Composition for gas permeable membranes, cured product for gas permeable membranes, and gas permeable membrane

Abstract

To provide: a composition for gas permeable membranes that is capable of forming a gas permeable membrane excellent in both of the CO2 gas permeability coefficient and the separation factor (CO2 / N2); a cured product for gas permeable membranes; and a gas permeable membrane.SOLUTION: A composition for gas permeable membranes comprises: a compound (A), which has a structure represented by the formula (1) defined by -(CH2-CH2-O)n- (where n is an integer equal to or greater than 2) and has three or more (meth)acryloyl groups as terminal groups; and a compound (B) represented by the formula (2) in the figure (where m is an integer equal to or greater than 1, and p is an integer equal to or greater than 1).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a composition for a gas-permeable membrane, a cured product for a gas-permeable membrane, and a gas-permeable membrane. [Background technology]

[0002] One technology that aims to reduce CO2 emissions into the atmosphere to zero is known as Carbon dioxide Capture, Utilization and Storage (CCUS), which involves separating and capturing CO2 from gases in the atmosphere and storing it underground or converting it into chemical products or fuel for use.

[0003] One of the issues with CO2 capture technology is that it can be costly depending on the CO2 concentration in the gas species being captured. In recent years, CO2 capture using membrane separation has been attracting attention as a technology that can be operated at low cost because it uses pressure difference as the driving force and requires small equipment size. In CO2 capture by membrane separation, there is a trade-off between the CO2 gas permeability coefficient and separation coefficient (CO2 / N2) of the material that composes the gas permeable membrane used. Therefore, the materials that can be used for gas permeable membranes that selectively capture CO2 are limited. Polyethylene oxide (PEO) is known as a material that has excellent affinity for CO2 and a high separation coefficient (CO2 / N2). However, PEO cannot be used as a gas permeable membrane because it crystallizes and its CO2 gas permeability coefficient drops significantly.

[0004] Materials capable of suppressing the decrease in CO2 gas permeability coefficient due to crystallization include cured products using ethylene oxide (EO)-modified bifunctional acrylate monomers. Non-Patent Document 1 discloses a cured product using a bifunctional acrylate monomer with an EO modification number (EO addition mole number) of 14, and a membrane composed of the cured product. Non-Patent Document 2 discloses a cured product using a bifunctional acrylate monomer with an EO modification number (EO addition mole number) of 15, and a membrane composed of the cured product. However, although the membranes described in Non-Patent Documents 1 and 2 have a sufficiently high CO2 gas permeability coefficient, they have a low separation coefficient (CO2 / N2). [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Kusuma et al., Journal of Membrane Science, 327, 2009, 195-207. [Non-Patent Document 2] Ricards et al., Chemical Engineering Science, 64, 2009, 4707-4718. Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention aims to provide a composition for a gas-permeable membrane, a cured material for a gas-permeable membrane, and a gas-permeable membrane, which can provide a gas-permeable membrane having an excellent CO2 gas permeability coefficient and also achieving a good separation coefficient (CO2 / N2). [Means for solving the problem]

[0007] The present invention includes the following configurations. [1] A compound (A) having a structure represented by the following formula (1) and having three or more (meth)acryloyl groups as terminal groups, A composition for a gas-permeable film, comprising: a compound (B) represented by the following formula (2): -(CH2-CH2-O) n - (1) (In the above formula (1), n ​​is an integer of 2 or more.)

[0008] [ka]

[0009] (In the above formula (2), m is an integer of 1 or more, and p is an integer of 1 or more.) [2] The composition for a gas-permeable film according to [1], wherein the compound (A) has a group represented by the following formula (3):

[0010] [ka]

[0011] (However, R in the above formula (3) 1 is a hydrogen atom or a methyl group. n is an integer of 2 or more. -* represents a bond. [3] The composition for a gas-permeable membrane according to [1] or [2], wherein the content of the compound (B) is 10% by mass or more and 90% by mass or less based on the total mass of the compound (A) and the compound (B). [4] A cured product for a gas-permeable membrane obtained by curing the composition for a gas-permeable membrane according to any one of [1] to [3]. [5] A gas-permeable membrane comprising the cured material for gas-permeable membrane according to [4]. [6] The gas-permeable membrane according to [5], having a CO2 gas permeability coefficient of 50 Barrer or more and a separation coefficient (CO2 / N2) of 40 or more. Effect of the Invention

