Laminate for CO2 separation, film roll, and CO2 separation method

Abstract

To provide a CO2 separation laminate with excellent CO2 permeability and high strength, a film roll in which the CO2 separation laminate is wound into a roll shape, and a CO2 separation method using the CO2 separation laminate. [Solution] A CO2 separation laminate having a CO2 separation laminate body, wherein the CO2 separation laminate body consists of a CO2 separation membrane and a support membrane, or consists of a CO2 separation membrane, a support membrane and a first adhesive layer that is permeable, and in the CO2 separation laminate body, the CO2 separation membrane and the support membrane are laminated via the first adhesive layer or directly, the CO2 separation membrane is a membrane made of a polymer having a siloxane skeleton, the thickness of the CO2 separation membrane is 1 μm or less, the support membrane is a porous membrane made of a thermoplastic resin, the average pore diameter of the support membrane is 400 nm or less, and the thickness of the CO2 separation laminate is 20 μm or more and 450 μm or less.

Description

【Technical Field】 【0001】 The present invention relates to a laminate for CO2 separation, a film roll, and a CO2 separation method. 【Background Art】 【0002】 In order to suppress global warming due to climate change and the like, a technique for separating and recovering carbon dioxide (CO2) using a CO2 separation membrane has been developed (for example, Patent Document 1). 【Prior Art Documents】 【Patent Documents】 【0003】 【Patent Document 1】 Japanese Unexamined Patent Application Publication No. 2018-15678 【Summary of the Invention】 【Problems to be Solved by the Invention】 【0004】 Members used for CO2 separation such as a CO2 separation membrane are preferably excellent in CO2 permeability. 【0005】 Also, members used for CO2 separation such as a CO2 separation membrane are preferably high in strength. When the strength of the members used for CO2 separation is high, deformation and breakage are less likely to occur, and it is also easy to stand alone. Therefore, as a laminate for CO2 separation in which a support membrane for supporting (reinforcing) the CO2 separation membrane is attached to the CO2 separation membrane, it can be considered to be used for CO2 separation. 【0006】 The present invention has been made in view of the above problems, and an object thereof is to provide a laminate for CO2 separation having excellent CO2 permeability and high strength, a film roll in which the laminate for CO2 separation is wound in a roll shape, and a CO2 separation method using the laminate for CO2 separation. 【Means for Solving the Problems】 【0007】 The present inventors have found that the above problems can be solved by a CO2 separation laminate having a CO2 separation laminate body, wherein the CO2 separation laminate body consists of a CO2 separation membrane and a support membrane, or a CO2 separation membrane, a support membrane and a first adhesive layer that is permeable, and in the CO2 separation laminate body, the CO2 separation membrane and the support membrane are laminated via the first adhesive layer or directly, the CO2 separation membrane is a membrane made of a polymer having a siloxane skeleton, the thickness of the CO2 separation membrane is 1 μm or less, the support membrane is a porous membrane made of a thermoplastic resin, the average pore size of the support membrane is 400 nm or less, and the thickness of the CO2 separation laminate is 20 μm or more and 450 μm or less, and have completed the present invention. Specifically, the present invention provides the following. 【0008】 [1] A CO2 separation laminate having a CO2 separation laminate body, The CO2 separation laminate body consists of a CO2 separation membrane and a support membrane, or the CO2 separation membrane, the support membrane, and a first adhesive layer that is permeable. In the CO2 separation laminate body, the CO2 separation membrane and the support membrane are laminated via the first adhesive layer or directly. The CO2 separation membrane is a membrane made of a polymer having a siloxane skeleton. The thickness of the CO2 separation membrane is 1 μm or less. The support membrane is a porous membrane made of thermoplastic resin. The average pore size of the support film is 400 nm or less. The CO2 separation laminate has a thickness of 20 μm or more and 450 μm or less. 【0009】 [2] A breathable film is laminated on at least one main surface of the CO2 separation laminate body, The CO2 separation laminate according to [1] above, wherein the breathable film is a film composed of a continuous phase made of resin. 【0010】 [3] The CO2 separation laminate according to [2] above, wherein the breathable film and the CO2 separation laminate body are bonded together via a second breathable adhesive layer. 【0011】 [4] The breathable film is laminated on the main surface of the CO2 separation laminate body on the CO2 separation membrane side, The CO2 separation laminate according to [3] above, wherein the main surface of the CO2 separation laminate body on the support film side is exposed. 【0012】 [5] The CO2 separation laminate according to [4] above, wherein the second adhesive layer is made of a silicone adhesive. 【0013】 [6] The breathable film is laminated on the main surface of the CO2 separation laminate body on the support film side, The CO2 separation laminate according to [3] above, wherein the main surface of the CO2 separation laminate body on the CO2 separation membrane side is exposed. 【0014】 [7] A protective film is laminated on the main surface of the CO2 separation laminate body on the CO2 separation membrane side. The CO2 separation laminate according to [6] above, wherein the protective film is a film that is breathable and does not correspond to the breathable film. 【0015】 [8] The CO2 separation laminate according to [7], wherein the protective film is laminated on the main surface of the CO2 separation laminate body on the CO2 separation film side via a third adhesive layer that has breathability. 【0016】 [9] The CO2 separation laminate according to any one of [1] to [8] above, wherein the polymer having the siloxane skeleton contains polydimethylsiloxane. 【0017】

[10] The CO2 separation laminate according to any one of [1] to [9] above, wherein the thermoplastic resin is at least one selected from the group consisting of polyolefins, polyesters, nylons, and acrylic resins. 【0018】

[11] The laminated body for CO2 separation according to any one of [2] to [8] above, wherein the ventilation film is a film made of polyethylene terephthalate. 【0019】

[12] The laminated body for CO2 separation according to [7] or [8] above, wherein the protective film is a film made of non-woven fabric. 【0020】

[13] A film roll in which the laminated body for CO2 separation according to any one of [1] to

[12] above is wound in a roll shape. 【0021】

[14] A CO2 separation method having a separation step of separating CO2 from a gas containing CO2 by passing the gas through the laminated body for CO2 separation according to any one of [1] to

[12] above. [Effect of the Invention] 【0022】 According to the present invention, it is possible to provide a laminated body for CO2 separation having excellent CO2 permeability and high strength, a film roll in which the laminated body for CO2 separation is wound in a roll shape, and a CO2 separation method using the laminated body for CO2 separation. [Brief Description of the Drawings] 【0023】 [Figure 1] It is a schematic cross-sectional view showing an example of the laminated body for CO2 separation. [Figure 2] It is a schematic cross-sectional view showing an example of the laminated body for CO2 separation. [Figure 3] It is a schematic cross-sectional view showing an example of the laminated body for CO2 separation. [Figure 4] It is a schematic cross-sectional view showing an example of the laminated body for CO2 separation. [Embodiments for Carrying Out the Invention] 【0024】 [[Laminated Body for CO2 Separation]] The CO2 separation laminate has a CO2 separation laminate body. The CO2 separation laminate body consists of a CO2 separation membrane and a support membrane, or a CO2 separation membrane, a support membrane, and a first adhesive layer that is permeable. In the CO2 separation laminate body, the CO2 separation membrane and the support membrane are laminated either via a first adhesive layer or directly. CO2 separation membranes are membranes made of polymers having a siloxane skeleton. The thickness of the CO2 separation membrane is 1 μm or less. The support membrane is a porous membrane made of thermoplastic resin. The average pore size of the support film is 400 nm or less. The thickness of the CO2 separation laminate is between 20 μm and 450 μm. 