Laminate manufacturing method and co2 separation method

Abstract

To provide a laminate manufacturing method that manufactures a laminate where a film and a support base material are laminated by forming a sacrificial layer on a support, forming a film such as a CO2 separation film on the sacrificial layer, bonding the support base material on the film, and then removing the support and the sacrificial layer, which can easily remove the sacrificial layer by a liquid such as water.SOLUTION: A laminate manufacturing method includes the steps of: forming a sacrificial layer using a composition for sacrificial layer formation on a support, forming a film on the sacrificial layer, bonding the support base material on the film, and peeling the support after the bonding step, and removing the sacrificial layer by dissolving the sacrificial layer in a liquid, after the peeling step, wherein the composition for sacrificial layer formation to be used contains a resin, polyol and a solvent, and the resin has a functional group I which is one or more groups selected from the group consisting of a hydroxyl group, a cyano group and a carboxyl group, and a functional group II which is a hydrophilic group or a hydrophobic group other than the functional group I.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a method for producing a laminate and a method for separating CO2. [Background technology]

[0002] In order to suppress global warming due to climate change and the like, technologies have been developed for separating and capturing carbon dioxide (CO2) using a CO2 separation membrane (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2018-15678 A Summary of the Invention [Problem to be solved by the invention]

[0004] For example, when the CO2 separation membrane is a thin or large membrane, it is difficult for the CO2 separation membrane to stand on its own and is prone to deformation and breakage. For this reason, a laminate in which a support substrate that supports (reinforces) the CO2 separation membrane is attached to the CO2 separation membrane may be used for CO2 separation. Such a laminate can be produced, for example, by forming a sacrificial layer on a support, forming a CO2 separation membrane on the sacrificial layer, adhering a support substrate onto the CO2 separation membrane, and then removing the support and the sacrificial layer. In such a manufacturing method, when the sacrificial layer containing the resin is dissolved in a liquid and removed, there is a problem that at least a part of the sacrificial layer is likely to remain without dissolving in the liquid. If the sacrificial layer remains, it becomes difficult to separate CO2. In order to remove the remaining sacrificial layer, it is necessary to further dissolve the sacrificial layer using, for example, an alkaline aqueous solution (basic aqueous solution). For this reason, it is desirable to be able to easily remove the sacrificial layer using only a liquid such as water, without using an alkali or the like. In addition, not only for the CO2 separation membrane, but also for other membranes, a laminate in which a membrane and a supporting substrate are laminated may be used. For this reason, when manufacturing a laminate in which other membranes and a supporting substrate are laminated, it is desired that the sacrificial layer can be easily removed with a liquid such as water.

[0005] The present invention has been made in consideration of the above problems, and aims to provide a method for manufacturing a laminate in which at least one membrane and a supporting substrate are stacked, by forming a sacrificial layer on the support, forming a membrane such as a CO2 separation membrane on the sacrificial layer, adhering the supporting substrate onto the membrane, and then removing the support and the sacrificial layer, thereby enabling the sacrificial layer to be easily removed with a liquid such as water during production, and a CO2 separation method using a laminate manufactured by the manufacturing method. [Means for solving the problem]

[0006] The present inventors have found that the above-mentioned problems can be solved by using a composition for forming a sacrificial layer, and have completed the present invention, in a method for producing a laminate comprising a sacrificial layer forming step of forming a sacrificial layer on a support, a film forming step of forming at least one film on the sacrificial layer, an adhesion step of adhering a support substrate on at least one film, a peeling step of peeling off the support after the adhesion step, and a sacrificial layer removing step of removing the sacrificial layer by dissolving it in a liquid, the method comprising: a resin (A), a polyol (B), and a solvent (C), the resin (A) having a functional group I which is one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group, and a functional group II which is a hydrophilic or hydrophobic group other than the functional group I, provided that the functional group II includes one or more groups selected from a hydroxyl group, a cyano group, and a carboxyl group, the resin (A) does not have to have the functional group I. Specifically, the present invention provides the following.

[0007] [1] A method for producing a laminate in which at least one film and a supporting substrate are laminated, comprising the steps of: A sacrificial layer forming step of forming a sacrificial layer on a support using a sacrificial layer forming composition; forming at least one film on the sacrificial layer; a bonding step of bonding a supporting substrate onto the at least one film; a peeling step of peeling off the support after the adhesion step; a sacrificial layer removing step of removing the sacrificial layer by dissolving the sacrificial layer in a liquid after the peeling step, The composition for forming a sacrificial layer contains a resin (A), a polyol (B), and a solvent (C), the resin (A) has a functional group I which is one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group, and a functional group II which is a hydrophilic group or a hydrophobic group other than the functional group I; However, when the functional group II contains one or more groups selected from a hydroxyl group, a cyano group, and a carboxyl group, the resin (A) may not have the functional group I. A method for manufacturing a laminate.

[0008] [2] The functional group II is a hydrophilic group and is represented by the following formula (A1): -NH-R 1 (A1): (In formula (A1), R 1 is an alkyl group having 1 to 4 carbon atoms substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group, or a hydrogen atom. or a group represented by the following formula (A2): -N + R 2 R 3 R 4 Z - (A2) (In formula (A2), R 2 , R 3 , and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; Z - is the counter anion.) The method for producing the laminate described in [1] above, wherein the quaternary ammonium base is represented by the following formula:

[0009] [3] The method for producing a laminate according to the above [1] or [2], wherein the resin (A) is a water-soluble resin having a structural unit derived from at least one monomer selected from the group consisting of (meth)acrylamide and (meth)acrylamide derivatives.

[0010] [4] The functional group I is represented by the following formula (A3): CH2=CR 5 -(R 6 ) a -CO-R 7 (A3) (In formula (A3), R 5 is a hydrogen atom or a methyl group, R 6 is a divalent hydrocarbon group, a is 0 or 1, R 7 -OH, -OR 8 or -NH-R 8 and R 8 is a hydrocarbon group substituted with one or more functional groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group. The method for producing a laminate according to any one of the above [1] to [3], wherein the group is derived from a monomer represented by the following formula:

[0011] [5] The method for producing a laminate according to any one of the above [1] to [4], wherein the liquid is water.

[0012] [6] The method for producing a laminate according to any one of the above [1] to [5], wherein the sacrificial layer has a thickness of 1 μm or more and 20 μm or less.

[0013] [7] The method for producing a laminate according to any one of the above [1] to [6], wherein the thickness of the at least one film is 100 nm or more and 1000 nm or less.

