Co2 separation laminate, film roll, and co2 separation method

Abstract

Provided are: a CO2 separation laminate having excellent CO2 permeability and superior strength; a film roll obtained by winding the CO2 separation laminate in the form of a roll; and a CO2 separation method in which the CO2 separation laminate is used.　This CO2 separation laminate has a CO2 separation laminate body. The CO2 separation laminate body comprises a CO2 separation membrane and a support membrane or comprises a CO2 separation membrane, a support membrane and an air-permeable first adhesive layer. In the CO2 separation laminate body, the CO2 separation membrane and the support membrane are laminated one directly on the other or with the first adhesive layer therebetween. The CO2 separation membrane comprises a polymer having a siloxane backbone. The thickness of the CO2 separation membrane is 1 μｍ or less. The support membrane is a porous membrane comprising a thermoplastic resin. The average pore diameter of the support membrane is 400 nm or less. The thickness of the CO2 separation laminate is 20 to 450 μm.

Description

CO₂ Separation Laminate, Film Roll, and CO₂ Separation Method 【0001】 This invention relates to a laminate for CO ２ separation, a film roll, and a CO ２ separation method. 【0002】 In order to suppress global warming due to climate change and the like, technologies have been developed to separate and recover carbon dioxide (CO ２ ) using a CO ２ separation membrane (for example, Patent Document 1). 【0003】 Japanese Patent Application Laid-Open No. 2018-15678 【0004】 For members used in CO ２ separation such as a CO ２ separation membrane, it is desirable that they have excellent CO ２ permeability. 【0005】 Also, for members used in CO ２ separation such as a CO ２ separation membrane, it is desirable that they have high strength. If the strength of the members used in CO ２ separation is high, deformation and breakage are less likely to occur, and it is easier to stand on its own. Therefore, as a CO ２ separation laminate in which a support membrane for supporting (reinforcing) the CO ２ separation membrane is attached to the CO ２ separation membrane, it can be considered to be used for CO ２ separation. 【0006】 This invention has been made in view of the above problems, and an object thereof is to provide a CO ２ separation laminate having excellent CO ２ permeability and high strength, a film roll in which the CO ２ separation laminate is wound in a roll shape, and a CO ２ separation method using the CO ２ separation laminate. 【0007】 The inventors of the present invention have a CO ２ separation laminate having a CO ２ separation laminate main body, and the CO ２ separation laminate main body is a CO ２It consists of a separation membrane and a support membrane, or CO ２ It consists of a separation membrane, a support membrane, and a first adhesive layer that has air permeability, CO ２ In the separation laminate body, CO ２ The separation membrane and the support membrane are laminated either via a first adhesive layer or directly, CO ２ The separation membrane is a membrane made of a polymer having a siloxane skeleton, CO ２ The separation membrane has a thickness of 1 μm or less, the support membrane is a porous membrane made of thermoplastic resin, and the average pore size of the support membrane is 400 nm or less, CO ２ The thickness of the separation laminate is 20 μm or more and 450 μm or less. ２ We discovered that the above problems can be solved by using a separation laminate, and thus completed the present invention. Specifically, the present invention provides the following: 【0008】 [1] CO ２ CO2 with a separation laminate body ２ A laminate for separation, the 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, and the 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, and the CO ２ The separation membrane is a membrane made of a polymer having a siloxane skeleton, and the CO ２ The 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 membrane is 400 nm or less, and the CO ２ The thickness of the separation laminate is 20 μm or more and 450 μm or less. ２ A laminate for separation. 【0009】 [2] The CO ２ The CO described in [1] above, wherein a breathable film is laminated on at least one main surface of the separation laminate body, and the breathable film is a film composed of a continuous phase made of resin. ２A laminate for separation. 【0010】 [3] The breathable film and the CO ２ The CO2 described in [2] above is bonded to the separation laminate body via a second adhesive layer that has breathability. ２ A laminate for separation. 【0011】 [4] The CO ２ The CO ２ The ventilation film is laminated on the main surface of the separation membrane, and the CO ２ In the separation laminate, the CO ２ The main surface of the supporting film side of the separation laminate body is exposed, as described in [3] above. ２ A laminate for separation. 【0012】 [5] The CO2 described in [4] above, wherein the second adhesive layer is made of a silicone adhesive. ２ A laminate for separation. 【0013】 [6] The CO ２ The ventilation film is laminated on the main surface of the separation laminate body on the support film side, and the CO ２ In the separation laminate, the CO ２ The CO ２ The main surface on the separation membrane side is exposed, CO as described in [3] above. ２ A laminate for separation. 【0014】 [7] The CO ２ The CO ２ A protective film is laminated on the main surface of the separation membrane, and the protective film is a film that is breathable and does not correspond to the breathable film, as described in [6] above. ２ A laminate for separation. 【0015】 [8] The protective film is connected to the CO through a third adhesive layer that has breathability. ２ The CO ２ The CO2 described in [7] above is laminated on the main surface of the separation membrane. ２ A laminate for separation. 【0016】[9] The polymer having the siloxane skeleton comprises polydimethylsiloxane, the CO2 according to any one of [1] to [8] above. ２ A laminate for separation. 【0017】

[10] The CO2 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. ２ A laminate for separation. 【0018】

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

[12] The CO2 according to [7] or [8] above, wherein the protective film is a film made of nonwoven fabric. ２ A laminate for separation. 【0020】

[13] CO2 as described in any one of [1] to

[12] above ２ A film roll in which the separation laminate is wound into a roll shape. 【0021】