【0025】 As shown in the examples described later, such CO2 separation laminates have excellent CO2 permeability and high strength. On the other hand, if the above requirements are not met, at least one of the CO2 permeability and intensity will be significantly inferior. Examples of cases where the above requirements are not met include when the CO2 separation membrane is not made of a polymer having a siloxane skeleton, when the support membrane is not made of a thermoplastic resin and is not a porous membrane with an average pore size of 400 nm or less, and when the thickness of the CO2 separation laminate is outside the range of 20 μm to 450 μm. 【0026】 The CO2 separation laminate will be described below with reference to Figures 1 to 4. Figures 1 to 4 are schematic cross-sectional views showing examples of CO2 separation laminates. 【0027】 The CO2 separation laminate has a CO2 separation laminate body 10. The CO2 separation laminate body 10 may consist of a CO2 separation membrane 11 and a support membrane 12 (Figure 1(a)). In this case, where the CO2 separation laminate body 10 consists of a CO2 separation membrane 11 and a support membrane 12, the CO2 separation membrane 11 and the support membrane 12 are directly laminated in the CO2 separation laminate body 10, as shown in Figure 1(a). Furthermore, the CO2 separation laminate body 10 may consist of a CO2 separation membrane 11, a support membrane 12, and a breathable first adhesive layer 13 (Figure 1(b)). When the CO2 separation laminate body 10 consists of a CO2 separation membrane 11, a support membrane 12, and a breathable first adhesive layer 13, as shown in Figure 1(b), the CO2 separation membrane 11 and the support membrane 12 are laminated in the CO2 separation laminate body 10 via the first adhesive layer 13. 【0028】 The CO2 separation laminate may consist only of the CO2 separation laminate body 10. Specifically, it may be a CO2 separation laminate 1a (Figure 1(a)) or a CO2 separation laminate 1b (Figure 1(b)). 【0029】 Furthermore, the CO2 separation laminate may be composed of a CO2 separation laminate body 10 and other components besides the CO2 separation laminate body 10. For example, the CO2 separation laminate may have a breathable film 14 laminated on at least one main surface of the CO2 separation laminate body 10. Specifically, the CO2 separation laminate may be a CO2 separation laminate 1c in which a breathable film 14 is laminated on the main surface of the CO2 separation laminate body 10 on the CO2 separation membrane 11 side (Figure 2(a)), or a CO2 separation laminate 1d in which a breathable film 14 is laminated on the main surface of the CO2 separation laminate body 10 on the support membrane 12 side (Figure 2(b)). 【0030】 In addition, the CO2 separation laminate may be formed by bonding the breathable film 14 and the CO2 separation laminate body 10 via a breathable second adhesive layer 15. Specifically, the CO2 separation laminate may be a CO2 separation laminate 1e in which a breathable film 14 is laminated on the main surface of the CO2 separation laminate body 10 on the CO2 separation membrane 11 side, and the breathable film 14 and the CO2 separation membrane 11 are bonded via a breathable second adhesive layer 15 (Figure 3(a)), or a CO2 separation laminate 1f in which a breathable film 14 is laminated on the main surface of the CO2 separation laminate body 10 on the support membrane 12 side, and the breathable film 14 and the support membrane 12 are bonded via a breathable second adhesive layer 15 (Figure 3(b)). 【0031】 Figures 2 and 3 show CO2 separation laminates 1c and 1e (Figures 2(a) and 3(a)) in which a breathable film 14 is laminated directly or via a second adhesive layer 15 to the main surface of the CO2 separation laminate body 10 on the CO2 separation membrane 11 side, and the main surface of the CO2 separation laminate body 10 on the support membrane 12 side is exposed, and CO2 separation laminates 1d and 1f (Figures 2(b) and 3(b)) in which a breathable film 14 is laminated directly or via a second adhesive layer 15 to the main surface of the CO2 separation laminate body 10 on the support membrane 12 side, and the main surface of the CO2 separation laminate body 10 on the CO2 separation membrane 11 side is exposed. However, in each case, additional members may be provided on the side of the CO2 separation laminate body 10 where the breathable film 14 is not laminated. 【0032】 Specifically, for example, the CO2 separation laminate may be a CO2 separation laminate 1g in which a breathable film 14 is laminated on the main surface of the CO2 separation laminate body 10 on the support membrane 12 side, and a protective film 16 is laminated on the main surface of the CO2 separation laminate body 10 on the CO2 separation membrane 11 side (Figure 4(a)). The protective film 16 is breathable and does not fall under the category of the breathable film 14. 【0033】 Further, the laminated body for CO2 separation may be a laminated body for CO2 separation 1h in which a ventilation film 14 is laminated on the main surface of the laminated body main body 10 for CO2 separation on the support film 12 side, and a protective film 16 is laminated on the main surface of the laminated body main body 10 for CO2 separation on the CO2 separation membrane 11 side via a breathable third adhesive layer 17 (Fig. 4(b)). In Fig. 4(b), although the mode in which the ventilation film 14 is laminated on the main surface of the laminated body main body 10 for CO2 separation on the support film 12 side via the second adhesive layer 15 is shown, the ventilation film 14 may be directly laminated on the main surface of the laminated body main body 10 for CO2 separation on the support film 12 side without passing through the second adhesive layer 15. 【0034】 Each layer of the laminated body for CO2 separation will be described in more detail below. 【0035】 <CO2 separation membrane> The CO2 separation membrane is a membrane made of a polymer having a siloxane skeleton (a resin having a siloxane bond as the main skeleton). 【0036】 A membrane made of a polymer having a siloxane skeleton has high permeability to CO2 and lower permeability to nitrogen etc. than to CO2, and thus, for example, CO2 can be separated from a gas containing CO2 (e.g., air). 【0037】 As the polymer having a siloxane skeleton, polyorganosiloxanes such as polydimethylsiloxane (PDMS), polyphenylmethylsiloxane, and polydiphenylsiloxane are preferable, and polydimethylsiloxane is more preferable. The polyorganosiloxane may be used together with a curing agent for the polyorganosiloxane. That is, the polymer having a siloxane skeleton may be a polyorganosiloxane cured with a curing agent. The curing agent used together with the polyorganosiloxane is a curing agent that cures the polyorganosiloxane. Examples of curing agents include tetramethoxysilane, trimethoxymethylsilane, dimethoxydimethylsilane, methoxytrimethylsilane, and alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane. 【0038】 Polymers having a siloxane skeleton may have hydroxyl groups or vinyl groups at both or one end of the molecular chain. Furthermore, the polymer having a siloxane skeleton may also be an elastomer. 【0039】 The mass-average molecular weight Mw of the polymer having a siloxane skeleton is preferably 2000 or more, more preferably 2200 to 200000, and even more preferably 2500 to 120000. In this specification, the mass-average molecular weight Mw can be defined as a relative value in terms of polystyrene equivalent in GPC (gel permeation chromatography) measurements. 【0040】 The thickness of the CO2 separation membrane 11 is 1 μm or less, preferably 0.9 μm or less, more preferably 0.8 μm or less, and even more preferably 0.7 μm or less. The lower limit of the thickness of the CO2 separation membrane 11 is not particularly limited, but for example, it is 0.5 μm or more. Since the thickness of the CO2 separation membrane 11 is 1 μm or less, the CO2 separation laminate having the CO2 separation membrane 11 has excellent CO2 permeability. The thinner the thickness of the CO2 separation membrane 11, the better the CO2 permeability. Here, the CO2 separation performance from air, specifically the performance in separating CO2 from nitrogen and oxygen in the air, does not substantially depend on the thickness of the CO2 separation membrane 11. Therefore, the thinner the thickness of the CO2 separation membrane 11, the more efficiently CO2 can be separated from air. 