[0014] [8] The method for producing a laminate according to any one of [1] to [7], which does not include a step of dissolving the sacrificial layer in an alkaline aqueous solution.

[0015] [9] The method for producing a laminate according to any one of [1] to [8], wherein the at least one membrane is a CO2 separation membrane.

[0016]

[10] A laminate production process for producing a laminate by the laminate production process described in [9] above; A CO2 separation method comprising a separation step of supplying a gas containing CO2 to the laminate and separating CO2 from the gas. Effect of the Invention

[0017] According to the present invention, a method for manufacturing a laminate in which at least one membrane and a supporting substrate are laminated can be provided, in which a sacrificial layer is formed on the supporting substrate, a membrane such as a CO2 separation membrane is formed on the sacrificial layer, the supporting substrate is adhered to the membrane, and then the supporting substrate and the sacrificial layer are removed, thereby enabling the sacrificial layer to be easily removed with a liquid such as water during production, and a CO2 separation method using a laminate manufactured by this manufacturing method can be provided. [Brief description of the drawings]

[0018] [Figure 1] 1A to 1C are schematic diagrams illustrating a method for producing a laminate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] <<Method for manufacturing laminate>> The method for producing a laminate is a method for producing a laminate in which at least one film and a supporting substrate are laminated together. The method for producing the laminate includes the steps of: A sacrificial layer forming step of forming a sacrificial layer on a support using a sacrificial layer forming composition; A film forming step of forming at least one film on the sacrificial layer; a bonding step of bonding a support substrate onto at least one of the films; a peeling step of peeling off the support after the adhesion step; After the peeling step, the method includes a sacrificial layer removing step of removing the sacrificial layer by dissolving the sacrificial layer in a liquid. The composition for forming a sacrificial layer contains a resin (A), a polyol (B), and a solvent (C). Resin (A) has functional group I which is one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group, and functional group II which is a hydrophilic group or a hydrophobic group other than functional group I. However, when functional group II contains one or more groups selected from a hydroxyl group, a cyano group, and a carboxyl group, resin (A) does not need to have functional group I. Each step will be described below with reference to Fig. 1. Fig. 1 is a schematic diagram illustrating the method for producing a laminate.

[0020] [Sacrificial layer formation process] In the sacrificial layer forming step, a sacrificial layer 2 is formed on a support 1 using a composition for forming a sacrificial layer (FIG. 1(a)). The composition for forming a sacrificial layer contains a resin (A), a polyol (B), and a solvent (C). The resin (A) has a functional group I which is one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group, and a functional group II which is a hydrophilic or hydrophobic group other than the functional group I. When the functional group II contains one or more groups selected from a hydroxyl group, a cyano group, and a carboxyl group, the resin (A) does not need to have the functional group I.

[0021] The resin (A) and polyol (B) contained in the composition for forming a sacrificial layer are easily dissolved in a liquid such as water at room temperature (e.g., 25° C.), so that the sacrificial layer can be easily removed with a liquid such as water in the subsequent sacrificial layer removal step. Furthermore, since the composition for forming a sacrificial layer contains the resin (A) and the polyol (B), it is possible to form a sacrificial layer that has self-supporting toughness, flexibility, and excellent handleability. Furthermore, since the resin (A) is difficult to dissolve in the polymer or solvent of the film-forming composition used in the subsequent film-forming step, mixing of the sacrificial layer and the film in the film-forming step or the like can be suppressed.

[0022] Essential and optional components contained in the composition for forming a sacrificial layer will be described below.

[0023] <Resin (A)> The resin (A) has functional groups I which are one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group.

[0024] The resin (A) has a functional group II other than the functional group I which is a hydrophilic group or a hydrophobic group. The hydrophilic group or hydrophobic group is not particularly limited as long as it is a functional group that has been conventionally recognized as a hydrophilic group or a hydrophobic group by those skilled in the art, and can be appropriately selected from among them.

[0025] The type of resin (A) is not particularly limited as long as the resin (A) has a predetermined functional group and is soluble in the solvent (C). Examples of the resin (A) include (meth)acrylic resin, novolac resin, polyester resin, polyamide resin, polyimide resin, polyamideimide resin, and silicone resin. Among these resins, (meth)acrylic resin is preferred because it is easy to introduce a functional group and adjust the content ratio of units having a functional group. In this specification, "(meth)acrylic" means both "acrylic" and "methacrylic".

[0026] Specific examples of the hydrophilic group include polyoxyalkylene groups (e.g., polyoxyethylene groups, polyoxypropylene groups, polyoxyalkylene groups in which oxyethylene groups and oxypropylene groups are block- or randomly bonded, etc.), amino groups, carboxyl groups, hydroxyl groups, sulfonic acid groups, etc. Organic groups containing these groups are also preferred as hydrophilic groups.

[0027] When the resin (A) has a hydrophilic or hydrophobic group containing a hydroxyl group, a cyano group, or a carboxyl group as the functional group II, the hydroxyl group, cyano group, or carboxyl group contained in the hydrophilic or hydrophobic group also serves as the functional group I. Therefore, when the resin (A) has a hydrophilic or hydrophobic group containing a hydroxyl group, a cyano group, or a carboxyl group as the functional group II, the resin (A) does not need to have the functional group I. The hydrophilic group containing a hydroxyl group and a carboxyl group includes a hydroxyl group itself and a carboxyl group itself.

[0028] In order to provide a sacrificial layer with excellent solubility in water, the hydrophilic group is preferably a group represented by the following formula (A1): -NH-R 1 (A1) (In formula (A1), R 1 is an alkyl group having 1 to 4 carbon atoms substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group, or a hydrogen atom. A group represented by the following formula is preferred.

[0029] R of the hydrophilic group represented by formula (A1) 1 Specific examples of the above include groups represented by the following formulas: [ka]

[0030] [ka]

[0031] [ka]

[0032] In order to provide a sacrificial layer with excellent solubility in water, the hydrophilic group is preferably a group represented by the following formula (A2): -N + R 2 R 3 R 4 Z - (A2) (In formula (A2), R 2 , R 3 , and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; Z - is the counter anion.) Quaternary ammonium bases represented by the following formula are also preferred.

[0033] Suitable examples of the hydrocarbon group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and a phenyl group. Z - The counter anion as the ion is not particularly limited as long as it is a monovalent anion, but is preferably a halide ion. Suitable examples of the halide ion include a chloride ion, a bromide ion, and an iodide ion.

