylenediamine . The reverse osmosis separation membrane according to any one of claims 1 to 4, wherein the polyfunctional group chloride contains trimesoyl chloride . The reverse osmosis separation membrane according to any one of claims 1 to 5, wherein the polyfunctional amine contains piperazine . The reverse osmosis separation membrane according to any one of claims 1 to 6, wherein the polyfunctional acid chloride contains trimesoyl chloride . The reverse osmosis separation membrane according to any one of claims 1 to 7, wherein the total thickness of the LbL selection layer is 100 nm or less. A method for producing a reverse osmosis separation membrane according to any one of claims 1 to 8 ,
An intermediate layer forming step of dipping the porous support in the polymer nanofilm forming solution to form an intermediate layer on the porous support;
A first selective layer forming step of immersing the porous support having the intermediate layer formed in an organic solvent containing a first organic monomer to form a first selective layer on the intermediate layer; and A porous support on which the first selective layer is formed is immersed in an organic solvent containing a second organic monomer to form a second selective layer on the first selective layer. Selective layer formation step;
A process for producing a reverse osmosis separation membrane, comprising: The intermediate layer forming step, the porous support immersed in the polyfunctional amine solution after immersion in the polyfunctional acid chloride (acid chloride) dissolved liquid is interfacial polymerization, forming an intermediate layer on top of the porous support The method for producing a reverse osmosis separation membrane according to claim 9 , comprising: In the intermediate layer forming step, the porous support is immersed in an anionic polymer electrolyte aqueous solution and then immersed in a cationic polymer electrolyte aqueous solution to be self-assembled to form an intermediate layer on the porous support. The method for producing a reverse osmosis separation membrane according to claim 9 , comprising: After the first and second selective layer forming steps, a washing step of washing each of the porous support formed with the first selective layer and the porous support formed with the second selective layer with an organic solvent. The method for producing a reverse osmosis separation membrane according to any one of claims 9 to 11 , further comprising: The method of manufacturing a reverse osmosis separation membrane according to claim 12 , wherein the washing step further comprises a step of washing with a rinsing solution. The method for producing a reverse osmosis separation membrane according to any one of claims 9 to 13 , wherein the first selective layer forming step and the second selective layer forming step are alternately repeated one or more times.