[0012] According to the present invention, there are provided a composition for a gas-permeable membrane, a cured material for a gas-permeable membrane, and a gas-permeable membrane, which can provide a gas-permeable membrane having an excellent CO2 gas permeability coefficient and also achieving a good separation coefficient (CO2 / N2). [Brief description of the drawings]

[0013] [Figure 1] FIG. 1 is a double logarithmic graph plotting the separation factor (CO2 / N2) versus the CO2 gas permeability coefficient for the gas permeable membranes prepared in the examples and comparative examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] [Gas-permeable membrane composition] The composition for a gas-permeable film according to the embodiment is a curable composition used for a gas-permeable film, and contains a compound (A) and a compound (B) described below.

[0015] (Compound (A)) Compound (A) is a compound having a structure represented by the following formula (1) (hereinafter also referred to as "structure (1)") and having three or more (meth)acryloyl groups as terminal groups. That is, compound (A) is a polyfunctional (meth)acrylic monomer having an EO modification number (EO addition mole number) of 2 or more and a functionality of 3 or more. -(CH2-CH2-O) n - (1) In the above formula (1), n ​​is an integer of 2 or more.

[0016] In formula (1), n, i.e., the EO modification number (the number of moles of EO added), is 2 or more, preferably 5 or more, and more preferably 8 or more. When n is equal to or more than the lower limit, a gas permeable membrane with a high separation factor (CO2 / N2) is easily obtained. n is preferably 20 or less, and more preferably 15 or less. The preferable lower and upper limits of n can be arbitrarily combined, and for example, 2 to 20 is preferable. Furthermore, when compound (A) contains a plurality of structures (1), the upper limit of the total number of n is preferably not more than 100, more preferably not more than 90, even more preferably not more than 80, and particularly preferably not more than 65. When the total number of n is not more than the upper limit, the crosslink density falls within an appropriate value, and the film is easily self-supporting.

[0017] The number of (meth)acryloyl groups that the compound (A) has as an end group is 3 or more, preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. If the number of (meth)acryloyl groups is equal to or more than the lower limit, the crosslink density increases, and the strength of the gas permeable membrane increases. In addition, a gas permeable membrane with a high separation coefficient (CO2 / N2) is easily obtained. The number of (meth)acryloyl groups that the compound (A) has as an end group is preferably 10 or less, more preferably 9 or less, even more preferably 8 or less, and particularly preferably 6 or less. If the number of (meth)acryloyl groups is equal to or less than the upper limit, the crosslink density becomes appropriate, and the membrane is easily molded. The preferable lower limit and upper limit of the number of (meth)acryloyl groups can be arbitrarily combined, and for example, 3 to 6 is preferable. It is to be noted that the number of (meth)acryloyl groups, which are the terminal groups of the compound (A), and the number of EO modifications (the number of moles of EO added) should be considered together rather than being selected independently. The above-mentioned preferred lower and upper limits of the number of (meth)acryloyl groups and the number of EO modifications (the number of moles of EO added) can be arbitrarily combined. For example, it is preferable that the number of (meth)acryloyl groups is 3 or more and the number of EO modifications (the number of moles of EO added) is 2 or more, more preferably that the number of (meth)acryloyl groups is 4 or more and the number of EO modifications (the number of moles of EO added) is 5 or more, and even more preferably that the number of (meth)acryloyl groups is 5 or more and the number of EO modifications (the number of moles of EO added) is 8 or more.

[0018] As compound (A), a compound having a group represented by the following formula (3) (hereinafter also referred to as "group (3)") is preferred, since it is easy to obtain a gas-permeable membrane having a high CO2 gas permeability coefficient and separation coefficient (CO2 / N2).

