JP5990555B2 - Method for producing acid gas separation membrane and wound product of acid gas separation membrane - Google Patents

Description

  The present invention relates to a method for producing an acid gas separation membrane for selectively separating an acid gas from a raw material gas, and a wound product of the acid gas separation membrane by this production method. Specifically, the present invention relates to a method for producing an acid gas separation membrane capable of producing an acid gas separation membrane having no facilitated transport membrane defect with high production efficiency, and a wound product of the acid gas separation membrane by this production method.

  In recent years, development of technology for selectively separating an acid gas from a source gas (a gas to be treated) has been advanced. For example, an acid gas separation membrane that separates an acid gas from a raw material gas using an acid gas separation membrane that selectively permeates the acid gas has been developed.

As an example, Patent Document 1 includes a carbon dioxide carrier on a carbon dioxide permeable support as an acidic gas separation membrane (carbon dioxide separation gel membrane) for separating carbon dioxide (carbon dioxide) from a raw material gas. An acidic gas separation membrane is disclosed in which a hydrogel membrane formed by absorbing an aqueous solution into a vinyl alcohol-acrylate copolymer having a crosslinked structure is formed.
Patent Document 1 discloses, as a method for producing this acidic gas separation membrane, an uncrosslinked vinyl alcohol-acrylate copolymer aqueous solution is applied in a film form on a carbon dioxide permeable support, A method for producing an acidic gas separation membrane is also disclosed in which an aqueous solution is heated and cross-linked to insolubilize water, and the water-insolubilized material absorbs a carbon dioxide carrier aqueous solution and gels.

  The acidic gas separation membrane shown in Patent Document 1 is an acidic gas separation membrane using a so-called facilitated transport membrane. The facilitated transport membrane has a carrier that reacts with an acidic gas such as the above-mentioned carbon dioxide carrier in the membrane, and the acidic gas is separated from the source gas by transporting the acidic gas to the opposite side of the membrane by this carrier. .

By the way, as a method for producing various functional membranes (functional films) such as acidic gas separation membranes with high productivity, so-called roll-to-roll (hereinafter also referred to as RtoR) is known. .
As is well known, RtoR means that a support is sent out from a roll formed by winding a long support, and this support is transported in the longitudinal direction while performing predetermined processing such as film formation and surface treatment. This is a production method in which the treated support is wound again into a roll.

As with various functional membranes, acidic gas separation membranes can be produced with high productivity by using this RtoR.
For example, Patent Document 2 discloses an application containing a water-absorbing polymer, a carbon dioxide carrier, and a gelling agent while transporting a long (band-shaped) support in the longitudinal direction and prepared at 50 ° C. or higher. The liquid is applied to a support, and the coating film formed on the support is cooled to 12 ° C. or less to form a gel membrane, and this gel membrane is dried with warm air to form a facilitated transport membrane (carbon dioxide separation membrane). An apparatus for producing an acid gas separation membrane is described.

Japanese Patent Publication No. 7-102310 JP 2012-143711 A

As described above, by using RtoR, an acidic gas separation membrane can be produced with high production efficiency.
However, according to the study of the present inventor, if RtoR is used for the production of an acidic gas separation membrane using a facilitated transport membrane, an appropriate product may not be produced stably.

An acid gas separation membrane using a facilitated transport membrane is often used in a gas environment having a water vapor partial pressure. In general, an acid gas separation membrane having a facilitated transport membrane tends to have a higher acid gas separation rate (permeation rate) as the hygroscopic property of the facilitated transport membrane is higher.
Therefore, the facilitated transport film has a configuration in which a hydrophilic compound such as a super water-absorbent resin is used as a binder and carriers are dispersed in the binder. Many carriers are also highly hygroscopic. Furthermore, it is common to use a highly hygroscopic additive for the facilitated transport film as required.
As a result, an acidic gas separation membrane having a facilitated transport membrane may swell due to absorption of water vapor in the air, for example, by simply leaving it in an environment with a relative humidity of 50% RH.

According to the study of the present inventors, when such an acid gas separation membrane is manufactured using RtoR, the facilitated transport membrane adheres to the pass roller or the like depending on the production environment such as the composition of the facilitated transport membrane and the atmosphere. In some cases, the acid gas separation membrane may be peeled off.
When such facilitated transport membrane peeling occurs, a defective portion is formed in the acidic gas separation membrane. In addition, there is a problem that the facilitated transport film attached to the pass roller or the like adheres to an acid gas separation membrane or the like produced thereafter and is contaminated.

It is also possible to wind up the acidic gas separation membrane without forming contact with the facilitated transport membrane after forming the facilitated transport membrane by designing the transport path or the like.
However, depending on the composition of the facilitated transport membrane, the production and storage atmosphere, when the acid gas separation membrane is sent out from the roll in a later step, the facilitated transport membrane adheres to the back surface of the acid gas separation membrane in a laminated state. Then, the film may be peeled off. Such peeling of the facilitated transport membrane similarly leads to contamination of the acid gas separation membrane and generation of defects.

  An object of the present invention is to solve such a problem of the prior art, and is a manufacturing method for manufacturing an acidic gas separation membrane having a facilitated transport membrane by RtoR with high productivity, which is in contact with a pass roller. In addition, it is possible to prevent peeling of the facilitated transport membrane by the acidic gas separation membranes laminated by winding, and a suitable acidic gas separation membrane with no defects can be stably produced with high productivity without causing contamination of production facilities etc. It is in providing the manufacturing method of the acidic gas separation membrane which can be manufactured in this way, and the wound product of the acidic gas separation membrane manufactured by this manufacturing method.

In order to achieve this object, the method for producing an acidic gas separation membrane of the present invention comprises a carrier that reacts with acidic gas on the surface of a porous support while transporting a long porous support in the longitudinal direction, And a step of applying a coating composition containing a hydrophilic compound for supporting the carrier,
Forming a facilitated transport film by drying the coating composition applied to the surface of the porous support;
A step of laminating a long release film on the facilitated transport film, and
There is provided a method for producing an acidic gas separation membrane comprising performing a step of winding a porous support and a laminate of a promoting gas separation membrane and a release film.

In such a method for producing an acidic gas separation membrane of the present invention, the coating composition is preferably coated on the porous support so that the thickness of the coating composition is 0.05 to 10 mm.
Moreover, it is preferable that the peeling force of a release film is 0.07-10N / mm.
Moreover, it is preferable that the film | membrane intensity | strength of a facilitated-transport film | membrane is 0.005 Mpa or more.
Further, it is preferable that one or both surfaces of the release film are hydrophobic, and the release film is laminated on the facilitated transport film with the hydrophobic surface facing the facilitated transport film.
Further, the laminate is sent out from the porous support and the roll of the laminate of the promoting gas separation membrane and the release film, and the release film is peeled off while being transported in the longitudinal direction to facilitate transport. A step of applying a coating composition containing a carrier that reacts with an acidic gas and a hydrophilic compound for supporting the carrier to the surface of the film, and a coating composition applied to the surface of the facilitated transport film are dried. Thus, it is preferable to perform a step of forming a facilitated transport film having a multilayer structure.
In addition, the temperature of the laminate in which the facilitated transport film is formed on the surface of the porous support and the temperature of the release film are set to 10 to 70 ° C., and a long release film is laminated on the facilitated transport film. Is preferred.
The carrier is preferably at least one selected from alkali metal carbonates, alkali metal bicarbonates, and alkali metal hydroxide salts.
The coating composition is preferably dried by hot air drying at a wind speed of 0.5 to 200 m / min and a film surface temperature of 1 to 120 ° C.
In addition, prior to the step of applying the coating composition, the surface of the porous support includes a component that becomes a hydrophobic intermediate layer having gas permeability while conveying the long porous support in the longitudinal direction. It is preferable to perform a step of applying the second coating composition and a step of curing the second coating composition to form an intermediate layer.
Moreover, it is preferable that the component used as an intermediate | middle layer is silicone.
Furthermore, the curing of the second coating composition is preferably started within 7 seconds after the second coating composition is applied.

  Moreover, the acidic gas separation membrane wound product of the present invention is an acidic gas formed on a porous support by forming a facilitated transport membrane having a carrier that reacts with the acidic gas and a hydrophilic compound that supports the carrier. An acidic gas separation membrane wound product is provided, which is obtained by winding a long laminate having a separation membrane and a release film laminated on a facilitated transport membrane in the longitudinal direction.

In such an acidic gas separation membrane roll of the present invention, it is preferable that the release force of the release film is 0.07 to 10 N / mm.
Moreover, it is preferable that the film | membrane intensity | strength of a facilitated-transport film | membrane is 0.005 Mpa or more.
Moreover, it is preferable that one or both surfaces of the release film are hydrophobic, and the release film is laminated with the hydrophobic surface facing the facilitated transport film.
Moreover, it is preferable that the thickness of a facilitated-transport film | membrane is 0.01-3 mm.
The carrier is preferably at least one selected from alkali metal carbonates, alkali metal bicarbonates, and alkali metal hydroxide salts.
Moreover, it is preferable to have a hydrophobic intermediate layer having gas permeability between the porous support and the acidic gas separation membrane.
Furthermore, the intermediate layer is preferably made of a silicone resin.

According to the present invention as described above, an acidic gas separation membrane having a facilitated transport membrane can be produced by roll-to-roll with high productivity without causing peeling of the facilitated transport membrane due to contact with the pass roller.
Therefore, according to the present invention, while preventing contamination of production facilities, acid gas separation membranes, etc., a high quality acid gas separation membrane free from defects caused by contamination or peeling of the facilitated transport membrane (the roll thereof) ) Can be stably produced with high productivity.

It is a figure which shows notionally an example of the manufacturing apparatus which enforces the manufacturing method of the acidic gas separation membrane of this invention. It is a figure which shows notionally an example of the laminated body manufactured with the manufacturing method of the acidic gas separation membrane of this invention. It is a figure which shows notionally another example of the manufacturing apparatus which enforces the manufacturing method of the acidic gas separation membrane of this invention.

  Hereinafter, the method for producing an acidic gas separation membrane and the wound product of the acidic gas separation membrane of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.

  In FIG. 1, an example of the manufacturing apparatus of the acidic gas separation membrane which implements the manufacturing method of the acidic gas separation membrane of this invention is shown notionally.

