JP4141566B2 - Method for producing a film having an impermeable portion - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a membrane having a porous layer in which an impermeable portion is formed in a part of the membrane, and more specifically, the membrane having a porous layer is a flat membrane, and the impermeable portion is More particularly, the present invention relates to a method of manufacturing a membrane formed in a shape surrounding a permeation portion of the flat membrane, and more specifically, a portion of the membrane is formed by closing pores of the membrane having a porous layer using an energy ray curable compound. The present invention relates to a method of forming an impermeable portion in the range.
[0002]
A membrane having a porous layer with an impermeable portion formed by the production method of the present invention is used for filtration, purification, recovery, concentration, dialysis, air purification in fields such as chemistry, biochemistry, medicine, food, pharmaceuticals, and the environment. Used in devices such as liquid gas exchange, membrane distillation, and pervaporation, and devices such as sensors, diagnostic agents, and analyzers, especially for devices that are integrated with microsynthesizers and analyzers in these fields of use. Is preferred.
[0003]
[Prior art]
As a method for producing a porous membrane having an impermeable portion, Japanese Patent Application Laid-Open No. 2-6827 discloses that the porous filter is structurally changed to a film state by heating a part of the porous filter so that the impermeable portion is formed. A method of forming is disclosed. JP-A-6-192467 discloses a polymerizable solution (I) that forms a porous body by irradiation with energy rays and a polymerizable liquid (II) that forms a non-porous polymer by irradiation with energy rays. Are disposed on the same support so as to be in contact with each other and cured by irradiating them with energy rays.
[0004]
[Problems to be solved by the invention]
However, in the method disclosed in the above Japanese Patent Laid-Open No. 2-6827, the thickness of the impermeable portion is inevitably thinner than that of the permeable portion. Therefore, when used for a minute separation membrane device, leakage from the seal portion Tended to occur. Further, in the method disclosed in JP-A-6-192467, the membrane is limited to a porous membrane, and the pore diameter is disturbed near the boundary between the porous portion and the non-porous portion. When formed, the pore size distribution of the filtration membrane tended to be widened.
[0005]
Furthermore, in an attempt to close the pores constituting the porous layer by applying a melt-type adhesive to the porous layer of the membrane having the porous layer and to form an impermeable portion, the melt-type adhesive is It was difficult to penetrate deeply into the pores, and it was difficult to completely block the porous layer over the entire thickness direction of the membrane. In addition, in an attempt to close the pores by applying a thermosetting adhesive or a solution-type adhesive, the adhesive infiltrates even a portion that should remain as a permeation portion, so that a minute permeation portion is formed. It was difficult to form.
[0006]
The problem to be solved by the present invention is that it is possible to produce a membrane in which the thickness of the impermeable portion is not thinner than the thickness of the permeated portion, and it is possible to produce a porous membrane excellent in pore diameter distribution, and the pores in the impermeable portion are completely An object of the present invention is to provide a method for producing a film having an impermeable portion, which can form a minute permeable portion or an impermeable portion while being closed, and can be produced by a simple process.