[0019] [ka]

[0020] However, R in the above formula (3) 1 is a hydrogen atom or a methyl group. -* indicates a bond. The structure to which -* is bonded is not particularly limited, but if it becomes an alcohol group, the free volume decreases, so a hydrocarbon group such as a methyl group or an ethyl group is preferable.

[0021] The group (3) is a group containing a (meth)acryloyl group as a terminal group and the structure (1). Since a gas-permeable membrane having a high CO2 gas permeability coefficient and a high separation coefficient (CO2 / N2) is easily obtained, it is preferable that the compound (A) has all of the (meth)acryloyl groups as terminal groups as part of the group (3).

[0022] The number of groups (3) in the compound (A) is preferably 3 or more, more preferably 4 or more, even more preferably 5 or more, and particularly preferably 6 or more. If the number of groups (3) is equal to or more than the lower limit, a gas permeable membrane with a high separation coefficient (CO2 / N2) is easily obtained. The number of groups (3) in the compound (A) is preferably 10 or less, more preferably 9 or less, even more preferably 8 or less, and particularly preferably 6 or less. If the number of groups (3) is equal to or less than the upper limit, the crosslinking density is appropriate and the membrane is easily molded. The preferred lower and upper limits of the number of groups (3) can be arbitrarily combined, and for example, 3 to 6 is preferred.

[0023] The compound (A) is preferably a compound in which three or more hydrogen atoms of a hydrocarbon which may have an etheric oxygen atom are substituted with a group (3). The hydrocarbon which may have an etheric oxygen atom may be linear, branched, or cyclic. The number of carbon atoms in the hydrocarbon which may have an etheric oxygen atom is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, and is preferably 15 or less, more preferably 14 or less, and even more preferably 12 or less.

[0024] Examples of the compound (A) include glycerin polyethoxy tri(meth)acrylate, dipentaerythritol polyethoxy hexa(meth)acrylate, a compound represented by the following formula (4), and a compound represented by the following formula (5). The composition for gas-permeable membrane according to the embodiment preferably contains, as compound (A), either or both of a compound represented by formula (4) and a compound represented by formula (5).More preferably, as compound (A), either or both of a compound represented by formula (4) and a compound represented by formula (5).

[0025] [ka]

[0026] In the formula (4), n1 to n3 each independently represents an integer of 2 or more. The preferred range for each of n1 to n3 is the same as the preferred range for n. The preferred upper limit for the total number of n1 to n3 is the same as the preferred upper limit for the total number of n.

[0027] [ka]

[0028] In the formula (5), n4 to n9 each independently represents an integer of 2 or more. The preferred range for each of n4 to n9 is the same as the preferred range for n. The preferred upper limit for the total number of n4 to n9 is the same as the preferred upper limit for the total number of n.

[0029] The method for producing compound (A) is not particularly limited. For example, compound (A) can be produced by reacting a polyhydric alcohol having three or more functional groups with ethylene oxide (EO) to obtain a reaction product, and then reacting the reaction product with (meth)acrylic acid. Examples of the polyhydric alcohol having three or more functional groups include polyglycerols such as triglycerin and tetraglycerin, trimethylolpropane, and sorbitol. As the polyhydric alcohol having three or more functional groups, one type may be used alone, or two or more types may be used in combination.

[0030] (Compound (B)) The compound (B) is a compound represented by the following formula (2). An example of the compound (B) is nonylphenoxy polyethylene glycol acrylate.

[0031] [ka]

[0032] In the above formula (2), m is an integer of 1 or more, and p is an integer of 1 or more. m in formula (2), i.e., the EO modification number (the number of moles of EO added), is preferably 2 or more, more preferably 4 or more, even more preferably 6 or more, and particularly preferably 8 or more. When m is equal to or more than the lower limit, a gas permeable membrane having a high CO2 gas permeability coefficient and separation coefficient (CO2 / N2) is easily obtained. m is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, and particularly preferably 10 or less. When m is equal to or less than the upper limit, the crosslink density is maintained and the membrane is easily self-supporting. The preferable lower and upper limits of m can be arbitrarily combined, and for example, 8 to 10 is preferable.