The manufacturing apparatus 10 shown in FIG. 1 manufactures an acidic gas separation membrane by the above-mentioned roll-to-roll (hereinafter also referred to as RtoR). That is, the manufacturing apparatus 10 sends out the porous support 12 from a support roll 12R formed by winding a long (web-like) porous support 12 into a roll, and transports the porous support 12 in the longitudinal direction. Meanwhile, the facilitated transport membrane 18 is formed on the surface of the porous support 12 to produce the acidic gas separation membrane 14, and the produced acidic gas separation membrane 14 is wound (wound up) in a roll shape.
Here, in the manufacturing apparatus 10 that implements the manufacturing method of the present invention, the facilitated transport membrane 18 is formed on the surface of the porous support 12 to produce the acid gas separation membrane 14, and then separated from the surface of the facilitated transport membrane 18. The mold film 20 is laminated and stuck, and the laminate 24 of the acidic gas separation membrane 14 and the release film 20 is wound into a roll. A laminate roll 24R formed by winding the laminate 24 is the acidic gas separation membrane wound product of the present invention.

  That is, as shown conceptually in FIG. 2, the laminate 24 is formed by forming the facilitated transport film 18 on the surface of the porous support 12 (the surface of the porous film 12a described later), and the acidic gas separation membrane 14 The release film 20 is laminated and pasted on the surface (on the facilitated transport film 18), and the laminate roll 24R is formed by winding the laminate 24 into a roll shape. is there.

The manufacturing apparatus 10 basically includes a supply unit 26, a coating unit 28, a drying unit 30, a stacking unit 32, and a winding unit 34.
In addition to the illustrated members, the manufacturing apparatus 10 manufactures a functional film (functional film) using RtoR, such as a pass roller (guide roller), a pair of conveyance rollers, a conveyance guide, and various sensors as necessary. You may have various members provided in the apparatus to do.

The supply unit 26 is loaded with a support roll 12R formed by winding a long porous support 12 in a roll shape around a rotation shaft 38, and rotates the rotation shaft 38, that is, the support roll 12R. This is the part where the quality support 12 is sent out.
In addition, what is necessary is just to perform sending out and conveyance of the porous support body 12 from the support body roll 12R by a well-known method.

The porous support 12 (hereinafter also referred to as the support 12) is permeable to an acidic gas such as carbon dioxide, and can be applied with the coating composition 40 for forming the facilitated transport film 18 (coating). Further, it is possible to support the membrane), and further supports the formed facilitated transport membrane 18.
Any known material can be used as the material for forming the support 12 as long as the material can exhibit this function.

Here, in the production method of the present invention, the support 12 may be a single layer, but as shown in FIG. 2, the support 12 has a two-layer structure including a porous film 12a and an auxiliary support film 12b. preferable. By having such a two-layer structure, the support 12 expresses the functions of the acidic gas permeability, the application of the coating composition to be the facilitated transport film 18 and the support of the facilitated transport film 18 more reliably. .
In the case where the support 12 is a single layer, various materials exemplified below as the porous film 12a and the auxiliary support film 12b can be used as the forming material.

In the two-layered support 12, the porous membrane 12 a is on the facilitated transport membrane 18 side.
The porous membrane 12a is preferably made of a material having heat resistance and low hydrolyzability. Specific examples of the porous membrane 12a include membrane filter membranes such as polysulfone, polyethersulfone, polypropylene and cellulose, interfacially polymerized thin films of polyamide and polyimide, polytetrafluoroethylene (PTFE) and high molecular weight polyethylene. The stretched porous membrane is exemplified.
Among them, a stretched porous membrane of PTFE or high molecular weight polyethylene has a high porosity, is small in inhibition of diffusion of acidic gas (especially carbon dioxide gas), and is preferable from the viewpoints of strength and manufacturing suitability. Among them, a stretched porous membrane of PTFE is preferably used in terms of heat resistance and low hydrolyzability.

The porous membrane 12a is hydrophobic so that the facilitated transport membrane 18 containing moisture can easily penetrate into the porous portion under the use environment and does not cause deterioration in film thickness distribution or performance over time. Is preferred. The same applies to the case where the support has a single layer structure.
The porous membrane 12a preferably has a maximum pore diameter of 1 μm or less.
The average pore diameter of the pores of the porous membrane 12a is preferably 0.001 to 10 μm, more preferably 0.002 to 5 μm, and particularly preferably 0.005 to 1 μm. By setting the average pore diameter of the porous membrane 12a within this range, it is preferable that the adhesive application region described later sufficiently infiltrate the adhesive and that the porous membrane 12a hinders the passage of acid gas. Can be prevented. Furthermore, by setting the average pore diameter of the porous film 12a within this range, it is possible to prevent the film surface from becoming non-uniform due to a capillary phenomenon or the like when a coating composition 40 described later is applied.

The auxiliary support membrane 12b is provided as a reinforcement of the porous membrane 12a.
Various materials can be used as the porous membrane 12a as long as it satisfies the required strength, stretch resistance and gas permeability. For example, a nonwoven fabric, a woven fabric, a net, and a mesh having an average pore diameter of 0.001 to 10 μm can be appropriately selected and used.

The auxiliary support membrane 12b is also preferably made of a material having heat resistance and low hydrolyzability, similar to the porous membrane 12a described above.
Considering this point, the fibers constituting the nonwoven fabric, woven fabric, and knitted fabric are excellent in durability and heat resistance, polyolefin such as polypropylene (PP), modified polyamide such as aramid (trade name), polytetrafluoro Fibers made of fluorine-containing resins such as ethylene and polyvinylidene fluoride are preferred. It is preferable to use the same material as the resin material constituting the mesh. Among these materials, a non-woven fabric made of PP that is inexpensive and has high mechanical strength is particularly preferably exemplified.

  When the support 12 has the auxiliary support film 12b, the mechanical strength can be improved. Therefore, even in the manufacturing method using RtoR as in the present invention, wrinkles on the support 12 can be prevented and productivity can be increased.

If the support 12 is too thin, the strength is difficult. Considering this point, the thickness of the porous membrane 12a is preferably 5 to 100 μm, and the thickness of the auxiliary support membrane 12b is preferably 50 to 300 μm.
In addition, when making the support body 12 into a single layer, as for the thickness of the support body 12, 30-500 micrometers is preferable.

In the manufacturing apparatus 10 shown in FIG. 1, the support 12 sent out from the support roll 12 </ b> R is transported in the longitudinal direction and then transported to the coating unit 28, and the coating composition 40 that becomes the facilitated transport film 18 is obtained. Applied.
Here, in the production method of the present invention, an intermediate layer may be formed on the surface of the support 12 prior to the application of the coating composition 40 to be the facilitated transport film 18. That is, in the acidic gas separation membrane roll of the present invention, the acidic gas separation membrane 14 may have an intermediate layer between the support 12 and the facilitated transport membrane 18.

  The intermediate layer is a layer for more effectively suppressing the penetration of the facilitated transport material (membrane) into the porous support (support 12). As such an intermediate layer, a layer made of various materials can be used as long as it is a hydrophobic layer having gas permeability, but it has air permeability and is a layer denser than the support 12. Is preferred. By providing such an intermediate layer, a highly uniform facilitated transport film can be formed while preventing it from entering the porous support.

  The intermediate layer only needs to be formed on the support 12, but may have a soaking area that is soaked in the support 12. The soaking area is preferably as small as possible within the range in which the adhesion between the support 12 and the intermediate layer is good.

As the intermediate layer, a polymer layer having a siloxane bond in the repeating unit is preferable.
Examples of such a polymer layer include silicone-containing polyacetylene such as organopolysiloxane (silicone resin) and polytrimethylsilylpropyne. Specific examples of the organopolysiloxane include those represented by the following general formula.

In the above general formula, n represents an integer of 1 or more. Here, from the viewpoints of availability, volatility, viscosity, and the like, the average value of n is preferably in the range of 10 to 1,000,000, and more preferably in the range of 100 to 100,000.
R _1n , R _2n , R ₃ , and R ₄ are each a group consisting of a hydrogen atom, an alkyl group, a vinyl group, an aralkyl group, an aryl group, a hydroxyl group, an amino group, a carboxyl group, and an epoxy group. Indicates which one is selected. Note that n existing R _1n and R _2n may be the same or different. In addition, the alkyl group, aralkyl group, and aryl group may have a ring structure. Further, the alkyl group, vinyl group, aralkyl group, and aryl group may have a substituent, and are selected from an alkyl group, vinyl group, aryl group, hydroxyl group, amino group, carboxyl group, epoxy group, or fluorine atom. It is. These substituents may further have a substituent if possible.
The alkyl group, vinyl group, aralkyl group, and aryl group selected from R _1n , R _2n , R ₃ , and R ₄ are each an alkyl group having 1 to 20 carbon atoms or vinyl from the viewpoint of availability. Group, an aralkyl group having 7 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms are more preferable.
In particular, R _1n , R _2n , R ₃ , and R ₄ are preferably methyl groups or epoxy-substituted alkyl groups. For example, epoxy-modified polydimethylsiloxane (PDMS) can be suitably used.

The intermediate layer is a film having gas permeability, but if it is too thick, the gas permeability may be significantly reduced. The intermediate layer may be thin as long as it covers the entire surface of the support 12 without leaving the surface.
Considering this point, the film thickness of the intermediate layer is preferably 0.01 to 30 μm, more preferably 0.1 to 15 μm.

Such an intermediate layer is preferably formed by a coating method.
A coating composition (second coating composition) serving as an intermediate layer includes a monomer, dimer, trimer, oligomer, prepolymer, or a mixture thereof, which is a compound serving as an intermediate layer such as the aforementioned PDMS derivative. Is a general coating composition (coating liquid / paint) used when forming a resin layer (resin film) or the like. This coating composition may be obtained by dissolving (dispersing) a monomer or the like in an organic solvent, and further contains a curing agent, a curing accelerator, a crosslinking agent, a thickener, a reinforcing agent, a filler, and the like. May be included.
Such a coating composition may be prepared by a known method.