[0008]
[Means for Solving the Problems]
The present invention solves the above problems.And manyThe energy ray curable compound of the irradiated part is filled by filling the energy ray curable composition containing the energy ray curable compound in the pores of the membrane having the porous layer and irradiating the energy ray in a part of the range. Method for producing a film having an impermeable spot that forms an impermeable spot in a part of the film having a porous layer by removing an uncured energy ray-curable compound after curingThe lawprovide.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
A membrane having a porous layer used in the production method of the present invention (hereinafter sometimes simply referred to as “membrane”) has a layer composed of a large number of pores communicating with each other in the membrane. A membrane through which the liquid can flow in a direction parallel to the surface of the membrane through the pores of the layer, and the pores are open on at least one surface of the membrane. is there. As such a membrane, a membrane in which the entire membrane is a porous layer, i.e., a so-called porous membrane in which pores communicate from the stock solution side to the filtrate side and liquid can permeate, or a porous support layer and a non-porous membrane. Examples include so-called heterogeneous membranes and composite membranes composed of porous separation layers. The porous membrane may be an isotropic membrane whose average pore size does not change in the depth direction of the membrane, or an asymmetric membrane comprising a separation layer having a small pore size and a support layer having a large pore size. Examples of the porous membrane may be a reverse osmosis membrane, an ultrafiltration membrane, a microfiltration membrane, a nonwoven fabric or a filter paper. Furthermore, it may be a hydrophilic membrane usually used for filtration, or a hydrophobic membrane used for a deaeration membrane or a distillation membrane. Examples of the membrane composed of the porous layer and the non-porous layer include a gas separation membrane, a degassing membrane, a dehumidifying membrane, and a pervaporation membrane. Among these membranes, a porous membrane, particularly a microfiltration membrane, is particularly preferable because the effect of the present invention is particularly exerted because it is required to be miniaturized. The average pore diameter of the porous layer is arbitrary, but is preferably in the range of 0.01 to 10 μm because the effects of the present invention are exhibited. The film thickness is arbitrary, but a range of 0.05 to 0.3 mm is preferable because the effect of the present invention is exhibited. ,
[0010]
The shape of the membrane is arbitrary, and it may be a flat membrane (flat membrane) or a hollow shape such as a tubular shape, a capillary shape, or a hollow fiber shape. Since an effect is exhibited, it is preferable. The size and shape of the membrane are arbitrary, and those having a suitable size and shape can be used depending on the required filtration area and the like. The shape can be, for example, a circle, a square, or other complicated shapes, but a minute separation membrane device can be formed by laminating and adhering to a plate-like member on which a channel is formed. Preferably there is. The area of the membrane is 0.1mm²~ 100cm²A small film in the range is preferable because the effects of the present invention are exhibited. Of course, a larger or longer film can be used, and a plurality of “films having non-permeable portions” can be formed in the film and cut into a film having a desired size.
[0011]
The material of the film is arbitrary, and can be a metal; a semiconductor; a glass; a crystal such as quartz; a ceramic; carbon; a polymer, etc., but a polymer is preferable from the viewpoint of high flexibility of use and cost. . The material of the film may be a composite of a plurality of materials.
[0012]
Examples of the polymer used for the material of the porous membrane include styrene-based polymers such as polystyrene, poly-α-methylstyrene, styrene / maleic acid copolymer, styrene / acrylonitrile copolymer; porsulfone, polyethersulfone, and the like. Polysulfone polymers; Poly (meth) acrylate polymers such as polymethyl methacrylate and polyacrylonitrile; Polymaleimide polymers; Polycarbonate polymers; Cellulose polymers such as cellulose acetate and methyl cellulose; Polyurethane polymers; Vinyl chloride and vinylidene chloride Chlorine-containing polymers; polyamide polymers such as nylon 6, nylon 66 and aromatic polyamide; polyimide polymers such as polyimide and polyetherimide; Polyolefin polymers such as propylene and poly (4-methyl-1-pentene); polyether or polythioether polymers such as polyphenylene oxide, polyphenylene sulfide and polyether ether ketone; polyester polymers such as polyethylene terephthalate and polyarylate; Examples thereof include fluorine-based polymers such as polytetrafluoroethane and polyvinylidene fluoride. Examples of the energy beam curable crosslinked polymer include a cured product of an energy beam curable compound having a (meth) acryloyl group and a cured product of an energy beam curable compound having a maleimide group. Of course, the polymer may be a homopolymer, a copolymer, a blend or an alloy.
[0013]
The first production method of the present invention comprises an energy ray curable composition containing an energy ray curable compound in a portion of a pore constituting a porous layer of a membrane having a porous layer, which should be an impermeable portion. The energy ray curable compound is cured by filling the material and irradiating energy rays, and a portion not filled with the cured product of the energy ray curable compound (that is, a membrane portion to selectively permeate the fluid). And, hereinafter, also referred to as a permeation location), relates to a method of forming a permeation location that is substantially impermeable to liquids and gases. When the fluid that permeates the membrane is a gas, some gas can permeate through the impermeable portion. However, it is preferable that the gas permeation rate per unit membrane area of the non-permeable portion is 1/10 or less of that of the permeable portion. When the fluid that permeates the membrane is a liquid, it is preferable that the non-permeated portion does not allow the liquid to permeate at all.