[0033] C p H 2p+1 The alkyl group represented by the formula (I) may have a straight chain structure or a branched structure. In formula (2), p is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, and particularly preferably 9 or more. When p is equal to or more than the lower limit, a gas permeable membrane having a high CO2 gas permeability coefficient is easily obtained. When p is equal to or less than the upper limit, a decrease in the separation factor (CO2 / N2) can be suppressed. The preferable lower and upper limits of p can be arbitrarily combined, and for example, 9 to 10 is preferable.

[0034] The content of compound (B) in the gas-permeable membrane composition according to the embodiment is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, based on the total mass of compound (A) and compound (B). If the content of compound (B) is equal to or more than the lower limit, the CO2 gas permeability coefficient and separation coefficient (CO2 / N2) of the gas-permeable membrane are improved. The content of compound (B) is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. If the content of compound (B) is equal to or less than the upper limit, the gas-permeable membrane composition is easily cured. The preferable lower limit and upper limit of the content of the compound (B) can be arbitrarily combined, and for example, 10 to 90 mass % is preferable, 15 to 85 mass % is more preferable, and 20 to 80 mass % is even more preferable.

[0035] (Other Monomers) The composition for a gas-permeable film according to the embodiment may contain, in addition to the compound (A) and the compound (B), another (meth)acrylic monomer other than the compound (A) and the compound (B). Examples of (meth)acrylic monomers other than the compound (A) and the compound (B) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenyloxypropyl (meth)acrylate, isoamyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, and the like. ) acrylate, 2-ethoxyethyl (meth)acrylate, ethoxy-diethylene glycol (meth)acrylate, butoxyethyl (meth)acrylate, 2-ethylhexyl diethoxy (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, carbitol (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy diethylene glycol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, hydrogenated dicyclopentadiene (meth)acrylate, acryloylmorpholine, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-Nonanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 2-n-butyl-2-ethyl-3-propanediol di(meth)acrylate, tricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, trimethylolpropane polypropoxy tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylol Examples of the acrylates include arylmethane tetra(meth)acrylate, glycerin polypropoxy tri(meth)acrylate, bisphenol A polyethoxy di(meth)acrylate, bisphenol A polypropoxy di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol polypropoxy hexa(meth)acrylate. As the other (meth)acrylic monomer, one type may be used alone, or two or more types may be used in combination.

[0036] The total content of the compound (A) and the compound (B) in the gas-permeable membrane composition according to the embodiment is preferably 90% by mass or more, more preferably 92.5% by mass or more, even more preferably 95% by mass or more, and particularly preferably 97.5% by mass or more, based on the total amount of the monomer components in the gas-permeable membrane composition. If the total content of the compound (A) and the compound (B) is equal to or more than the lower limit, a gas-permeable membrane having a high CO2 gas permeability coefficient and separation coefficient (CO2 / N2) is easily obtained. The upper limit of the total content of the compound (A) and the compound (B) is not particularly limited, and may be 100% by mass.

[0037] (Photoinitiator) The composition for a gas-permeable film according to the embodiment preferably contains a photoinitiator. The photoinitiator is not particularly limited, and examples thereof include ketones such as 1-hydroxycyclohexyl phenyl ketone (HCPK), benzophenone, etc. As the photoinitiator, one type may be used alone, or two or more types may be used in combination.

[0038] The content of the photoinitiator in the composition for gas permeable film is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, based on 100 parts by mass of the monomer component. If the content of the photoinitiator is equal to or more than the lower limit, the composition for gas permeable film is easily cured. The content of the photoinitiator is preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, and even more preferably 0.3 parts by mass or less. If the content of the photoinitiator is equal to or less than the upper limit, the gas permeability coefficient is not affected. The preferred lower and upper limits of the content of the photoinitiator can be arbitrarily combined, and for example, 0.1 to 0.3 parts by mass is preferable.

[0039] [Cured material for gas permeable membrane] The cured product for a gas-permeable film according to the embodiment is a cured product obtained by curing the composition for a gas-permeable film according to the embodiment described above.

[0040] The cured product for a gas-permeable film according to the embodiment can be obtained, for example, by curing the above-mentioned composition for a gas-permeable film with active energy rays. Examples of the active energy rays include electron beams, X-rays, ultraviolet rays, and visible light in the low wavelength region, with ultraviolet rays being preferred.