In addition, as for the coating method of the coating composition to be the intermediate layer, various known methods can be used as in the coating composition 40 described later. The coating thickness of the coating composition is appropriately set according to the type of the intermediate layer to be formed, the concentration of the coating composition, etc., so that the thickness of the intermediate layer is 0.01 to 30 μm as described above. do it.
Furthermore, as the curing method of the coating composition, various known methods corresponding to the monomer serving as the intermediate layer, such as UV irradiation, heat curing, and electron beam irradiation, can be used. Of these, UV irradiation is preferable. Prior to curing of the coating composition, the coating composition such as evaporation of an organic solvent may be dried as necessary.

Here, in forming the intermediate layer, it is preferable to form the intermediate layer by applying the coating composition to be the intermediate layer and then starting the curing of the coating composition (monomer or the like) within 7 seconds.
Thereby, the penetration of the coating composition into the support 12 which is a porous film is suitably suppressed, and a high-quality intermediate layer having a thin intermediate layer component in the support 12 can be obtained. The time from the application of the coating composition serving as the intermediate layer to the start of curing is particularly preferably within 5 seconds.

As described above, the support body 12 (or the support body 12 on which the intermediate layer is formed) sent out from the support body roll 12R is transported in the longitudinal direction and then transported to the coating unit 28, and the facilitated transport film A coating composition 40 to be 18 is applied.
In the production method of the present invention, the conveying speed of the support 12 may be appropriately set according to the type of the support 12 and the viscosity of the coating composition 40. When the conveyance speed of the support 12 is too fast, the film thickness uniformity of the coating film of the coating composition 40 may be lowered, and when too slow, the productivity is lowered. Considering this point, the conveying speed of the support 12 is preferably 0.5 m / min or more, more preferably 0.75 to 200 m / min, and particularly preferably 1 to 200 m / min.

The facilitated transport film 18 contains a hydrophilic compound such as a hydrophilic polymer, a carrier that reacts with an acidic gas, water, and the like.
Therefore, the coating composition 40 for forming such a facilitated transport film 18 is a composition containing a hydrophilic compound, a carrier and water (room temperature water or warm water), or a necessary component such as a crosslinking agent. (Paint / coating liquid). The hydrophilic compound may be cross-linked, partially cross-linked, or non-cross-linked, or a mixture thereof.

  The hydrophilic compound functions as a binder. In addition, the hydrophilic compound retains moisture in the facilitated transport film 18 and exerts a function of separating a gas such as carbon dioxide by the carrier. The hydrophilic compound preferably has a crosslinked structure from the viewpoint of heat resistance.

From the viewpoint that the hydrophilic compound can be dissolved in water to form a coating solution, and the facilitated transport film 18 preferably has high hydrophilicity (moisturizing properties), those having high hydrophilicity are preferable.
Specifically, the hydrophilic compound preferably has a hydrophilicity of 0.5 g / g or more, more preferably 1 g / g or more, more preferably 5 g / g of the physiological saline. More preferably, it has a hydrophilicity of g or more, particularly preferably has a hydrophilicity of 10 g / g or more, and most preferably has a hydrophilicity of 20 g / g or more.

What is necessary is just to select the weight average molecular weight of a hydrophilic compound suitably in the range which can form a stable film | membrane. Specifically, 20,000 to 2,000,000 is preferable, 25,000 to 2,000,000 is more preferable, and 30,000 to 2,000,000 is particularly preferable.
By setting the weight average molecular weight of the hydrophilic compound to 20,000 or more, the facilitated transport film 18 having a sufficient film strength can be obtained stably.
In particular, the hydrophilic compound preferably has a weight average molecular weight of 30,000 or more when it has —OH as a crosslinkable group. In this case, the weight average molecular weight of the hydrophilic compound is more preferably 40,000 or more, and more preferably 50,000 or more. Moreover, when a hydrophilic compound has -OH as a crosslinkable group, it is preferable that a weight average molecular weight is 6,000,000 or less from a viewpoint of manufacture aptitude.
The hydrophilic compound preferably has a weight average molecular weight of 10,000 or more when it has —NH ₂ as a crosslinkable group. In this case, the weight average molecular weight of the hydrophilic compound is more preferably 15,000 or more, and particularly preferably 20,000 or more. Further, hydrophilic compound, if having a -NH ₂ as crosslinkable groups, from the viewpoint of production suitability, weight average molecular weight is preferably not more than 1,000,000.
For example, when PVA is used as the hydrophilic compound, the weight average molecular weight of the hydrophilic compound may be a value measured according to JIS K 6726. Moreover, when using a commercial item, what is necessary is just to use the molecular weight nominally mentioned in a catalog, a specification, etc.

As the crosslinkable group forming the hydrophilic compound, those capable of forming a hydrolysis-resistant crosslinked structure are preferably selected.
Specific examples include a hydroxy group, an amino group, a chlorine atom, a cyano group, a carboxy group, and an epoxy group. Among these, an amino group and a hydroxy group are preferably exemplified. Furthermore, most preferably, a hydroxy group is illustrated from the viewpoint of affinity with a carrier and a carrier carrying effect.

  Specific examples of hydrophilic compounds include those having a single crosslinkable group such as polyallylamine, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyethyleneimine, polyvinylamine, polyornithine, polylysine, Examples include polyethylene oxide, water-soluble cellulose, starch, alginic acid, chitin, polysulfonic acid, polyhydroxymethacrylate, poly-N-vinylacetamide and the like. Most preferred is polyvinyl alcohol. These copolymers are also exemplified as the hydrophilic compound.

Examples of the hydrophilic compound having a plurality of crosslinkable groups include polyvinyl alcohol-polyacrylic acid copolymers. A polyvinyl alcohol-polyacrylic salt copolymer is preferable because of its high water absorption ability and high hydrogel strength even at high water absorption.
The content of polyacrylic acid in the polyvinyl alcohol-polyacrylic acid copolymer is, for example, 1 to 95 mol%, preferably 2 to 70 mol%, more preferably 3 to 60 mol%, and particularly preferably 5 to 50 mol%. It is. The acrylic acid content can be controlled by a known synthesis method.
In the polyvinyl alcohol-polyacrylic acid copolymer, the polyacrylic acid may be a salt. Examples of the polyacrylic acid salt in this case include ammonium salts and organic ammonium salts in addition to alkali metal salts such as sodium salts and potassium salts.

Polyvinyl alcohol is also available as a commercial product. Specific examples include PVA117 (manufactured by Kuraray Co., Ltd.), poval (manufactured by Kuraray), polyvinyl alcohol (manufactured by Aldrich), J-poval (manufactured by Nippon Vinegarten Poval). Although there are various molecular weight grades, those having a weight average molecular weight of 130,000 to 300,000 are preferred.
A polyvinyl alcohol-polyacrylate copolymer (sodium salt) is also available as a commercial product. For example, Crustomer AP20 (made by Kuraray Co., Ltd.) is exemplified.

  In the facilitated transport film 18 of the production method of the present invention, two or more hydrophilic compounds may be mixed and used.

The content of the hydrophilic compound in the coating composition 40 is such that the hydrophilic compound functions as a binder and can sufficiently hold moisture in the formed facilitated transport film 18, and the amount of the hydrophilic composition, the carrier, etc. It may be set appropriately according to the above.
Specifically, the content of the hydrophilic compound in the facilitated transport film 18 is preferably 0.5 to 50% by mass, more preferably 0.75 to 30% by mass, and 1 to 15% by mass. Is particularly preferred. By setting the content of the hydrophilic compound within this range, the above-mentioned function as a binder and the moisture retention function can be stably and suitably expressed.

The crosslinked structure of the hydrophilic compound can be formed by a known method such as thermal crosslinking, ultraviolet crosslinking, electron beam crosslinking, radiation crosslinking, or photocrosslinking.
Photocrosslinking or thermal crosslinking is preferred, and thermal crosslinking is most preferred.

The coating composition 40 preferably contains a crosslinking agent.
As the crosslinking agent, one containing a crosslinking agent that reacts with a hydrophilic compound and has two or more functional groups capable of crosslinking such as thermal crosslinking or photocrosslinking is selected. The formed crosslinked structure is preferably a hydrolysis-resistant crosslinked structure.
From such a viewpoint, the crosslinking agent added to the coating composition 40 includes epoxy crosslinking agent, polyvalent glycidyl ether, polyhydric alcohol, polyvalent isocyanate, polyvalent aziridine, haloepoxy compound, polyvalent aldehyde, polyvalent amine. An organic metal crosslinking agent is preferably exemplified. More preferred are polyvalent aldehydes, organometallic crosslinking agents and epoxy crosslinking agents, and among them, polyvalent aldehydes such as glutaraldehyde and formaldehyde having two or more aldehyde groups are preferred.

As an epoxy crosslinking agent, it is a compound which has 2 or more of epoxy groups, and the compound which has 4 or more is also preferable. Epoxy crosslinking agents are also available as commercial products, for example, trimethylolpropane triglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., Epolite 100MF, etc.), Nagase ChemteX Corporation EX-411, EX-313, EX-614B, Examples include EX-810, EX-811, EX-821, EX-830, NOF Corporation Epiol E400, and the like.
Moreover, as a compound similar to an epoxy crosslinking agent, an oxetane compound having a cyclic ether is also preferably used. As the oxetane compound, polyvalent glycidyl ether having two or more functional groups is preferable. Commercially available oxetane compounds are also available. Examples of commercially available oxetane compounds include EX-411, EX-313, EX-614B, EX-810, EX-811, EX-821, and EX-830 manufactured by Nagase ChemteX Corporation.

  Examples of the polyvalent glycidyl ether include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, propylene Examples include glycol glycidyl ether and polypropylene glycol diglycidyl ether.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, polyglycerin, propylene glycol, diethanolamine, triethanolamine, polyoxypropyl, and oxyethylene oxypropylene block copolymer. Examples include coalescence, pentaerythritol, and sobitol.

Examples of the polyvalent isocyanate include 2,4-toluylene diisocyanate and hexamethylene diisocyanate.
Examples of the polyvalent aziridines include 2,2-bishydroxymethylbutanol-tris [3- (1-acylidinyl) propionate], 1,6-hexamethylenediethyleneurea, diphenylmethane-bis-4,4′-N, N. Examples include '-diethylene urea.

