KR20160123900A - Method for manufacturing water-treatment membrane - Google Patents
Method for manufacturing water-treatment membrane Download PDFInfo
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- KR20160123900A KR20160123900A KR1020150054724A KR20150054724A KR20160123900A KR 20160123900 A KR20160123900 A KR 20160123900A KR 1020150054724 A KR1020150054724 A KR 1020150054724A KR 20150054724 A KR20150054724 A KR 20150054724A KR 20160123900 A KR20160123900 A KR 20160123900A
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- isocyanate group
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- water treatment
- blocked isocyanate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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Abstract
Description
The present invention relates to a method for producing a water treatment separation membrane.
Due to the serious pollution and water shortage in recent years, it is urgent to develop new water resources. Studies on the pollution of water quality are aiming at the treatment of high quality living and industrial water, various domestic sewage and industrial wastewater, and interest in the water treatment process using the separation membrane having the advantage of energy saving is increasing. In addition, the accelerated enforcement of environmental regulations is expected to accelerate the activation of membrane technology. Conventional water treatment process is difficult to meet the regulations that are strengthened, but membrane technology is expected to become a leading technology in the water treatment field because it guarantees excellent treatment efficiency and stable treatment.
Liquid separation is classified into micro filtration, ultrafiltration, nano filtration, reverse osmosis, sedimentation, active transport and electrodialysis depending on the pores of the membrane. Among them, the reverse osmosis method refers to a process of desalting using a semi-permeable membrane which is permeable to water but impermeable to salt. When high-pressure water containing salt is introduced into one side of the semipermeable membrane, Will come out on the other side with low pressure.
In recent years, approximately 1 billion gal / day of water has been subjected to dechlorination through the reverse osmosis process. Since the first reverse osmosis process using the reverse osmosis in the 1930s was announced, many of the semi- Research was conducted. Among them, cellulose-based asymmetric membranes and polyamide-based composite membranes are the main commercial successes. The cellulosic membranes developed at the beginning of the reverse osmosis membrane have various drawbacks such as narrow operating pH range, high temperature deformation, high cost of operation due to high pressure, and vulnerability to microorganisms Is a rarely used trend.
On the other hand, the polyamide-based composite membrane is formed by forming a polysulfone layer on a nonwoven fabric to form a microporous support, and immersing the microporous support in an aqueous solution of m-phenylenediamine (hereinafter referred to as mPD) (TMC) in an organic solvent to form a polyamide layer by interfacial polymerization of the mPD layer in contact with the TMC. By contacting the nonpolar solution with the polar solution, the polymerization takes place at the interface only and forms a very thin polyamide layer. The polyamide-based composite membrane has higher stability against pH change, can be operated at lower pressure, and has excellent salt rejection ratio compared to conventional cellulose-based asymmetric membranes, and is currently the main species of water treatment separator.
The present specification is intended to provide a method for producing a water treatment separation membrane.
One embodiment of the present invention provides a method of manufacturing a semiconductor device, comprising: preparing a laminate including a porous support, a polyamide active layer provided on the porous support, and a polyvinyl alcohol (PVA) layer provided on the polyamide active layer; Preparing a pressure-sensitive adhesive film comprising a substrate and a pressure-sensitive adhesive layer comprising a compound containing a blocked isocyanate group (-NCO) on at least one side of the substrate; Attaching the adhesive film so that the polyvinyl alcohol (PVA) layer and the adhesive layer are in contact with each other; And a heating step of heating at least the region provided with the adhesive film to activate the compound containing the blocked isocyanate group (-NCO).
The water treatment separation membrane produced according to one embodiment of the present invention is advantageous in that the adhesion strength between the water treatment separation membrane and the adhesive tape is excellent even when a long time passes in water.
The water treatment separation membrane produced according to one embodiment of the present invention has an advantage that the cracking rate of the region folded by the adhesive film is remarkably reduced.
The method for producing a water treatment separation membrane according to one embodiment of the present invention can manufacture a water treatment separation membrane having excellent durability through a simple process.
The method for producing a water treatment separation membrane according to one embodiment of the present invention can prevent the isocyanate group in the adhesive film during use from reacting with moisture in the air to lower the activity of the isocyanate group upon bonding the water treatment separation membrane and the pressure sensitive adhesive film . In addition, the method of manufacturing a water treatment separation membrane according to one embodiment of the present invention can control the activity of an isocyanate group in an adhesive film through a simple heating process.
