KR20170079563A - Membrane - Google Patents
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- KR20170079563A KR20170079563A KR1020150190274A KR20150190274A KR20170079563A KR 20170079563 A KR20170079563 A KR 20170079563A KR 1020150190274 A KR1020150190274 A KR 1020150190274A KR 20150190274 A KR20150190274 A KR 20150190274A KR 20170079563 A KR20170079563 A KR 20170079563A
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- separation membrane
- sensitive adhesive
- diisocyanate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present application relates to a separation membrane, a method of manufacturing the same, and a water treatment module including the separation membrane. The present application relates to a separation membrane comprising a pressure-sensitive adhesive tape which is attached to a separation membrane with a high adhesive force so that the separation membrane can not be separated even when it is in contact with an external material such as seawater during use, And a water treatment module including the separation membrane.
Description
The present application relates to a separation membrane, a method of manufacturing the same, and a water treatment module including the separation membrane.
The separation membrane is a material capable of separating the mixture through selective permeation, including a seawater desalination process; Ultrapure water production; Manufacture of chemicals or chemicals; Drinking water production; And wastewater treatment.
The separation membrane can be used, for example, for water treatment. Studies on the application of separators for efficient supply of high quality living and industrial water, various domestic sewage and industrial wastewater have been conducted.
A separation membrane frequently used in a separation membrane for water treatment is a separation membrane using a polyamide-based polymer membrane. This separation membrane is a TFC membrane (Thin Film Composite membrane) comprising a polyamide-based thin film as an active layer, and is excellent in mechanical strength, thermal stability, chemical stability, hydraulic stability and separation selectivity. Due to such advantages, for example, a composite separator in which polysulfone is used as a porous support and polyamide is used as an active layer is frequently used (see, for example, Patent Document 1).
However, the polyamide-based composite membrane has a disadvantage that its performance is deteriorated even when it is exposed to a trace amount of chlorine or the like because it contains an amino group which is vulnerable to chlorine and chlorate, and thus a protective layer is formed on the surface of the active layer .
Since such a separation membrane is often used in a folded state in a water treatment module or the like, a reinforcing tape for protecting the separation membrane can be attached to the folded portion. However, if the folded membrane is exposed to seawater or the like, the reinforcing tape is detached and removed due to dissolution of the membrane, thereby deteriorating separation performance of the membrane.
The present application aims to provide a separation membrane, a method for producing the separation membrane, and a water treatment module including the separation membrane. The present application relates to a separation membrane comprising a pressure-sensitive adhesive tape which is attached to a separation membrane with a high adhesive force so that the separation membrane can not be separated even when it is in contact with an external material such as seawater during use, And a water treatment module including the separation membrane.
The present application is directed to a membrane. The separation membrane of the present application can be applied to a variety of uses including seawater desalination process, ultrapure water, manufacture of chemicals or chemicals, production of drinking water, and wastewater treatment, and can be used, for example, for water treatment.
The separation membrane of the present application comprises a porous support; An active layer; And a protective layer. The kind of the porous support, the active layer and the protective layer included in the separation membrane of the present application is not particularly limited.
Figure 1 shows an exemplary separation membrane of the present application. 1, the separation membrane comprises a
The type of the porous support included in the separation membrane is not particularly limited, and a general porous support in the separation membrane field can be used. For example, the porous support may be a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane or a reverse osmosis membrane. Such a porous support includes a glass plate; Synthetic resin films such as polyester films; Nonwoven fabric and polysulfone or nonwoven fabric-polyvinylidene fluoride, and the like.
The active layer formed on the porous support may be a known material. The active layer is commonly used as a polyamide-based active layer. Such an active layer may be applied to the present application, but an active layer suitable for the purpose may be used.
A protective layer is formed on the active layer. This protective layer is formed to protect the active layer which is vulnerable to external factors such as chlorine. As the protective layer, a known material can be used without any particular limitation. Generally, the protective layer is made of polyvinyl alcohol, glycerin, polyvinylpyrrolidone, sorbitol, or polyethylene glycol series polymer. In the present application, a protective layer containing such a polymer may also be used.