【0041】 The CO2 separation membrane may contain liquids such as solvents contained in the raw material composition (composition for forming a coating film) that includes the raw materials for the CO2 separation membrane 11, but it is preferable that it does not contain liquids. 【0042】 <Support membrane> The support membrane 12 is a member that supports (reinforces) the CO2 separation membrane 11. By having a support membrane 12 that supports (reinforces) the CO2 separation membrane 11, deformation and rupture of the CO2 separation membrane 11 can be suppressed, and the functions of the CO2 separation membrane 11, such as its separation performance, can be maintained. 【0043】 The support film 12 is a porous film made of thermoplastic resin. Thermoplastic resins are not particularly limited. Specific examples of thermoplastic resins include polyolefins such as polyethylene, thermoplastic polyesters such as polyethylene terephthalate and polybutylene terephthalate, nylon, and acrylic resins. The shape of the support film 12 is not limited and may be, for example, a plate or a film. A film drawn from a film roll can be used as the support film 12. The heat resistance temperature of the support film 12 is preferably 400°C or less, more preferably 50°C to 300°C, and even more preferably 70°C to 250°C. 【0044】 The average pore size of the support film 12 is 400 nm or less, preferably 1 nm to 100 nm, and more preferably 2 nm to 50 nm. The average pore size (average micropore diameter) of the support film 12 can be measured by measuring the pore size distribution using a through-pore size evaluation device based on the ASTM F316-86 (JIS K 3832) bubble point method. An example of a porometer (through-pore size distribution measuring device) used for measurement is the nanopalm porometer manufactured by Seika Digital Image Co., Ltd. The pores in the support film 12 may be, for example, voids formed when the support film 12 is manufactured by a stretching method. 【0045】 The thickness of the support film 12 is preferably 5 μm or more and 150 μm or less. In particular, when the CO2 separation laminate consists only of the CO2 separation laminate body 10 (i.e., when the CO2 separation laminate is a CO2 separation laminate 1a consisting of a CO2 separation membrane 11 and a support membrane 12, or a CO2 separation laminate 1b in which the CO2 separation membrane 11 and the support membrane 12 are laminated via a first adhesive layer 13), the thickness of the support membrane 12 is preferably 20 μm or more and 150 μm or less, and more preferably 70 μm or more and 130 μm or less. Furthermore, for example, if the CO2 separation laminate further has a breathable film 14 (i.e., if the CO2 separation laminate has a breathable film 14 laminated on at least one main surface of the CO2 separation laminate body 10), the thickness of the support film 12 is preferably 5 μm or more and 150 μm or less, and more preferably 10 μm or more and 130 μm or less. 【0046】 The arithmetic mean roughness (surface roughness Ra) of the main surface of the support film 12 on the CO2 separation film 11 side is preferably 2.0 μm or less, more preferably 0.01 μm or more and 1.5 μm or less, and even more preferably 0.02 μm or more and 1.0 μm or less. The surface roughness Ra is a value specified by JIS B 0601 (1994). Surface roughness Ra can be measured, for example, using a DektakXT-S (manufactured by Bruker) under the following measurement conditions: measurement range 6.5 μm, length 30,000 μm, duration 60 seconds, and stylus pressure 3 mg. 【0047】 <First adhesive layer> The first adhesive layer 13 is a component that adheres the support film 12 and the CO2 separation film 11. 【0048】 The first adhesive layer 13 is breathable. Specifically, for example, the first adhesive layer 13 has pores that allow good permeability of a CO2-containing gas (e.g., air) to be processed using a CO2 separation laminate, or it is made of a material that allows good permeability of a CO2-containing gas. The permeability of the first adhesive layer 13 should be such that, for example, the CO2 separation laminate allows air to pass through at a rate of 500 s / 100 ml or less at 24°C using the JIS P 8117 Gurley method. 【0049】 The material constituting the first adhesive layer 13 is not particularly limited, as long as it is a material capable of bonding the support film 12 and the CO2 separation film 11. Examples of the first adhesive layer 13 include silicone-based adhesives. 【0050】 If the first adhesive layer 13 is not present, the support film 12 and the CO2 separation film 11 are directly laminated without the first adhesive layer 13. When the support film 12 and the CO2 separation film 11 are directly laminated without the first adhesive layer 13, the support film 12 and the CO2 separation film 11 are bonded together, for example, by intermolecular forces such as electrostatic force or by lamination (thermocompression bonding). 【0051】 <Breathable film> The breathable film 14 is a component that protects and reinforces the CO2 separation membrane 11 and the support membrane 12. By having the breathable film 14, deformation and rupture of the CO2 separation membrane 11 and the support membrane 12 can be suppressed when transporting or using the CO2 separation laminate. In addition, the strength of the CO2 separation laminate can be improved by having the breathable film 14. 【0052】 The breathable film 14 is preferably a film composed of a continuous phase made of resin. Therefore, nonwoven fabric, which is an aggregate of discontinuous short fibers, does not qualify as a breathable film 14 composed of a continuous phase. Examples of breathable film 14 include films made of polyethylene terephthalate. 【0053】 Furthermore, the breathable film 14 is breathable. Specifically, the breathable film 14 has pores that allow a CO2-containing gas (e.g., air) to pass through well when processed using the CO2 separation laminate. The permeability of the permeable film 14 is such that, for example, the CO2 separation laminate allows air to pass through at a rate of 500 s / 100 ml or less at 24°C using the JIS P 8117 Gurley method. The holes in the breathable film 14 that allow CO2-containing gas to pass through may be, for example, through holes made by punching or other processes, or connecting holes made up of multiple interconnected pores. 【0054】 The thickness of the breathable film 14 is preferably 20 μm or more and 120 μm or less, and more preferably 50 μm or more and 100 μm or less. 【0055】 <Second adhesive layer> The second adhesive layer 15 is a component that adheres the breathable film 14 to the CO2 separation laminate body 10. 【0056】 The second adhesive layer 15 is permeable. Specifically, for example, the second adhesive layer 15 has pores that allow a CO2-containing gas (e.g., air) to pass through well when processed using a CO2 separation laminate, or it is made of a material that allows a CO2-containing gas to pass through well. The permeability of the second adhesive layer 15 should be such that, for example, the CO2 separation laminate allows air to pass through at a rate of 500 s / 100 ml or less at 24°C using the JIS P 8117 Gurley method. 【0057】 The material constituting the second adhesive layer 15 is not particularly limited, as long as it is a material capable of bonding the support film 12 or CO2 separation film 11 to the breathable film 14. Examples of the second adhesive layer 15 include silicone-based adhesives. 【0058】 If the second adhesive layer 15 is not present, the support film 12 or CO2 separation film 11 and the breathable film 14 are directly laminated without the second adhesive layer 15. When the support film 12 or CO2 separation film 11 and the breathable film 14 are directly laminated without the second adhesive layer 15, the support film 12 or CO2 separation film 11 and the breathable film 14 are bonded together, for example, by intermolecular forces such as electrostatic force or by lamination (thermocompression bonding). 【0059】 <Protective film> The protective film 16 is a component that protects the CO2 separation membrane 11. By having the protective film 16 in the CO2 separation laminate, deformation and rupture of the CO2 separation membrane 11 can be suppressed when transporting or using the CO2 separation laminate. 