FIG. 1 illustrates the structure of a water treatment separator manufactured according to an embodiment of the present invention.
2 is a cross-sectional view of a water treatment separator fabricated according to an embodiment of the present invention.
When a member is referred to herein as being "on " another member, it includes not only a member in contact with another member but also another member between the two members.
Whenever a component is referred to as "comprising ", it is understood that it may include other components as well, without departing from the other components unless specifically stated otherwise.
Due to the nature of the water treatment separator, it is essential to maintain adhesion in water as it will operate in water. Furthermore, the polyvinyl alcohol (PVA) layer of the water treatment separation membrane has a problem that the adhesive strength with the adhesive film deteriorates with time due to the swelling property in water. If the adhesive force between the adhesive film and the water treatment separator is reduced and the adhesive film is separated from the water treatment separator membrane, the adhesive film may be physically damaged by the water treatment separator membrane, which may cause deterioration of the performance of the water treatment separator membrane. Therefore, it is necessary to develop a water treatment separation membrane in which water adhesion between the water treatment separation membrane and the pressure sensitive adhesive film is maintained in water, and the present inventors have developed a method for producing the following water treatment separation membrane.
Hereinafter, the present invention will be described in more detail.
One embodiment of the present invention provides a method of manufacturing a semiconductor device, comprising: preparing a laminate including a porous support, a polyamide active layer provided on the porous support, and a polyvinyl alcohol (PVA) layer provided on the polyamide active layer; Preparing a pressure-sensitive adhesive film comprising a substrate and a pressure-sensitive adhesive layer comprising a compound containing a blocked isocyanate group (-NCO) on at least one side of the substrate; Attaching the adhesive film so that the polyvinyl alcohol (PVA) layer and the adhesive layer are in contact with each other; And a heating step of heating at least the region provided with the adhesive film to activate the compound containing the blocked isocyanate group.
The polyvinyl alcohol (PVA) layer not only prevents the polyamide active layer from being dried and damaged, but also protects the polyamide active layer from external physical and chemical factors.
The blocked isocyanate group-containing compound is activated through heating to maintain adhesion between the water treatment separator and the adhesive film. Particularly, even when the polyvinyl alcohol (PVA) layer swells in water, the adhesive force of the adhesive film can be maintained.
The blocking may mean treating the isocyanate group such that the isocyanate group is deactivated. Specifically, the blocking may be an addition of an additional substituent to the isocyanate group such that the isocyanate group is inactivated.
The adhesive film may be one having a base material and an adhesive layer on one side of the base material, and attaching the side provided with the adhesive layer toward the member to be adhered. According to one embodiment of the present disclosure, the adhesive layer may have viscoelasticity that is fluid at room temperature.
According to one embodiment of the present disclosure, the adhesive layer may include a compound containing the blocked isocyanate group in the adhesive material.
According to one embodiment of the present disclosure, the adhesive layer can be formed by applying a composition comprising a solvent, an acrylic resin, and a compound containing a blocked isocyanate group onto at least one side of the substrate. In addition, the adhesive film may be provided with a release film on the adhesive layer. Specifically, when the adhesive film is adhered to the water treatment separation membrane, the adhesive film may be attached such that the polyvinyl alcohol (PVA) layer and the adhesive layer are in contact with each other after removing the release film.
According to one embodiment of the present invention, the acrylic resin is not limited as long as it is an acrylic resin used for adhesive application. Specifically, according to one embodiment of the present invention, the acrylic resin may be an acrylic resin containing an -OH group.
According to one embodiment of the present invention, the content of the blocked isocyanate group-containing compound may be 0.1 part by weight or more and 3 parts by weight or less based on 100 parts by weight of the solid content of the acrylic resin.
According to one embodiment of the present invention, the compound including the blocked isocyanate group can improve the adhesive force of the adhesive film in water even if it is contained only in a small amount in the composition. Specifically, according to one embodiment of the present invention, the compound containing the blocked isocyanate group may exhibit a sufficiently excellent effect even if it is contained in an amount of 0.1 part by weight to 3 parts by weight based on 100 parts by weight of the solid content of the acrylic resin.