[0041] [Gas permeable membrane] The gas-permeable membrane according to the embodiment includes a cured material for a gas-permeable membrane according to the embodiment. The gas-permeable membrane according to the embodiment may be a membrane consisting of a single non-porous layer formed from the cured material for a gas-permeable membrane according to the embodiment, or may be a membrane including a porous support and a non-porous layer formed on the porous support from the cured material for a gas-permeable membrane according to the embodiment.

[0042] The form of the gas permeable membrane is not particularly limited, and may be a flat membrane or a hollow fiber membrane. For example, when the gas permeable membrane is a flat membrane, it may be a flat membrane of a two-layer structure having a porous support and a non-porous layer, or a flat membrane of a three-layer structure having a porous support on both sides of a non-porous layer. For example, when the gas permeable membrane is a hollow fiber membrane, it may be a two-layer hollow fiber membrane having a non-porous layer on the inside or outside of a hollow porous support, or it may be a three-layer hollow fiber membrane having a porous support on the inside and outside of a hollow non-porous layer.

[0043] The thickness of the non-porous layer is preferably 0.1 μm or more, more preferably 0.5 μm or more. If the thickness of the non-porous layer is equal to or more than the lower limit, CO2 can be efficiently and selectively separated and captured. The thickness of the non-porous layer is preferably 10 μm or less, more preferably 1 μm or less. If the thickness of the non-porous layer is equal to or less than the upper limit, the permeation resistance can be reduced, and CO2 can be efficiently captured.

[0044] The porous support is not particularly limited as long as it has sufficient mechanical strength to reinforce the non-porous layer and can be integrated with the non-porous layer. Examples of materials constituting the porous support include polyolefin polymers such as polyethylene, polypropylene, poly-3-methylbutene-1, poly-4-methylpentene-1, etc., fluorine-based polymers such as polyvinylidene fluoride, polytetrafluoroethylene, etc., and hydrophobic polymers such as polystyrene, polyether ketone, etc. The materials constituting the porous support may be used alone or in combination of two or more.

[0045] The gas permeable membrane according to the embodiment preferably has a CO2 gas permeability coefficient of 50 Barrer or more and a separation factor (CO2 / N2) of 40 or more.

[0046] The higher the CO2 gas permeability coefficient of the gas permeable membrane, the better, but generally, it is preferably 50 Barrer or more, more preferably 100 Barrer or more, and even more preferably 150 Barrer or more. There is no particular upper limit to the CO2 gas permeability coefficient of the gas permeable membrane, and it is substantially 300 Barrer or less. The CO2 gas permeability coefficient of the gas-permeable membrane is a value measured by the method described in the Examples section below.

[0047] The higher the separation factor (CO2 / N2) of the gas permeable membrane, the better, but generally, it is preferably 40 or more, more preferably 50 or more, and even more preferably 60 or more. There is no particular upper limit to the separation factor (CO2 / N2) of the gas permeable membrane, and it is substantially 100 or less. The separation factor (CO2 / N2) of the gas permeable membrane is a value measured by the method described in the Examples below. The preferred lower and upper limits can be combined in any way. It is generally said that it is difficult to achieve both a high CO2 gas permeability coefficient and a high separation factor (CO2 / N2) for a gas permeable membrane. For example, the line k in Figure 1 shows the Robson upper limit performance for CO2 / N2. Therefore, the CO2 gas permeability coefficient and the separation factor (CO2 / N2) of the gas permeable membrane are not considered independently of each other, and it is most ideal that both are high.

[0048] As described above, in the present invention, by using a combination of compound (A) and compound (B), it is possible to obtain a gas-permeable membrane that has a particularly excellent CO2 gas permeability coefficient and also achieves a good separation coefficient (CO2 / N2).

[0049] The composition for a gas-permeable film, the cured product for a gas-permeable film, and the gas-permeable film of the present invention are not limited to the above-mentioned configurations. Within the scope of the present invention, the components in the above-mentioned embodiment may be appropriately replaced with well-known components, and the above-mentioned modified examples may be appropriately combined. EXAMPLES

[0050] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following description.