【0060】 The protective film 16 is breathable and does not fall under the category of the breathable film 14. Specifically, the protective film 16 is a film that has pores that allow a CO2-containing gas (e.g., air) to pass through well, and is not a breathable film 14, and is processed using a CO2 separation laminate. The permeability of the protective film 16 should be such that, for example, the CO2 separation laminate allows air to pass through at a rate of 500 s / 100 ml or less at 24°C using the JIS P 8117 Gurley method. 【0061】 The protective film 16 is preferably made of a nonwoven fabric. When the protective film 16 is a nonwoven fabric, the voids in the nonwoven fabric correspond to the pores in the protective film 16 that allow CO2-containing gas to pass through well. 【0062】 The material of the protective film 16 is not particularly limited and includes, for example, cellulose, nylon, polyolefin, rayon, polyester, etc. 【0063】 The thickness of the protective film 16 is preferably 20 μm or more and 170 μm or less, and more preferably 50 μm or more and 150 μm or less. 【0064】 <Third adhesive layer> The third adhesive layer 17 is a component that adheres the protective film 16 and the CO2 separation film 11. 【0065】 The third adhesive layer 17 is breathable. Specifically, for example, the third adhesive layer 17 has pores that allow good permeability of a CO2-containing gas (e.g., air) to be processed using a CO2 separation laminate, or it is formed of a material that allows good permeability of a CO2-containing gas. The permeability of the third adhesive layer 17 should be such that, for example, the CO2 separation laminate allows air to pass through at a rate of 500 s / 100 ml or less at 24°C using the JIS P 8117 Gurley method. 【0066】 The material constituting the third adhesive layer 17 is not particularly limited, as long as it is a material capable of bonding the protective film 16 and the CO2 separation film 11. Examples of the third adhesive layer 17 include silicone adhesives. 【0067】 If the third adhesive layer 17 is not present, the protective film 16 and the CO2 separation film 11 are directly laminated without the third adhesive layer 17. When the protective film 16 and the CO2 separation film 11 are directly laminated without the third adhesive layer 17, the protective film 16 and the CO2 separation film 11 are bonded together, for example, by intermolecular forces such as electrostatic force or by lamination (thermocompression bonding). 【0068】 The thickness of the CO2 separation laminate is 20 μm to 450 μm, preferably 50 μm to 400 μm, and more preferably 80 μm to 380 μm. 【0069】 The CO2 separation laminate can also be in the form of a film roll. Using a film roll makes it easier to transport, store, and apply to large-scale equipment. 【0070】 ≪Manufacturing method for CO2 separation laminates≫ The method for manufacturing the CO2 separation laminate described above is not particularly limited. CO2 separation laminates 1a and 1b (Figures 1(a) and 1(b)), which consist only of the CO2 separation laminate body 10, are, for example, A coating film formation step involves forming a coating film of a raw material composition containing the raw materials for the CO2 separation membrane 11 on a sacrificial layer, A support film bonding step involves bonding a support film 12 onto the coated film, It can be manufactured by a method for manufacturing a CO2 separation laminate, which includes a sacrificial layer removal step for removing the sacrificial layer. 【0071】 A method for producing a CO2 separation laminate may include a curing step in which the polyorganosiloxane, such as polydimethylsiloxane, is cured if the raw material composition containing the raw materials for the CO2 separation membrane contains a polyorganosiloxane such as polydimethylsiloxane. Furthermore, the method for manufacturing a CO2 separation laminate may include a sacrificial layer formation step, in which a sacrificial layer is formed on a support member for the sacrificial layer, before the coating film formation step, and a support member peeling step, in which the support member for the sacrificial layer is peeled off from the sacrificial layer. 【0072】 Furthermore, if the CO2 separation laminate comprises a CO2 separation laminate body 10 and other components (breathable film 14, protective film 16), for example, the CO2 separation laminate can be manufactured by further including a breathable film bonding step for bonding the breathable film 14 and a protective film bonding step for bonding the protective film 16 in the above-described method for manufacturing the CO2 separation laminate. 【0073】 Specifically, for example, when manufacturing a CO2 separation laminate 1e (Figure 3(a)) having a CO2 separation laminate body 10 consisting of a CO2 separation membrane 11 and a support membrane 12, and a breathable film 14, wherein the breathable film 14 and the CO2 separation membrane 11 are bonded via a second adhesive layer 15, it can be manufactured by a manufacturing method having, in this order, a coating film formation step, a breathable film bonding step, a sacrificial layer removal step, and a support membrane bonding step. 【0074】 Furthermore, when manufacturing a CO2 separation laminate 1f (Figure 3(b)) which has a CO2 separation laminate body 10 consisting of a CO2 separation membrane 11 and a support membrane 12, and a breathable film 14, and the breathable film 14 and the support membrane 12 are bonded via a second adhesive layer 15, it can be manufactured by a manufacturing method having, in this order, a coating film formation step, a support membrane bonding step, a breathable film bonding step, and a sacrificial layer removal step. 【0075】 Furthermore, when manufacturing a CO2 separation laminate 1h having a CO2 separation laminate body 10 consisting of a CO2 separation membrane 11 and a support membrane 12, a breathable film 14 and a protective film 16, wherein the breathable film 14 and the support membrane 12 are bonded via a second adhesive layer 15, and the CO2 separation membrane 11 and the protective film 16 are bonded via a third adhesive layer 17, it can be manufactured by a manufacturing method having, in this order, a coating film formation step, a support membrane bonding step, a breathable film bonding step, a sacrificial layer removal step and a protective film bonding step. 【0076】 Each step is explained below. 【0077】 [Sacrificial layer formation process] In the sacrificial layer formation process, the sacrificial layer is formed on a support member for the sacrificial layer. The sacrificial layer is typically formed using a sacrificial layer-forming composition. The sacrificial layer-forming composition is not particularly limited as long as it is a composition that can form a sacrificial layer that can be removed in a subsequent sacrificial layer removal step. Typically, the sacrificial layer-forming composition comprises a resin and a solvent. 【0078】 Examples of resins included in the sacrificial layer-forming composition include polyvinyl alcohol resin, dextrin, gelatin, animal glue, casein, shellac, gum arabic, starch, protein, polyacrylamide, sodium polyacrylate, polyvinyl methyl ether, copolymer of methyl vinyl ether and maleic anhydride, copolymer of vinyl acetate and itaconic acid, polyvinylpyrrolidone, acetylcellulose, acetylbutylcellulose, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, sodium alginate, and the like. 【0079】 The amount of resin contained in the sacrificial layer-forming composition is not particularly limited as long as it does not hinder the objective of the present invention, and is determined appropriately taking into consideration the applicability of the sacrificial layer-forming composition, etc. When the mass of the resin in the sacrificial layer forming composition is 100 parts by mass, the amount of solvent 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 700 parts by mass or more and 6,000 parts by mass or less. 【0080】 The solvent included in the sacrificial layer-forming composition is not particularly limited as long as it is a solvent in which the resin is soluble. The sacrificial layer-forming composition may also contain undissolved resin, as long as a predetermined amount of resin is dissolved in it. Preferably, the resin is completely dissolved in the sacrificial layer-forming composition. 【0081】 The solvent may be water, an organic solvent, or an aqueous solution of an organic solvent. 