When the content of the blocked isocyanate group is within the above range, the adhesive film can be strongly bonded to the laminate through a heating step.
According to one embodiment of the present invention, the solvent can be used without limitation as long as it is capable of dissolving the acrylic resin and the compound containing a blocked isocyanate group.
When the shape of the water treatment separation membrane is physically processed, the pressure sensitive adhesive film can increase the physical strength of the water treatment separation membrane and prevent cracking. In addition, the adhesive film may serve to protect the water treatment separator from external physical impact or the like.
Since the polyvinyl alcohol (PVA) layer has a property of dissolving in water, it can be removed through the operation of the water treatment separator. However, the activated isocyanate group of the compound containing the blocked isocyanate group and the hydroxyl group (-OH) of the polyvinyl alcohol (PVA) layer forms a strong bond, so that even when the polyvinyl alcohol (PVA) layer is dissolved and removed, The bonding between the amide active layer and the adhesive film can be maintained. Specifically, according to one embodiment of the present disclosure, the activated isocyanate group of the compound containing the blocked isocyanate group and the hydroxyl group (-OH) of the polyvinyl alcohol (PVA) layer forms a urethane bond, It is possible to maintain a strong adhesive force with the polyvinyl alcohol (PVA) layer or the polyamide active layer. According to one embodiment of the present invention, the urethane bond remains between the adhesive film and the polyamide active layer to maintain the adhesive force of the adhesive film even if the polyvinyl alcohol (PVA) layer is dissolved by water can do.
According to one embodiment of the present invention, the thickness of the adhesive layer may be 1 占 퐉 or more and 50 占 퐉 or less. Specifically, according to one embodiment of the present invention, the thickness of the adhesive layer may be 10 占 퐉 or more and 30 占 퐉 or less, and 20 占 퐉 or more and 30 占 퐉 or less.
According to an embodiment of the present invention, the step of attaching the adhesive film may further include the step of folding the water treatment separator so that the area to which the adhesive film is adhered is folded.
According to one embodiment of the present invention, the water treatment separator may be folded so as to have two or more layers as one sheet. In this case, since there is a risk that cracks may occur in the folding region of the water treatment separation membrane, the adhesive film may be provided in the folding region to prevent cracking. Further, the adhesive film strongly bonds with the polyvinyl alcohol (PVA) layer or the polyamide active layer due to the bonding structure of the isocyanate group and the hydroxyl group (-OH), and specifically, the strong bonding state is maintained even at the terminal portion of the adhesive film The damage of the water treatment separation membrane can be minimized and the performance deterioration can be prevented.
FIG. 1 illustrates the structure of a water treatment separator manufactured according to an embodiment of the present invention.
2 is a cross-sectional view of a water treatment separator fabricated according to an embodiment of the present invention.
1, an
According to one embodiment of the present invention, the heating step may be performed at a temperature of 80 ° C or more and 100 ° C or less, or 170 ° C to 190 ° C or less.
According to one embodiment of the present invention, when the isocyanate composition is a low temperature curable type, the blocked isocyanate group may be activated through a heating step at a temperature of 80 ° C or more and 100 ° C or less. Specifically, when the isocyanate composition is a low-temperature curing type, the blocked isocyanate group may be activated through a heating step at a temperature of 85 캜 to 95 캜.
According to one embodiment of the present invention, when the isocyanate composition is a high-temperature curable type, the blocked isocyanate group may be activated through a heating step at a temperature of 170 ° C or more and 190 ° C or less. Specifically, according to one embodiment of the present invention, when the isocyanate composition is a high temperature curable type, the blocked isocyanate group may be activated through a heating step at a temperature of 175 ° C or higher and 185 ° C or lower.
According to one embodiment of the present disclosure, the heating step may be performed with a heating time of 20 minutes to 1 hour. Specifically, according to one embodiment of the present disclosure, the heating step may be performed with a heating time of 30 minutes or more.
In general, a compound containing an isocyanate group may lose its activity by reacting with water in the air, and therefore, it is inconvenient to keep it in a sealed state. Specifically, when a compound containing an isocyanate group is exposed to the outside for a long time, an isocyanate group in an isocyanate group-containing adhesive layer reacts with water in the air, thereby deteriorating the physical properties of the adhesive layer.