[0051] [Abbreviation] The abbreviations for the raw materials used in this example are as follows. (Compound (A)) A-1: MIRAMER M3150 (manufactured by Miwon, number of acryloyl groups: 3, compound represented by formula (4), n1 = n2 = n3 = 5) A-2: Syntech SA-TE60 (manufactured by Sakamoto Pharmaceutical Co., Ltd., number of acryloyl groups: 6, compound represented by formula (5), n4 = n5 = n6 = n7 = n8 = n9 = 10) (Compound (B)) B-1:CH2=CH-C(=O)-(O-CH2-CH2)4-O-C6H4-C9H 19 (Compound represented by formula (2) above, m=4, p=9 (linear structure)) B-2:CH2=CH-C(=O)-(O-CH2-CH2)8-O-C6H4-C9H 19 (Compound represented by formula (2) with m=8 and p=9 (linear structure)) (Comparative compound) B'-1:CH2=CH-C(=O)-(O-CH2-CH2)4-O-C6H5 (Photoinitiator) HCPK: 1-hydroxycyclohexyl phenyl ketone

[0052] [Measurement of gas permeability coefficient P (Barrer) and separation factor] (1) Preparation of gas-permeable membrane The composition for gas permeable membrane was applied onto a polyester film (hereinafter referred to as "PET film") (Cosmo Sunshine, manufactured by Toyobo Co., Ltd., thickness: 188 μm) with a spacer attached, and a PET film was further placed on top of it, and the film was spread so that the thickness of the film after curing between the two films would be about 200 μm. Next, a high-pressure mercury lamp (commercially available) was used to irradiate the film with ultraviolet light of 340 to 380 nm in wavelength in the air at an integrated light intensity of 500 mJ / cm. 2 The composition for a gas-permeable film was cured to form a gas-permeable film.

[0053] (2)Measurement method The resulting laminate including the gas-permeable membrane was cut into a circular shape with a diameter of 35 mm, and the PET film was peeled off to collect a measurement sample consisting of the gas-permeable membrane. Using a gas permeability measuring device (K-315N-01, manufactured by Tsukubarika Seiki Co., Ltd.), the CO2 gas permeability coefficient and N2 gas permeability coefficient of the obtained measurement sample were measured under the conditions of a temperature of 25.5°C and a measurement pressure of 102 kPa by the pressure method using nitrogen and carbon dioxide as the supply gases. The gas permeability coefficient P (Barrer) was calculated from the following formula (6). In addition, the separation factor (CO2 / N2) was calculated by dividing the CO2 gas permeability coefficient by the N2 gas permeability coefficient.

[0054]

number

[0055] The symbols in the formula (6) have the following meanings. V: Low pressure tank volume (cm 3 ) A: Permeable area (cm) of the measurement sample (gas permeable membrane) 2 ) T: Temperature in the cell (K) l: Thickness of the measurement sample (gas permeable membrane) (cm) P H : High pressure tank pressure (cmHg) P L : Low pressure tank pressure (cmHg)

[0056] [Example 1] A liquid composition for a gas-permeable membrane was prepared by mixing 80 parts by mass of compound (A-2) as compound (A), 20 parts by mass of compound (B-1) as compound (B), and 0.1 parts by mass of HCPK as a photoinitiator. A gas permeable membrane was prepared using the composition for a gas permeable membrane, and the CO2 gas permeability coefficient and separation coefficient (CO2 / N2) were measured.

[0057] [Examples 2 to 4] A composition for a gas-permeable membrane was prepared in the same manner as in Example 1, except that the monomer composition was changed as shown in Table 1, and the CO2 gas permeability coefficient and separation coefficient (CO2 / N2) of the gas-permeable membrane prepared using the composition for a gas-permeable membrane were measured.

[0058] [Example 5] A composition for a gas-permeable membrane was prepared in the same manner as in Example 1, except that compound (A-1) was used instead of compound (A-2), and the CO2 gas permeability coefficient and separation coefficient (CO2 / N2) of the gas-permeable membrane prepared using the composition for a gas-permeable membrane were measured.