【0082】 Specific examples of organic solvents used as solvents include: Methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethyl-1-butanol, sec-heptanol, 3-heptanol, 1-octanol, 2-ethylhexanol Monoalcohol solvents such as sanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-vundecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, methylisobutylcarbinol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, and cresol; 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; 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, and other ethers; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; Alkyl lactate 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, methyl-3-methoxybutyl acetate, methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-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, ethyl 2-oxobutanoate, etc. Lactones such as β-propyrolactone, 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; Examples include terpenes such as p-menthane, diphenylmenthane, limonene, terpinene, bornane, norbornane, and pinan. 【0083】 When the solvent is a mixed solvent of water and an organic solvent, the content of the organic solvent in the solvent is preferably 10% by mass or more, and more preferably 20% by mass or more. 【0084】 The sacrificial layer-forming composition may contain various components other than the resin and solvent, as long as they do not hinder the objective of the present invention. Examples of other components include viscosity modifiers, surfactants, and defoaming agents. 【0085】 The method for preparing the sacrificial layer-forming composition is not particularly limited. Typically, the sacrificial layer-forming composition is prepared by uniformly mixing a predetermined amount of resin, a solvent, and other components as may be included. 【0086】 Support members for the sacrificial layer include resin films such as PET (polyethylene terephthalate) film, and substrates such as silicon substrates and glass substrates. The surface of the support member on which the sacrificial layer is formed may or may not be treated with a release agent. The shape of the support member is not particularly limited and may be in the form of a film or a plate. If the shape of the support member is in the form of a film, a film pulled from a film roll can be used as the support member. 【0087】 The method for forming a sacrificial layer on a support member using a sacrificial layer-forming composition is not particularly limited and includes, for example, coating methods such as bar coating, slit die coating, gravure coating, spin coating, spray coating, roller coating, and immersion coating. 【0088】 After applying the sacrificial layer-forming composition to the support member, the coated film of the sacrificial layer-forming composition may be heated (dried) as needed to remove at least a portion of the solvent of the sacrificial layer-forming composition. The heating temperature of the coating film of the sacrificial layer-forming composition is, for example, 50°C to 90°C. Alternatively, the coating film may be heated at a low temperature (for example, 50°C to less than 70°C) and then heated at a high temperature (for example, 70°C to 90°C). 【0089】 The thickness of the sacrificial layer is not particularly limited, but from the viewpoint of CO2 separation performance from air, a thinner sacrificial layer is preferable. The thickness of the sacrificial layer is preferably 1 μm to 20 μm, more preferably 2 μm to 18 μm, and even more preferably 3 μm to 15 μm. 【0090】 [Coating film formation process] In the coating film formation process, a coating film is formed on the sacrificial layer using a raw material composition (composition for coating film formation) that contains the raw materials for the CO2 separation membrane 11. The raw material composition (composition for forming CO2 separation membranes) typically comprises a polymer having the siloxane skeleton described above and a solvent. 【0091】 If the raw material composition contains a polyorganosiloxane, the raw material composition may also contain a curing agent for the polyorganosiloxane. The content of the curing agent in the raw material composition is not particularly limited. In the raw material composition, the content of the curing agent is preferably 1 part by mass or more and 20 parts by mass or less, and more preferably 5 parts by mass or more and 15 parts by mass or less, per 100 parts by mass of polyorganosiloxane. 【0092】 Examples of solvents included in the raw material 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, terpenes, and the like. Dimethyl sulfoxide is an example of a 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 (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. Other ethers include, for example, 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, acetic acid Examples 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 propyrolactone, 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-vundecane, 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. 【0093】 The viscosity of the raw material composition is preferably 5 cp to 500 cp at 24°C, more preferably 10 cp to 200 cp, and even more preferably 20 cp to 100 cp. Furthermore, the solid content concentration of the raw material composition is preferably 1% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 18% by mass or less, and even more preferably 5% by mass or more and 15% by mass or less. 【0094】 The method for preparing the raw material composition is not particularly limited. The raw material composition is prepared by uniformly mixing the components, such as the polymer having the siloxane skeleton described above. 【0095】 After applying the raw material composition onto the sacrificial layer, the coated film may be heated (dried) as needed to remove at least a portion of the solvent in the film-forming composition. The heating (drying) temperature of the coated film is, for example, between 40°C and 90°C. The heating (drying) time for the coated film is, for example, 0.5 minutes or more and 10 minutes or less. 【0096】 [Support film adhesion process] In the support film bonding step, the support film 12 described above is bonded to the coated film formed in the coating film formation step. The CO2 separation film 11 is formed from the coated film. 【0097】 The method for adhering the support film 12 to the coated film is not particularly limited. Examples include lamination and transfer methods utilizing intermolecular forces such as electrostatic forces. The coated film and the support film 12 can be adhered without using an adhesive. For example, the coating film (CO2 separation film 11) may be laminated (heat-pressed) onto the support film 12 using a roll or the like at a pressure that does not damage the support film 12. The conditions for heat pressing are a roller pressure of 0.1 kgf / cm². 2 More than 10kgf / cm 2 The following is preferred: 0.2 kgf / cm² 2 More than 5kgf / cm 2 The following is more preferable: The roller temperature is preferably between 20°C and 120°C, and more preferably between 25°C and 100°C. When utilizing intermolecular forces such as electrostatic forces, for example, the coated film (CO2 separation film 11) and the support film 12 can be brought into contact. 【0098】 Alternatively, the support film 12 may be bonded to the coated film (CO2 separation film 11) using an adhesive. For example, the coated film (CO2 separation film 11) and the support film 12 may be bonded via the first adhesive layer 13 by providing the first adhesive layer 13 at a desired position on the coated film (CO2 separation film 11) using an inkjet method or the like. Alternatively, by using a support film 12 on which the first adhesive layer 13 is provided on one main surface, the coated film (CO2 separation film 11) and the support film 12 may be bonded via the first adhesive layer 13. 【0099】 [Curing process] If the raw material composition for forming the coating film in the coating film formation process includes a polyorganosiloxane such as polydimethylsiloxane as a polymer having a siloxane skeleton, the process may include a curing step for curing the polyorganosiloxane such as polydimethylsiloxane. In the curing process, the coating film hardens to become a cured film (CO2 separation film 11). If there is no curing process, the coating film may be the CO2 separation film 11. 【0100】 One method of curing is heating the coated film. The solvent may be removed during the heating process of the curing. The heating temperature of the coating film is, for example, 100°C to 160°C, and preferably 105°C to 150°C. Furthermore, the heating time for the coating film is, for example, 1 minute or more and 10 minutes or less, and preferably 2 minutes or more and 5 minutes or less. 