The separation membrane including the above-described structure can be manufactured in various forms. For example, the separation membrane may be manufactured in various forms including a flat membrane, a tubular membrane or a hollow fiber membrane.
An adhesive tape is attached to the protective layer of the separation membrane, and an isocyanate treatment layer may be present between the adhesive tape and the protective layer. The isocyanate-treated layer may be a layer formed by coating an isocyanate solution on the pressure-sensitive adhesive layer of the protective layer or the pressure-sensitive adhesive tape before the adhesion of the pressure-sensitive adhesive tape, as in the manufacturing method of a separation membrane described later. The isocyanate treatment layer may contain an isocyanate compound, and the compound may be present in the treatment layer in a state of reacting with the components of the pressure-sensitive adhesive layer and / or the protective layer. The isocyanate-treated layer may be formed over the entire surface of the pressure-sensitive adhesive layer or the protective layer, or may be formed in a part of the area.
The adhesive tape may be attached to the entire surface of the protective layer or may be attached to only a part of the protective layer. The adhesive tape is at least folded at the folded portion of the separator, that is, folded at the time of use or attached to the bent portion. As a result, the adhesive tape can efficiently reinforce the separator.
The adhesive tape may include a base film and a pressure-sensitive adhesive layer formed on one surface of the base film.
The type of the base film included in the adhesive tape is not particularly limited as long as it can have properties that can reinforce the separation membrane.
For example, cellulose-based films such as TAC (triacetyl cellulose); Polyethersulfone-based films; A polyester film such as a PET (poly (ethylene terephthalate)) film, a PBT (poly (butylenes terephthalate)) film or a PC (polycarbonate) film; A polyolefin film such as a PP (polypropylene) film, a PE (polyethylene) film or a COP (cycloolefin) film; Acrylic films, polyamide films, polyimide films, poly (vinyl chloride) (PVC) films; Or a polystyrene film may be used. The films may be unstretched films or monoaxially or biaxially stretched films. The base film may be a single layer film or a multilayer film of two or more layers.
The thickness of the base film can be set in an appropriate range in consideration of the reinforcing efficiency. For example, the base film may have a thickness within a range of 5 占 퐉 to 50 占 퐉.
A pressure-sensitive adhesive layer is present on one surface of the base film. The pressure-sensitive adhesive layer can be formed through a pressure-sensitive adhesive composition. For example, the pressure-sensitive adhesive composition may be coated on one side of the base film and dried or cured to form a pressure-sensitive adhesive layer.
The pressure-sensitive adhesive layer may include an adhesive polymer. As the adhesive polymer, an acrylic polymer, a urethane polymer, an olefin polymer, a silicone polymer, or the like can be used without particular limitation.
The acrylic polymer can be used in consideration of convenience in use and the like. As used herein, the term acrylic polymer may refer to a polymer comprising acrylic monomers as polymerized units. In the above, the acrylic monomer means acrylic acid, methacrylic acid or a derivative thereof. The acrylic polymer may include the acrylic monomer as a main component. In the present application, the term " main component " refers to a composition containing 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% . As used herein, the term " polymerized unit " may mean a form in which a monomer forms a part of an adhesive polymer through polymerization.
As the acrylic polymer, for example, a polymer comprising polymerized units of an alkyl (meth) acrylate and a crosslinkable comonomer can be used.
The alkyl (meth) acrylate is preferably an alkyl (meth) acrylate having a carbon number of 1 to 20, a carbon number of 1 to 16, a carbon number of 1 to 12, a carbon number of 1 to 8, or a carbon number of 1 (Meth) acrylate having an alkyl group of 4 to 4 can be used. The alkyl group in the above may be straight-chain, branched-chain or cyclic. Examples of such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (Meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate or lauryl (meth) acrylate. Of these, Can be selected and used.