Accordingly, the present inventors have found that, by blocking the compound containing an isocyanate group to facilitate the storage of the pressure-sensitive adhesive film and to easily control the activity of the isocyanate group to maximize the bonding between the water treatment separator and the pressure- Method. The compound containing the blocked isocyanate group has no activity when the heating step is not carried out, and thus does not react with moisture in the air. Therefore, the adhesive film comprising the blocked isocyanate group is easy to store, and the activity of the isocyanate group can be controlled through a simple heating step. Specifically, through the heating step, the blocking can be removed to activate the isocyanate group.
According to one embodiment of the present invention, through the heating step, the activated isocyanate group of the compound containing the blocked isocyanate group may be bonded to the hydroxyl group (-OH) of the polyvinyl alcohol (PVA) layer.
The activated isocyanate group of the blocked isocyanate group-containing compound may bond with the hydroxyl group (-OH) of the polyvinyl alcohol (PVA) layer to strongly bond the adhesive film and the water treatment separator. Further, even when the polyvinyl alcohol (PVA) layer is swollen in water, the adhesive force of the adhesive film can be maintained, so that the adhesive film can prevent the water treatment separator from cracking, So that the water treatment separation membrane is not damaged.
According to one embodiment of the present disclosure, the blocked isocyanate group may be a combination of a block material with a monomolecular material containing an isocyanate group.
According to one embodiment of the present disclosure, the blocked isocyanate group may be a block agent combined with an isocyanate group. Specifically, according to one embodiment of the present disclosure, the blocked isocyanate group may be in the form of -NHCO-BL. The BL may mean that the block hydrogen is bonded to the isocyanate. Through the heating process, the blocked isocyanate may be separated into the isocyanate group (-NCO) and the blocking agent H-BL to activate the isocyanate group.
According to one embodiment of the present invention, the blocking agent may include at least one member selected from the group consisting of phenols, oximes, active methylenes,? -Caprolactams, triazoles, and pyrazoles . Specifically, according to one embodiment of the present disclosure, the blocking agent is selected from the group consisting of 3,5-dimethylpyrazole (DMP), dimethylmalonate (DEM), methylethylketoxime (MEKO), and epsilon -caprolactam And at least one selected from the group consisting of
Also, according to one embodiment of the present invention, the compound containing the blocked isocyanate group may be obtained by blocking a reaction product of a polyol with a monomolecular substance containing an isocyanate group. Specifically, according to one embodiment of the present invention, the compound containing the blocked isocyanate group may be a compound in which the block agent is bonded to a reactant of a polyol with a monomolecular substance containing an isocyanate group.
According to one embodiment of the present disclosure, the polyol may be trimethylolpropane.
According to one embodiment of the present invention, specific examples of the monocomponent substance containing the isocyanate group include toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, Tetramethyl xylylene diisocyanate, and naphthalene diisocyanate.
According to one embodiment of the present invention, the isocyanate group-containing compound is a compound selected from the group consisting of trimethylol propane adduct type TDI (toluene diisocyanate) isocyanate and TMP (trimethylol propane) adduct type XDI (xylene diisocyanate) And at least one of isocyanates.
According to one embodiment of the present invention, the compound containing the blocked isocyanate group is a compound having at least two isocyanate groups in one molecule, and is preferably an aromatic group such as tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, and naphthalene diisocyanate Diisocyanate; Aliphatic diisocyanates such as hexamethylene diisocyanate and dimer acid diisocyanate; Alicyclic diisocyanates such as isophorone diisocyanate and cyclohexane diisocyanate; And adducts of polyisocyanates with biuret type adducts, isocyanatomic adducts and the like are blocked with blocking agents such as phenols, oximes, active methylenes,? -Caprolactams, triazoles, and pyrazoles, Organotin catalysts such as dibutyl tin dilaurate are used as dissociation promoters for block agents. Commercially available products include, for example, Desmodel BL 1100, BL 1265 MPA / X, VPLS 2253, BL 3475 BS / SN, BL 3272 MPA, BL 3370 MPA, BL 4265 SN, Desmoser 2170, Commercially available products; DuraNAate 17B-60PX, TPAB80X, MF-B60X and MF-K60X manufactured by Asahi Kasei Kogyo; Available from Dainippon Ink and Chemicals, Inc., such as Banok DB-980K, D-550, B3-867 and B7-887-60; And NONPON POLYURETHANE HIGH-CERTIFICATION products such as Colonate 2515, 2507, 2513 and the like, which can be used alone or in combination.