【0101】 [Support member removal process] In the support member removal process, the support member is separated from the sacrificial layer. The method for detaching the support member from the sacrificial layer is not particularly limited. Examples include using a detaching solution or peeling the support member from the sacrificial layer without using a detaching solution. If the support member is in the form of a film, it can be detached from the sacrificial layer by unwinding the film. When detaching the support member from the sacrificial layer, a portion of the sacrificial layer may be peeled off together with the support member. 【0102】 [Sacrificial layer removal process] In the sacrificial layer removal process, the sacrificial layer is removed. After removing the sacrificial layer, the material may be dried using airflow, a dryer, or other means as needed. 【0103】 The sacrificial layer is typically removed by dissolving it in a liquid. The liquid used to dissolve the sacrificial layer may be water, an organic solvent, or a mixture of water and an organic solvent. When dissolving the sacrificial layer with these liquids, some of the sacrificial layer may remain undissolved. To remove the remaining sacrificial layer, it is preferable to further dissolve it using, for example, an alkaline aqueous solution (basic aqueous solution). 【0104】 The method for dissolving the sacrificial layer in a liquid is not particularly limited, but examples include washing the sacrificial layer with running water, immersing the sacrificial layer in a liquid, or spraying the sacrificial layer with liquid from a shower. The time for rinsing the sacrificial layer with running water is not particularly limited, but for example, it is between 1 minute and 30 minutes. The immersion time in the sacrificial layer is not particularly limited, but is, for example, between 5 minutes and 120 minutes. The duration for spraying the liquid onto the sacrificial layer is not particularly limited, but is, for example, between 2 and 5 minutes. Furthermore, the liquid temperature is not particularly limited, but for example, it may be between 10°C and 40°C, or between 20°C and 30°C. 【0105】 [Breathable film bonding process] In the breathable film bonding process, the breathable film 14 is bonded to the CO2 separation membrane 11 and the support membrane 12. The method for adhering the breathable film 14 to the CO2 separation membrane 11 and the support membrane 12 is not particularly limited. For example, the breathable film 14 may be bonded to the CO2 separation membrane 11 or the support membrane 12 using an adhesive. Specifically, the CO2 separation membrane 11 or the support membrane 12 may be bonded to the breathable film 14 via the second adhesive layer 15 by providing the above-mentioned second adhesive layer 15 at a desired position on the CO2 separation membrane 11 or the support membrane 12 using an inkjet method or the like. Alternatively, the CO2 separation membrane 11 or the support membrane 12 may be bonded to the breathable film 14 via the second adhesive layer 15 by using a breathable film 14 in which the second adhesive layer 15 is provided on one main surface. stomach. 【0106】 Alternatively, the breathable film 14 may be bonded to the CO2 separation membrane 11 or the support membrane 12 without going through the second adhesive layer 15 by lamination or a transfer method utilizing intermolecular forces such as electrostatic force. For example, the breathable film 14 may be laminated (heat-pressed) onto the CO2 separation membrane 11 and the support membrane 12 using a roll or the like, at a pressure that does not damage the CO2 separation membrane 11 or the support membrane 12. 【0107】 [Protective film adhesion process] In the protective film bonding process, the protective film 16 is bonded to the main surface of the CO2 separation laminate body 10 on the CO2 separation membrane 11 side. The method for adhering the protective film 16 to the main surface of the CO2 separation laminate body 10 on the CO2 separation membrane 11 side (i.e., the CO2 separation membrane 11) is not particularly limited. For example, the protective film 16 may be bonded to the CO2 separation membrane 11 using an adhesive. Specifically, the CO2 separation membrane 11 and the protective film 16 may be bonded via the third adhesive layer 17 by providing the above-mentioned third adhesive layer 17 at a desired position on the CO2 separation membrane 11 using an inkjet method or the like. Alternatively, the CO2 separation membrane 11 and the protective film 16 may be bonded via the third adhesive layer 17 by using a protective film 16 in which the third adhesive layer 17 is provided on one of the main surfaces. stomach. 【0108】 Alternatively, the protective film 16 may be adhered to the CO2 separation film 11 without going through the third adhesive layer 17 by lamination or a transfer method utilizing intermolecular forces such as electrostatic force. For example, the protective film 16 may be laminated (heat-pressed) onto the CO2 separation membrane 11 using a roll or the like, at a pressure that does not damage the CO2 separation membrane 11. 【0109】 ≪CO2 separation method≫ The CO2 separation method includes a separation step of separating CO2 from a gas by passing a gas containing CO2 through the aforementioned CO2 separation laminate. The aforementioned CO2 separation laminate has excellent CO2 permeability and high strength, allowing for efficient separation of CO2 from gases containing CO2, while also suppressing deformation and rupture of the CO2 separation membrane 11 and maintaining its separation performance and other functions. It is preferable to allow the CO2-containing gas to permeate from the CO2 separation membrane 11 side to the support membrane 12 side of the CO2 separation laminate described above. When passing a gas containing CO2 through the aforementioned CO2 separation laminate, it is preferable to apply pressure to allow the gas to pass through. By separating and recovering CO2 using this CO2 separation method, it is possible to suppress global warming caused by CO2. Furthermore, the captured CO2 can be used as a carbon resource. [Examples] 【0110】 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. 【0111】 <Preparation of Composition for Sacrificial Layer Formation> 200 parts by mass of polyvinyl alcohol and 1900 parts by mass of water were uniformly mixed to prepare Composition 1 for sacrificial layer formation. 【0112】 <Preparation of Raw Material Composition (Composition for Coating Film Formation) Containing Raw Materials for CO2 Separation Membrane> Polydimethylsiloxane (SYLGARD (registered trademark) 184, manufactured by Dow Corning, mass average molecular weight Mw 5000) and a curing agent (trimethoxymethylsilane) were dissolved in heptane so that the solid content concentration was 5% by mass with 10 parts by mass of the curing agent with respect to 100 parts by mass of polydimethylsiloxane to prepare Raw Material Composition 1. Further, the following D1 (styrene elastomer, mass average molecular weight Mw 50000) was dissolved in decahydronaphthalene so that the concentration was 5% by mass to prepare Raw Material Composition 2. 【0113】 【Chemical formula】 【0114】 [Example 1] First, Composition 1 for sacrificial layer formation was applied onto a support member (PET film) by slit die coating, heated at 60°C for 2 minutes, and then heated at 80°C for 3 minutes to form a sacrificial layer with a film thickness of 15 μm. 【0115】 Next, Raw Material Composition 1 was applied onto the sacrificial layer 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 PDMS film (CO2 separation membrane 11) with a film thickness of 0.7 μm. 【0116】 Next, a support film 12 (porous polyethylene film, average pore size 100 nm, surface roughness Ra 0.3 μm) with a thickness of 100 μm was placed on the PDMS film (CO2 separation film 11), and the support film 12 and the PDMS film (CO2 separation film 11) were brought into contact with each other using a roller, thereby bonding the support film 12 and the PDMS film (CO2 separation film 11) by electrostatic force. 【0117】 Subsequently, the support member (PET film) was unwound at a transport speed of 0.6 m / min, thereby separating the support member from the sacrificial layer. 【0118】 After peeling off the support member, the sacrificial layer was immersed in pure water at room temperature (25°C) for 60 minutes to remove the sacrificial layer, thereby obtaining a CO2 separation laminate body 10 consisting of a CO2 separation membrane 11 and a support membrane 12. The obtained CO2 separation laminate body 10 (CO2 separation laminate 1a (Figure 1(a))) was used as the CO2 separation laminate of Example 1. 