The crosslinkable comonomer may mean a monomer having a crosslinkable functional group and having a functional group capable of copolymerizing with the alkyl (meth) acrylate. Examples of the crosslinkable functional group include a carboxyl group, a hydroxyl group, a glycidyl group, an isocyanate group or a nitrogen-containing functional group. BACKGROUND ART [0002] In the field of the production of an adhesive polymer, various known crosslinking functional groups and comonomers containing such functional groups can be used.
Examples of the crosslinkable comonomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (Meth) acrylate or 2-hydroxypropyleneglycol (meth) acrylate such as 2-hydroxyethyleneglycol (meth) acrylate or 8-hydroxyoctyl A comonomer having a hydroxy group such as a hydroxyalkylene glycol (meth) acrylate such as a carboxylate; (Meth) acryloyloxypropionic acid, 4- (meth) acryloyloxybutyric acid, acrylic acid dimer, itaconic acid, maleic acid, or And comonomers having a carboxyl group such as maleic anhydride.
The acrylic polymer may include, for example, 0.1 to 20 parts by weight or 0.1 to 15 parts by weight, relative to 100 parts by weight of the alkyl (meth) acrylate and the alkyl (meth) acrylate, polymerized units of the crosslinkable comonomer. Unless otherwise specified, the unit weight portion in the present specification may mean a weight ratio between the components. In this range, the tackiness and the cohesive force of the pressure-sensitive adhesive layer can be suitably maintained.
The weight ratio between the monomers can be controlled depending on the kind of the crosslinkable functional group. For example, in the case where the crosslinkable comonomer is the carboxyl group-containing comonomer, the adhesive polymer may be used in an amount of 0.1 to 20 parts by weight, more preferably 5 to 15 parts by weight, based on 100 parts by weight of the alkyl (meth) acrylate and the alkyl (meth) Or 5 to 10 parts by weight of a carboxyl group-containing comonomer, and in the case where the crosslinkable comonomer is the hydroxy group-containing comonomer, the pressure-sensitive adhesive polymer may comprise the alkyl (meth) acrylate and the alkyl 0.1 to 20 parts by weight, 0.1 to 18 parts by weight, 0.1 to 16 parts by weight, 0.1 to 14 parts by weight, 0.1 to 12 parts by weight, 0.1 to 10 parts by weight, 0.1 to 8 parts by weight, 0.1 to 6 parts by weight, 0.1 to 4 parts by weight, 0.5 to 3 parts by weight, 0.5 to 2 parts by weight or 0.5 to 1.5 parts by weight of polymerized units of the hydroxyl group-containing comonomer. In this range, the tackiness and the cohesive force of the pressure-sensitive adhesive layer can be suitably maintained.
The adhesive polymer may further comprise, for example, a polymerization unit of any other comonomer when necessary for the purpose of controlling the glass transition temperature and the like. Examples of the comonomer include (meth) acrylonitrile, (meth) acrylamide, N-methyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-vinylpyrrolidone, Nitrogen-containing monomers such as lactam and the like; Styrene-based monomers such as styrene or methylstyrene; Glycidyl group-containing monomers such as glycidyl (meth) acrylate; And carboxylic acid vinyl esters such as vinyl acetate, but are not limited thereto. These comonomers may be included in the polymer by selecting one kind or more than two types as appropriate according to need. Such a comonomer may be contained in the polymer in a proportion of, for example, 20 parts by weight or less, or 0.1 parts by weight to 15 parts by weight, based on 100 parts by weight of the alkyl (meth) acrylate.
The molecular weight of the adhesive polymer, for example, the weight average molecular weight is not particularly limited and may be, for example, from 300,000 to 3,000,000, from 300,000 to 2.5 million, from 300,000 to 2,000,000, from 300,000 to 1,500,000, 1 million, 500,000 to 1 million, or 500,000 to 900,000.
Such an adhesive polymer may be prepared by a conventional polymerization method such as solution polymerization, photo polymerization, bulk polymerization, suspension polymerization or emulsion polymerization, and the like. Can be manufactured.