According to one embodiment of the present invention, the substrate may be a general substrate film used in the art, and is not particularly limited. For example, polyolefins such as polyethylene and polypropylene, polyolefins such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, polyurethane, polyethylene terephthalate and polyethylene naphthalate, polycarbonate, polyetheretherketone, Polyimide, polyetherimide, polyamide, polyvinyl chloride, polyvinylidene chloride, paper, metal, and the like.
According to one embodiment of the present invention, the porous support may be formed with a coating layer of a polymer material on a nonwoven fabric. Examples of the polymeric material include polymeric materials such as polysulfone, polyethersulfone, polycarbonate, polyethylene oxide, polyimide, polyetherimide, polyetheretherketone, polypropylene, polymethylpentene, polymethyl chloride and polyvinylidene fluoride Rides, and the like may be used, but the present invention is not limited thereto. Specifically, polysulfone may be used as the polymer material.
According to one embodiment of the present invention, the polyamide active layer may be formed by interfacial polymerization of an aqueous solution containing an amine compound and an organic solution containing an acyl halide compound. Specifically, the polyamide active layer is formed by forming an aqueous solution layer containing an amine compound on a porous support; And contacting the organic solvent containing an organic solvent with an acyl halide compound on an aqueous solution layer containing the amine compound to form a polyamide active layer.
When the aqueous solution containing the amine compound is brought into contact with the organic solution, the amine compound coated on the surface reacts with the acyl halide compound to form a polyamide by interfacial polymerization and adsorbed on the microporous support to form a thin film. In the contact method, a polyamide active layer may be formed by a method such as dipping, spraying, or coating.
According to one embodiment of the present invention, a method of forming an aqueous solution layer containing an amine compound on the porous support is not particularly limited, and any method can be used as long as it is capable of forming an aqueous solution layer on a support. Specifically, a method of forming an aqueous solution layer containing an amine compound on the porous support includes spraying, coating, dipping, dropping, and the like.
At this time, the aqueous solution layer may be further subjected to a step of removing an aqueous solution containing an excess of the amine compound, if necessary. The aqueous solution layer formed on the porous support may be unevenly distributed when the aqueous solution present on the support is excessively large. If the aqueous solution is unevenly distributed, a non-uniform polyamide active layer may be formed by subsequent interfacial polymerization have. Therefore, it is preferable to remove the excess aqueous solution after forming the aqueous solution layer on the support. The removal of the excess aqueous solution is not particularly limited, but can be performed using, for example, a sponge, an air knife, nitrogen gas blowing, natural drying, or a compression roll.
According to one embodiment of the present invention, in the aqueous solution containing the amine compound, the amine compound is not limited as long as it is an amine compound used in the preparation of a water treatment separation membrane, but specific examples include m-phenylenediamine, p - phenylenediamine, 1,3,6-benzenetriamine, 4-chloro-1,3-phenylenediamine, 6-chloro-1,3-phenylenediamine, 3- Or a mixture thereof.
According to one embodiment of the present disclosure, the acyl halide compounds include, but are not limited to, for example, aromatic compounds having 2 to 3 carboxylic acid halides, such as trimethoyl chloride, isophthaloyl chlorides, Terephthaloyl chloride, and mixtures of at least one compound selected from the group consisting of terephthaloyl chloride.
According to one embodiment of the present invention, the organic solvent may be an aliphatic hydrocarbon solvent, for example, a hydrophobic liquid such as Freon and a water-immiscible hydrophobic liquid such as hexane, cyclohexane, heptane or alkane having 5 to 12 carbon atoms, An alkane having 5 to 12 carbon atoms and mixtures thereof such as IsoPar (Exxon), ISOL-C (SK Chem), and ISOL-G (Exxon) may be used.
One embodiment of the present invention provides a water treatment separation membrane produced by the above production method.
According to one embodiment of the present invention, the water treatment separation membrane can be used as a microfiltration membrane, an ultrafiltration membrane, a nano filtration membrane or a reverse osmosis membrane, Can be used.
One embodiment of the present invention provides a water treatment module including at least one of the above-mentioned water treatment separation membranes.