[14] CO ２ A gas containing CO as described in any one of [1] to

[12] above. 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. 【0022】 According to the present invention, CO ２ CO has excellent permeability and high strength. ２ Separation laminate, the CO ２ A film roll in which the separation laminate is wound into a roll shape, and the CO ２ CO2 separation using a laminate ２ A separation method can be provided. 【0023】 CO ２ This is a schematic cross-sectional view showing an example of a separation laminate. ２ This is a schematic cross-sectional view showing an example of a separation laminate. ２It is a schematic cross-sectional view showing an example of a laminate for separation. CO ２ It is a schematic cross-sectional view showing an example of a laminate for separation. 【0024】 ≪CO ２ ≫ Laminate for separation CO ２ The laminate for separation is CO ２ provided with a laminate body for separation. CO ２ The laminate body for separation is CO ２ composed of a separation membrane and a support membrane, or CO ２ composed of a separation membrane, a support membrane, and a first adhesive layer having air permeability. CO ２ In the laminate body for separation, CO ２ the separation membrane and the support membrane are laminated via the first adhesive layer or directly. CO ２ The separation membrane is a membrane made of a polymer having a siloxane backbone. CO ２ The thickness of the 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. CO ２ The thickness of the laminate for separation is 20 μm or more and 450 μm or less. 【0025】 Such CO ２ The laminate for separation, as shown in the examples described later, CO ２ has excellent permeability and high strength. On the other hand, when the above requirements are not met, CO ２ at least one of the permeability and strength of CO is significantly inferior. Examples of cases where the above requirements are not met include, for example, CO ２ when the separation membrane is not a membrane made of a polymer having a siloxane backbone, when the support membrane is not a porous membrane made of a thermoplastic resin and having an average pore diameter of 400 nm or less, and CO ２ when the thickness of the laminate for separation is outside the range of 20 μm or more and 450 μm or less. 【0026】 CO ２ The laminate for separation will be described below using FIGS. 1 to 4. FIGS. 1 to 4 are each CO ２ a schematic cross-sectional view showing an example of the laminate for separation. 【0027】 CO２ The separation laminate is CO ２ It has a separation laminate body 10. ２ The separation laminate body 10 is CO ２ It may consist of a separation membrane 11 and a support membrane 12 (Figure 1(a)). In this way, CO ２ The separation laminate body 10 is CO ２ When it consists of a separation membrane 11 and a support membrane 12, as shown in Figure 1(a), CO ２ In the separation laminate body 10, CO ２ The separation membrane 11 and the support membrane 12 are directly laminated. ２ The separation laminate body 10 is CO ２ It may consist of a separation membrane 11, a support membrane 12, and a breathable first adhesive layer 13 (Figure 1(b)). ２ The separation laminate body 10 is CO ２ When the separation membrane 11, the support membrane 12, and the first adhesive layer 13 which has air permeability are used, as shown in Figure 1(b), CO ２ In the separation laminate body 10, CO ２ The separation membrane 11 and the support membrane 12 are laminated together via the first adhesive layer 13. 【0028】 CO ２ The separation laminate is CO ２ It may consist only of the separation laminate body 10. Specifically, CO ２ It may also be a separation laminate 1a (Figure 1(a)), CO ２ A separation laminate 1b may also be used (Figure 1(b)). 【0029】 Also, CO ２ The separation laminate is CO ２ Separation laminate body 10, CO ２ It may be composed of members other than the main body 10 of the separation laminate. For example, CO ２ The separation laminate is CO ２ A breathable film 14 may be laminated on at least one main surface of the separation laminate body 10. Specifically, CO ２ The separation laminate is CO ２ CO ２A breathable film 14 is laminated on the main surface of the separation membrane 11. ２ A separation laminate 1c may be used (Figure 2(a)), CO ２ A breathable film 14 is laminated on the main surface of the separation laminate body 10 on the support film 12 side. ２ A separation laminate 1d may also be used (Figure 2(b)). 【0030】 CO ２ The separation laminate consists of a breathable film 14 and CO ２ The separation laminate body 10 may be bonded to the CO2 laminate body via a second adhesive layer 15 that is breathable. Specifically, CO2 ２ The separation laminate is CO ２ CO ２ A breathable film 14 is laminated on the main surface of the separation membrane 11, and CO ２ CO2 is bonded to the separation membrane 11 via a second adhesive layer 15 that has air permeability. ２ It may be a separation laminate 1e (Figure 3(a)), CO ２ A breathable film 14 is laminated on the main surface of the separation laminate body 10 on the side of the support film 12, and the breathable film 14 and the support film 12 are bonded together via a breathable second adhesive layer 15. ２ A separation laminate 1f may also be used (Figure 3(b)). 【0031】 In Figures 2 and 3, CO ２ CO ２ A breathable film 14 is laminated on the main surface of the separation membrane 11, either directly or via the second adhesive layer 15, CO ２ In the separation laminate, CO ２ The main surface of the support film 12 side of the separation laminate body 10 is exposed CO ２ Separation laminates 1c, 1e (Figures 2(a), 3(a)), and CO ２ A breathable film 14 is laminated on the main surface of the separation laminate body 10 on the support film 12 side, either directly or via the second adhesive layer 15, CO ２ In the separation laminate, CO ２ CO ２ CO2 is exposed on the main surface of the separation membrane 11.２ Separation laminates 1d and 1f (Figures 2(b) and 3(b)) are shown, and each is CO ２ An additional component may be provided on the side of the separation laminate body 10 where the breathable film 14 is not laminated. 【0032】 Specifically, for example, CO ２ The separation laminate is CO ２ A breathable film 14 is laminated on the main surface of the separation laminate body 10 on the support film 12 side, CO ２ CO ２ A protective film 16 is laminated on the main surface of the separation membrane 11. ２ The separation laminate may be 1 g (Figure 4(a)). The protective film 16 is a film that is breathable and does not correspond to the breathable film 14. 【0033】 Also, CO ２ The separation laminate is CO ２ A breathable film 14 is laminated on the main surface of the separation laminate body 10 on the support film 12 side, CO ２ CO ２ A protective film 16 is laminated on the main surface of the separation membrane 11 via a third adhesive layer 17 that has breathability. ２ A separation laminate 1h may also be used (Figure 4(b)). Note that in Figure 4(b), CO ２ The diagram shows a configuration in which a breathable film 14 is laminated on the main surface of the separation laminate body 10 on the support film 12 side via a second adhesive layer 15, ２ The breathable film 14 may be directly laminated to the main surface of the separation laminate body 10 on the support film 12 side, without the second adhesive layer 15 in between. 【0034】 CO ２ Each layer of the separation laminate is described in more detail below. 【0035】 <CO ２ Separation membrane > CO ２ The separation membrane is a membrane made of a polymer having a siloxane skeleton (a resin having siloxane bonds as its main structure). 