Examples of the haloepoxy compound include epichlorohydrin and α-methylchlorohydrin.
Examples of the polyvalent aldehyde include glutaraldehyde and glyoxal.
Examples of the polyvalent amine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and polyethyleneimine.
Furthermore, examples of the organometallic crosslinking agent include organic titanium crosslinking agents and organic zirconia crosslinking agents.

For example, when polyvinyl alcohol having a weight average molecular weight of 130,000 or more is used as the hydrophilic compound, it is possible to form a crosslinked structure having good reactivity with this hydrophilic compound and excellent hydrolysis resistance. Therefore, an epoxy crosslinking agent and glutaraldehyde are preferably used.
When a polyvinyl alcohol-polyacrylic acid copolymer is used as the hydrophilic compound, an epoxy crosslinking agent or glutaraldehyde is preferably used.
When a polyallylamine having a weight average molecular weight of 10,000 or more is used as the hydrophilic compound, it is possible to form a crosslinked structure having good reactivity with this hydrophilic compound and excellent hydrolysis resistance. Epoxy crosslinking agents, glutaraldehyde, and organometallic crosslinking agents are preferably used.
When polyethyleneimine or polyallylamine is used as the hydrophilic compound, an epoxy crosslinking agent is preferably used.

What is necessary is just to set the quantity of a crosslinking agent suitably according to the kind of hydrophilic compound added to the coating composition 40, or a crosslinking agent.
Specifically, the amount is preferably 0.001 to 80 parts by weight, more preferably 0.01 to 60 parts by weight, and particularly preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the crosslinkable group possessed by the hydrophilic compound. preferable. By setting the content of the cross-linking agent in the above range, a facilitated transport film having good cross-linking structure formation and excellent shape maintainability can be obtained.
Further, when focusing on the crosslinkable group possessed by the hydrophilic compound, the crosslinked structure is formed by reacting 0.001 to 80 mol of a crosslinking agent with respect to 100 mol of the crosslinkable group possessed by the hydrophilic compound. preferable.

In the facilitated transport film 18, the carrier (acid gas carrier) reacts with an acid gas (for example, carbon dioxide gas (CO ₂ )) to transport the acid gas.

The carrier is a water-soluble compound having affinity with acidic gas and showing basicity. Specifically, an alkali metal compound, a nitrogen-containing compound, a sulfur compound, etc. are illustrated.
The carrier may react indirectly with the acid gas, or the carrier itself may react directly with the acid gas.
The former reacts with other gas contained in the supply gas, shows basicity, and the basic compound reacts with acidic gas. More specifically, OH react with steam (water) ^- was released, the OH ^- that reacts with CO _2, a compound can be incorporated selectively CO ₂ in facilitated transport membrane 18 For example, an alkali metal compound.
The latter is such that the carrier itself is basic, for example, a nitrogen-containing compound or a sulfur compound.

  Examples of the alkali metal compound include alkali metal carbonates, alkali metal bicarbonates, and alkali metal hydroxides. As the alkali metal, an alkali metal element selected from cesium, rubidium, potassium, lithium and sodium is preferably used. In the present invention, the alkali metal compound includes not only the alkali metal itself but also its salt and its ions.

Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate.
Examples of the alkali metal bicarbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate.
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide.
Among these, alkali metal carbonate is preferable. From the viewpoint of good affinity with acidic gas, a compound containing potassium, rubidium, and cesium having high solubility in water is preferable.

Moreover, when using an alkali metal compound as a carrier, two or more kinds of carriers may be used in combination.
When two or more kinds of carriers are present in the facilitated transport film 18, different carriers can be separated from each other in the film. Thereby, due to the difference in deliquescence of a plurality of carriers, due to the hygroscopicity of the facilitated transport film 18, the facilitated transport films 18 or the facilitated transport film 18 and other members are adhered to each other at the time of manufacture. (Blocking) can be suitably suppressed.
When two or more alkali metal compounds are used as a carrier, it is preferable to include a first compound having deliquescence and a second compound having lower deliquescence and lower specific gravity than the first compound. By containing such a 1st compound and a 2nd compound, the inhibitory effect of blocking is acquired more suitably. As an example, the first compound is exemplified by cesium carbonate, and the second compound is exemplified by potassium carbonate.

Nitrogen-containing compounds include amino acids such as glycine, alanine, serine, proline, histidine, taurine, diaminopropionic acid, hetero compounds such as pyridine, histidine, piperazine, imidazole, triazine, monoethanolamine, diethanolamine, triethanolamine , Alkanolamines such as monopropanolamine, dipropanolamine and tripropanolamine, cyclic polyetheramines such as cryptand [2.1] and cryptand [2.2], cryptand [2.2.1] and cryptand [ And bicyclic polyetheramines such as 2.2.2], porphyrin, phthalocyanine, ethylenediaminetetraacetic acid and the like.
Further, examples of the sulfur compound include amino acids such as cystine and cysteine, polythiophene, dodecylthiol and the like.

What is necessary is just to set content of the carrier in the coating composition 40 suitably according to the kind etc. of a carrier or a hydrophilic compound. Specifically, the amount of the carrier in the facilitated transport film 18 is preferably 0.3 to 30% by mass, more preferably 0.5 to 25% by mass, and 1 to 20% by mass. Is particularly preferred.
By setting the content of the carrier in the coating composition 40 within the above range, salting out before coating can be suitably prevented, and the formed facilitated transport film 18 reliably exhibits the function of separating acidic gas. it can.
In addition, the quantitative ratio of the hydrophilic compound to the carrier in the coating composition 40 is preferably 1: 9 to 2: 3 or less, more preferably 1: 4 to 2: 3 or less in terms of the mass ratio of the hydrophilic compound to the carrier. 3: 7-2: 3 is particularly preferred.

The coating composition 40 may contain a thickener as needed.
As the thickener, for example, thickening polysaccharides such as agar, carboxymethylcellulose, carrageenan, chitansan gum, guar gum and pectin are preferable. Among these, carboxymethylcellulose is preferable from the viewpoints of film forming property, availability, and cost.
By using carboxymethylcellulose, the coating composition 40 having a desired viscosity can be easily obtained with a small amount of content, and at least a part of components other than the solvent contained in the coating solution cannot be dissolved in the coating solution and deposited. There is little fear of doing.

The content of the thickener in the coating composition is preferably as small as possible if the content of the thickener in the composition (coating liquid) can be adjusted to the target viscosity.
As a general index, 10% by mass or less is preferable, 0.1 to 5% by mass is more preferable, and 0.1 to 2% by mass or less is more preferable.

  The coating composition 40 (facilitated transport film 18) may contain various components as required in addition to such a hydrophilic compound, a crosslinking agent and a carrier, or a thickener.

Examples of such components include an antioxidant such as dibutylhydroxytoluene (BHT), a compound having 3 to 20 carbon atoms or a fluorinated alkyl group having 3 to 20 carbon atoms and a hydrophilic group, and a siloxane structure. Specific compounds such as compounds having a surfactant, surfactants such as sodium octoate and sodium 1-hexasulfonate, polymer particles such as polyolefin particles and polymethyl methacrylate particles, and the like.
In addition, a catalyst, a moisturizing (moisture absorbing) agent, an auxiliary solvent, a film strength adjusting agent, a defect detecting agent, and the like may be used as necessary.

The coating composition 40 may be prepared by a known method. That is, first, the hydrophilic compound, the carrier, and other components to be added as necessary are respectively added to water (room temperature water or warm water) in appropriate amounts and sufficiently stirred to facilitate the transport film 18. A coating composition 40 is prepared.
In preparation of this coating composition 40, you may accelerate | stimulate melt | dissolution of each component by heating, stirring as needed. Moreover, after adding a hydrophilic compound to water and melt | dissolving, precipitation (salting out) of a hydrophilic compound can be effectively prevented by adding a carrier gradually and stirring.

The application unit 28 (application process) is a part where such an application composition 40 is applied to the support 12 conveyed in the longitudinal direction.
In the illustrated example, the coating unit 28 is a known roll coater and includes a filling tank 42 that fills the coating composition 40, a coating roller 46, a metering roller 48, and a backup roller 50.
The support 12 is conveyed while being kept at a predetermined application position by the backup roller 50, attached to the application roller 46 from the filling tank 42, and the application amount is adjusted by a metering roller 48 that rotates in the reverse direction of the application roller 46. The coating composition 40 is applied by a coating roller 46.

In the production method of the present invention, as the roll coater, a direct gravure coater, an offset gravure coater, a single roll kiss coater, a three reverse roll coater, a positive rotation roll coater, etc. can be used in addition to the illustrated examples.
In addition to the roll coater, the coating composition 40 can be applied to various types such as curtain flow coaters, extrusion die coaters, air doctor coaters, blade coaters, rod coaters, knife coaters, squeeze coaters, reverse roll coaters, bar coaters and the like. The coating device (coating method) can be used.

The thickness (coating thickness / coating film thickness) of the coating composition 40 applied to the support 12 depends on the concentration of the hydrophilic compound, carrier, etc. in the coating composition 40, the desired film thickness of the facilitated transport film 18, etc. And may be determined as appropriate.
Specifically, the thickness of the coating composition 40 applied to the support 12 is preferably 0.05 to 10 mm, and more preferably 0.1 to 5 mm.
By setting the thickness of the coating composition 40 in the above range, the facilitated transport film 18 that prevents the film thickness from becoming excessively thin and expresses the target performance can be stably formed. It is preferable in that it is possible to suitably suppress the occurrence of defects due to bubbles and foreign matters and the occurrence of an undried state due to being too much.

In the production method of the present invention, the film thickness of the facilitated transport film 18 formed by drying the coating composition 40 described later depends on the concentration of the hydrophilic compound, the carrier, etc., the composition of the intended facilitated transport film 18, and the like. The film thickness that provides the desired performance may be set as appropriate.
Specifically, 0.01 to 3 mm is preferable, 0.05 to 2.5 mm is more preferable, and 0.1 to 2 mm is particularly preferable. By making the thickness of the facilitated transport film 18 in the above range, it is preferable in that sufficient gas permeability and separation selectivity can be realized.
That is, in the coating part 28, the coating film thickness of the coating composition 40 is set so that the facilitated transport film 18 having such a desired film thickness can be obtained.
Therefore, in the production method of the present invention, the coating composition 40 is prepared so that the facilitated transport film 18 having a film thickness of 0.01 to 3 mm can be obtained with the coating thickness of the coating composition 40 of 0.05 to 10 mm. It is preferable to do this.