The pressure-sensitive adhesive composition may further comprise a crosslinking agent. Accordingly, the pressure-sensitive adhesive polymer in the pressure-sensitive adhesive layer may be in a crosslinked state. The crosslinking state may be formed by the crosslinking agent. As used herein, the term crosslinking agent may mean a compound having two or more functional groups capable of reacting with the crosslinkable functional group of the adhesive polymer. Such a crosslinking agent can control the cohesive force of the pressure-sensitive adhesive and control the adhesive property.
The kind of the crosslinking agent is not particularly limited, and a known crosslinking agent may be used. As such a crosslinking agent, an isocyanate compound, an epoxy compound, an aziridine compound or a metal chelate compound can be exemplified, and one or two or more crosslinking agents can be appropriately selected in consideration of the crosslinkable functional group of the polymer. Examples of the isocyanate compound include tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, and naphthalene diisocyanate, An addition reaction product of an isocyanate compound and a polyol, or the like can be used. Examples of the polyols include triols such as trimethylol propane, alkylene glycols, dialkylene glycols, benzene diols (e.g., catechol, resorcinol or hydroquinone), benzene triols (eg, 1,2,3-benzene triol), dialcohol amine, tri alcohol amine, arabitol, mannitol, isomalt, glycerol, xylitol, sorbitol sorbitol, maltitol, erythritol, ribitol, dulcitol, lactitol, threitol, iditol or polyglycitol (for example, polyglycitol) and the like can be used. Examples of the epoxy compound include ethylene glycol diglycidyl ether, triglycidyl ether, trimethylol propane triglycidyl ether, N, N, N ', N'-tetraglycidylethylenediamine or glycerin diglycidyl ether And aziridine compounds such as N, N'-toluene-2,4-bis (1-aziridine carboxamide), N, N'-diphenylmethane- (1-aziridine carboxamide), triethylene melamine, bisisopropanoyl-1- (2-methyl aziridine), or tri-1-aziridinyl phosphine oxide. Can be used. As the metal chelate compound, there can be used a compound in which the polyvalent metal exists in a state of being poured into acetylacetone, ethyl acetate or the like. As the polyvalent metal, there can be used aluminum, iron, zinc, tin, , Magnesium or vanadium, and the like.
In the pressure-sensitive adhesive layer or the pressure-sensitive adhesive composition, the crosslinking agent may be contained in an amount of 0.01 to 20 parts by weight, 0.01 to 15 parts by weight, 0.01 to 10 parts by weight, or 0.01 to 5 parts by weight relative to 100 parts by weight of the adhesive polymer.
The pressure-sensitive adhesive layer or the pressure-sensitive adhesive composition may further comprise any components required in addition to the above components. Such components include silane coupling agents; Tackifiers; Epoxy resin; Ultraviolet stabilizer; Antioxidants; Coloring agent; Reinforcing agents; Filler; Defoamer; A surfactant, a plasticizer, and the like may be further included.
The thickness of the pressure-sensitive adhesive layer can be set in an appropriate range in consideration of adhesiveness and the like. For example, the pressure-sensitive adhesive layer may have a thickness within a range of 5 占 퐉 to 50 占 퐉.
An isocyanate-treated layer is present between the adhesive tape and the protective layer in the separation membrane or between the pressure-sensitive adhesive layer of the adhesive tape and the protective layer. Such a treatment layer can be formed by coating an isocyanate solution during the production of the separation membrane as described later.
The isocyanate-treated layer may contain at least one isocyanate compound selected from tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate and naphthalene diisocyanate, Or an addition reaction product of the at least one isocyanate compound and the polyol. Examples of the polyols include triols such as trimethylolpropane, alkylene glycols, dialkylene glycols, benzene diols (e.g., catechol, resorcinol or hydroquinone) , Benzenetriol (ex. 1,2,3-benzenetriol), dialcohol amine, tri alcohol amine, arabitol, mannitol, isomalt, glycerol, xylitol xylitol, sorbitol, maltitol, erythritol, ribitol, dulcitol, lactitol, threitol, iditol or Polyglycitol and the like can be used. Such an isocyanate compound may be present in such a state in the treatment layer or in a state of reacting with any component of the pressure-sensitive adhesive layer and / or the protective layer.