【0119】 [Example 2] A sacrificial layer was formed in the same manner as in Example 1, and a PDMS film (CO2 separation film 11) was formed on the sacrificial layer. On the other hand, a PET film with a thickness of 75 μm, on which an adhesive layer (second adhesive layer 15) made of silicone adhesive is provided over the entire surface of one main surface, is punched, resulting in a 1 m in plan view. 2 A breathable film 14 having a second adhesive layer 15 was obtained by creating through holes with a diameter of 1 mm at a ratio of 450,000 per hole. The adhesive layer (second adhesive layer 15), which is made of a silicone adhesive, is an extremely thin film whose thickness is negligible. 【0120】 Next, a breathable film 14 having a second adhesive layer 15 was placed on the PDMS membrane (CO2 separation membrane 11) so that the side with the second adhesive layer 15 was in contact with the PDMS membrane, and the breathable film 14 and the PDMS membrane (CO2 separation membrane 11) were bonded together by bringing the breathable film 14 and the PDMS membrane (CO2 separation membrane 11) into contact with each other using a roller. 【0121】 Subsequently, the support member (PET film) was unwound at a transport speed of 0.6 m / min, thereby separating the support member from the sacrificial layer. 【0122】 After removing the support members, the exposed sacrificial layer was immersed in pure water for 60 minutes at room temperature (25°C) to remove it. 【0123】 After removing the sacrificial layer, a support film 12 (porous polyethylene film, average pore size 100 nm, surface roughness Ra 0.3 μm) with a thickness of 100 μm was placed on the PDMS film (CO2 separation film 11), and the support film 12 and the PDMS film (CO2 separation film 11) were brought into contact with each other using a roller, thereby bonding the support film 12 and the PDMS film (CO2 separation film 11) by electrostatic force. The resulting CO2 separation laminate 1e (Figure 3(a)) is defined as the CO2 separation laminate of Example 2. It has a CO2 separation laminate body 10 consisting of a PDMS membrane (CO2 separation membrane 11) and a support membrane 12, and a breathable film 14, wherein the breathable film 14 and the CO2 separation membrane 11 are bonded together via a second adhesive layer 15. 【0124】 [Example 3] A sacrificial layer was formed in the same manner as in Example 1, and a PDMS film (CO2 separation film 11) was formed on the sacrificial layer. 【0125】 Next, a support film 12 (porous polyethylene film, average pore size 100 nm, surface roughness Ra 0.3 μm) with a thickness of 100 μm was placed on the PDMS film (CO2 separation film 11), and the support film 12 and the PDMS film (CO2 separation film 11) were brought into contact with each other using a roller, thereby bonding the support film 12 and the PDMS film (CO2 separation film 11) by electrostatic force. 【0126】 Next, a breathable film 14 having a second adhesive layer 15, prepared in the same manner as in Example 2, was placed on the support film 12 so that the side with the second adhesive layer 15 was in contact with the support film 12. The breathable film 14 and the support film 12 were then bonded together by bringing them into contact with a roller. 【0127】 Subsequently, the support member (PET film) was unwound at a transport speed of 0.6 m / min, thereby separating the support member from the sacrificial layer. 【0128】 After removing the support members, the exposed sacrificial layer was immersed in pure water for 60 minutes at room temperature (25°C) to remove it. The resulting CO2 separation laminate 1f (Figure 3(b)), which has a CO2 separation laminate body 10 consisting of a PDMS membrane (CO2 separation membrane 11) and a support membrane 12, and a breathable film 14, with the breathable film 14 and the support membrane 12 bonded together via a second adhesive layer 15, was used as the CO2 separation laminate for Example 3. 【0129】 [Example 4] A nonwoven fabric made of cellulose with a thickness of 75 μm, on which an adhesive layer (third adhesive layer 17) made of a silicone adhesive is provided on the fibers of one main surface, was used as the protective film 16 having the third adhesive layer 17. The adhesive layer (third adhesive layer 17) made of a silicone adhesive is an extremely thin film whose thickness is negligible. 【0130】 In Example 3, a CO2 separation laminate 1f (Figure 3(b)) was obtained, which had a CO2 separation laminate body 10 consisting of a PDMS membrane (CO2 separation membrane 11) and a support membrane 12, and a breathable film 14, with the breathable film 14 and the support membrane 12 being bonded via a second adhesive layer 15. A protective film 16 having a third adhesive layer 17 was placed on the CO2 separation membrane 11 so that the side with the third adhesive layer 17 was in contact with the CO2 separation membrane 11, and the protective film 16 and the CO2 separation membrane 11 were bonded together by bringing the protective film 16 and the CO2 separation membrane 11 into contact with each other using a roller. The obtained CO2 separation laminate 1h (Figure 4(b)), which has a CO2 separation laminate body 10 consisting of a PDMS membrane (CO2 separation membrane 11) and a support membrane 12, a breathable film 14 and a protective film 16, wherein the breathable film 14 and the support membrane 12 are bonded via a second adhesive layer 15, and the CO2 separation membrane 11 and the protective film 16 are bonded via a third adhesive layer 17, was used as the CO2 separation laminate of Example 4. 【0131】 [Example 5] A CO2 separation laminate of Example 5 was obtained in the same manner as in Example 3, except that a support film 12 with a thickness of 11 μm (porous polyethylene film, average pore size 20 nm, surface roughness Ra 0.3 μm) was used as the support film 12. 【0132】 [Example 6] A CO2 separation laminate of Example 6 was obtained in the same manner as in Example 1, except that a support film 12 with a thickness of 147 μm (porous polyethylene film, average pore size 20 nm, surface roughness Ra 0.6 μm) was used as the support film 12. 【0133】 [Example 7] A nonwoven fabric made of polyethylene terephthalate with a thickness of 130 μm, on which an adhesive layer (third adhesive layer 17) made of a silicone-based adhesive is provided on the fibers of one of the main surfaces, was used as the protective film 16 having the third adhesive layer 17. The adhesive layer (third adhesive layer 17) made of a silicone-based adhesive is an extremely thin film whose thickness is negligible. 【0134】 A sacrificial layer was formed in the same manner as in Example 1, and a PDMS film (CO2 separation film 11) was formed on the sacrificial layer. 【0135】 Next, a support film 12 (porous polyethylene terephthalate film, average pore size 100 nm, surface roughness Ra 0.3 μm) with a thickness of 147 μm was placed on the PDMS film (CO2 separation film 11), and the support film 12 and the PDMS film (CO2 separation film 11) were brought into contact with each other using a roller, thereby bonding the support film 12 and the PDMS film (CO2 separation film 11) by electrostatic force. 【0136】 Next, a breathable film 14 having a second adhesive layer 15, prepared in the same manner as in Example 2, was placed on the support film 12 so that the side with the second adhesive layer 15 was in contact with the support film 12. The breathable film 14 and the support film 12 were then bonded together by bringing them into contact with a roller. 【0137】 Subsequently, the support member (PET film) was unwound at a transport speed of 0.6 m / min, thereby separating the support member from the sacrificial layer. 【0138】 After removing the support members, the exposed sacrificial layer was immersed in pure water for 60 minutes at room temperature (25°C) to remove it. The obtained CO2 separation laminate 1f (Figure 3(b)) has a CO2 separation laminate body 10 consisting of a PDMS membrane (CO2 separation membrane 11) and a support membrane 12, and a breathable film 14, with the breathable film 14 and the support membrane 12 being bonded via a second adhesive layer 15. A protective film 16 having a third adhesive layer 17 was placed on the CO2 separation membrane 11 of the CO2 separation laminate 1f (Figure 3(b)) with the surface on which the third adhesive layer 17 is provided in contact with the CO2 separation membrane 11, and the protective film 16 and the CO2 separation membrane 11 were bonded together by bringing the protective film 16 and the CO2 separation membrane 11 into contact with each other using a roller. The obtained CO2 separation laminate 1h (Figure 4(b)), which has a CO2 separation laminate body 10 consisting of a PDMS membrane (CO2 separation membrane 11) and a support membrane 12, a breathable film 14 and a protective film 16, wherein the breathable film 14 and the support membrane 12 are bonded via a second adhesive layer 15, and the CO2 separation membrane 11 and the protective film 16 are bonded via a third adhesive layer 17, was used as the CO2 separation laminate for Example 7. 