[0034] Specific examples of the hydrophilic group represented by formula (A2) include groups represented by the following formulas.

[0035] [ka]

[0036] Specific examples of the hydrophobic group include a fluorinated hydrocarbon group, a silyl group, a siloxane group, an alkyl group having 6 to 20 carbon atoms, and an aromatic hydrocarbon group having 10 to 20 carbon atoms. As the fluorinated hydrocarbon group, the groups described below with respect to formula (A4) are preferred. A suitable example of the silyl group is a group represented by the formula (A5) described below, in which n is 0. Specific examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, and a triphenylsilyl group. Suitable examples of the siloxane group include groups represented by the formula (A5) described below, in which n is 1 or greater.

[0037] The resin (A) is preferably a polymer of a monomer having an unsaturated bond, since it is easy to introduce various functional groups and adjust the amount of functional groups. Such a polymer may be a homopolymer or a copolymer.

[0038] In this case, the functional group I of the resin (A) is represented by the following formula (A3): CH2=CR5 -(R 6 ) a -CO-R 7 (A3) (In formula (A3), R 5 is a hydrogen atom or a methyl group, R 6 is a divalent hydrocarbon group, a is 0 or 1, R 7 -OH, -OR 8 or -NH-R 8 and R 8 is a hydrocarbon group substituted with one or more functional groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group. It is preferable that the group is derived from a monomer represented by the following formula:

[0039] In the above formula (A3), R 6 is a divalent hydrocarbon group. The number of carbon atoms in the divalent hydrocarbon group is not particularly limited as long as it does not impair the object of the present invention. R 6 The divalent hydrocarbon group as the alkyl group preferably has 1 or more and 20 or less carbon atoms, more preferably has 1 or more and 12 or less carbon atoms, particularly preferably has 1 or more and 10 or less carbon atoms, and most preferably has 1 or more and 6 or less carbon atoms.

[0040] R 6 The divalent hydrocarbon group as may be an aliphatic group, an aromatic group, or a hydrocarbon group containing an aliphatic portion and an aromatic portion. When the divalent hydrocarbon group is an aliphatic group, the aliphatic group may be a saturated aliphatic group or an unsaturated aliphatic group. The structure of the aliphatic group may be linear, branched, cyclic, or a combination of these structures.

[0041] R 6Preferred specific examples of the alkyl group include a methylene group, an ethane-1,2-diyl group, an ethane-1,1-diyl group, a propane-1,3-diyl group, a propane-1,1-diyl group, a propane-2,2-diyl group, a n-butane-1,4-diyl group, a n-pentane-1,5-diyl group, a n-hexane-1,6-diyl group, a n-heptane-1,7-diyl group, a n-octane-1,8-diyl group, a n-nonane-1,9-diyl group, a n-decane-1,10-diyl group, an o-phenylene group, a m-phenylene group, a p-phenylene group, a naphthalene-2,6-diyl group, a naphthalene-2,7-diyl group, a naphthalene-1,4-diyl group, and a biphenyl-4,4'-diyl group.

[0042] R 7 -OH, -OR 8 or -NH-R 8 and R 8 is a hydrocarbon group substituted with one or more functional groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group. R 8 The hydrocarbon group constituting the main skeleton of the group may be a linear, branched or cyclic aliphatic group, or an aromatic hydrocarbon group. The linear, branched, or cyclic aliphatic group preferably has 1 or more and 20 or less carbon atoms, and more preferably has 1 or more and 12 or less carbon atoms. Suitable examples of the linear or branched aliphatic group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a sec-pentyl group, a tert-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group. Preferred examples of the cyclic aliphatic group include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; groups in which one hydrogen atom has been removed from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and groups in which one hydrogen atom has been removed from alkyl-substituted versions of these polycycloalkanes having 1 to 4 carbon atoms. Suitable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthranyl group, a phenanthrenyl group, and a biphenylyl group, etc. The aromatic hydrocarbon group may be substituted with an alkyl group having 1 to 4 carbon atoms, such as a methyl group or an ethyl group.

[0043] Particularly preferred specific examples of the units derived from the monomer represented by formula (A3) include the following units a3-1 to a3-9. Among the following units a3-1 to a3-9, units a3-1 to a3-4 are more preferred. [ka]

[0044] In the case where the resin (A) has a hydrophobic group as the functional group II, the functional group II is represented by the following formula (A4): CH2=CR 9 -(CO-O) b -R 10 (A4) (In formula (A4), R 9 is a hydrogen atom or a methyl group, b is 0 or 1, R 10 is a fluorinated hydrocarbon group, or the following formula (A5): -SiR 11 R 12 -(-O-SiR 11 R 12 -) n -R 13 (A5) R 11 , R 12 , and R 13are each independently a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 0 or more. It is preferable that the monomer is derived from a monomer represented by the formula:

[0045] In formula (A4), R 10 is a fluorinated hydrocarbon group, the hydrocarbon group constituting the main skeleton of the fluorinated hydrocarbon group is the same as the above-mentioned R 8 The fluorinated hydrocarbon group may be a hydrocarbon group in which all of the hydrogen atoms have been substituted with fluorine atoms. R 10 Specific examples of the fluorinated hydrocarbon group as the aryl group include -CF3, -CF2CF3, -(CF2)2CF3, -(CF2)3CF3, -(CF2)4CF3, -(CF2)5CF3, -(CF2)6CF3, -(CF2)7CF3, -(CF2)8CF3, -(CF2)9CF3, -CH2CF3, -CH2CF2CF3, -CH2(CF2)2CF3, -CH2(CF2)3CF3, -CH2(CF2)4CF3, -CH2(CF2)5CF3, -CH2(CF2)6CF3, -CH2(CF2)7CF3, -CH2(CF2)8CF3, and -CH2CH2CF3. chain-like fluorinated alkyl groups such as -CH2CH2CF2CF3, -CH2CH2(CF2)2CF3, -CH2CH2(CF2)3CF3, -CH2CH2(CF2)4CF3, -CH2CH2(CF2)5CF3, -CH2CH2(CF2)6CF3, -CH2CH2(CF2)7CF3, and -CH(CF3)2; fluorinated aromatic hydrocarbon groups such as a pentafluorophenyl group, an o-trifluoromethylphenyl group, an m-trifluoromethylphenyl group, and a p-trifluoromethylphenyl group; and fluorinated alicyclic groups such as an octafluoroadamantyl group.