The thickness of the isocyanate-treated layer is not particularly limited, and can be adjusted within a range in which a desired adhesive force can be secured.
The separator of the present application basically includes the above elements, and if necessary, may further include known elements that can be applied to the separator.
The present application is also a method for producing a separator, which may be a method for producing the separator. The manufacturing method of the present application includes, for example, sequentially stacking a porous support; And adhering an adhesive tape to the protective layer of the laminate including the active layer and the protective layer with a pressure-sensitive adhesive layer.
In the above description, specific details of the components included in the separation membrane, such as the porous support, and the adhesive tape adhered thereto may be applied to the description or the known matters.
The manufacturing method may further include a step of applying an isocyanate solution to the pressure-sensitive adhesive layer or the protective layer before the adhering. The isocyanate solution can be applied to the pressure-sensitive adhesive layer for convenience of process. The isocyanate treatment layer described above can be formed by applying the coated isocyanate solution.
The method of applying the isocyanate solution is not particularly limited and a known method can be applied. For example, an isocyanate solution may be coated using a variety of coaters or dispensers, or an isocyanate solution may be applied to a sponge or cloth, and the coating may be performed using the sponge or cloth.
The isocyanate solution can be prepared by mixing an isocyanate compound and a solvent.
Examples of the isocyanate compound include compounds described above, such as tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, and naphthalene diisocyanate. One or more selected isocyanate compounds or additional reactants of the at least one isocyanate compound with the polyol may be used. Examples of the polyols include triols such as trimethylolpropane, alkylene glycols, dialkylene glycols, benzene diols (e.g., catechol, resorcinol or hydroquinone) , Benzenetriol (ex. 1,2,3-benzenetriol), dialcohol amine, tri alcohol amine, arabitol, mannitol, isomalt, glycerol, xylitol xylitol, sorbitol, maltitol, erythritol, ribitol, dulcitol, lactitol, threitol, iditol or Polyglycitol and the like can be used. Such an isocyanate compound may be present in such a state in the treatment layer or in a state of reacting with any component of the pressure-sensitive adhesive layer and / or the protective layer.
As the solvent which can be applied to the preparation of the isocyanate solution, a known solvent can be used without particular limitation. As the solvent, for example, ethyl acetate, ketone solvent (methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK)), aromatic solvent such as toluene, saturated hydrocarbon solvent (hexane, heptane, etc.) . However, it is preferable that an alcohol-based solvent is not applied as a solvent in order to ensure an appropriate effect.
The isocyanate solution may be prepared, for example, from about 0.1 to 10 wt%, from about 0.1 to 9 wt%, from about 0.1 to 8 wt%, from about 0.1 to 7 wt%, from about 0.1 to 6 wt% To 5% by weight or about 0.5% by weight to 5% by weight.
After coating the isocyanate solution in the same manner as above, adhering an adhesive tape, and if necessary, the separator can be manufactured through an appropriate post-treatment such as drying.
The present application also relates to a water treatment module comprising the separation membrane.
The specific type of the module that can be configured using the separation membrane is not particularly limited, and examples thereof include a plate & frame module, a tubular module, a hollow fiber module, or a spiral wound module. ) Modules. As long as the water treatment module includes the above-described separation membrane, the other types of constitution and the manufacturing method thereof are not particularly limited, and the general structure and means of this field can be employed without limitation.
The present application relates to a separation membrane comprising a pressure-sensitive adhesive tape which is attached to a separation membrane with a high adhesive force so that the separation membrane can not be separated even when it is in contact with an external material such as seawater during use, And a water treatment module including the separation membrane.