【0036】 A film made of a polymer having a siloxane skeleton is CO２ It has high permeability to CO2, and also high permeability to nitrogen, etc. ２ Because its permeability is lower than that of CO, for example, ２ CO2 is extracted from a gas containing CO2 (e.g., air). ２ It can be separated. 【0037】 Preferred polymers having a siloxane skeleton include polyorganosiloxanes such as polydimethylsiloxane (PDMS), polyphenylmethylsiloxane, and polydiphenylsiloxane, with polydimethylsiloxane being more preferred. Polyorganosiloxanes may also be used together with a curing agent for polyorganosiloxanes. 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 alkoxysilanes such as tetramethoxysilane, trimethoxymethylsilane, dimethoxydimethylsilane, methoxytrimethylsilane, and 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, polymers having a siloxane skeleton may also be elastomers. 【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 in GPC (gel permeation chromatography) measurements. 【0040】 CO ２ The thickness of the 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. ２ The lower limit of the thickness of the separation membrane 11 is not particularly limited, but for example, it is 0.5 μm or more. ２ Since the thickness of the separation membrane 11 is 1 μm or less, CO２ CO having a separation membrane 11 ２ The separation laminate is CO ２ It has excellent permeability. ２ The thinner the film thickness of the separation membrane 11, the more CO ２ The permeability of CO2 from the air is improved. ２ Its separation performance, specifically, the separation of nitrogen and oxygen from the air and CO2. ２ The ability to separate CO ２ It is substantially independent of the thickness of the separation membrane 11. Therefore, CO ２ The thinner the film thickness of the separation membrane 11, the less CO2 is released from the air. ２ This allows for efficient separation. 【0041】 CO ２ The separation membrane is CO ２ The raw material composition (composition for forming a coating film) containing the raw materials for the separation membrane 11 may contain liquids such as solvents, but it is preferable that it does not contain liquids. 【0042】 <Support film> The support film 12 is CO ２ This is a member that supports (reinforces) the separation membrane 11. ２ By having a support membrane 12 that supports (reinforces) the separation membrane 11, CO ２ Suppresses deformation and rupture of the separation membrane 11, CO ２ The separation performance and other functions of the separation membrane 11 can be maintained. 【0043】 The support film 12 is a porous film made of a thermoplastic resin. The thermoplastic resin is 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 diameter 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 diameter (average pore size) 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 of 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 the stretching method. 【0045】 The thickness of the support film 12 is preferably 5 μm or more and 150 μm or less. In particular, CO ２ The separation layer is CO ２ If it consists only of the separation laminate body 10 (i.e., CO ２ The separation layer is CO ２ CO2 ２ It is a separation laminate 1a, or CO ２ CO2 is laminated with the separation membrane 11 and the support membrane 12 via the first adhesive layer 13. ２ In the case of the separation laminate 1b, the thickness of the support film 12 is preferably 20 μm or more and 150 μm or less, and more preferably 70 μm or more and 130 μm or less. Also, for example, CO ２ If the separation laminate further has a breathable film 14 (i.e., CO ２ The separation layer is CO ２ If a breathable film 14 is laminated on at least one main surface of the 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】 CO of support film 12 ２The arithmetic mean roughness (surface roughness Ra) of the main surface on the separation membrane 11 side is preferably 2.0 μm or less, more preferably 0.01 μm to 1.5 μm, and even more preferably 0.02 μm to 1.0 μm. The surface roughness Ra is a value specified by JIS B 0601 (1994). The surface roughness Ra can be measured, for example, using a Dektak XT-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 made of a support film 12 and CO ２ This is a component that adheres to the separation membrane 11. 【0048】 The first adhesive layer 13 is breathable. Specifically, for example, the first adhesive layer 13 is CO ２ CO is processed using a separation layer. ２ It has pores that allow a gas containing CO to pass through well (for example, air), or CO ２ It is made of a material that can easily permeate gases containing CO. The permeability of the first adhesive layer 13 is, for example, CO. ２ The separation laminate should be permeable to air at a rate of 500 s / 100 ml or less using the JIS P 8117 Gurley method at 24°C. 【0049】 The materials constituting the first adhesive layer 13 are a support film 12 and CO ２ The material is not particularly limited as long as it can adhere to the separation membrane 11. Examples of the first adhesive layer 13 include silicone adhesives. 【0050】 If the first adhesive layer 13 is not present, the support film 12 and CO ２ The separation membrane 11 is directly laminated without the first adhesive layer 13 in between. The support membrane 12 and CO ２ When the separation membrane 11 is directly laminated without the first adhesive layer 13, the support membrane 12 and CO ２ The separation membrane 11 is bonded to the other membrane by, for example, intermolecular forces such as electrostatic force or by lamination (thermocompression bonding). 【0051】 <Breathable film> Breathable film 14 is CO ２This is a component that protects and reinforces the separation membrane 11 and the support membrane 12. By having a breathable film 14, CO ２ CO ２ Deformation and rupture of the separation membrane 11 and support membrane 12 can be suppressed. In addition, by having a breathable film 14, CO ２ The strength of the separation laminate can be improved. 【0052】 The breathable film 14 is preferably a film composed of a continuous phase made of resin. Therefore, nonwoven fabrics, which are aggregates of discontinuous short fibers, do not qualify as breathable films 14 composed of a continuous phase. An example of a breathable film 14 is a film made of polyethylene terephthalate. 【0053】 Furthermore, the breathable film 14 has breathability. Specifically, the breathable film 14 is CO ２ CO is processed using a separation layer. ２ It has pores that allow a gas containing (e.g., air) to pass through well. The permeability of the permeable film 14 is, for example, CO ２ The separation laminate should allow air to permeate at a rate of 500 s / 100 ml or less at 24°C using the JIS P 8117 Gurley method. The breathable film 14 has CO ２ The holes that can permeate the gas containing the substance may be, for example, through holes made by punching or other processes, or connecting holes consisting 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 consists of a breathable film 14 and CO ２ This is a component used to bond the laminate body 10 for separation to the main body. 【0056】 The second adhesive layer 15 is breathable. Specifically, for example, the second adhesive layer 15 is CO ２ CO is processed using a separation layer. ２ It has pores that allow a gas containing CO to pass through well (for example, air), or CO ２It is made of a material that can easily permeate gases containing CO. The permeability of the second adhesive layer 15 is, for example, CO. ２ The separation laminate should be permeable to air at a rate of 500 s / 100 ml or less using the JIS P 8117 Gurley method at 24°C. 