[0014]
The energy ray-curable compound used in the production method of the present invention is a compound having a polymerizable carbon-carbon double bond as long as it can be cured by irradiation with energy rays regardless of organic or inorganic. Is preferable because of its high curing rate, and among them, a compound having a (meth) acryloyl group having a high curing rate and a compound having a maleimide group that does not require a photopolymerization initiator are particularly preferable. These compounds can also be used independently and can also be used in mixture of 2 or more types.
[0015]
Examples of the (meth) acrylic monomer that can be used as the energy ray curable compound include ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenyl (meth ) Acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 3-methacryloxypropyltris (trimethylsiloxy) silane, trifluoroethyl (meth) acrylate, tetra Fluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, methyl-2-chloroacrylate, 3-chloro-2-hydroxypropyl ( 1) Monofunctional monomer such as acrylate; diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2,2′-bis (4- (meth) acryloyl Bifunctional monomers such as oxypolyethyleneoxyphenyl) propane, 2,2′-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane; trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate A trifunctional monomer such as this; a tetrafunctional monomer such as pentaerythritol tetra (meth) acrylate; a hexafunctional monomer such as dipentaerythritol hexa (meth) acrylate, and the like.
[0016]
Moreover, the energy ray-curable compound used in the production method of the present invention may be a polymerizable oligomer having a weight average molecular weight of 500 to 50,000 (also referred to as a prepolymer), preferably a (meth) acrylic oligomer. Examples of the (meth) acrylic oligomer that can be used as the energy ray curable compound include (meth) acrylic acid ester of epoxy resin, (meth) acrylic acid ester of polyether resin, (meth) acrylic acid ester of polybutadiene resin, Examples thereof include a polyurethane resin having a (meth) acryloyl group at the molecular end. These monomers and oligomers can be used alone or in combination of two or more.
[0017]
Examples of maleimide monomers that can be used as energy ray-curable compounds include monofunctional maleimides such as maleimide, N-cyclohexylmaleimide, N-butylmaleimide, N-ethylmaleimide, N-methylmaleimide, and N-benzylmaleimide; 4 , 4′-N, N′-bismaleimide diphenylmethane, 1,6-N, N′-hexamethylene bismaleimide, bifunctional maleimide such as 1,2-N, N′-ethylene bismaleimide, and the like. These maleimide monomers can be used alone or in combination of two or more. These maleimide monomers can also be used by mixing with other polymerizable compounds such as vinyl ethers and acrylic monomers and / or oligomers.
[0018]
In order to sufficiently increase the strength and hardness of the cured product composed of the energy beam curable composition, the cured product composed of the energy beam curable composition is preferably a cross-linked polymer, and therefore, the energy beam curable composition. The product is preferably, for example, a single or mixture of 2-6 functional polyfunctional monomers and / or oligomers.
[0019]
It is also possible to add a photopolymerization initiator, a modifier, a thickener, a reinforcing material and the like to the energy ray curable composition.
[0020]
The photopolymerization initiator that can be added to the energy beam curable composition as necessary is active with respect to the energy beam used in the present invention, and is capable of polymerizing the energy beam curable compound. If there is no particular limitation, for example, a radical polymerization initiator, an anionic polymerization initiator, or a cationic polymerization initiator may be used. Examples of such photopolymerization initiators include acetophenones such as p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one; Ketones such as benzophenone, 4,4'-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone; benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether Benzoin ethers such as benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone.
[0021]
Examples of the thickener that can be added to the energy ray curable composition as necessary include nonreactive polymers that are soluble in an energy ray curable compound such as polysulfone, polyimide, and polycarbonate.
[0022]
Examples of the modifier that can be added to the energy ray curable composition as necessary include, for example, an adhesion improver, a hydroxyl group, a carboxyl group, a sulfone group, an amino group, an ammonium salt, an amide bond, an ether bond, and the like. And non-reactive compounds and surfactants containing a hydrophilic group or a hydrophilic part; silicone oil that functions as a water repellent, fluorine-substituted hydrocarbons, and the like.