1 is a view showing the structure of an exemplary separation membrane.
The phthalonitrile resin and the like of the present application will be specifically described by way of examples and comparative examples, but the range of the resins and the like is not limited to the following examples.
1. Measurement of Adhesion
The separator prepared in Example or Comparative Example was allowed to stand for 1 day, then immersed in water at about 55 ° C for 5 minutes, removed from the separator using a tensile tester, and the adhesive tape was peeled at a peel rate of 300 mm / min and a peel angle of 180 degrees While peeling off, the adhesive strength was evaluated according to the following criteria.
<Evaluation Criteria>
A: When the adhesive tape is not separated from the protective layer and the separation membrane itself is broken
B: When the adhesive tape is peeled off naturally or without force
Production Example 1. Preparation of adhesive polymer (A)
N-butyl acrylate (n-BA) and acrylic acid (AA) were fed in a weight ratio of 93: 7 (n-BA: AA) to a 1 L reactor equipped with a cooling device Respectively. Subsequently, about 150 parts by weight of ethyl acetate (EAc) was added as a solvent to 100 parts by weight of the total of the monomers. To remove oxygen, nitrogen gas was purged for 60 minutes, AIBN (Azobisisobutyronitrile) as a initiator and dodecanediol as a chain transfer agent were added to 0.04 part by weight and 0.03 part by weight, respectively, relative to 100 parts by weight of the total amount of the monomers, and the reaction was diluted with ethyl acetate (EAc) An adhesive polymer solution having a weight average molecular weight of about 710,000 was prepared.
Production Example 2. Preparation of adhesive polymer (B)
(N-BA) and 4-hydroxybutyl acrylate (HBA) in a weight ratio of 99: 1 (n-butyl acrylate) to a 1 L reactor equipped with a cooling device, BA: HBA). Subsequently, about 150 parts by weight of ethyl acetate (EAc) was added as a solvent to 100 parts by weight of the total of the monomers. To remove oxygen, nitrogen gas was purged for 60 minutes, AIBN (Azobisisobutyronitrile) as a initiator and dodecanediol as a chain transfer agent were added to 0.04 part by weight and 0.03 part by weight, respectively, relative to 100 parts by weight of the total amount of the monomers, and the reaction was diluted with ethyl acetate (EAc) An adhesive polymer solution having a weight average molecular weight of about 700,000 was prepared.
Example 1.
Preparation of isocyanate solution
As an isocyanate compound, an isocyanate solution was prepared by diluting an additional reactant (BHS-8515, Toyochem) with TMP (trimethylol propane) of toluene diisocyanate to a concentration of about 3% by weight in ethyl acetate.
Production of adhesive tape
1 part by weight of an addition reaction product (BHS-8515, manufactured by Toyo Kagoshima) of TMP (trimethylol propane) of Toluene diisocyanate (TDI) as a crosslinking agent was uniformly mixed with 100 parts by weight of the solid content of the adhesive polymer (A) To prepare a pressure-sensitive adhesive composition. Subsequently, the pressure-sensitive adhesive composition was coated on an oriented polypropylene (OPP) film (thickness: 25 μm) so that the pressure-sensitive adhesive layer had a thickness of about 25 μm and treated at 120 ° C. for 3 minutes to form a pressure- Respectively.
Preparation of Membrane
(Thickness: 100 m), a polysulfone porous layer (thickness: 50 m), a polyamide active layer (thickness: 100 nm) and PVA (poly (vinyl alcohol)) protection Layer (thickness: about 1 mu m) were sequentially laminated on the substrate. The prepared isocyanate solution was applied to the pressure sensitive adhesive layer of the manufactured pressure sensitive adhesive tape, and the pressure sensitive adhesive layer was attached to the PVA protective layer of the RO separation membrane to prepare a separation membrane.
Example 2.