The specific type of the water treatment module is not particularly limited, and examples thereof include a plate & frame module, a tubular module, a hollow & fiber module, or a spiral wound module. In addition, as long as the water treatment module includes the water treatment separation membrane according to one embodiment of the present invention, other structures and manufacturing methods are not particularly limited and general means known in the art can be employed without limitation have.
On the other hand, the water treatment module according to one embodiment of the present invention has excellent salt removal rate and permeation flow rate, and is excellent in chemical stability, and thus can be used for water treatment devices such as household / industrial water purification devices, sewage treatment devices, have.
Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the embodiments described below. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art.
[ Manufacturing example ] - Production of acrylic resin
acrylate resin containing n-butyl acrylate (BA): hydroxybutyl acrylate (HBA) in a weight ratio of 99: 1, ethyl acrylate as a solvent based on 100 parts by weight of the acrylate resin, 150 parts by weight of ethyl acetate, and 0.02 part by weight of dodecane thiol based on 100 parts by weight of the acrylate resin. Subsequently, azobisisobutyronitrile (AIBN) as an initiator was added to the composition in an amount of 0.04 parts by weight based on 100 parts by weight of the acrylate resin. Then, after the reaction for 4 hours, it was diluted with ethyl acetate so as to have a viscosity as shown in Table 1 below.
(%)
(cP)
In the physical properties of the acrylic resin in Table 1, TSC is the total solid content, Mw is the weight-average molecular weight, PDI is the polydispersity index, and Viscosity is the viscosity do.
[Comparative Example 1]
A composition was prepared by adding an acrylic resin prepared according to Preparation Example to an ethyl acetate solvent. The composition was coated on a PET substrate to a thickness of 25 탆 and then dried to form a pressure-sensitive adhesive layer having a thickness of 25 탆. Then, a release film was provided on the adhesive layer to produce an adhesive film.
The adhesive film thus prepared was allowed to stand for 1 day, 3 days, and 7 days, cut to a width of 25 mm, and the release film was removed to obtain a laminate including a polyvinyl alcohol (PVA) layer provided on the polyamide active layer To prepare a water treatment membrane.
[Comparative Example 2]
A composition was prepared by adding 0.2 part by weight of isocyanate of a trifunctional group of TMP (trimethylol propane) adduct type TDI (toluene diisocyanate) to 100 parts by weight of an acrylic resin solid component prepared according to Preparation Example in ethyl acetate solvent. The composition was coated on a PET substrate to a thickness of 25 탆 and then dried to form a pressure-sensitive adhesive layer having a thickness of 25 탆. Then, a release film was provided on the adhesive layer to produce an adhesive film.
The adhesive film thus prepared was allowed to stand for 1 day, 3 days, and 7 days, cut to a width of 25 mm, and the release film was removed to obtain a laminate including a polyvinyl alcohol (PVA) layer provided on the polyamide active layer To prepare a water treatment membrane.
[Comparative Example 3]
A water treatment separation membrane was prepared as in Comparative Example 2, except that the content of isocyanate was adjusted to 0.6 part by weight with respect to 100 parts by weight of the solid content of the acrylic resin.
[Comparative Example 4]
A water treatment separation membrane was prepared as in Comparative Example 2, except that the content of isocyanate was adjusted to 1 part by weight with respect to 100 parts by weight of the solid content of the acrylic resin.
[Comparative Example 5]
A water treatment separation membrane was prepared as in Comparative Example 2, except that the content of isocyanate was adjusted to 2 parts by weight based on 100 parts by weight of the solid content of the acrylic resin.
[Comparative Example 6]
A water treatment separation membrane was prepared as in Comparative Example 2, except that the content of isocyanate was adjusted to 3 parts by weight with respect to 100 parts by weight of the solid content of the acrylic resin.
The water treatment separator prepared according to the comparative example was allowed to stand in water at 55 ° C for 5 minutes, and then the adhesive film and the laminate were peeled off and the adhesive strength of the adhesive film in water was tested.
Further, the residual isocyanate and the adhesive strength of the pressure-sensitive adhesive films of comparative examples in which the water-treated separator was prepared after storing the pressure-sensitive adhesive film in the same manner as in the comparative example except for the content of isocyanate and the different conditions are shown in Table 2 below.