[0046] In formula (A4), R 10 is a group represented by formula (A5), R 11 , R 12 , and R 13 are each preferably independently a methyl group, an ethyl group, or a phenyl group; R 11 , R 12 , and R 13More preferably, all of are methyl groups. In formula (A5), the upper limit of n is not particularly limited as long as it does not impair the object of the present invention. n is preferably an integer of 0 to 35, more preferably an integer of 0 to 10.

[0047] Particularly preferred specific examples of the unit having a hydrophobic group derived from the monomer represented by formula (A4) include the following units a4-1 to a4-22. Among the following units, units a4-8, a4-18, a4-19, and a4-22 are more preferred. [ka]

[0048] Furthermore, when the resin (A) has a hydrophilic group as the functional group II, it is preferable that the resin (A) is a water-soluble resin having a structural unit derived from at least one monomer selected from the group consisting of (meth)acrylamide and (meth)acrylamide derivatives. Specifically, when the resin (A) has a hydrophilic group as the functional group II, the functional group II is preferably derived from at least one monomer selected from the group consisting of (meth)acrylamide and (meth)acrylamide derivatives.

[0049] For example, when the resin (A) has a hydrophilic group as the functional group II, the functional group II is represented by the following formula (A6): CH2=CR 14 -CO-NH-R 1 (A6) (In formula (A6), R 1 is an alkyl group having 1 to 4 carbon atoms substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group, or a hydrogen atom; R 14 is a hydrogen atom or a methyl group. It is preferable that the monomer is derived from a monomer represented by the formula:

[0050] In formula (A6), R 1 As mentioned above,

[0051] Particularly preferred specific examples of the unit having a hydrophilic group derived from the monomer represented by formula (A6) include the following units a6-1 to a6-5. Among the following units, the units a6-1 to a6-4 are more preferred. [ka]

[0052] In addition, in the case where the resin (A) has a hydrophilic group as the functional group II, the functional group II is represented by the following formula (A7): CH2=CR 15 -CO-NH-R 16 -N + R 2 R 3 R 4 Z - (A7) (In formula (A7), R 2 , R 3 , and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; Z - is the counter anion, and R 15 is a hydrogen atom or a methyl group, R 16 is a single bond or a hydrocarbon group having 1 to 6 carbon atoms. It is also preferred that the aryl group is derived from a monomer represented by the following formula:

[0053] In formula (A7), R 2 , R 3 , R 4 , Z - As mentioned above, In formula (A7), R 16 Examples of the hydrocarbon group having 1 to 6 carbon atoms as the aryl group include a methylene group, an ethane-1,2-diyl group, an ethane-1,1-diyl group, a propane-1,3-diyl group, a propane-1,1-diyl group, a propane-2,2-diyl group, an n-butane-1,4-diyl group, an n-pentane-1,5-diyl group, and an n-hexane-1,6-diyl group.

[0054] Particularly preferred specific examples of the unit having a hydrophilic group derived from the monomer represented by formula (A7) include the following structural units a7-1 to a7-10.

[0055] [ka]

[0056] When the resin (A) is a polymer of a monomer having an unsaturated bond, the polymer may contain other structural units than the units derived from the monomer represented by the above-mentioned formula (A3), the units derived from the monomer represented by the formula (A4), the units derived from the monomer represented by the formula (A6), and the units derived from the monomer represented by the formula (A7), within the scope of the invention.

[0057] Other structural units include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, phenyl (meth)acrylate, methoxyethyl (meth)acrylate, (meth)acryloylmorpholine, pyridine (meth)acrylic acid, imidazole (meth)acrylic acid, vinylimidazole, vinylpyridine, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, Nn-propyl (meth)acrylate, Examples of structural units derived from monomers such as acrylamide, N-isopropyl(meth)acrylamide, Nn-butyl(meth)acrylamide, Nn-pentyl(meth)acrylamide, N-isopentyl(meth)acrylamide, N-phenyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-di-n-propyl(meth)acrylamide, N,N-di-n-butyl(meth)acrylamide, N,N-di-n-pentyl(meth)acrylamide, styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and chlorostyrene.

[0058] When the resin (A) is a polymer of a monomer having an unsaturated bond, the molar ratio of the structural units derived from the monomer represented by formula (A3) in all structural units contained in such polymer is preferably from 0.1 mol% to 50 mol%, more preferably from 1 mol% to 20 mol%, and particularly preferably from 1 mol% to 15 mol%.

[0059] When the resin (A) is a polymer of a monomer having an unsaturated bond, the molar ratio of the structural units derived from the monomer represented by formula (A4), (A6) or (A7) in all structural units contained in such polymer is preferably from 50 mol% to 99.9 mol%, more preferably from 60 mol% to 99 mol%, and particularly preferably from 70 mol% to 99 mol%. However, when a structural unit derived from a monomer represented by formula (A4), (A6) or (A7) contains any one of a hydroxyl group, a cyano group and a carboxyl group, the ratio of the structural units derived from the monomer represented by formula (A4), (A6) or (A7) to all structural units contained in the polymer may be 100%.

[0060] The amount of the resin (A) contained in the composition for forming a sacrificial layer is not particularly limited as long as it does not impair the object of the present invention, and is appropriately determined in consideration of the coating property of the composition for forming a sacrificial layer, etc. Typically, the amount of the resin (A) in the composition for forming a sacrificial layer is preferably an amount in which the relationship between the amount of the resin (A) in the composition for forming a sacrificial layer and the amount of the solvent (C) described later is as follows. When the mass of the resin (A) in the composition for forming a sacrificial layer is 100 parts by mass, the amount of the solvent (C) is preferably 100 parts by mass or more and 10,000 parts by mass or less, more preferably 500 parts by mass or more and 8,000 parts by mass or less, and particularly preferably 1,000 parts by mass or more and 6,000 parts by mass or less.

[0061] <Polyol (B)> The composition for forming a sacrificial layer contains a polyol (B). The polyol (B) functions as a plasticizer. Examples of the polyol (B) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, butylene glycol, trimethylolpropane, trimethylolethane, ditrimethylolpropane, polytrimethylolpropane, pentaerythritol, dipentaerythritol, polypentaerythritol, sorbitol, mannitol, arabitol, xylitol, galactitol, glycerin, diglycerin, triglycerin, polyglycerin, 1,3-butanediol, 1,4-butanediol, polybutylene glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 1,2-dodecanediol, 2-phenyl-1,2-propanediol, 1,4-benzenedimethanol, and neopentyl glycol.