The support 12 coated with the coating composition 40 in the coating unit 28 is guided to the pass roller 54 that contacts the back surface (the surface opposite to the coating surface of the coating composition 40) and is conveyed to the drying unit 30.
The drying unit 30 (drying step) removes at least a part of water from the coating composition 40 coated on the support 12 and dries, or further crosslinks the hydrophilic compound, thereby forming the facilitated transport film 18. This is the part where the acid gas separation membrane 14 is formed.
In the production method of the present invention, after the coating composition 40 is dried, the facilitated transport film 18 may be formed by crosslinking a hydrophilic compound as necessary.

As the drying method, various known methods for drying by removing water, such as hot air drying or a drying method by heating the support 12, can be used.
When performing warm air drying, the speed of the warm air may be set as appropriate so that the coating composition 40 can be dried quickly and the coating film (gel film) of the coating composition 40 does not collapse. Specifically, 0.5 to 200 m / min is preferable, 0.75 to 200 m / min is more preferable, and 1 to 200 m / min is particularly preferable.
The temperature of the warm air may be appropriately set to a temperature at which the support 12 is not deformed and the coating composition 40 can be dried quickly. Specifically, the film surface temperature is preferably 1 to 120 ° C, more preferably 2 to 115 ° C, and particularly preferably 3 to 110 ° C.

When drying by heating the support 12, the temperature at which the support 12 is not deformed and the coating composition 40 can be dried quickly may be set as appropriate. You may use blowing of a dry wind for heating of the support body 12 together.
Specifically, the temperature of the support 12 is preferably 60 to 120 ° C, more preferably 60 to 90 ° C, and particularly preferably 70 to 80 ° C. In this case, the film surface temperature is preferably 15 to 80 ° C, and more preferably 30 to 70 ° C.

Moreover, the film strength of the facilitated transport film 18 formed in this way is the type and thickness of the release film 20, the mechanical strength of the release film 20 (so-called stiffness, etc.), and the release film 20. Set appropriately according to the adhesive strength, the use of the acid gas separation membrane 14, the use conditions of the acid gas separation membrane 14 (pressure, temperature, supply amount of raw material gas, raw material gas composition, water vapor partial pressure of the raw material gas, etc.) do it.
Specifically, the film strength of the facilitated transport film 18 is preferably 0.005 MPa or more, more preferably 0.01 MPa or more, and particularly preferably 0.015 MPa or more. The membrane strength is the membrane strength of the facilitated transport membrane 18 alone, excluding the release film 20 and the support 12 from the laminate 24.
By setting the film strength of the facilitated transport film 18 within this range, the film can be bonded to the release film 20 or peeled off from the release film 20 without causing film defects in the facilitated transport film 18. This is preferable. In the present invention, it is also preferable to select the release film 20 according to the film strength of the facilitated transport film 18.

The acidic gas separation membrane 14 produced by forming the facilitated transport film 18 by drying the coating composition 40 in the drying unit 30 is then conveyed to the stacking unit 32. The acidic gas separation membrane 14 includes a laminate 24 in which the release film 20 is laminated and pasted on the surface of the facilitated transport membrane 18 in the lamination portion 32, and the acidic gas separation membrane 14 and the release film 20 are laminated. Is done. In the present invention, it is preferable that nothing is in contact with the facilitated transport film 18 until the release film 20 is laminated downstream of the drying unit 30 (downstream in the transport direction).
The operation in the laminating section 32, that is, the step of laminating and sticking the release film 20 (lamination step) is a characteristic step of the production method of the present invention.

In the illustrated example, the stacking unit 32 includes a stacking roller 56, a backup roller 58, and a rotating shaft 60.
The rotary shaft 60 is loaded with a film roll 20R formed by winding a long (web-like) release film 20. The rotating shaft 60 sends out the release film 20 from the film roll 20R by rotating the film roll 20R.
The lamination roller 56 and the backup roller 58 form a conveying roller pair.

The acidic gas separation membrane 14 on which the facilitated transport membrane 18 is formed is nipped and conveyed by the laminating roller 56 and the backup roller 58.
The release film 20 sent out from the film roll 20R is also brought into contact with the facilitated transport film 18 of the acidic gas separation film 14, supplied (conveyed) between the lamination roller 56 and the backup roller 58, and nipped and conveyed.
Therefore, the release film 20 is laminated on the facilitated transport film 18 of the acidic gas separation film 14 by the sandwiching and transporting of the acidic gas separation film 14 and the release film by the lamination roller 56 and the backup roller 58. A laminated body 24 in which the acidic gas separation membrane 14 and the release film 20 are laminated is formed by being attached.

  By having such a configuration, the production method of the present invention can prevent the facilitated transport membrane 18 from peeling (membrane peeling) in the production of the acidic gas separation membrane 14 by RtoR.

As described above, the facilitated transport film 18 is very hygroscopic. Therefore, according to the study of the present inventors, when the acidic gas separation membrane 14 having a facilitated transport membrane is manufactured by RtoR, the facilitated transport membrane adheres to the pass roller or the like depending on the composition or atmosphere of the facilitated transport membrane 18, In some cases, the acid gas separation membrane may be peeled off. Further, after the facilitated transport film 18 is formed, the facilitated transport film adheres to the back surface of the acidic gas separation film and is peeled off even if the member is not in contact with the facilitated transport film 18 until it is wound into a roll. There is a case where it ends up.
As a result, a defective portion is formed in the acidic gas separation membrane. Further, there is a problem that the facilitated transport film attached to the back surface of the pass roller or the acid gas separation membrane adheres to the acid gas separation membrane or the like manufactured thereafter and is contaminated.

On the other hand, in the production method of the present invention, in the production of the acidic gas separation membrane 14 by RtoR, after the facilitated transport membrane 18 is formed, before any object contacts the facilitated transport membrane 18, The release film 20 is laminated and pasted on. That is, the surface of the facilitated transport film 18 is covered with the release film 20.
Therefore, according to the present invention, after the facilitated transport film 18 is formed, no objects (including acid gas separation membranes) come into direct contact with the facilitated transport film 18. Can be prevented. As a result, according to the present invention, contamination of the manufacturing apparatus and the acidic gas separation membrane, generation of defects in the acidic gas separation membrane, and the like caused by peeling of the facilitated transport membrane 18 are prevented, and there are no defects or contamination. A high-quality acid gas separation membrane can be stably produced with high productivity by RtoR.

In the production method of the present invention, the release film 20 has sufficient adhesion to the acidic gas separation membrane 14 (facilitated transport membrane 18), and the facilitated transport membrane 18 peels off in a later step. Various sheet-like materials (film-like materials) can be used as long as they can be peeled off from the acidic gas separation membrane 14 and can prevent the peeling of the facilitated transport membrane 18 due to contact with other members. Is possible.
Specifically, plastic films such as polyethylene terephthalate (PET), polymethylpentene (TPX), polypropylene (unstretched polypropylene (CPP), biaxially stretched polypropylene (OPP)), polyethylene (PAC), paper, etc. Is exemplified.

The release film 20 may have a single layer configuration. Alternatively, the release film 20 has a multi-layer configuration such as a configuration in which one or more layers (functional layers) expressing various functions are formed on a laminate of a plurality of sheet-like materials or a substrate (base material). May be.
The release film 20 having a configuration in which a functional layer is formed on a substrate may be a configuration having a functional layer only on one side or a configuration having a functional layer on both sides. In the release film 20 having functional layers on both surfaces, the functional layers formed on each surface may be the same or different.

As an example, a release film 20 in which a thin film having good peelability such as a silicon-based thin film is formed on a plastic film such as a PET film is illustrated.
The release film 20 is required to be in close contact with the facilitated transport film 18 and to be peeled off. On the other hand, the facilitated transport film 18 may have adhesiveness due to its hygroscopicity. In this case, it is conceivable to use a release film having good peelability. However, release films with good releasability often have high lubricity, and winding does not work well, and even if the film is wound well, the wound product may collapse during handling.
In such a case, it is preferable to use a release film 20 in which a silicon-based thin film is formed on a PET film, and laminate and paste the silicon-based thin film with the facilitated transport film 18 side. Thereby, the peelability to the facilitated transport film 18 can be secured by the silicon-based thin film, and further, the friction force can be secured by the PET film so that the laminate 24 can be reliably wound and the wound material is prevented from collapsing. it can.
In the present invention, as described above, the release film 20 in which a silicon-based thin film is formed on a PET film can be suitably used as a film in which a silicon-based thin film is formed on only one side or a film on both sides. However, in consideration of the above points, a PET film in which a silicon-based thin film is formed only on one side is more preferably used.

In the present invention, a PAC film, a CCP film, an OPP film or the like on which a silicon thin film is formed can be suitably used in addition to the PET film on which such a silicon thin film is formed (silicon coating). Among these, a PET film or a PAC film on which a silicon-based thin film is formed is more preferably used.
In these films, the silicon-based thin film may be formed on both sides or only on one side, as described above, but more preferably on only one side.
As the silicon-based thin film, specifically, a thin film made of silicone is preferably exemplified. When the release film 20 has a silicon-based thin film or the like, the total thickness of the release film 20 including the silicon-based thin film or the like is preferably 200 μm or less from the viewpoint of handling and the like.

The release film 20 is preferably laminated on the acidic gas separation membrane 14 so that at least one surface is hydrophobic and the hydrophobic surface faces the facilitated transport membrane 18.
By laminating the hydrophobic surface of the release film 20 toward the facilitated transport film 18, it is possible to prevent peeling of the facilitated transport film 18 when the release film 20 is detached from the laminate 24 in a later step. It is preferable in that it can be properly peeled off.

What is necessary is just to set the thickness of the release film 20 suitably according to the thickness of the acidic gas separation membrane 14, the kind of the facilitated-transport film | membrane 18, etc.
Specifically, 0.005 to 0.1 mm is preferable, and 0.01 to 0.1 mm is more preferable.
By setting the thickness of the release film 20 within this range, the facilitated transport film 18 can be reliably laminated and adhered, and the release film 20 can be prevented from being peeled off. This is preferable in that it can be easily performed, and the handleability of the release film 20 is improved.