In Table 2, the PA layer means the polyamide layer of the laminate, and the IR value means the fraction of the isocyanate group of the pressure-sensitive adhesive relative to the carbonyl group. The higher the IR value, the more isocyanate is present, It means that it can exhibit a high bonding force at the time of bonding.
The adhesive force is in g / in unit, which means a force applied to peel a distance of 1 inch after 30 minutes from adhering the adhesive film.
When the adhesive strength is less than 300 g / in, the adhesive film adheres to the water treatment separator and is gently adhered to the PA layer after peeling off after 30 minutes, so that the PA layer is not damaged. Therefore, the adhesive force measured in the state of not destroying the PA layer in Table 2 means that the adhesive force is very weak.
The IR value refers to the fraction of isocyanate groups relative to the carbonyl group measured by Fourier transform infrared spectroscopy (FTIR).
According to Table 2, in the case of attaching the adhesive film according to Comparative Example 1 not containing an isocyanate group, the adhesive force can not be maintained in water, and in the case of the adhesive film containing an unblocked isocyanate group, It can be seen that the water adhesion by the isocyanate group is remarkably lowered. Specifically, according to the comparative example, it can be seen that, when the adhesive film is attached after being stored for 3 days or more, the adhesion force in water is unexpected.
Further, in the case of the pressure-sensitive adhesive films according to Comparative Examples 2 to 6 including unblocked isocyanate groups, the isocyanate group may remain when an isocyanate group which is not blocked in excess is included although it also reacts with the -OH group of the pressure-sensitive adhesive. However, in this case, the isocyanate group reacts with moisture in the air over time, and the IR value decreases.
This can be confirmed by maintaining the IR value in a vacuum atmosphere in which contact with air is minimized. However, it is obvious that storing the adhesive film in a vacuum state is disadvantageous in terms of maintenance cost and equipment.
[Example 1]
A composition containing 0.2 part by weight of a blocked isocyanate compound having 3.5-Dimethyl Pyrazole (DMP) as an isocyanate blocking agent was prepared on 100 parts by weight of the solid content of the acrylic resin prepared according to Preparation Example, And then dried to form a pressure-sensitive adhesive layer having a thickness of 25 탆. Then, a release film was provided on the adhesive layer to produce an adhesive film.
The adhesive film thus prepared was allowed to stand for 1 day, 3 days, and 7 days, cut to a width of 25 mm, and the release film was removed to obtain a laminate including a polyvinyl alcohol (PVA) layer provided on the polyamide active layer And heated at 100 DEG C for 30 minutes to activate an isocyanate group in the adhesive film to prepare a water treatment separation membrane.
[Example 2]
A water treatment separation membrane was prepared in the same manner as in Example 1, except that the content of blocked isocyanate group-containing compound was adjusted to 0.6 parts by weight with respect to 100 parts by weight of the acrylic resin solid fraction.
[Example 3]
A water treatment separation membrane was prepared in the same manner as in Example 1, except that the content of the blocked isocyanate group-containing compound was adjusted to 1 part by weight based on 100 parts by weight of the solid content of the acrylic resin.
[Example 4]
A water treatment separation membrane was prepared in the same manner as in Example 1, except that the content of the blocked isocyanate group-containing compound was adjusted to 2 parts by weight based on 100 parts by weight of the solid content of the acrylic resin.
[Example 5]
A water treatment separation membrane was prepared in the same manner as in Example 1, except that the content of the blocked isocyanate group-containing compound was adjusted to 3 parts by weight based on 100 parts by weight of the solid content of the acrylic resin.
Each of the water treatment membranes prepared according to the above examples was adhered with an adhesive film, left for one day, and left in water at 55 ° C for 5 minutes. Then, the adhesive film and the laminate were peeled off, and the adhesive force of the adhesive film in water was tested.
Table 3 shows the residual isocyanate and the adhesive strength of the pressure-sensitive adhesive films of comparative examples in which the water-treated separator was prepared after storing the pressure-sensitive adhesive film in the same manner as in the comparative example except that the content of isocyanate and the content of isocyanate were different.
In Table 3, the PA layer means the polyamide layer of the laminate, and the IR value means the fraction of the isocyanate group of the pressure-sensitive adhesive relative to the carbonyl group. The higher the IR value, the more isocyanate is present, It means that it can exhibit a high bonding force at the time of bonding.