[0023]
Examples of the reinforcing agent that can be added to the energy ray curable composition as necessary include nonreactive polymers that are soluble in an energy ray curable compound such as polysulfone, polyimide, and polycarbonate.
[0024]
The energy ray curable compound that becomes the opaque portion can be selected in consideration of adhesiveness to the film, wettability of the film, viscosity, and the like. In the first production method of the present invention, the contact angle of the energy ray-curable compound with the material constituting the film is preferably 15 to 90 degrees, and more preferably 20 to 60 degrees. When the contact angle is smaller than this, the energy ray curable compound is infiltrated into a part to be left as a transmission part, and it tends to be difficult to form a minute transmission part. When the contact angle is larger than this, the blockage of the pores that should be impermeable portions over the entire range in the film thickness direction tends to be incomplete. The contact angle here is preferably measured with a coating film or a molded product having a smooth surface made of a material constituting the film. The contact angle between the energy ray curable compound and the film itself may be different from the value for a smooth surface.
[0025]
Moreover, in the 1st manufacturing method of this invention, it is preferable that the viscosity in 20 degreeC of an energy-beam curable composition exists in the range of 100-10000 mPa * s. When the viscosity of the energy beam curable composition is lower than 100 mPa · s, the energy beam curable composition is liable to infiltrate the portion to be left as the permeation site. If it is higher than 10000 mPa · s, it is not preferable because the pores of the portion which should be impermeable portions tend to be incompletely clogged over the entire range in the film thickness direction.
[0026]
The shape of the impermeable portion is arbitrary, but it is preferable to completely surround the permeation portion used as the separation membrane. The opaque part does not necessarily need to be the whole other than the transparent part, and may be, for example, a belt-like part surrounding the transparent part. It is also possible to form a non-transmission portion so that a plurality of transmission portions are formed in one film.
[0027]
The method of filling the portion of the membrane where the pores should be impermeable with the energy ray-curable composition with the energy ray curable composition from the side of the pore where the pores should be impermeable It can be carried out by applying the composition. When the film is a porous film, the coated surface may be one side or both sides.
[0028]
As the coating method, any coating method that can be applied to the porous layer in a portion that should be an impermeable portion can be adopted. For example, methods such as screen printing, letterpress printing, ink jet, applicator, spin coating, roller coating, bar coater, and spraying can be used. When the method of applying to the entire film is employed, the portion that remains as the transmission portion can be masked to form a non-application portion. The masking may be masking of the membrane surface, and there may be a method in which a pore in a portion to be a permeation portion of the membrane is previously filled with a substance that is inert to energy rays.
[0029]
When using a high-viscosity energy ray-curable composition, the energy ray-curable compound can be applied as a volatile solvent solution. The application may be performed under reduced pressure so that the energy ray-curable composition can be sufficiently impregnated into the pores of the portion that should be impermeable in the membrane, or after application, the pressure may be reduced. Further, the pore surface of the membrane may be surface-treated in advance so that the energy ray-curable composition can be sufficiently impregnated into the pores of the portion to be the non-permeable portion of the membrane. The surface treatment is optional, and for example, plasma treatment, corona treatment, fluorine treatment, sulfonation treatment, surfactant treatment and the like can be used.
[0030]
After the energy ray curable composition is applied, the energy ray curable compound is cured by irradiating energy rays. The time from application to energy ray irradiation is the time that the energy ray curable composition impregnates the pores of the portion that should be impermeable to the membrane and does not infiltrate the pores of the portion that should be permeated. Must be selected. Since this time varies depending on the viscosity of the energy beam curable composition, the contact angle of the energy beam curable compound with the film material, the coating method, the film thickness, the pore diameter, the size / shape of the opaque portion, etc. However, the optimum time can be easily obtained by experimenting with the target system.