【0057】 The material constituting the second adhesive layer 15 is the support film 12 or CO ２ The material is not particularly limited as long as it can bond the separation membrane 11 and the breathable film 14. Examples of the second adhesive layer 15 include silicone adhesives. 【0058】 If the second adhesive layer 15 is not present, the support film 12 or CO ２ The separation membrane 11 and the breathable film 14 are directly laminated without the second adhesive layer 15. Support membrane 12 or CO ２ When the separation membrane 11 and the breathable film 14 are directly laminated without the second adhesive layer 15, the support membrane 12 or CO ２ The separation membrane 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 CO ２ This is a component that protects the separation membrane 11. ２ The separation laminate has a protective film 16, ２ CO2 ２ This can suppress deformation and rupture of the separation membrane 11. 【0060】 The protective film 16 is a film that is breathable and does not fall under the category of a breathable film 14. Specifically, the protective film 16 is CO ２ CO is processed using a separation layer. ２ It is a membrane that has pores that allow a gas containing (e.g., air) to pass through well, and is not a breathable film 14. The breathability of the protective membrane 16 is, for example, CO ２ The separation laminate should be permeable to air at a rate of 500 s / 100 ml or less using the JIS P 8117 Gurley method at 24°C. 【0061】The protective film 16 is preferably a film made of nonwoven fabric. When the protective film 16 is a nonwoven fabric, the voids in the nonwoven fabric are the CO2 in the protective film 16. ２ This corresponds to a pore that allows gases containing [the substance] to pass through easily. 【0062】 The material of the protective film 16 is not particularly limited, and examples include 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 consists of a protective film 16 and CO ２ This is a component that adheres to the separation membrane 11. 【0065】 The third adhesive layer 17 is breathable. Specifically, for example, the third adhesive layer 17 is CO ２ CO is processed using a separation layer. ２ It has pores that allow a gas containing CO to pass through well (for example, air), or CO ２ It is formed of a material that can easily permeate gases containing CO. The permeability of the third adhesive layer 17 is, for example, CO. ２ The separation laminate should be permeable to air at a rate of 500 s / 100 ml or less using the JIS P 8117 Gurley method at 24°C. 【0066】 The materials constituting the third adhesive layer 17 are a protective film 16 and CO ２ The material is not particularly limited as long as it can adhere to the separation membrane 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 CO ２ The separation membrane 11 is directly laminated without the third adhesive layer 17. When the protective membrane 16 and the CO2 separation membrane 11 are directly laminated without the third adhesive layer 17, the protective membrane 16 and CO ２ The separation membrane 11 is bonded to the other membrane by, for example, intermolecular forces such as electrostatic force or by lamination (thermocompression bonding). 【0068】 CO ２The thickness of the separation laminate is 20 μm or more and 450 μm or less, preferably 50 μm or more and 400 μm or less, and more preferably 80 μm or more and 380 μm or less. 【0069】 CO ２ The separation laminate can also be in the form of a film roll wound into a roll shape. Using a film roll makes it easier to transport, store, and apply to large-scale equipment, for example. 【0070】 ≪CO ２ Method for manufacturing the separation laminate: CO ２ The method for manufacturing the separation laminate is not particularly limited. ２ CO2 is composed only of the separation laminate body 10. ２ The separation layers 1a and 1b (Figures 1(a) and 1(b)) are, for example, made of CO on a sacrificial layer. ２ CO2 has a coating film forming step of forming a coating film of a raw material composition containing the raw materials for the separation film 11, a support film bonding step of bonding a support film 12 onto the coating film, and a sacrificial layer removal step of removing the sacrificial layer. ２ It can be manufactured by a method for manufacturing a separation laminate. 【0071】 CO ２ The method for manufacturing the separation laminate is CO ２ If the raw material composition containing the raw materials for the separation membrane contains a polyorganosiloxane such as polydimethylsiloxane, it may have a curing step to cure the polyorganosiloxane such as polydimethylsiloxane. ２ A method for manufacturing a 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】 Also, CO ２ The separation layer is CO ２ Separation laminate body 10, CO ２ When the separation laminate body 10 has members other than the main body 10 (breathable film 14, protective film 16), for example, the above CO ２In the method for manufacturing the separation laminate, the product can be manufactured by further including a breathable film bonding step for bonding a breathable film 14 and a protective film bonding step for bonding a protective film 16. 【0073】 Specifically, for example, CO ２ CO2 ２ It has a separation laminate body 10 and a breathable film 14, and the breathable film 14 and CO ２ CO2 is bonded to the separation membrane 11 via the second adhesive layer 15. ２ When manufacturing the separation laminate 1e (Figure 3(a)), it can be manufactured by a manufacturing method that includes, in this order, a coating film formation step, a breathable film bonding step, a sacrificial layer removal step, and a support film bonding step. 【0074】 Also, CO ２ CO2 ２ The CO2 has a separation laminate body 10 and a breathable film 14, and the breathable film 14 and the support film 12 are bonded together via a second adhesive layer 15. ２ When manufacturing the separation laminate 1f (Figure 3(b)), it can be manufactured by a manufacturing method that includes, in this order, a coating film formation step, a support film bonding step, a breathable film bonding step, and a sacrificial layer removal step. 【0075】 Also, CO ２ CO2 ２ It has a separation laminate body 10, a breathable film 14, and a protective film 16, and the breathable film 14 and the support film 12 are bonded via a second adhesive layer 15, CO ２ CO2 is bonded to the separation membrane 11 and the protective membrane 16 via the third adhesive layer 17. ２ When manufacturing the separation laminate 1h, it can be manufactured by a manufacturing method that includes, in this order, a coating film formation step, a support film 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, a sacrificial layer is formed on a support member for the sacrificial layer. Typically, the sacrificial layer is formed using a sacrificial layer formation composition. The sacrificial layer formation composition is not particularly limited as long as it is a composition that can form a sacrificial layer that can be removed in the subsequent sacrificial layer removal process. Typically, the sacrificial layer formation 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 considering the applicability of the sacrificial layer-forming composition, etc. When the mass of 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; 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, and tetrahydrofuran; 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, δ-pentyrolactone, etc. Examples include 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; and 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. When the shape of the support member is in the form of a film, a film drawn 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 coated film of the sacrificial layer-forming composition is, for example, 50°C to 90°C. Alternatively, the coated 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 CO2 from the air ２ From the viewpoint of separation performance, a thinner sacrificial layer is preferable. The thickness of the sacrificial layer is preferably 1 μm or more and 20 μm or less, more preferably 2 μm or more and 18 μm or less, and even more preferably 3 μm or more and 15 μm or less. 