The laminated body 24 is required to be able to be peeled off easily without causing the acidic gas separation membrane 14 and the release film 20 to be in close contact with each other and causing the peeling of the facilitated transport membrane 18 to occur.
Considering this point, the peeling force of the release film 20 is preferably 0.07 to 10 N / mm, and more preferably 0.07 to 1 N / mm.
The release force of the release film 20 is No. manufactured by Nitto Denko Corporation. It is the average value of the peeling force when a 31B tape is applied and peeled at a speed of 300 mm / min and an angle of 180 °.

As described above, when the facilitated transport film 18 has adhesiveness (adhesiveness / sticking property) and sufficient adhesion can be obtained, the acidic gas separation membrane 14 (facilitated transport film 18) is used. The release film 20 may be attached using the adhesiveness of the facilitated transport film 18. That is, in this case, the peeling force of the release film 20 may be weak, and the release film 20 itself may not have adhesiveness.
On the other hand, when the facilitated transport film 18 does not have adhesiveness, it is preferable that the release film 20 has moderate adhesiveness and a certain degree of peelability.
Further, both the facilitated transport film 18 and the release film 20 may have adhesiveness as long as sticking and peeling can be performed appropriately.
That is, in the present invention, the adhesion (adhesion / adhesion) between the facilitated transport film 18 (acid gas separation film 14) and the release film 20 is in an appropriate range according to the adhesive strength of the facilitated transport film 18. It is preferable to select the release film 20 having an appropriate peeling force, adjust the peeling force of the release film 20, and so on.
For example, the adhesion of the facilitated transport film 18 varies depending on the type and composition of the hydrophilic compound (binder) contained, the amount of the carrier contained in the facilitated transport film 18, and the like.

In the production method of the present invention, such a release film 20 does not cause the acid gas separation membrane 14 to be wrinkled or cause peeling or defects of the facilitated transport membrane 18. What can be laminated and adhered to the transport membrane 18) and can be peeled off from the acidic gas separation membrane 14 may be appropriately selected.
Specifically, the mechanical strength and thickness of the acid gas separation membrane 14, the type and thickness of the support 12 (formation material and layer structure), the type of the facilitated transport membrane 18 (type and content of the hydrophilic compound) In consideration of the type and content of the carrier, other components and the content thereof, the thickness, and the like, a suitable release film 20 may be appropriately selected.

In the production method of the present invention, the temperature of the acidic gas separation membrane 14 and the release film 20 when the release film 20 is laminated and adhered to the acidic gas separation membrane 14 (facilitated transport membrane 18) is the acidic gas separation. What is necessary is just to set suitably according to the kind and thickness of the film | membrane 14, the kind and thickness of the release film 20, etc. Specifically, 10-70 degreeC is preferable and 20-60 degreeC is more preferable.
By laminating and sticking the acid gas separation membrane 14 and the release film 20 at the above temperature, it is preferable in that proper lamination and sticking are possible without causing wrinkles or the like in both.
In addition, when laminating | stacking and sticking the release film 20 on the acidic gas separation membrane 14, at least one of the acidic gas separation membrane 14 and the release film 20 should just be the said temperature.

The atmosphere between the laminated unit 32 and the drying unit 30 and the laminated unit 32 is basically preferably low humidity.
By making these parts low humidity, it is preferable in terms of preventing the facilitated transport film 18 from absorbing excess moisture.

  The temperature adjustment of the acid gas separation membrane 14 and / or the release film 20 may be performed by a known method. Moreover, what is necessary is just to perform control of the atmospheric humidity between the lamination | stacking part 32 and the drying part 30, and the lamination | stacking part 32 by a well-known method.

The shorter the distance between the drying unit 30 and the stacked unit 32, the better.
By shortening this distance, it is preferable in terms of preventing foreign matters and the like from adhering to the surface of the facilitated transport film 18 and preventing moisture absorption of the facilitated transport film 18.

The tension applied to the conveyed sheet-like material may be the same in the upstream and downstream of the stacked unit 32, but it is preferable to increase the downstream tension.
Thereby, it is preferable at the point that appropriate lamination | stacking and sticking are possible, without producing wrinkles etc. in the acidic gas separation membrane 14 and the release film 20. FIG.
Note that the tension applied to the conveyed sheet-like material may be controlled by a known method.

  In the production method of the present invention, the release film 20 may be laminated by various known sheet-like lamination methods other than the method using the lamination roller 56 (a pair of rollers for lamination). Is possible.

The acidic gas separation membrane 14, that is, the laminate 24, on which the release film 20 is laminated in the lamination unit 32, is then conveyed to the winding unit 34.
The winding unit 34 is a part that winds (winds up) the laminate 24 around the take-up shaft 62 to form the laminate roll 24R. This laminated body roll 24R is the acid gas separation membrane wound product of the present invention.

The winding unit 34 includes the above-described winding shaft 62 and four pass rollers 64a to 64d.
The laminated body 24 is guided along a predetermined transport station path by the pass rollers 64a to 64d, and is taken up by the take-up shaft 62 (laminated body roll 24R) to form a laminated body roll 24R.
The four pass rollers 64a to 64d also act as tension cutters between the laminated portion 32 and the winding shaft 62, and guide the laminated body 24 so as to meander.

Hereinafter, an example of the operation of the manufacturing apparatus 10 will be described.
First, the support roll 12R is mounted on the rotation shaft 38 of the supply unit 26, and the rotation shaft 38 is rotated to feed the support 12 from the support roll 12R. Next, the support body 12 sent out from the support body roll 12R is applied to the coating unit 28 (backup roller 50), the pass roller 54, the drying unit 30, the stacking unit 32 (the backup roller 58 and the stacking roller 56), and the pass rollers 64a to 64d. Then, the leading end of the support 12 is wound around the take-up shaft 62 through a predetermined conveyance path that reaches the take-up shaft 62 (insertion / sheet feeding).
Next, the film roll 20R is mounted on the rotating shaft 60, the release film 20 is sent out, conveyed to the stacking section 32, and brought into contact with the surface on which the facilitated transport film 18 of the support 12 is formed. It is sandwiched between the lamination rollers 56.
On the other hand, the filling tank 42 is filled with a necessary amount of the coating composition 40.

  When the support 12 is passed through a predetermined conveyance path, the release film 20 is sandwiched between the backup roller 58 and the laminating roller 56, and the coating composition 40 is filled in the filling tank 42, the rotary shaft 38 and the winding shaft 62 are filled. , And the backup roller 58 and the like are driven in synchronization, and the conveyance of the support 12 and the release film 20 is started.

The support 12 delivered from the support roll 12R is first transported while being supported at a predetermined application position by the backup roller 50 in the coating unit 28 while being transported in the longitudinal direction. A thick (coating amount) coating composition is applied.
Next, the support 12 is guided by the pass roller 54 to reach the drying unit 30, and the coating composition 40 is dried in the drying unit 30, whereby the facilitated transport film 18 is formed, and the acid gas separation film 14 is produced. The

Next, the acid gas separation membrane 14 is laminated and pasted by the release film 20 while being sandwiched and conveyed between the backup roller 58 and the lamination roller 56 in the lamination unit 32, thereby forming the laminate 24.
The laminated body 24 is conveyed to the winding unit 34, guided along a predetermined conveyance path by the pass rollers 64a to 64d, and wound around the winding shaft 62 (laminated body roll 24R).
Here, in the manufacturing apparatus 10 that implements the manufacturing method of the present invention, since the release film 20 is laminated on the acidic gas separation film 14, the facilitated transport film 18 that has been peeled off is attached to the pass rollers 64a to 64d. Further, the facilitated transport film 18 does not adhere to the back surface of the wound acid gas separation membrane 14 (the surface opposite to the facilitated transport film 18).

In the acidic gas separation membrane 14, it is often desirable to make the facilitated transport membrane 18 thick. However, in many cases, the facilitated transport film 18 having a desired thickness cannot be formed by a single application due to the application apparatus and the application composition 40.
On the other hand, in the manufacturing method of the present invention, the laminate 24 is further fed out from the laminate roll 24R, the release film 20 is peeled off, and the coating composition is applied onto the facilitated transport film 18 previously created. Alternatively, the facilitated transport film 18 having a two-layer (or three or more layers) structure may be formed by drying.

FIG. 3 conceptually shows a manufacturing apparatus that performs this operation.
The manufacturing apparatus 70 shown in FIG. 3 has the same configuration as the above-described manufacturing apparatus 10 except that the peeling unit 72 is provided between the supply unit 26 and the coating unit 28. In addition, the following description mainly performs different parts.

As described above, the manufacturing apparatus 70 includes the peeling unit 72 between the supply unit 26 and the coating unit 28. The peeling portion 72 includes a peeling roller pair 74 and a winding shaft 76.
The peeling roller pair 74 is a known peeling roller pair, and peels the release film 20 from the laminate 24 (acid gas separation membrane 14). The take-up shaft 76 is a film roll 20aR formed by winding up the used release film 20a peeled off by the peeling roller pair 74 and winding the used release film 20a.

When the second layer (third and subsequent layers) facilitated transport film 18 is formed by the manufacturing apparatus 70 shown in FIG. 3, the laminate roll 24 </ b> R is mounted on the rotation shaft 38 of the supply unit 26.
When the laminate roll 24R is mounted on the rotating shaft 38, the laminate 24 is sent out, passes through the peeling portion 72 (peeling roller pair 74), and thereafter, similarly to the above, the application portion 28, the drying portion 30, and the lamination portion. The laminated body 24 is passed through a predetermined conveyance path that passes through 32 and reaches the winding shaft 62 of the winding unit 34.
Here, when the laminated body 24 is passed through the peeling roller pair 74, the release film 20 is peeled from the laminated body 24 immediately downstream of the peeling roller pair 74, and the used release film 20 a is taken up by the winding shaft. The leading end of the used release film 20 a is wound around the winding shaft 76 through a predetermined path leading to 76.

While the laminate 24 fed from the laminate roll 24R is conveyed in the longitudinal direction, the release film 20 is first peeled off by the pair of peeling rollers 74 of the peeling portion 72, and the acidic gas separation membrane 14 alone is applied. It is conveyed to the section 28.
Moreover, the used release film 20a peeled from the laminated body 24 is wound up by the winding shaft 76 (film roll 20aR).