[0031]
The energy ray is arbitrary as long as it can cure the energy ray-curable compound, and examples thereof include ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, electron rays, beta rays, and heavy particle rays. From the viewpoint of handleability and curing speed, light rays such as ultraviolet rays and visible light are preferable, and ultraviolet rays are particularly preferable. In addition, for the purpose of increasing the curing rate and completely curing, it is preferable to irradiate energy rays in a low oxygen concentration atmosphere. The low oxygen concentration atmosphere is preferably a nitrogen stream, a carbon dioxide stream, an argon stream, a vacuum or a reduced pressure atmosphere. When light is used as an energy ray, the light intensity is 1-1000 mw / cm.²The irradiation time is preferably 0.1 to 180 seconds.
[0032]
In the second production method of the present invention, the energy ray-curable composition is filled in the pores constituting the porous layer of the membrane having the porous layer, and the energy rays are irradiated only in a part of the range. By curing the energy ray curable compound in the irradiated part and then removing the uncured energy ray curable compound remaining in the non-irradiated part, the transmission part is substantially liquid compared to the part. And a method of forming an impermeable portion where gas is impermeable.
[0033]
In the second production method of the present invention, the energy ray-curable composition can be filled in the pores of the entire film. Of course, there may be a part where the energy ray curable compound is not filled in a part or all of the part to be the transmission part. Therefore, a method such as dipping can be used as a coating method. In addition, since there is no fear of infiltration of the energy beam curable composition into the transmission site, it is easy to irradiate the energy beam after applying the volatile solvent solution of the energy beam curable composition and removing the solvent. Can be implemented. Furthermore, in the 2nd manufacturing method of this invention, the restriction | limiting of the relationship of the viscosity of an energy-beam curable composition or the wettability with a film | membrane material is small, and a freedom degree is high.
[0034]
The energy ray is irradiated to a portion to be an opaque portion, and the energy ray curable compound in the portion is cured. Of course, if a portion where the energy beam curable composition is not applied is left, this portion may be irradiated. For irradiating the portion that should be the opaque portion of the energy beam, a photolithography technique can be used. That is, it can be carried out by a photomasking method or an energy beam scanning method.
[0035]
The second production method of the present invention is suitable particularly when a minute transmission portion is formed because infiltration of the energy ray-curable composition into the transmission portion does not occur in principle.
[0036]
About the thing except the above, it is the same as the description about the 1st manufacturing method of this invention.
[0037]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to the range of these Examples. In the following examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.
[0038]
[Example 1]
[Membrane with porous layer]
As the membrane (1) having a porous layer, an acetylcellulose microfiltration membrane (manufactured by Gelman Science, “GN-4 Metricel # 64679”) having a pore diameter of 0.8 μm and a thickness of about 150 μm was used.
[0039]
(Preparation of energy beam curable composition)
50 parts of 10 ethylene oxide modified bisphenol A diacrylate ("BPE-10" manufactured by Daiichi Kogyo Co., Ltd.), 50 parts of 4 ethylene oxide modified bisphenol A diacrylate ("BPE-4" manufactured by Daiichi Kogyo Co., Ltd.) 2 parts of 1-hydroxycyclohexyl phenyl ketone (UV polymerization initiator “Irgacure 184” manufactured by Ciba Geigy) was mixed to prepare an energy ray-curable composition [E-1]. The energy beam curable composition [E-1] had a viscosity of 1090 mPa · s at 20 ° C.
[0040]
[Formation of opaque areas]
In the part of the shape shown in FIG. 1 that becomes a non-transparent portion (3) of a square of 25 mm × 25 mm surrounding a transmission portion (2) in which four squares of 5 mm × 5 mm are arranged in a lattice shape with a center distance of 5 mm. The energy beam curable composition [E-1] was applied using a screen printer, and about 10 seconds after application, using a “light source unit for multi-light 200 type exposure apparatus” manufactured by USHIO INC., 10mW / cm in nitrogen atmosphere² Is irradiated with ultraviolet rays for 30 seconds to cure the energy ray curable compound and cut out a 25 mm × 25 mm portion where the opaque portion is formed, thereby forming a film having an opaque portion of the shape shown in FIG. M-1] was obtained.