【0090】 [Coating film formation process] In the coating film formation process, CO is applied to the sacrificial layer. ２ A coating film is formed using a raw material composition (composition for forming a coating film) containing the raw materials for the separation film 11. ２ The separation membrane-forming composition typically comprises a polymer having the siloxane skeleton described above and a solvent. 【0091】If the raw material composition contains 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, etc. Examples of 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 (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, 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 pinan. 【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. The solid content concentration of the raw material composition is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 18% by mass, and even more preferably 5% by mass to 15% by mass. 【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 coating film may be heated (dried) as needed to remove at least a portion of the solvent of the film-forming composition. The heating (drying) temperature of the coating film is, for example, 40°C to 90°C. The heating (drying) time of the coating film is, for example, 0.5 minutes to 10 minutes. 【0096】 [Support film bonding process] In the support film bonding process, the support film 12 described above is bonded to the coating film formed in the coating film formation process. ２ The separation membrane 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 coated film (CO) can be bonded using a roll or the like with pressure that does not damage the support film 12. ２ The separation membrane 11) may be laminated (heat-pressed) onto the support membrane 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 20°C to 120°C, and more preferably 25°C to 100°C. When utilizing intermolecular forces such as electrostatic force, for example, the coating film (CO ２ The separation membrane 11) and the support membrane 12 should be brought into contact. 【0098】 Furthermore, an adhesive can be used to create a coated film (CO ２ A support film 12 may be adhered to the separation film 11). For example, a coated film (CO ２ By applying the above-mentioned first adhesive layer 13 to the separation film 11) at a desired position using an inkjet method or the like, the coated film (CO ２ The separation film 11) and the support film 12 may be bonded via the first adhesive layer 13. Alternatively, by using a support film 12 on which the first adhesive layer 13 is provided on one main surface, the coated film (CO ２ The separation membrane 11) and the support membrane 12 may be bonded together 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 contains 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 step, the coating film hardens to form a cured film (CO ２ It becomes a separation film 11). If there is no curing process, the coated film becomes CO ２ A separation membrane 11 may also be used. 【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 coated film is, for example, 100°C to 160°C, and preferably 105°C to 150°C. The heating time of the coated film is, for example, 1 minute to 10 minutes, and preferably 2 minutes to 5 minutes. 【0101】 [Support Member Detachment Process] In the support member detachment process, the support member is detached from the sacrificial layer. The method for detaching the support member from the sacrificial layer is not particularly limited. Examples include using a detachment solution or peeling the support member from the sacrificial layer without using a detachment solution. If the support member is in the form of a film, the support member 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 the like, if necessary. 【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 in 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 the liquid is not particularly limited, but examples include washing the sacrificial layer with running water, immersing the sacrificial layer in the liquid, or spraying the sacrificial layer with liquid from a shower. The time for washing the sacrificial layer with running water is not particularly limited, but for example, it is between 1 minute and 30 minutes. The time for immersing the sacrificial layer in the liquid is not particularly limited, but for example, it is between 5 minutes and 120 minutes. The time for spraying the sacrificial layer with liquid is not particularly limited, but for example, it is between 2 minutes and 5 minutes. The temperature of the liquid is not particularly limited, but for example, it is between 10°C and 40°C, and may also be between 20°C and 30°C. 【0105】 [Breathable film bonding process] In the breathable film bonding process, CO ２ The breathable film 14 is adhered to the separation membrane 11 and the support membrane 12. ２ The method for adhering the breathable film 14 to the separation membrane 11 and the support membrane 12 is not particularly limited. For example, using an adhesive, ２ A breathable film 14 may be adhered to the separation membrane 11 or the support membrane 12. Specifically, CO ２ By applying the above-mentioned second adhesive layer 15 to the separation membrane 11 and support membrane 12 at a desired position using an inkjet method or the like, CO ２ The separation membrane 11 or support membrane 12 and the breathable film 14 may be bonded via the second adhesive layer 15. Alternatively, by using a breathable film 14 in which the second adhesive layer 15 is provided on one main surface, CO ２The separation membrane 11 and the support membrane 12 may be bonded to the breathable film 14 via the second adhesive layer 15. 【0106】 Furthermore, by lamination or transfer methods utilizing intermolecular forces such as electrostatic forces, CO can be transferred without going through the second adhesive layer 15. ２ A breathable film 14 may be adhered to the separation membrane 11 or the support membrane 12. For example, CO ２ Using a roll or the like, CO is injected at a pressure that does not damage the separation membrane 11 or the support membrane 12. ２ The separation membrane 11 and the support membrane 12 may be laminated (heat-pressed) with a breathable film 14. 【0107】 [Protective film bonding process] In the protective film bonding process, CO ２ CO ２ A protective film 16 is adhered to the main surface of the separation membrane 11. ２ CO ２ Main surface on the separation membrane 11 side (i.e., CO ２ The method for adhering the protective film 16 to the separation film 11) is not particularly limited. For example, using an adhesive, ２ A protective film 16 may be attached to the separation film 11. Specifically, CO ２ By providing the above-mentioned third adhesive layer 17 at a desired position on the separation membrane 11 using an inkjet method or the like, CO ２ The separation membrane 11 and the protective membrane 16 may be bonded via the third adhesive layer 17. Alternatively, by using a protective membrane 16 in which the third adhesive layer 17 is provided on one of the main surfaces, CO ２ The separation film 11 and the protective film 16 may be bonded together via the third adhesive layer 17. 