[0062] The content of the polyol (B) in the composition for forming a sacrificial layer is not particularly limited. The content of the polyol (B) in the composition for forming a sacrificial layer is preferably 10 parts by mass or more and 70 parts by mass or less, more preferably 20 parts by mass or more and 60 parts by mass or less, and particularly preferably 30 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the resin (A).

[0063] <Solvent (C)> The solvent (C) is not particularly limited as long as it is a solvent in which the resin (A) and the polyol (B) are soluble. As long as the resin (A) and the polyol (B) are dissolved in a predetermined amount in the composition for forming a sacrificial layer, the composition for forming a sacrificial layer may contain the resin (A) and the polyol (B) in a non-dissolved state. It is preferable that the resin (A) and the polyol (B) are completely dissolved in the composition for forming a sacrificial layer.

[0064] The solvent (C) may be water, an organic solvent, or an aqueous solution of an organic solvent, but is preferably water.

[0065] Specific examples of organic solvents used as the solvent (C) include: Sulfoxides such as dimethyl sulfoxide; Sulfones such as dimethyl sulfone, diethyl sulfone, bis(2-hydroxyethyl) sulfone, and tetramethylene sulfone; Amides such as N,N-dimethylformamide, N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, and N,N-diethylacetamide; Lactams such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, and N-hydroxyethyl-2-pyrrolidone; Imidazolidinones such as 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, and 1,3-diisopropyl-2-imidazolidinone; dialkyl glycol ethers such as dimethyl glycol, dimethyl diglycol, dimethyl triglycol, methyl ethyl diglycol, diethyl glycol, and triethylene glycol butyl methyl ether; (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; Other ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisoamyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; other esters such as ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; Lactones such as β-propylolactone, γ-butyrolactone, and δ-pentyrolactone; Linear, branched, or cyclic aliphatic hydrocarbons, such as n-hexane, n-heptane, n-octane, n-nonane, methyloctane, n-decane, n-undecane, n-dodecane, 2,2,4,6,6-pentamethylheptane, 2,2,4,4,6,8,8-heptamethylnonane, cyclohexane, and methylcyclohexane; Aromatic hydrocarbons such as benzene, toluene, xylene, 1,3,5-trimethylbenzene, and naphthalene; Terpenes such as p-menthane, diphenylmenthane, limonene, terpinene, bornane, norbornane, and pinane;

[0066] When the solvent (C) is a mixed solvent of water and an organic solvent, the content of the organic solvent in the solvent (C) is preferably 10% by mass or more, more preferably 20% by mass or more.

[0067] <Other ingredients> The sacrificial layer forming composition may contain various components other than the resin (A), the polyol (B), and the solvent (C) within a range that does not impair the object of the present invention. Examples of other components include a viscosity modifier, a surfactant, and the like. The sacrificial layer forming composition may contain an antifoaming agent, but the sacrificial layer forming composition containing the above-mentioned resin (A) may not contain an antifoaming agent because it can suppress foaming.

[0068] <Method for preparing composition for forming sacrificial layer> The method for preparing the composition for forming a sacrificial layer is not particularly limited. The composition for forming a sacrificial layer is typically prepared by uniformly mixing predetermined amounts of the resin (A), the polyol (B), the solvent (C), and other components as necessary.

[0069] Examples of the support 1 on which the sacrificial layer 2 is formed using such a sacrificial layer-forming composition include resin films such as PET (polyethylene terephthalate) films, and substrates such as silicon substrates and glass substrates. In the support 1, the surface on which the sacrificial layer 2 is formed may or may not be treated with a release agent. The shape of the support 1 is not particularly limited, and may be a film or a plate. When the support is in the form of a film, a film pulled out from a film roll can be used as the support 1.

[0070] The method for forming the sacrificial layer 2 on the support 1 using the composition for forming a sacrificial layer is not particularly limited, and examples of the method include coating methods such as slit die coating, gravure coating, spin coating, spraying, roller coating, and dipping. Among these, the slit die coating method using a slit die is preferred.

[0071] After the composition for forming a sacrificial layer is applied to the support 1, the applied film may be heated (dried) as necessary to remove at least a part of the solvent (C) of the composition for forming a sacrificial layer. The heating (drying) temperature of the coating film is, for example, 50° C. or more and 90° C. or less. In addition, the coating film may be heated at a low temperature (for example, 50° C. or more and less than 70° C.) and then heated at a high temperature (for example, 70° C. or more and 90° C. or less).

[0072] The film thickness of the sacrificial layer 2 is not particularly limited, but is preferably 1 μm or more and 20 μm or less, more preferably 3 μm or more and 18 μm or less, and even more preferably 5 μm or more and 15 μm or less. The sacrificial layer 2 formed using the above-mentioned composition for forming a sacrificial layer has self-supporting properties and excellent handleability even if it is thin.

[0073] [Film formation process] In the film formation step, at least one film 3 is formed on the sacrificial layer 2 (FIG. 1(b)). Although FIG. 1(b) shows an embodiment in which one film is formed as the film 3, two or more films may be formed as the film 3.

[0074] The material of the film 3 is preferably a polymer. Suitable polymers include, for example, silicon-containing resins such as silicone resins, polyamic acids, polyimides, polyamides, polybenzoxazoles, polyethylene oxides, epoxy resins, and acrylic resins, as well as copolymers thereof, etc. The polymer may be an elastomer. Further examples include styrene-based polymers such as isoprene-butadiene-styrene copolymers, hydrogenated products of isoprene-butadiene-styrene copolymers, butadiene-styrene copolymers, hydrogenated products of butadiene-styrene copolymers, isoprene-styrene copolymers, hydrogenated products of isoprene-styrene copolymers, ethylene-propylene-styrene copolymers, propylene-styrene copolymers, ethylene-styrene copolymers, ethylene-propylene-1-butene-styrene copolymers, and polystyrene. Further examples include cyclic olefin copolymers such as ethylene-norbornene copolymer, propylene-norbornene copolymer, ethylene-tetracyclododecene copolymer, propylene-tetracyclododecene copolymer, ethylene-propylene-norbornene copolymer, and ethylene-propylene-tetracyclododecene copolymer. When the polymer is a copolymer, it may be a random copolymer or a block copolymer. When the polymer is a block copolymer containing a unit derived from styrene, it is preferable that the block copolymer has a block of a unit derived from styrene at both ends of the molecular chain. Furthermore, the polymer may have a hydroxyl group at both ends or one end of the molecular chain.