The acidic gas separation membrane 14 conveyed to the coating unit 28 is coated with the coating composition 40a on the facilitated transport membrane 18 in the same manner as described above.
The coating composition 40a (that is, the facilitated transport film formed by this operation) may be the same as the coating composition 40 previously applied. Alternatively, the coating composition 40a may be different from the coating composition 40 previously coated in composition, type and number of components to be contained, pH, concentration of each component to be contained, viscosity, and the like.

After that, the acidic gas separation membrane 14 coated with the coating composition 40a is dried from the coating composition 40a by the drying unit 30 to form a second facilitated transport membrane, as in the previous manufacturing apparatus 10. The acid gas separation membrane 14a.
Next, as a preferred embodiment, in the laminated portion 32, the release film 20 is laminated and pasted to obtain a laminated body 24a. This release film 20 may be a used release film 20a. That is, in the manufacturing apparatus 70, the film roll 20R may be the film roll 20aR.
Furthermore, it is conveyed to the winding unit 34, guided along a predetermined conveyance path by the pass rollers 64a to 64d, wound around the winding shaft 62, and is formed into a laminated body roll 24aR formed by winding the laminated body 24a.

Although the manufacturing apparatus 70 shown in FIG. 3 peels the release film 20 using the peeling roller pair 74, various structures other than this structure can be used. For example, instead of the pair of peeling rollers 74, one peeling roller is provided in contact with the backup roller 50 of the coating unit 28, and the release film 20 is peeled from the acid gas separation film 14 of the laminate 24. May be.
In the production method of the present invention, the facilitated transport membrane 18 is formed on the support 12 by the production apparatus 70 shown in FIG. 3 to produce the acid gas separation membrane 14, and the release film 20 is laminated to obtain the laminate. 24 may be formed to form a laminate roll 24R. In this case, the separation roller pair 74 may be separated from the roller so as not to contact the support 12.

  As mentioned above, although the manufacturing method of the acidic gas separation membrane and acidic gas separation membrane winding material of this invention were demonstrated in detail, this invention is not limited to the above-mentioned example, In the range which does not deviate from the summary of this invention, it is various. Of course, improvements and changes may be made.

  Hereinafter, the specific Example of this invention is given and the manufacturing method of an acidic gas separation membrane of this invention and an acidic gas separation membrane winding thing are demonstrated in detail.

[Example 1]
`` T.Sato, et al. (1993) .Synthesis of poly (vinyl alcohol) having a thiol group at one end and new block copolymers containing poly (vinyl alcohol) as one cinsistent. Macromolecular Chemistry and Physics, 194,175-185 '' A polyvinyl alcohol-polyacrylic acid copolymer was synthesized with reference to the method described. The polyvinyl alcohol-polyacrylic acid copolymer was synthesized by adjusting the raw materials so that the molar ratio of polyvinyl alcohol to polyacrylic acid was 3: 7.
An aqueous solution containing 2.4% by mass of this polyvinyl alcohol-polyacrylic acid copolymer and 0.01% by mass of a cross-linking agent (25% by mass glutaraldehyde aqueous solution manufactured by Wako Pure Chemical Industries, Ltd.) was prepared. To this aqueous solution, 1 M hydrochloric acid was added until the pH reached 1.7 to cause crosslinking.
After crosslinking, a 40% aqueous cesium carbonate solution (manufactured by Rare Metal Co., Ltd.) was added so that the concentration of cesium carbonate was 6.0% by weight. That is, in this example, cesium carbonate becomes a carrier of the facilitated transport film 18.
Furthermore, a surfactant (1% by mass of Lapisol A-90 manufactured by NOF Corporation) was added in an amount of 0.003% by mass to prepare a coating composition 40.

On the other hand, a support roll 12R formed by winding a long (porous) support body 12 having a width of 500 mm and a thickness of 200 μm in a roll shape was prepared. This support 12 is a laminate (manufactured by GE) formed by laminating porous PTFE on the surface of a PP nonwoven fabric.
Furthermore, a film roll 20R formed by winding a long release film 20 having a width of 500 mm and a thickness of 38 μm into a roll was prepared. This release film 20 is a PET film (manufactured by Mitsui Chemicals, Inc.) made by forming a silicon-based thin film on one surface. Further, the release film 20 is a film having a peel force (silicon thin film side) of 0.07 N / mm (measured using a desktop peel test apparatus).

First, the support roll 12R was mounted on the rotating shaft 38 of the supply unit 26 of the manufacturing apparatus 10 shown in FIG. 1 so that the coating composition 40 was applied to the porous PTFE side. Next, the support 12 is sent out from the support roll 12R, and as described above, the support 12 passes through the coating unit 28, the drying unit 30 and the stacking unit 32 through a predetermined transport path to the winding unit 34, and the support 12 The tip was wound around the winding shaft 62.
Thereafter, the film roll 20 </ b> R was mounted on the rotating shaft 60 of the laminated portion 32 of the manufacturing apparatus 10 so that the silicon thin film faced the coating surface of the coating composition 40. Next, the release film 20 is sent out from the film roll 20R, and the front end is sandwiched between the backup roller 58 and the lamination roller 56 so as to be in contact with the formation surface (porous PTEF surface) of the facilitated transport film 18 of the support 12. It was.
On the other hand, a necessary amount of the prepared coating composition 40 was filled in the filling tank 42 of the coating unit 28.

After the above preparation is completed, the conveyance of the support 12 is started, and the coating composition 40 is applied to the surface of the support 12 in the coating unit 28 as described above, and the coating composition 40 is coated in the drying unit 30. The facilitated transport film 18 is dried to form the acid gas separation film 14, the release film 20 is laminated and pasted at the lamination part 32 to form the laminate 24, and the produced laminate 24 is further wound onto the winding shaft 62. The laminate roll 24R was produced.
The conveyance speed of the support 12 was 3 m / min.
Application | coating of the coating composition 40 was performed so that the thickness of the coating composition 40 on the support body 12 might be set to 0.6 mm. The thickness of the coating composition 40 is such that the facilitated transport film 18 formed by drying has a thickness of 0.03 mm.
Drying in the drying unit 30 was performed at a multistage heating temperature of 70 ° C., 80 ° C., 90 ° C., 100 ° C., 110 ° C. and 120 ° C. using a warm air drying furnace.
In this example, in order to show the effect of the present invention more remarkably, the humidity of the atmosphere from the laminated portion 32 to the pass roller 64a was controlled to 70% RH, which is higher than usual.

When the laminated body 24 was manufactured to 200 m, conveyance of the support 12 was stopped, and the laminated body 24 was cut between the backup roller 58 and the pass roller 64a. Next, the laminate 24 was wound up to the end, and the laminate roll 24 </ b> R was removed from the take-up shaft 62.
When the pass rollers 64a to 64d were confirmed, adhesion of the facilitated transport film 18 that was peeled off was not observed.
Further, when the laminated body 24 of 150 m was pulled out from the laminated body roll 24R, the facilitated transport film 18 that was peeled off and adhered to the laminated body 24 was not recognized.

[Example 2]
A coating composition 40 was prepared in the same manner as in Example 1 except that a 40% aqueous cesium carbonate solution was added so that the concentration of cesium carbonate was 3.0% by weight.
Except for using this coating composition and using a release film (manufactured by Mitsui Chemicals Tosero Co., Ltd.) having a peel strength of 0.15 N / mm and a silicon-based thin film formed on one surface as the release film 20. In the same manner as in Example 1, a laminate roll 24R was produced.
When confirmed in the same manner as in Example 1, neither the pass rollers 64a to 64d nor the laminate 24 was found to adhere to the facilitated transport film 18 that had been peeled off.

[Example 3]
A coating composition 40 was prepared in the same manner as in Example 1 except that polyvinyl alcohol (PVA117 manufactured by Kuraray Co., Ltd.) was used instead of the polyvinyl alcohol-polyacrylic acid copolymer.
A laminate roll 24R was prepared in the same manner as in Example 1 except that this coating composition 40 was used and a PAC film (manufactured by Sanei Kaken Co., Ltd.) having a peeling force of 1 N / mm was used as the release film 20. Produced.
When confirmed in the same manner as in Example 1, neither the pass rollers 64a to 64d nor the laminate 24 was found to adhere to the facilitated transport film 18 that had been peeled off.

[Example 4]
In the same manner as in Example 1, a laminate roll 24R formed by winding a 230m laminate 24 was produced.
This laminate roll 24R was mounted on the rotating shaft 38 of the supply unit 26 of the manufacturing apparatus 70 shown in FIG. 3 so that the coating composition 40a was applied to the facilitated transport film 18 side. Next, similarly to Example 1, the laminated body 24 was pulled out from the laminated body roll 24 </ b> R, passed through the winding unit 34, and the tip was wound around the winding shaft 62. At the time of this paper passing, the release film 20 was peeled immediately downstream of the pair of peeling rollers 74, passed through a predetermined path of the peeling portion 72, and the tip was wound around the winding shaft 76.
Further, a film roll 20R formed by winding the same release film 20 as in Example 1 is mounted on the rotating shaft 60 in the same manner as in Example 1, and the leading edge of the release film 20 is attached to the backup roller 58 and the lamination roller 56. I was pinched. As described above, the release film 20 is a PET film with a silicon-based thin film, and the peeling force is 0.07 N / mm.
The filling tank 42 was filled with the same coating composition as in Example 1 as the coating composition 40a.

After completing the above preparation, the coating composition 40a (same as the coating composition 40) was applied to the surface of the acidic gas separation membrane 14 (facilitated transport membrane 18) and dried in the same manner as in Example 1. A layered facilitated transport film 18 is formed, and a release film 20 is laminated and adhered thereon to produce a laminated body 24a, wound around a take-up shaft 62, and wound around a 200m laminated body 24a. A laminate roll 24aR was prepared.
When confirmed in the same manner as in Example 1, neither the pass rollers 64a to 64d nor the laminate 24 was found to adhere to the facilitated transport film 18 that had been peeled off.