【0108】 Furthermore, by lamination or transfer methods utilizing intermolecular forces such as electrostatic forces, CO can be transferred without going through the third adhesive layer 17. ２ A protective film 16 may be attached to the separation film 11. For example, CO ２ Using a roll or the like, CO is injected at a pressure that does not damage the separation membrane 11. ２ A protective film 16 may be laminated (heat-pressed) onto the separation film 11. 【0109】 ≪CO ２ Separation method≫ CO ２The separation method is CO ２ The gas containing the above CO ２ By allowing the separation layer to permeate, CO2 can be separated from the gas. ２ It has a separation step for separating the above CO. ２ The separation laminate is CO ２ Because it has excellent permeability and high strength, CO ２ CO from gases containing CO ２ This allows for efficient separation of CO ２ Suppresses deformation and rupture of the separation membrane 11, CO ２ The separation performance and other functions of the separation membrane 11 can be maintained. ２ The above CO ２ CO2 in the separation layer ２ It is preferable to allow CO to permeate from the separation membrane 11 side to the support membrane 12 side. ２ The above CO2 is used to represent the protein gas. ２ When passing the gas through the separation layer, it is preferable to apply pressure to allow the gas to pass through. ２ Depending on the separation method, CO ２ By separating and recovering CO ２ It can mitigate global warming caused by CO2. ２ It can be used as a carbon resource. 【0110】 The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. 【0111】 <Preparation of Sacrificial Layer Formation Composition> Sacrificial layer formation composition 1 was prepared by uniformly mixing 200 parts by mass of polyvinyl alcohol and 1900 parts by mass of water. 【0112】 <CO ２Preparation of raw material composition (composition for forming a coating film) containing raw materials for separation membranes: Polydimethylsiloxane (SYLGARD® 184, manufactured by Dow Corning, mass average molecular weight Mw 5000) and a curing agent (trimethoxymethylsilane) were dissolved in heptane at a ratio of 10 parts by mass of curing agent to 100 parts by mass of polydimethylsiloxane, so that the solid content concentration was 5% by mass, to prepare raw material composition 1. In addition, D1 (styrene elastomer, mass average molecular weight Mw 50000) was dissolved in decahydronaphthalene at a concentration of 5% by mass to prepare raw material composition 2. 【0113】 【0114】 [Example 1] First, the sacrificial layer forming composition 1 was applied to a support member (PET film) by a slit die coating method, heated at 60°C for 2 minutes, and then heated at 80°C for 3 minutes to form a sacrificial layer with a thickness of 15 μm. 【0115】 Next, the raw material composition 1 is applied to the sacrificial layer by gravure coating (microgravure®), heated at 60°C for 5 minutes, and then heated at 140°C for 10 minutes to form a PDMS film (CO2) with a thickness of 0.7 μm. ２ A separation membrane 11) was formed. 【0116】 Next, PDMS film (CO ２ A support film 12 (porous polyethylene film, average pore size 100 nm, surface roughness Ra 0.3 μm) with a thickness of 100 μm is placed on the separation membrane 11), and the support film 12 and the PDMS membrane (CO) are separated by a roller. ２ By bringing the separation membrane 11) into contact with the support membrane 12 and the PDMS membrane (CO) by electrostatic force, ２ The separation membrane 11) was bonded to it. 【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 removing the support member, the sacrificial layer is immersed in pure water at room temperature (25°C) for 60 minutes to remove the sacrificial layer, thereby reducing CO2 ２ CO2 ２ A laminate body 10 for separation was obtained.２ Separation laminate body 10 (CO ２ Separation laminate 1a (Figure 1(a)) is the CO of Example 1. ２ It was used as a laminate for separation. 【0119】 [Example 2] A sacrificial layer is formed in the same manner as in Example 1, and a PDMS film (CO) is placed on the sacrificial layer. ２ A separation membrane 11) was formed. On the other hand, a PET film with a thickness of 75 μm, on which an adhesive layer (second adhesive layer 15) made of a silicone adhesive was provided over the entire surface of one main surface, was 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, PDMS film (CO ２ A breathable film 14 having a second adhesive layer 15 is placed on the separation membrane 11) such that the side with the second adhesive layer 15 is in contact with the PDMS membrane, and the breathable film 14 and the PDMS membrane (CO) are rolled together. ２ By bringing the separation membrane 11) into contact with the breathable film 14 and the PDMS membrane (CO ２ The separation membrane 11) was bonded to it. 【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, the PDMS film (CO ２ A support film 12 (porous polyethylene film, average pore size 100 nm, surface roughness Ra 0.3 μm) with a thickness of 100 μm is placed on the separation membrane 11), and the support film 12 and the PDMS membrane (CO) are separated by a roller. ２ By bringing the separation membrane 11) into contact with the support membrane 12 and the PDMS membrane (CO) by electrostatic force, ２ The separation membrane 11) was bonded to it. The resulting PDMS membrane (CO ２CO2, consisting of a separation membrane 11) and a support membrane 12 ２ It has a separation laminate body 10 and a breathable film 14, and the breathable film 14 and CO ２ CO2 is bonded to the separation membrane 11 via the second adhesive layer 15. ２ Separation laminate 1e (Figure 3(a)) is the CO2 of Example 2. ２ It was used as a laminate for separation. 【0124】 [Example 3] A sacrificial layer is formed in the same manner as in Example 1, and a PDMS film (CO) is placed on the sacrificial layer. ２ A separation membrane 11) was formed. 【0125】 Next, PDMS film (CO ２ A support film 12 (porous polyethylene film, average pore size 100 nm, surface roughness Ra 0.3 μm) with a thickness of 100 μm is placed on the separation membrane 11), and the support film 12 and the PDMS membrane (CO) are separated by a roller. ２ By bringing the separation membrane 11) into contact with the support membrane 12 and the PDMS membrane (CO) by electrostatic force, ２ The separation membrane 11) was bonded to it. 【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 member, the exposed sacrificial layer was immersed in pure water for 60 minutes at room temperature (25°C) to remove the sacrificial layer. The obtained PDMS film (CO ２ CO2, consisting of a separation membrane 11) and a support membrane 12 ２ The CO2 has a separation laminate body 10 and a breathable film 14, and the breathable film 14 and the support film 12 are bonded together via a second adhesive layer 15. ２ Separation laminate 1f (Figure 3(b)) is the CO of Example 3. ２ It was used as a laminate for separation. 【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. Note that the adhesive layer (third adhesive layer 17) made of a silicone adhesive is an extremely thin film whose thickness is negligible. 