The IR value in Table 3 means the fraction of the isocyanate group relative to the carbonyl group measured by Fourier transform infrared spectroscopy (FTIR) before the heating step after attachment of the adhesive film.
According to Table 3, in the case of the adhesive film comprising a blocked isocyanate group, the isocyanate group stably exists even after the storage time of the adhesive film, and the adhesive force of the adhesive film can be increased through the heating process after adhesion of the adhesive film .
In other words, it can be seen that the ease of storage after production of the pressure-sensitive adhesive film is improved in Examples, compared with the comparative examples, and it is understood that the adhesion of the pressure-sensitive adhesive film in water can be greatly improved through a simple heating process.
101: Water treatment membrane
201: Adhesive film
301: Folding area
Claims (11)
Preparing an adhesive film having a substrate and an adhesive layer comprising a compound having a blocked isocyanate group on at least one side of the substrate;
Attaching the adhesive film so that the polyvinyl alcohol (PVA) layer and the adhesive layer are in contact with each other; And
And a heating step of heating at least a region provided with the adhesive film to activate the compound including the blocked isocyanate group.
Wherein the adhesive layer is formed by coating a composition comprising a solvent, an acrylic resin and a compound containing a blocked isocyanate group on at least one surface of the substrate, followed by drying.
Wherein the content of the blocked isocyanate group-containing compound is 0.1 part by weight or more and 3 parts by weight or less based on 100 parts by weight of the solid content of the acrylic resin.
Wherein the thickness of the pressure-sensitive adhesive layer is 1 占 퐉 or more and 50 占 퐉 or less.
Further comprising the step of folding the water treatment separator so that the area to which the adhesive film is adhered is folded after the step of attaching the pressure sensitive adhesive film.
Wherein the heating step is performed at a temperature of 80 ° C or higher and 100 ° C or lower, or 170 ° C or higher and 190 ° C or lower.
Wherein the heating step is performed at a heating time of 20 minutes to 1 hour.
Through the heating step, the activated isocyanate group of the blocked isocyanate group-containing compound is bonded to the hydroxyl group (-OH) of the polyvinyl alcohol (PVA) layer.
Wherein the blocked isocyanate group is a block material combined with a monomolecular material containing an isocyanate group.
Wherein the block agent comprises at least one selected from the group consisting of phenols, oximes, active methylenes,? -Caprolactams, triazoles, and pyrazoles.
Wherein the blocked isocyanate group-containing compound is a block-treated product of a reaction product of a mono molecular substance containing an isocyanate group and a polyol.
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| KR1020150054724A KR101966827B1 (en) | 2015-04-17 | 2015-04-17 | Method for manufacturing water-treatment membrane |
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| KR1020150054724A KR101966827B1 (en) | 2015-04-17 | 2015-04-17 | Method for manufacturing water-treatment membrane |
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| KR20160123900A true KR20160123900A (en) | 2016-10-26 |
| KR101966827B1 KR101966827B1 (en) | 2019-04-08 |
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| KR1020150054724A KR101966827B1 (en) | 2015-04-17 | 2015-04-17 | Method for manufacturing water-treatment membrane |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007100088A (en) * | 2005-09-30 | 2007-04-19 | General Electric Co <Ge> | Hydrophilic membrane and method for forming the same |
| US20100140161A1 (en) * | 2008-12-09 | 2010-06-10 | Haynes Thomas N | Membrane leaf packet with reinforced fold |
| KR20100073795A (en) | 2008-12-23 | 2010-07-01 | 주식회사 엘지화학 | Polymer compositions, water-treatment membranes and water-treatment modules comprising the same |
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2015
- 2015-04-17 KR KR1020150054724A patent/KR101966827B1/en active IP Right Grant
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007100088A (en) * | 2005-09-30 | 2007-04-19 | General Electric Co <Ge> | Hydrophilic membrane and method for forming the same |
| US20100140161A1 (en) * | 2008-12-09 | 2010-06-10 | Haynes Thomas N | Membrane leaf packet with reinforced fold |
| KR20100073795A (en) | 2008-12-23 | 2010-07-01 | 주식회사 엘지화학 | Polymer compositions, water-treatment membranes and water-treatment modules comprising the same |
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| KR101966827B1 (en) | 2019-04-08 |
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