[0075] When the membrane 3 is a CO2 separation membrane, the material of the membrane 3 is preferably a silicon-containing resin such as a silicone resin. As the silicone resin (a resin having a siloxane bond in the main skeleton), a polyorganosiloxane such as polydimethylsiloxane, polyphenylmethylsiloxane, or polydiphenylsiloxane is preferable, and polydimethylsiloxane is more preferable. The polyorganosiloxane may be used together with a curing agent for the polyorganosiloxane.

[0076] The method for forming the film 3 on the sacrificial layer 2 is not particularly limited, and examples thereof include a method for applying a film-forming composition containing the raw material of the film 3 and a solvent by a slit die coating method, a gravure coating method, a spin coating method, a spray method, a roller coating method, a dipping method, etc. When a large film 3 is formed, a gravure coating method such as microgravure coating using a gravure roll is preferred.

[0077] Examples of the solvent contained in the film-forming composition include sulfoxides, sulfones, amides, lactams, imidazolidinones, dialkyl glycol ethers, (poly)alkylene glycol monoalkyl ethers, (poly)alkylene glycol monoalkyl ether acetates, other ethers, ketones, other esters, lactones, linear, branched, or cyclic aliphatic hydrocarbons, aromatic hydrocarbons, and terpenes. The sulfoxides include dimethyl sulfoxide. Examples of sulfones include dimethyl sulfone, diethyl sulfone, bis(2-hydroxyethyl) sulfone, and tetramethylene sulfone. Examples of amides include N,N-dimethylformamide, N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, and N,N-diethylacetamide. Examples of lactams include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, and N-hydroxyethyl-2-pyrrolidone. Examples of imidazolidinones include 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, and 1,3-diisopropyl-2-imidazolidinone. Examples of dialkyl glycol ethers include dimethyl glycol, dimethyl diglycol, dimethyl triglycol, methyl ethyl diglycol, diethyl glycol, and triethylene glycol butyl methyl ether. Examples of (poly)alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether. Examples of the (poly)alkylene glycol monoalkyl ether acetates include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Examples of other ethers include dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisoamyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monobutyl ether, diethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, and tetrahydrofuran. Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and 2,6-dimethyl-4-heptanone. Other esters include, for example, alkyl lactate esters such as methyl lactate and ethyl lactate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, and acetic acid. Examples of the ethyl acetate include n-propyl, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, butyl butyrate, methyl n-octanoate, methyl decanoate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, dimethyl adipate, and propylene glycol diacetate. Examples of lactones include propylolactone, γ-butyrolactone, and 6-pentyrolactone. Examples of linear, branched, or cyclic aliphatic hydrocarbons include n-hexane, n-heptane, n-octane, n-nonane, methyloctane, n-decane, n-pentane, n-dodecane, 2,2,4,6,6-pentamethylheptane, 2,2,4,4,6,8,8-heptamethylnonane, cyclohexane, and methylcyclohexane. Examples of aromatic hydrocarbons include benzene, toluene, benzotrifluoride, xylene, 1,3,5-trimethylbenzene, naphthalene, and decahydronaphthalene. Examples of terpenes include p-menthane, diphenylmenthane, limonene, terpinene, bornane, norbornane, and pinane.

[0078] The method for preparing the film-forming composition is not particularly limited. The film-forming composition is typically prepared by uniformly mixing the raw materials of the film 3, a solvent, and other components as necessary.

[0079] After the film-forming composition is applied onto the sacrificial layer 2, the applied film may be heated (dried) as necessary to remove at least a part of the solvent of the film-forming composition. The heating (drying) temperature of the coating film is, for example, 50° C. or higher and 160° C. or lower. In addition, the coating film may be heated at a low temperature (for example, 50° C. or higher and lower than 100° C.) and then heated at a high temperature (for example, 100° C. or higher and 160° C. or lower). When heated at a high temperature, silicone resins such as polydimethylsiloxane may be cured (crosslinked).

[0080] The film thickness of the film 3 is not particularly limited, but is preferably 10 nm or more and 3000 nm or less, more preferably 50 nm or more and 1000 nm or less, and even more preferably 100 nm or more and 500 nm or less.

[0081] [Adhesion process] In the bonding step, a supporting substrate 4 is bonded onto at least one of the films 3 (FIG. 1(c)). When the membrane 3 is, for example, a thin membrane or a large membrane, the membrane 3 is difficult to support by itself and is prone to deformation and breakage. By adhering a support substrate 4 that supports (reinforces) the membrane 3 to the membrane 3, deformation and breakage can be suppressed and functions such as the separation performance of the membrane 3 can be maintained.

[0082] The material of the support substrate 4 may be an organic material or an inorganic material, but is preferably an organic material, which is typically a resin. Examples of the resin include polyacetal, polyamide, polycarbonate, polyester (polybutylene terephthalate, polyethylene terephthalate, polyarylate, etc.), FR-AS resin, FR-ABS resin, AS resin, ABS resin, polyphenylene oxide, polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, fluorine-based resin (polytetrafluoroethylene, polyvinylidene fluoride, etc.), polyimide, polyamideimide, polyamide bismaleimide, polyetherimide, polybenzoxazole, polybenzothiazole, polybenzimidazole, silicone resin, BT resin, polymethylpentene, ultra-high molecular weight polyethylene, FR-polypropylene, (meth)acrylic resin (polymethyl methacrylate, etc.), and polystyrene. Among the resins, polyvinylidene fluoride, polyethersulfone, polyimide, and polyamideimide are preferred because they are thermally and chemically stable and can easily give a membrane having excellent mechanical strength. As the material for the film, a mixture of two or more resins may be used. The support substrate 4 may be a porous body. When the membrane 3 is a gas separation membrane such as a CO2 separation membrane, the support substrate 4 is preferably a porous body that is gas permeable. The shape of the supporting substrate 4 is not particularly limited, and may be a film or a plate. When the supporting substrate is in the form of a film, a film pulled out from a film roll can be used as the supporting substrate 4.

[0083] The thickness of the supporting substrate 4 is not particularly limited, but is preferably from 1 μm to 100 μm, more preferably from 10 μm to 80 μm, and even more preferably from 20 μm to 60 μm.