[0041]
[Confirmation of infiltration of energy ray curable compounds]
The membrane [M-1] having an impermeable portion is dipped in a 0.03% aqueous solution of Malachite Green (manufactured by Wako Pure Chemical Industries, Ltd.), pulled up, absorbed moisture with a filter paper, and then visually permeable and impermeable. When the portion was observed, the transmission portion was stained with a dye, and the non-transmission portion was not stained. When the boundary part between the transmission part and the non-transmission part was observed with an optical microscope, the boundary was considerably uneven, but on average, the energy ray-curable compound penetrated into the transmission part about 0.15 mm. Admitted.
[0042]
[Example 2]
[Formation of opaque areas]
In Example 1, (1) the use of a polyamide microfiltration membrane (“Nirasolv # 66508” manufactured by Gelman Science) with a pore diameter of 1 μm and a thickness of about 150 μm as the membrane, and (2) the shape of the permeation site As shown in FIG. 2, the shape shown in FIG. 2 is the same as that shown in FIG. 2, except that four rectangles each having a width of 1.2 mm and a length of 15 mm are formed at intervals of 5 mm. A film [M-2] having an impermeable portion was prepared.
[0043]
[Confirmation of infiltration of energy ray curable compounds]
When the same observation as in Example 1 was performed, the boundary was considerably uneven, but on average the infiltration of the energy ray curable compound into the transmission site was about 0.1 mm.
[0044]
[Example 3]
(Preparation of energy beam curable composition)
10 parts of trifunctional urethane acrylate oligomer ("Unidic V-4263" manufactured by Dainippon Ink & Chemicals, Inc.), 40 parts of 1,6-hexanediol diacrylate ("New Frontier HDDA" manufactured by Daiichi Kogyo Co., Ltd.) and cyclohexyl An energy ray-curable composition [E-3] was prepared by mixing 50 parts of maleimide.
[0045]
[Formation of opaque areas]
In Example 1, it replaced with energy-beam curable composition [E-1], and except having used energy-beam curable composition [E-3], it carried out similarly to Example 1, and showed in FIG. A film [M-3] having a shape-impermeable portion was produced.
[0046]
[Confirmation of infiltration of energy ray curable compounds]
When the same observation as in Example 1 was performed, the boundary was considerably uneven, but on average the infiltration of the adhesive into the transmission site was about 0.15 mm.
[0047]
[Example 4]
[Formation of opaque areas]
In Example 1, (1) the energy ray curable compound was applied to the entire film using a coating roller, and (2) the photo-masked portion of the same shape and size as in Example 1 was irradiated with ultraviolet rays. (3) Impervious portions having the shape shown in FIG. 1 in the same manner as in Example 1 except that the uncured energy ray-curable compound was washed and removed with isopropanol after ultraviolet irradiation and air-dried. A film [M-4] having
[0048]
[Confirmation of infiltration of energy ray curable compounds]
When the same observation as in Example 1 was performed, no infiltration of the energy ray-curable compound into the transmission site was observed.
[0049]
[Comparative Example 1]
[Formation of opaque areas]
In Example 2, instead of (1) the energy ray curable compound, an epoxy adhesive [bisphenol A type epoxy resin (“Epiclon 857” manufactured by Dainippon Ink & Chemicals, Inc.) and an amine type curing agent (large A mixture with “Epiclon B1170-70” manufactured by Nippon Ink Chemical Co., Ltd. (viscosity at 1100 mPa · s at 20 ° C.)] was used. (2) Instead of UV irradiation, kept at 55 ° C. for 20 minutes A film [M-C1] having an impermeable portion having the shape shown in FIG. 2 was produced in the same manner as in Example 2 except that the film was cured by the above method.
[0050]
[Confirmation of adhesive infiltration]
When the film [M-C1] having an impermeable portion was observed with a microscope in the same manner as in Example 1, most of the portion to be the permeable portion was not colored, and the adhesive infiltrated the permeable portion, It was confirmed that most of the pores in the portion were blocked.
[0051]
[Application Example 1]
In this application example, a manufacturing method of a membrane filtration device incorporating a membrane manufactured by the manufacturing method of the present invention will be described.