Except that a solution prepared by diluting an addition reaction product (BXX-5627, Toyochemsa) of TMP (trimethylol propane) of XDI (Xylene Diisocyanate) to ethyl acetate at a concentration of about 3% by weight was used as an isocyanate solution A separation membrane was prepared in the same manner as in Example 1.
Example 3.
Except that a solution prepared by diluting an HDI (hexamethylene diisocyanate) -based trimer (Duranate TPA-100, Ashai Kasei) with ethyl acetate at a concentration of about 3% by weight was used as an isocyanate solution. The separation membrane was prepared.
Example 4.
Except that a solution prepared by diluting IPDI (isophorone diisocyanate) -based trimer (IPDI, Evonik) with ethyl acetate at a concentration of about 3 wt% was used as an isocyanate solution. In the same manner as in Example 1, .
Example 5.
0.3 parts by weight of an addition reaction product of TMP (trimethylol propane) of TDI (Toluene diisocyanate) as a crosslinking agent (BHS-8515, Toyocampa) was uniformly mixed with 100 parts by weight of a solid content of the adhesive polymer (A) To prepare a pressure-sensitive adhesive composition. Subsequently, the pressure-sensitive adhesive composition was coated on an oriented polypropylene (OPP) film (thickness: 25 μm) so that the pressure-sensitive adhesive layer had a thickness of about 25 μm and treated at 120 ° C. for 3 minutes to form a pressure- Respectively. A separator was prepared in the same manner as in Example 1, except that the pressure-sensitive adhesive tape prepared above was used.
Comparative Example 1
A separation membrane was prepared in the same manner as in Example 1, except that application of the isocyanate solution was not carried out.
Comparative Example 2
A separator was prepared in the same manner as in Example 1, except that ethyl acetate alone was applied instead of the isocyanate solution.
The evaluation results of the adhesive strength of each of the separators were as follows.
10: Porous support
20:
30: Protective layer
40: Adhesive tape
41: pressure-sensitive adhesive layer
42: base film
Claims (15)
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KR20020001035A (en) * | 2000-06-23 | 2002-01-09 | 노기호 | Multi-component composite membrane and method for preparing the same |
JP2007238939A (en) * | 2006-03-10 | 2007-09-20 | Natl Starch & Chem Investment Holding Corp | Reactive hot-melt adhesive containing non-polymeric aliphatic bifunctional material |
US20100140161A1 (en) * | 2008-12-09 | 2010-06-10 | Haynes Thomas N | Membrane leaf packet with reinforced fold |
KR20130103106A (en) * | 2012-03-09 | 2013-09-23 | (주)우리나노필 | Separator structure used in electrochemical device |
WO2013176508A1 (en) | 2012-05-23 | 2013-11-28 | 주식회사 엘지화학 | Polyamide-based reverse osmosis membrane having excellent initial permeate flow rate and method for manufacturing same |
KR20130143575A (en) * | 2010-10-26 | 2013-12-31 | 도레이 카부시키가이샤 | Separation membrane, separation membrane element and separation membrane production method |
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KR20020001035A (en) * | 2000-06-23 | 2002-01-09 | 노기호 | Multi-component composite membrane and method for preparing the same |
JP2007238939A (en) * | 2006-03-10 | 2007-09-20 | Natl Starch & Chem Investment Holding Corp | Reactive hot-melt adhesive containing non-polymeric aliphatic bifunctional material |
US20100140161A1 (en) * | 2008-12-09 | 2010-06-10 | Haynes Thomas N | Membrane leaf packet with reinforced fold |
KR20130143575A (en) * | 2010-10-26 | 2013-12-31 | 도레이 카부시키가이샤 | Separation membrane, separation membrane element and separation membrane production method |
KR20130103106A (en) * | 2012-03-09 | 2013-09-23 | (주)우리나노필 | Separator structure used in electrochemical device |
WO2013176508A1 (en) | 2012-05-23 | 2013-11-28 | 주식회사 엘지화학 | Polyamide-based reverse osmosis membrane having excellent initial permeate flow rate and method for manufacturing same |
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