[Example 5]
Coating composition 40 was carried out in the same manner as in Example 1 except that a commercially available polyvinyl alcohol-polyacrylic acid copolymer (Clastomer AP20 manufactured by Kuraray Co., Ltd.) was used instead of the synthesized polyvinyl alcohol-polyacrylic acid copolymer. Was prepared.
A laminate roll 24R having a length of 230 m was produced in the same manner as in Example 1 except that this coating composition 40 was used and the same release film 20 as that in Example 3 was used. As described above, the release film 20 is a PAC film, and the peeling force is 1 N / mm.

Except for using this laminate roll 24R and using the same release film 20 as in Example 2 (release film with silicon-based thin film peeling force 0.15 N / mm), Example 4 and In the same manner (that is, the coating composition 40a is the same as in Example 1), a laminate roll 24aR formed by winding a 200 m laminate 24a was produced.
When confirmed in the same manner as in Example 1, neither the pass rollers 64a to 64d nor the laminate 24 was found to adhere to the facilitated transport film 18 that had been peeled off.

[Example 6]
Prior to the formation of the facilitated transport film 18, a laminate roll 24 </ b> R was produced in the same manner as in Example 1 except that an intermediate layer was formed on the surface of the support 12.
As a coating composition for forming an intermediate layer, epoxy-modified polydimethylsiloxane (KF-102 manufactured by Shin-Etsu Chemical Co., Ltd.), and as a curing agent, 4-isopropyl-4′-methyldiphenyliodonium tetrakis (manufactured by Tokyo Chemical Industry Co., Ltd.) A coating composition in which 0.5% by weight of pentafluorophenyl) borate was added to the silicone resin was prepared.
The coating composition is applied to the support 12 while transporting the support 12 in the longitudinal direction using a general known apparatus using RtoR, and then irradiated with ultraviolet rays by a curing device to apply the coating composition. Was cured to form an intermediate layer made of silicone resin on the support 12. The thickness of the intermediate layer was 10 μm. Here, the thickness of the intermediate layer was the sum of the thickness of the silicone resin soaked in the support 12 and the thickness of the silicone resin formed on the support 12. The thickness of the silicone resin soaked into the support 12 was measured by Si element distribution by EDX (energy dispersive X-ray absorption method).

[Comparative Example 1]
Except not using the release film 20, the acidic gas separation membrane 14 was produced similarly to Example 1, and the roll formed by winding this acidic gas separation membrane 14 was produced. The laminating roller 56 was moved upward so as not to contact the produced facilitated transport film 18.
When confirmed in the same manner as in Example 1, the humidity of the atmosphere from the laminated portion 32 to the pass roller 64a may be as high as 70% RH, and adhesion of the peeled facilitated transport film 18 to the pass rollers 64b and 64d was confirmed. . For the same reason, peeling of the facilitated transport film 18 is observed in some places on the acidic gas separation membrane 14 drawn from the roll, and further, the facilitated transport film 18 is peeled off from the back surface of the support 12. Was recognized.

[Performance evaluation]
<Appearance evaluation of facilitated transport film 18>
The laminate 24 (24a) was pulled out from the produced separation membrane roll, and the release film 20 was peeled off to obtain the acidic gas separation membrane 14 (14a).
The acid gas separation membrane 14 was cut into a 1 cm square at an arbitrary position in the longitudinal direction of the acid gas separation membrane 14 at the center in the short direction, and five samples for defect evaluation were produced.
The smoothness of each sample was visually confirmed, and further, the presence or absence of defects was confirmed by observing the coated surface with a scanning electron microscope (SEM) and evaluated as follows. Here, the “defect” refers to a portion where the facilitated transport film 18 can be confirmed by observation with an SEM.
A: In all samples, the surface of the facilitated transport film 18 is smooth and free from defects.
B: Concavities and convexities are observed on the surface of the facilitated transport film 18 in one or more samples, but all the samples are free of defects.
C: Defects are observed in one or more samples.

<Gas permeability test>
The acidic gas separation membrane 14 obtained by the appearance evaluation of the membrane was cut out to produce a circular acidic gas separation membrane 14 having a diameter of 47 mm. The circular acidic gas separation membrane 14 was sampled at four locations at intervals of 100 mm with respect to 500 mm in the width direction.
Using two PTFE membrane filters (pore size 0.10 μm, manufactured by ADVANTEC), a permeation test sample (effective area 2.40 cm ² ) was prepared by sandwiching the cut-out circular acidic gas separation membrane 14 from both sides of the membrane.
A mixed gas of CO ₂ / H ₂ : 10/90 (volume ratio) was used as a test gas. This mixed gas was supplied to each produced permeation test sample under the conditions of a relative humidity of 70%, a flow rate of 100 ml / min, a temperature of 130 ° C., and a total pressure of 3 atm. Ar gas (flow rate 90 ml / min) was allowed to flow on the permeate side.
The permeated gas was analyzed with a gas chromatograph, and the separation factor α was calculated from the ratio of the H ₂ permeation rate and the CO ₂ permeation rate, and evaluated as follows.
A: α ≧ 80 in all four places.
B: 10 <α <80 is included even at one place.
C: α ≦ 10 is included even at one location.
The above results are shown in the following table.

As shown in the above table, according to the present invention, even if the humidity of the atmosphere from the laminated portion 32 to the pass roller 64a is under a high humidity of 70% RH, accelerated transportation caused by contact with other members or the like The acidic gas separation membrane having good appearance and gas permeability can be produced by suppressing the peeling of the membrane 18.
On the other hand, in Comparative Example 1 in which the release film 20 is not used, the humidity of the atmosphere from the stacking portion 32 to the pass roller 64a may be as high as 70% RH, and the adhesion to the pass roller 64a and the like is accelerated. The transport film 18 was peeled off, and the film was peeled off so that the gas permeability could not be evaluated.
From the above results, the effects of the present invention are clear.

DESCRIPTION OF SYMBOLS 10,70 Production apparatus 12 (Porous) support body 14,14a Acid gas separation membrane 18 Accelerated transport film 20 Release film 24, 24a Laminate body 26 Supply part 28 Application part 30 Drying part 32 Lamination part 34 Winding part 38, 60 Rotating shaft 40 Coating composition 42 Filling tank 46 Coating roller 48 Metering roller 50, 58 Backup roller 54, 64a to 64d Pass roller 56 Laminating roller 62, 76 Rolling shaft 72 Peeling part 74 Peeling roller pair

Claims (18)

While conveying a long porous support in the longitudinal direction, a coating composition containing a carrier that reacts with an acidic gas and a hydrophilic compound for supporting the carrier is applied to the surface of the porous support. The process of
Forming a facilitated transport film by drying the coating composition applied to the surface of the porous support;
A step of laminating a long release film on the facilitated transport film, and
A method for producing an acidic gas separation membrane, comprising the step of winding the porous support and a laminate of a promoting gas separation membrane and a release film.   The method for producing an acidic gas separation membrane according to claim 1, wherein the coating composition is applied onto the porous support so that the thickness of the coating composition is 0.05 to 10 mm. The method for producing an acidic gas separation membrane according to claim 1 or 2 , wherein the facilitated transport membrane has a membrane strength of 0.005 MPa or more. Wherein a first surface or both the hydrophobicity of the release film, toward the hydrophobic surface in the facilitated transport membrane, any one of claims 1 to 3 laminated release film on the facilitated transport membrane 2. A method for producing an acid gas separation membrane according to item 1. Further, from the wound product of the laminate of the porous support and the promoting gas separation membrane and the release film, the laminate is sent out and conveyed in the longitudinal direction, and the release film is peeled off, Applying a coating composition containing a carrier that reacts with an acidic gas and a hydrophilic compound for supporting the carrier to the surface of the facilitated transport film; and
The manufacturing method of the acidic gas separation membrane of any one of Claims 1-4 which performs the process of forming the facilitated-transport film | membrane of a multilayer structure by drying the coating composition apply | coated to the surface of the said facilitated-transport film | membrane. . The temperature of the laminate in which the facilitated transport film is formed on the surface of the porous support and the temperature of the release film are set to 10 to 70 ° C., and a long release film is laminated on the facilitated transport film. The method for producing an acidic gas separation membrane according to any one of claims 1 to 5 . The acid gas separation membrane according to any one of claims 1 to 6 , wherein the carrier is at least one selected from alkali metal carbonates, alkali metal bicarbonates, and alkali metal hydroxide salts. Production method. The method for producing an acidic gas separation membrane according to any one of claims 1 to 7 , wherein the coating composition is dried by hot air drying at a wind speed of 0.5 to 200 m / min and a membrane surface temperature of 1 to 120 ° C. . Prior to the step of applying the coating composition,
Applying a second coating composition containing a component that becomes a hydrophobic intermediate layer having gas permeability to the surface of the porous support while transporting the long porous support in the longitudinal direction; and ,
The method for producing an acidic gas separation membrane according to any one of claims 1 to 8 , wherein a step of curing the second coating composition to form an intermediate layer is performed. The method for producing an acidic gas separation membrane according to claim 9 , wherein the component serving as the intermediate layer is silicone. The method for producing an acidic gas separation membrane according to claim 9 or 10 , wherein the curing of the second coating composition is started within 7 seconds after the second coating composition is applied.   On the porous support, an acidic gas separation membrane formed by forming a carrier that reacts with an acidic gas and a facilitated transport membrane having a hydrophilic compound that supports the carrier, and the laminated on the facilitated transport membrane. An acidic gas separation membrane wound product obtained by winding a long laminate having a release film in the longitudinal direction. 13. The acidic gas separation membrane roll according to claim 12 , wherein the facilitated transport membrane has a membrane strength of 0.005 MPa or more. The acid gas separation membrane winding according to claim 12 or 13 , wherein one or both surfaces of the release film are hydrophobic, and the release film is laminated with the hydrophobic surface facing the facilitated transport membrane. Recycle. The acid gas separation membrane roll according to any one of claims 12 to 14 , wherein the facilitated transport membrane has a thickness of 0.01 to 3 mm. The acidic gas separation membrane winding according to any one of claims 12 to 15 , wherein the carrier is at least one selected from alkali metal carbonates, alkali metal bicarbonates, and alkali metal hydroxide salts. Recycle. The acid gas separation membrane roll according to any one of claims 12 to 16 , further comprising a hydrophobic intermediate layer having gas permeability between the porous support and the acid gas separation membrane. The acid gas separation membrane roll according to claim 17 , wherein the intermediate layer is made of a silicone resin.