[0052]
[Production of members]
A 25 mm x 25 mm x 3 mm thick plate made by cutting a flat plate made of polystyrene ("Dick Styrene XC-520" manufactured by Dainippon Ink and Chemicals, Inc.) is used to form a grid with 10 mm intervals using a drill. A member [P-1] (7) having a channel (8) having the shape shown in FIG. 3 was prepared by drilling four 0.5 mm diameter drill holes penetrating the member.
[0053]
[Preparation of membrane separation device ice]
Using a coating roller, a 30% ethanol solution of the energy ray curable compound [E-1] is applied to a thickness of about 40 μm on each of the two surfaces of each of the members [P-1] (7) at 40 ° C. For 10 minutes to evaporate the solvent. After removing the energy ray curable compound [E-1] that has entered the flow path (8) by suction, two members [P with the energy ray curable compound applied surface facing the film side in a nitrogen gas atmosphere [P -1] and (7), the film [M-1] (1) having an impermeable portion produced in Example 1 is laminated so as to be sandwiched, and sandwiched by a clamp with a force of about 100 kN. About 10 seconds after 10 seconds, using two 3kw metal halide lamps, 60mw / cm from both sides²The ultraviolet ray was simultaneously irradiated to cure and bond the energy ray curable compound to obtain a membrane separation device [D-1] having the shape shown in FIG.
[0054]
[Leakage test]
One of the spaces of the membrane separation part of the membrane separation device [D-1] thus obtained was filled with water colored with malachite green (manufactured by Wako Pure Chemical Industries, Ltd.), and one member (7) After closing the flow path (8), a test was performed for each of the four permeation points from the flow path (8) of the other member, with the water pressure of 0.1 MPa being applied for 1 hour. No water leakage to other permeation points or water leakage outside the membrane separation device was observed.
[0055]
【The invention's effect】
According to the method for producing a membrane having a porous layer provided with an impermeable portion according to the present invention, a membrane whose thickness of the impermeable portion is not thinner than that of the permeable portion, that is, even when used for a minute separation membrane device. A film with less risk of leakage from the part can be manufactured. Further, according to the production method of the present invention, it is possible to form a minute permeable portion or an impermeable portion while completely blocking the pores at the impermeable portion. Furthermore, according to the production method of the present invention, it is possible to produce a porous membrane having an impermeable portion having an excellent pore size distribution.
[Brief description of the drawings]
FIG. 1 is a plan view of a film having an impermeable portion produced in Example 1, Example 3 and Example 4 as seen from a direction perpendicular to the surface.
[Explanation of symbols]
1 Membrane with impermeable location
2 transmission points
3 opaque parts
FIG. 2 is a plan view of a film having an impermeable portion produced in Example 2 as seen from a direction perpendicular to the surface.
[Explanation of symbols]
4 Membranes with impervious points
5 Transmission points
6 Impervious point
FIG. 3 is a plan view of a member used in Application Example 1 viewed from a direction perpendicular to a surface in contact with a film.
[Explanation of symbols]
7 members
8 channels
4 is an overhead view of a membrane separation device manufactured in Application Example 1. FIG.
[Explanation of symbols]
1 Membrane with impermeable location
7 members
8 channels

Claims (4)

  The energy ray curable compound containing the energy ray curable compound is filled in the pores of the membrane having the porous layer, and the energy ray curable compound in the irradiated portion is irradiated by irradiating the energy ray in a part of the range. Of a film having an impermeable portion, wherein an impermeable portion is formed in a part of the film having a porous layer by removing an uncured energy ray-curable compound after curing Method. It said membrane having a porous layer is flat membrane, the impermeable portion The method for producing a film having opaque portions of claim 1 wherein formed in the shape surrounding the remaining portion as a transparent portion. The method for producing a film having an impermeable portion according to claim 1 or 2, wherein the film having the porous layer is a porous film. The energy ray-curable compound, (meth) film manufacturing method of having opaque portions of claims 1, 2 or 3, wherein the energy ray-curable compound having an acryloyl group or a maleimide group.

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