【0130】 The PDMS film (CO) obtained in Example 3 ２ CO2, consisting of a separation membrane 11) and a support membrane 12 ２ The CO2 has a separation laminate body 10 and a breathable film 14, and the breathable film 14 and the support film 12 are bonded together via a second adhesive layer 15. ２ CO ２ A protective film 16 having a third adhesive layer 17 is placed on the separation membrane 11, and the surface on which the third adhesive layer 17 is provided is CO ２ Place it so that it is in contact with the separation membrane 11, and use a roller to remove the protective membrane 16 and CO ２ By bringing the separation membrane 11 into contact with the protective membrane 16 and CO ２ The separation membrane 11 was bonded to it. The resulting PDMS membrane (CO ２ CO2, consisting of a separation membrane 11) and a support membrane 12 ２ It has a separation laminate body 10, a breathable film 14, and a protective film 16, and the breathable film 14 and the support film 12 are bonded via a second adhesive layer 15, CO ２ CO2 is bonded to the separation membrane 11 and the protective membrane 16 via the third adhesive layer 17. ２ Separation laminate 1h (Figure 4(b)) is the CO of Example 4. ２ It was used as a laminate for separation. 【0131】 [Example 5] Except for using a support film 12 with a thickness of 11 μm (porous polyethylene film, average pore size 20 nm, surface roughness Ra 0.3 μm) as the support film 12, the CO of Example 5 was prepared in the same manner as in Example 3. ２ A laminate for separation was obtained. 【0132】 [Example 6] Except for using a support film 12 with a thickness of 147 μm (porous polyethylene film, average pore size 20 nm, surface roughness Ra 0.6 μm) as the support film 12, the CO of Example 6 was prepared in the same manner as in Example 1. ２A laminate for separation was obtained. 【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 adhesive is provided on the fibers of one main surface, was used as the protective film 16 having the third adhesive layer 17. Note that the adhesive layer (third adhesive layer 17) made of a silicone adhesive is an extremely thin film whose thickness is negligible. 【0134】 A sacrificial layer is formed in the same manner as in Example 1, and a PDMS film (CO) is placed on the sacrificial layer. ２ A separation membrane 11) was formed. 【0135】 Next, PDMS film (CO ２ 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 is placed on the separation membrane 11), and the support film 12 and the PDMS membrane (CO) are separated by a roller. ２ By bringing the separation membrane 11) into contact with the support membrane 12 and the PDMS membrane (CO) by electrostatic force, ２ The separation membrane 11) was bonded to it. 【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 member, the exposed sacrificial layer was immersed in pure water for 60 minutes at room temperature (25°C) to remove the sacrificial layer. The obtained PDMS film (CO ２ CO2, consisting of a separation membrane 11) and a support membrane 12 ２ The CO2 has a separation laminate body 10 and a breathable film 14, and the breathable film 14 and the support film 12 are bonded together via a second adhesive layer 15. ２ CO ２A protective film 16 having a third adhesive layer 17 is placed on the separation membrane 11, and the surface on which the third adhesive layer 17 is provided is CO ２ Place it so that it is in contact with the separation membrane 11, and use a roller to remove the protective membrane 16 and CO ２ By bringing the separation membrane 11 into contact with the protective membrane 16 and CO ２ The separation membrane 11 was bonded to it. The resulting PDMS membrane (CO ２ CO2, consisting of a separation membrane 11) and a support membrane 12 ２ It has a separation laminate body 10, a breathable film 14, and a protective film 16, and the breathable film 14 and the support film 12 are bonded via a second adhesive layer 15, CO ２ CO2 is bonded to the separation membrane 11 and the protective membrane 16 via the third adhesive layer 17. ２ Separation laminate 1h (Figure 4(b)) is CO of Example 7 ２ It was used as a laminate for separation. 【0139】 [Comparative Example 1] The CO2 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. ２ A laminate for separation was obtained. 【0140】 【0141】 [Comparative Example 2] The CO2 of 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. ２ A laminate for separation was obtained. 【0142】 [Comparative Example 3] 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, and raw material composition 2 was used instead of raw material composition 1. The CO of Comparative Example 3 was obtained in the same manner as in Example 3. ２ A laminate for separation was obtained. 【0143】 [Comparative Example 4] The CO2 in Comparative Example 4 was prepared in the same manner as in Example 1, except that a support film 12 with a thickness of 12 μm (porous polyethylene film, average pore size 30 nm, surface roughness Ra 0.3 μm) was used as the support film 12. ２ A laminate for separation was obtained. 【0144】 CO obtained in Examples 1-7 and Comparative Examples 1-4 ２ Regarding the separation laminate, CO2 is used in the following way. ２ The permeability and intensity were evaluated. The results are shown in Table 1. 【0145】 <CO ２ Evaluation of permeability > Obtained CO ２ Regarding the separation laminate, CO ２ CO permeates from the separation membrane 11 side to the support membrane 12 side. ２ The gas is supplied and the CO2 permeates. ２ Measure the flow rate value of CO ２ The gas permeability (GPU) was calculated. The method conformed to JIS K7126-1:2006 Plastics - Films and Sheets - Gas Permeability Test Methods - Part 2: Differential Pressure Method. The measurement conditions were as follows: Measurement device: Differential pressure type gas / vapor permeability measuring device [GTR-21A] Detector: Gas chromatograph [Thermal conductivity detector (TCD)] Test conditions: CO2 at a temperature of 25°C, humidity of 0% RH, and a gas pressure of 3.8 cmHg. ２ Gas permeability area: 0.159 cm² ２ 【0146】 Furthermore, in the above, CO ２ Instead, N at a gas pressure of 72.2 cmHg ２ Using gas, in the same manner as above, N ２ Calculate the transmittance (GPU) and CO ２ Transmittance and N ２ Ratio to transmittance (CO ２ / N ２ ) and CO ２ Separation performance was evaluated. Acceptable: CO ２ / N ２ 9-11 Not possible: CO ２ / N ２ If less than 9 or greater than 11 【0147】 <Evaluation of tensile strength> The obtained CO ２ The tensile strength of the 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 were each CO ２A sample (shape: dumbbell-shaped test piece, size: length 25 mm, width 4 mm) cut from the separation laminate was used. The stretching speed was set to 50 mm / min. 【0148】 As shown in Table 1, CO ２ The separation membrane is a membrane made of a polymer having a siloxane skeleton, CO ２ The separation membrane has a thickness of 1 μm or less, the support membrane is a porous membrane made of thermoplastic resin, the average pore size of the support membrane is 400 nm or less, and the thickness is 20 μm or more and 450 μm or less. ２ In Examples 1 to 7 using the separation laminate, CO ２ It can be seen that it has excellent permeability and high strength. On the other hand, CO ２ Comparative Examples 2 and 3, in which the separation membrane is not a membrane made of a polymer having a siloxane skeleton, and in Comparative Examples 1 and 3, in which the support membrane is not a porous membrane made of a thermoplastic resin, and CO ２ Comparative Example 4, in which the thickness of the separation laminate is outside the range of 20 μm to 450 μm, is CO ２ It can be seen that at least one of the permeability and intensity is significantly inferior. 【0149】 【0150】 1a-1h CO ２ Separation laminate 10 CO ２ Separation laminate body 11 CO ２ Separation membrane 12 Support membrane 13 First adhesive layer 14 Breathable film 15 Second adhesive layer 16 Protective membrane 17 Third adhesive layer