【0139】 [Comparative Example 1] A CO2 separation laminate of Comparative Example 1 was obtained in the same manner as in Example 3, except that a support film 12 with a thickness of 100 μm (porous polyimide: PI, average pore size 300 nm, surface roughness Ra 0.2 μm) was used as the support film 12. 【0140】 [ka] 【0141】 [Comparative Example 2] A CO2 separation laminate for Comparative Example 2 was obtained in the same manner as in Example 3, except that raw material composition 2 was used instead of raw material composition 1. 【0142】 [Comparative Example 3] As the support membrane 12, a support membrane 12 with a thickness of 100 μm (porous polyimide: PI, average pore diameter 300 nm, surface roughness Ra 0.2 μm) was used, and a laminate for CO2 separation of Comparative Example 3 was obtained in the same manner as in Example 3, except that raw material composition 2 was used instead of raw material composition 1. 【0143】 〔Comparative Example 4〕 A laminate for CO2 separation of Comparative Example 4 was obtained in the same manner as in Example 1, except that a support membrane 12 with a thickness of 12 μm (porous polyethylene film, average pore diameter 30 nm, surface roughness Ra 0.3 μm) was used as the support membrane 12. 【0144】 For the laminates for CO2 separation obtained in Examples 1 to 7 and Comparative Examples 1 to 4, the CO2 permeability and strength were evaluated by the following methods. The results are shown in Table 1. 【0145】 <Evaluation of CO2 Permeability> For the obtained laminate for CO2 separation, CO2 gas was supplied so as to permeate from the CO2 separation membrane 11 side to the support membrane 12 side, the flow rate value of the permeating CO2 was measured, and the CO2 permeability (GPU) was calculated. Note that it was in accordance with JIS K7126-1:2006 Plastics - Films and Sheets - Gas Permeability Test Methods - Part 2: Differential Pressure Method. The measurement conditions were as follows. Measuring device: Differential pressure type gas / vapor permeability measuring device [GTR-21A] Detector: Gas chromatograph [thermal conductivity detector (TCD)] Test conditions: CO2 gas at a gas pressure of 3.8 cmHg at a temperature of 25°C and a humidity of 0%RH Permeation area: 0.159 cm 2 【0146】 Also, in the above, instead of CO2, N2 gas at a gas pressure of 72.2 cmHg was used and the N2 permeability (GPU) was calculated in the same manner as above, and the ratio of the CO2 permeability to the N2 permeability (CO2 / N2) was obtained, and the CO2 separation performance was evaluated according to the following criteria. Acceptable: CO2 / N2 is 9 - 11 Unacceptable: CO2 / N2 is less than 9 or more than 11 【0147】 <Evaluation of tensile strength> The tensile strength of the obtained CO2 separation laminate was measured in accordance with JIS K 7161-1:2014 under conditions of 23°C and 50%RH using an Ez Test device (manufactured by Shimadzu Corporation). The test specimens used were samples cut from each CO2 separation laminate (shape: dumbbell-shaped specimen, size: length 25 mm, width 4 mm). The stretching speed was set to 50 mm / min. 【0148】 As shown in Table 1, in Examples 1 to 7, which used a CO2 separation laminate in which the CO2 separation membrane was a membrane made of a polymer having a siloxane skeleton, the thickness of the CO2 separation membrane was 1 μm or less, and the support membrane was a porous membrane made of thermoplastic resin, the average pore size of the support membrane was 400 nm or less, and the thickness was 20 μm to 450 μm, it can be seen that the CO2 permeability was excellent and the strength was high. On the other hand, Comparative Examples 2 and 3, in which the CO2 separation membrane is not made of a polymer having a siloxane skeleton, Comparative Examples 1 and 3, in which the support membrane is not a porous membrane made of thermoplastic resin, and Comparative Example 4, in which the thickness of the CO2 separation laminate is outside the range of 20 μm to 450 μm, show a significant inferiority in at least one of the CO2 permeability and strength. 【0149】 [Table 1] [Explanation of Symbols] 【0150】 1a~1h CO2 separation laminate 10 CO2 separation laminate body 11 CO2 separation membrane 12 Support membrane 13 First adhesive layer 14 Breathable film 14 15 Second adhesive layer 16 Protective film 17 Third adhesive layer

Claims

[Claim 1] CO ２ CO2 with a separation laminate body ２ A laminate for separation, The aforementioned CO ２ The separation laminate body is CO ２ It consists of a separation membrane and a support membrane, or the CO ２ It consists of a separation membrane, the support membrane, and a first adhesive layer that is breathable. The aforementioned CO ２ In the laminate body for separation, the CO ２ The separation membrane and the support membrane are laminated either via the first adhesive layer or directly. The aforementioned CO ２ The separation membrane is a membrane made of a polymer having a siloxane skeleton. the CO mentioned above ２ the film thickness of the separation membrane is 1 μm or less, The support membrane is a porous membrane made of thermoplastic resin. The average pore size of the support film is 400 nm or less. The aforementioned CO ２ The thickness of the separation laminate is 20 μm or more and 450 μm or less. ２ A laminate for separation. [Claim 2] The aforementioned CO ２ A breathable film is laminated on at least one main surface of the separation laminate body, The CO2 film described in claim 1 is a film composed of a continuous phase made of resin. ２ A laminate for separation. [Claim 3] The aforementioned breathable film and the CO ２ The CO2 according to claim 2, wherein the separation laminate body is bonded to the CO2 bonded via a second adhesive layer that has breathability. ２ A laminate for separation. [Claim 4] The aforementioned CO ２ The CO ２ The permeable film is laminated on the main surface of the separation membrane. The aforementioned CO ２ In the separation laminate, the CO ２ The CO2 structure according to claim 3, wherein the main surface of the separation laminate body on the support film side is exposed. ２ A laminate for separation. [Claim 5] The CO2 according to claim 4, wherein the second adhesive layer is made of a silicone adhesive. ２ A laminate for separation. [Claim 6] The aforementioned CO ２ The breathable film is laminated on the main surface of the separation laminate body on the support film side. The aforementioned CO ２ In the separation laminate, the CO ２ The CO ２ The CO2 in the separation membrane side is exposed, as described in claim 3. ２ A laminate for separation. [Claim 7] The aforementioned CO ２ The CO ２ A protective film is laminated on the main surface of the separation membrane. The CO2 according to claim 6, wherein the protective film is a film that is breathable and does not correspond to the breathable film. ２ A laminate for separation. [Claim 8] The protective film, via a breathable third adhesive layer, ２ The CO ２ CO according to claim 7, which is laminated on the main surface on the separation membrane side. ２ A laminate for separation. [Claim 9] The CO2 according to any one of claims 1 to 8, wherein the polymer having the siloxane skeleton comprises polydimethylsiloxane. ２ A laminate for separation. [Claim 10] The CO2 according to any one of claims 1 to 8, wherein the thermoplastic resin is at least one selected from the group consisting of polyolefins, polyesters, nylons, and acrylic resins. ２ A laminate for separation. [Claim 11] The CO2 according to any one of claims 2 to 8, wherein the aforementioned breathable film is a film made of polyethylene terephthalate. ２ A laminate for separation. [Claim 12] The CO according to claim 7 or 8, wherein the protective film is a film made of nonwoven fabric. ２ A laminate for separation. [Claim 13] CO according to any one of claims 1 to 8 ２ A film roll in which the separation laminate is wound into a roll shape. [Claim 14] CO ２ A gas containing CO as described in any one of claims 1 to 8. ２ By allowing the separation laminate to permeate, CO2 is released from the gas. ２ CO has a separation step for separating CO ２ Separation method.

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