[0059] [Example 6] A composition for a gas-permeable membrane was prepared in the same manner as in Example 5, except that the monomer composition was changed as shown in Table 1, and the CO2 gas permeability coefficient and separation coefficient (CO2 / N2) of the gas-permeable membrane prepared using the composition for a gas-permeable membrane were measured.

[0060] [Comparative Example 1] A composition for a gas-permeable membrane was prepared in the same manner as in Example 3, except that compound (B'-1) was used instead of compound (B-1), and the CO2 gas permeability coefficient and separation coefficient (CO2 / N2) of the gas-permeable membrane prepared using the composition for a gas-permeable membrane were measured.

[0061] [Comparative Example 2] A composition for a gas-permeable membrane was prepared in the same manner as in Example 1, except that compound (B-1) was not used and 100 parts by mass of compound (A-2) was used, and the CO2 gas permeability coefficient and separation coefficient (CO2 / N2) of the gas-permeable membrane prepared using the composition for a gas-permeable membrane were measured.

[0062] [Comparative Example 3] A composition for a gas-permeable membrane was prepared in the same manner as in Example 5, except that 100 parts by mass of compound (A-1) was used without using compound (B-1), and the CO2 gas permeability coefficient and separation coefficient (CO2 / N2) of the gas-permeable membrane prepared using the composition for a gas-permeable membrane were measured.

[0063] The measurement results of the CO2 gas permeability coefficient and separation factor (CO2 / N2) of the gas permeable membrane of each example are shown in Table 1. In addition, the "EO modification number" in Table 1 means the total number of EO modifications in the compound. Also, a double logarithmic graph plotting the separation factor (CO2 / N2) against the CO2 gas permeability coefficient of each example is shown in Figure 1. The straight line k in Figure 1 is the straight line that shows the Robson upper limit performance for CO2 / N2.

[0064] [Table 1]

[0065] As shown in Table 1, Examples 1 to 4 in which compound (A-2) and compound (B) were used in combination had a higher CO2 gas permeability coefficient and a good separation factor (CO2 / N2) was achieved compared to Comparative Example 2 in which compound (B) was not used. Example 3 in which compound (A-2) and compound (B) were used in combination gave a particularly high CO2 gas permeability coefficient compared to Comparative Example 1 in which compound (B'-1) was used in combination at the same ratio. In Examples 5 and 6, in which compound (A-1) was used in combination with compound (B), a high CO2 gas permeability coefficient and separation coefficient (CO2 / N2) were achieved in comparison with Comparative Example 3, in which compound (B) was not used. In addition, as shown in FIG. 1, by using compound (A) and compound (B) in combination, a gas permeable membrane having a performance exceeding the line k indicating the Robson upper limit performance was obtained (Example 5).

Claims

1. A compound (A) having a structure represented by the following formula (1) and having three or more (meth)acryloyl groups as terminal groups, A composition for a gas-permeable membrane comprising a compound (B) represented by the following formula (2): -(CH ２ -CH ２ -O) ｎ - ・・・(1) (In the above formula (1), n ​​is an integer of 2 or more.) 【Chemistry 1】 (In the above formula (2), m is an integer of 1 or more, and p is an integer of 1 or more.)

2. The gas-permeable film composition according to claim 1 , wherein the compound (A) has a group represented by the following formula (3): 【Chemistry 2】 (However, R in the above formula (3) １ is a hydrogen atom or a methyl group. n is an integer of 2 or more. -* indicates a bond.

3. 2. The composition for a gas-permeable film according to claim 1, wherein the content of said compound (B) is 10% by mass or more and 90% by mass or less based on the total mass of said compound (A) and said compound (B).

4. A gas-permeable film cured product obtained by curing the gas-permeable film composition according to any one of claims 1 to 3.

5. A gas-permeable membrane comprising the cured product for gas-permeable membrane according to claim 4.

6. CO ２ The gas permeability coefficient is 50 Barrer or more, and the separation coefficient (CO ２ / N ２ 6. The gas-permeable membrane according to claim 5, wherein the molecular weight distribution (Mg) is 40 or more.

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