Claims

1. CO ２ A CO separation laminate body ２ A separation laminate, wherein the CO ２ separation laminate body consists of a CO separation membrane and a support membrane, or the CO ２ separation laminate body consists of a CO separation membrane, the support membrane, and a first adhesive layer having air permeability, and in the CO ２ separation laminate body, the CO separation membrane and the support membrane are laminated via the first adhesive layer or directly, and the CO ２ separation membrane is a membrane made of a polymer having a siloxane skeleton, and the CO ２ thickness of the 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 CO ２ thickness of the separation laminate is 20 μm or more and 450 μm or less. A CO separation laminate. ２ The thickness of the 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 CO ２ The thickness of the separation laminate is 20 μm or more and 450 μm or less. A CO ２ separation laminate.

2. The aforementioned CO ２ The CO2 according to claim 1, wherein a breathable film is laminated on at least one main surface of the separation laminate body, and the breathable film is a film composed of a continuous phase made of resin. ２ A laminate for separation.

3. The 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.

4. The aforementioned CO ２ The CO ２ The ventilation film is laminated on the main surface of the separation membrane, and the 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.

5. The CO2 according to claim 4, wherein the second adhesive layer is made of a silicone adhesive. ２ A laminate for separation.

6. The aforementioned CO ２ The ventilation film is laminated on the main surface of the separation laminate body on the support film side, and the 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.

7. The aforementioned CO ２ The CO ２ A protective film is laminated on the main surface on the separation membrane side, and the protective film is a film that is breathable and does not correspond to the breathable film, as described in claim 6. ２ A laminate for separation.

8. The protective film, via a third adhesive layer having breathability, the CO 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.

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.

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.

11. The CO2 according to any one of claims 2 to 8, wherein the breathable film is a film made of polyethylene terephthalate. ２ A laminate for separation.

12. The CO2 according to claim 7 or 8, wherein the protective film is a film made of a nonwoven fabric. ２ A laminate for separation.

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.

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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