[0084] There is no particular limitation on the method for adhering the support substrate 4 onto the film 3. For example, lamination, a transfer method utilizing intermolecular forces, etc. may be used. For example, the film 3 may be laminated (thermocompression bonded) to the support substrate 4 using a roll 11 or the like, with a pressure that does not damage the support substrate 4. The conditions for thermocompression bonding are a roller pressure of 0.1 kgf / cm2 More than 10kgf / cm 2 Less than 0.2kgf / cm is preferable. 2 More than 5kgf / cm 2 The temperature of the roller is preferably 20° C. or higher and 120° C. or lower, and more preferably 25° C. or higher and 100° C. or lower. When using intermolecular forces, the membrane 3 and the supporting substrate 4 may be brought into contact with each other using, for example, a roller.

[0085] [Peeling process] In the peeling step, after the bonding step, the support 1 is peeled off (FIG. 1(d)). The method for peeling the support 1 from the sacrificial layer 2 is not particularly limited. Examples include a method in which the support 1 is peeled off from the sacrificial layer 2 without using a peeling liquid or the like. For example, when the support 1 is in the form of a film, the support 1 can be peeled off from the sacrificial layer 2 by unwinding the film. When the support 1 is peeled off from the sacrificial layer 2, a part of the sacrificial layer 2 may be peeled off together with the support 1.

[0086] [Sacrificial layer removal process] In the sacrificial layer removal process, after the peeling process, the sacrificial layer 2 is removed by dissolving it in a liquid (Figure 1(e)). This produces a laminate 10 in which the membrane 3 and the supporting substrate 4 are laminated (Figure 1(f)). The laminate 10 may be dried using an air flow, a dryer, etc., if necessary.

[0087] The liquid in which the sacrificial layer 2 is dissolved may be water, an organic solvent, or a mixed solvent of water and an organic solvent, but is preferably water. Here, when attempting to remove the resin-containing sacrificial layer by dissolving it in a liquid, there is a problem that at least a part of the sacrificial layer is likely to remain without dissolving in the liquid. In order to remove the remaining sacrificial layer, it is necessary to further dissolve the sacrificial layer using, for example, an alkaline aqueous solution (basic aqueous solution). However, by forming the sacrificial layer 2 using the above-mentioned composition for forming a sacrificial layer, the resin (A) and polyol (B) contained in the composition for forming a sacrificial layer are easily dissolved in a liquid such as water at room temperature (e.g., 25°C). Therefore, for example, the sacrificial layer 2 can be easily removed with a liquid such as water without using an alkali, and the sacrificial layer 2 can also be easily removed with water alone. Therefore, for example, even if a step of dissolving the sacrificial layer 2 in an alkaline aqueous solution is not included, the laminate 10 from which the sacrificial layer 2 has been removed can be manufactured.

[0088] The method for dissolving the sacrificial layer 2 in liquid is not particularly limited, but examples include a method of immersing the sacrificial layer 2 in liquid such as water, or a method of spraying liquid such as water from a shower onto the sacrificial layer 2. The time for which the sacrificial layer 2 is immersed in the liquid is not particularly limited, but is, for example, from 5 minutes to 120 minutes. The time for spraying the liquid onto the sacrificial layer 2 is not particularly limited, but is, for example, from 2 minutes to 5 minutes. The temperature of the liquid is not particularly limited, but may be, for example, 10°C or higher and 40°C or lower, and may be 20°C or higher and 30°C or lower.

[0089] ≪CO2 separation method≫ The CO2 separation method includes a laminate manufacturing process for manufacturing a laminate in which a CO2 separation membrane and a support substrate are stacked by the above-mentioned laminate manufacturing method, and a separation process for separating CO2 from the gas by supplying a gas containing CO2 to the laminate. By using such a CO2 separation method, it is possible to prevent global warming caused by CO2 by separating and capturing the CO2. In addition, the captured CO2 can be used as a carbon resource. EXAMPLES

[0090] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0091] [Examples 1 to 8 and Comparative Examples 1 to 16] <Preparation of sacrificial layer forming compositions 1 and 2> 100 parts by mass of the following resin A1 (resin (A)), 40 parts by mass of trimethylolpropane (polyol (B)), and 1900 parts by mass of water (solvent (C)) were uniformly mixed to prepare a sacrificial layer-forming composition 1. The numbers in the brackets in each structural unit in the following structural formula indicate the content (mol%) of the structural unit in the resin. In the following structural formula, the left structural unit of resin A1 is a structural unit that introduces functional group II, which is a hydrophilic group, into resin (A). The right structural unit of resin A1 is a structural unit that introduces functional group I into resin (A).

[0092] [ka]

[0093] Furthermore, 200 parts by mass of resin A2 (polyvinyl alcohol) and 1900 parts by mass of water were uniformly mixed to prepare a sacrificial layer-forming composition 2.

[0094] <Preparation of Film-Forming Compositions 1 to 4> The following D1 (polyimide (U-Varnish A, manufactured by Ube Industries, Ltd.)) was dissolved in a mixed solvent (mass ratio 1:1) of NMP (N-methyl-2-pyrrolidone) and PGME (propylene glycol monomethyl ether) to a concentration of 5 mass %, to prepare a film-forming composition 1. The following D2 (polyamide-polyethylene oxide block copolymer (Pebax MH1657, manufactured by Arkema)) was dissolved in benzyl alcohol to a concentration of 5 mass % to prepare a film-forming composition 2. The following D3 (styrene-olefin block copolymer (Tuftec H1051, manufactured by Asahi Kasei Corporation)) was dissolved in decahydronaphthalene to a concentration of 5 mass % to prepare a film-forming composition 3. D4 (polydimethylsiloxane (SYLGARD (registered trademark) 184, manufactured by Dow Corning)) was dissolved in heptane to a concentration of 5 mass % to prepare a film-forming composition 4.

[0095] [ka]

[0096] <Production of Laminate> A laminate 10 was produced by the method shown in Figure 1 using the sacrificial layer forming compositions 1-2 and the film forming compositions 1-4 obtained by the above-mentioned methods, a PET film as a support 1, and a porous polyimide film as a support substrate 4. Specifically, first, a composition for forming a sacrificial layer shown in Table 1 was applied onto a support (PET film) 1 using a slit die coating method, and then heated at 60°C for 2 minutes, followed by heating at 80°C for 3 minutes to form a sacrificial layer 2 having a thickness of 10 μm (sacrificial layer formation process).

[0097] Next, a film-forming composition shown in Table 1 was applied onto the sacrificial layer 2 by gravure coating (Microgravure (registered trademark)), heated at 60°C for 5 minutes, and then heated at 140°C for 10 minutes to form a film (CO2 separation membrane) 3 with a thickness of 500 nm (membrane formation process).

[0098] Next, a support substrate (porous polyimide film) 4 is placed on the membrane (CO2 separation membrane) 3, and the roller pressure is 3 kgf / cm 2 The supporting substrate 4 was adhered onto the film 3 by laminating (thermocompression bonding) under conditions of a roller temperature of 80° C. and a conveying speed of 0.6 m / min (adhesion step).

[0099] After the adhesion step, the support (PET film) 1 was unwound at a transport speed of 0.6 m / min, thereby peeling the support 1 from the sacrificial layer 2 (peeling step).

[0100] After the peeling process, the sacrificial layer removal method described in Table 1 was performed at room temperature (25°C), specifically, the sacrificial layer 2 was immersed in pure water for 60 minutes (referred to as "water immersion" in Table 1) or pure water ejected from a shower was sprayed onto the sacrificial layer 2 for 5 minutes (referred to as "water shower" in Table 1) (sacrificial layer removal process).

[0101] In Comparative Examples 9 to 16, after the sacrificial layer removal step, an alkaline treatment was also performed in which the remaining sacrificial layer 2 was immersed in an alkaline aqueous solution (a 1 mass % aqueous solution of sodium hydroxide) at room temperature (25° C.) and dissolved.

[0102] Thereafter, the laminate 10 in which the membrane 3 and the supporting substrate 4 were laminated was obtained by air drying and drying in a dryer (60° C.).

[0103] <Evaluation of laminated body (CO2 separation)> The CO2 permeability of the obtained laminate 10 was measured under the following conditions in accordance with JIS K7126-2:2006 Plastics-Films and sheets-Gas permeability test method-Part 1: Constant pressure method. Measurement equipment: Differential pressure gas / vapor transmission rate measurement equipment [GTR-10XF] Detector: Gas chromatograph [thermal conductivity detector (TCD)] Test conditions: Mixture of 5% CO2 and 95% N2. Temperature 25℃, humidity 0%RH, gas pressure 3.8cmHg for CO2, 72.2cmHg for N2. Transmission area: 0.159cm 2 The measured N2 to CO2 permeability ratio (CO2 / N2) was evaluated according to the following criteria, and the results are shown in Table 1. Possible: CO2 / N2 is 9-11 Not acceptable: CO2 / N2 is less than 9 or more than 11

[0104] [Table 1]

[0105] According to Examples 1 to 8, when a laminate 10 is manufactured using a composition for forming a sacrificial layer, which contains a resin (A) having a predetermined functional group, a polyol (B), and a solvent (C), by a manufacturing method having the above-mentioned sacrificial layer formation step, film formation step, adhesion step, peeling step, and sacrificial layer removal step, the sacrificial layer can be easily removed with water and can be used satisfactorily as a CO2 separation membrane.

[0106] On the other hand, in Comparative Examples 1 to 16, which used a composition for forming a sacrificial layer that did not contain a resin (A) having a predetermined functional group, the sacrificial layer could not be easily removed with water. As shown in Comparative Examples 13 to 16, it is clear that in order to remove the sacrificial layer so that it can be used satisfactorily as a CO2 separation membrane, an alkaline treatment is required after the sacrificial layer removal step of spraying water. [Explanation of symbols]

[0107] 1 Support 2 Sacrificial Layer 3 membrane 4 Supporting base material 10 Laminate 11 Rolls

Claims

1. A method for producing a laminate in which at least one film and a supporting substrate are laminated, comprising the steps of: A sacrificial layer forming step of forming a sacrificial layer on a support using a sacrificial layer forming composition; forming at least one film on the sacrificial layer; a bonding step of bonding a supporting substrate onto the at least one film; a peeling step of peeling off the support after the adhesion step; a sacrificial layer removing step of removing the sacrificial layer by dissolving the sacrificial layer in a liquid after the peeling step, The composition for forming a sacrificial layer contains a resin (A), a polyol (B), and a solvent (C), the resin (A) has a functional group I which is one or more groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group, and a functional group II which is a hydrophilic group or a hydrophobic group other than the functional group I; However, when the functional group II contains one or more groups selected from a hydroxyl group, a cyano group, and a carboxyl group, the resin (A) does not need to have the functional group I. A method for manufacturing a laminate.

2. The functional group II is a hydrophilic group and is represented by the following formula (A1): -NH-R １ (A1): (In formula (A1), R １ is an alkyl group having 1 to 4 carbon atoms substituted with one or more groups selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group, or a hydrogen atom. or a group represented by the following formula (A2): -N ＋ R ２ R ３ R ４ ・Z － (A2) (In formula (A2), R ２ , R ３ , and R ４ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; Z － is the counter anion.) The method for producing a laminate according to claim 1 , wherein the quaternary ammonium base is represented by the following formula:

3. The method for producing a laminate according to claim 2, wherein the resin (A) is a water-soluble resin having a structural unit derived from at least one monomer selected from the group consisting of (meth)acrylamide and (meth)acrylamide derivatives.

4. The functional group I is represented by the following formula (A3): CH ２ =CR ５ -(R ６ ) ａ -CO-R ７ (A3) (In formula (A3), R ５ is a hydrogen atom or a methyl group, R ６ is a divalent hydrocarbon group, a is 0 or 1, R ７ is -OH, -O-R ８ or -NH-R ８ and R ８ is a hydrocarbon group substituted with one or more functional groups selected from the group consisting of a hydroxyl group, a cyano group, and a carboxyl group. The method for producing a laminate according to claim 1 , wherein the group is derived from a monomer represented by the following formula:

5. The method for producing a laminate according to claim 1 , wherein the liquid is water.

6. The method for manufacturing a laminate according to claim 1 , wherein the sacrificial layer has a thickness of 1 μm or more and 20 μm or less.

7. The method for producing a laminate according to claim 1 , wherein the at least one film has a thickness of 100 nm or more and 1000 nm or less.

8. The method for producing a laminate according to claim 1 , which does not include a step of dissolving the sacrificial layer in an alkaline aqueous solution.

9. The at least one membrane is ２ The method for producing the laminate according to claim 1 , which is a separation membrane.

10. A laminate manufacturing process for manufacturing a laminate by the laminate manufacturing process according to claim 9; The laminate is coated with CO ２ By supplying a gas containing ２ A separation step of separating CO ２ Separation method.

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