Water vapor adsorption composite

Abstract

By making the metal-organic structure water-resistant, a composite containing a metal-organic structure with water vapor adsorption properties and a coating film made of this composite are provided. [Solution] A composite comprising a metal-organic structure and a crosslinking agent, wherein the metal-organic structure comprises a metal ion and an organic ligand coordinated to the metal ion, and the crosslinking agent is bonded to the metal ion or organic ligand of the metal-organic structure.

Description

[Technical Field]

[0001] The present invention relates to a composite containing a metal-organic structure, and more particularly to a composite containing a metal-organic structure and a crosslinking agent, capable of adsorbing water vapor, and a coating film containing this composite. [Background technology]

[0002] Metal-organic frameworks (MOFs) or porous coordination polymers (PCPs), which consist of a central metal and polydentate organic ligands coordinating to it, are porous, three-dimensional structures formed by the accumulation of metal complexes composed of a central metal and organic ligands. Unlike other porous materials such as zeolites and activated carbon, the pore size and internal space of metal-organic frameworks can be designed, and many types have been reported based on combinations of metal ions and organic ligands, and they are used as adsorbents for various substances.

[0003] When using metal-organic structures as adsorbents in the form of resin compositions or dispersions, it is not easy to uniformly disperse powdered metal-organic structures in the resin composition or dispersion. As a result, aggregates of the metal-organic structures may be present in resin compositions containing metal-organic structures, and in such cases, the excellent adsorption performance of the metal-organic structures cannot be fully exhibited. To solve these problems, the present inventors have proposed a resin composition or dispersion in which a metal-organic structure is uniformly dispersed in a resin or dispersion medium by including a specific dispersant together with the metal-organic structure (Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-173766 [Overview of the Initiative]

Problems to be Solved by the Invention

[0005] In the resin composition and dispersion liquid described in Patent Document 1, the metal organic structure is uniformly dispersed in the resin or the dispersion medium, and the adsorption performance of the metal organic structure can be efficiently exhibited. However, since the metal organic structure itself is inferior in water resistance, depending on the type of the dispersion medium, it may dissolve itself or lose the pores that exhibit the adsorption performance. Therefore, in order for the metal organic structure to have water vapor adsorption properties, it is necessary for the metal organic structure to have water resistance. Although it is possible to improve the water resistance by using it in combination with an organic binder or the like as in Patent Document 1, when it contains an organic compound such as a resin which is a binder component, there is a risk that they will block the pores of the metal organic structure and the excellent adsorption performance inherent to the metal organic structure cannot be fully exhibited. Therefore, it is desired to achieve both an improvement in the water resistance of the metal organic structure itself and excellent adsorption performance.

[0006] Therefore, an object of the present invention is to provide a composite containing a metal organic structure having water vapor adsorption properties and a coating film composed of this composite by making the metal organic structure water-resistant.

Means for Solving the Problems

[0007] According to the present invention, there is provided a composite containing a metal organic structure and a crosslinking agent, wherein the metal organic structure is a metal organic structure comprising metal ions and an organic ligand coordinated to the metal ions, and the crosslinking agent is bonded to the metal ions or organic ligands of the metal organic structure, and the composite has water vapor adsorption properties.

[0008] In the composite having water vapor adsorption properties of the present invention, (1) the crosslinking agent has at least one of a hydroxyl group, an epoxy group, an amino group, and a carboxyl group; (2) The crosslinking agent is any one of polyhydric alcohol glycidyl ethers, polyamines, and cellulose acetate. (3) The organic ligand is cyclodextrin. is preferable.

[0009] According to the present invention, there is also provided a coating film containing the above complex. According to the present invention, there is further provided a laminate having the above coating film. [Effects of the Invention]

[0010] In the present invention, by containing a crosslinking agent having a coordination site and a bonding site capable of chemical bonding or physical bonding to the metal ions or organic ligands of the metal organic structure together with the metal organic structure, a crosslinked structure having crosslinking by chemical bonding and / or crosslinking by physical bonding is formed in the metal organic structure. As a result, it becomes possible to obtain a composite containing a metal organic structure having improved water resistance, and it becomes possible to exhibit excellent water vapor adsorption properties. Further, since the composite of the present invention can form a coating film alone, it can be made into a film alone, or a coating film made of the composite of the present invention can be formed on a substrate to form a laminate, and it is possible to efficiently perform gas adsorption and separation as an adsorbent. Also, as is clear from the results of the examples described later, the composite of the present invention has water resistance even in the state of a solid molded product as compared with the metal organic structure (Comparative Example 1), and not only water vapor adsorption properties, but also depending on its composition, It can exhibit gas adsorption properties for gases such as nitrogen and carbon dioxide. Further, by appropriately changing the type and blending amount of the metal organic structure and crosslinking agent used, or the molding conditions of the composite, etc., the type and adsorption amount of the gas that can be adsorbed can be changed, and gas adsorption and separation can be efficiently performed. Further, by containing the composite of the present invention in a coating film, gas separation can also be performed without reducing the separation efficiency of the permeating gas even under wet conditions. [Embodiments for Carrying out the Invention]

[0011] (complex) The composite of the present invention comprises a metal-organic structure having a metal ion having a coordination site and an organic ligand coordinated to the metal ion, and a crosslinking agent having a coordination site or binding site, wherein the coordination site or binding site of the crosslinking agent is chemically or physically bonded to the metal ion or organic ligand of the metal-organic structure. In metal-organic structures, metal ions and organic ligands are bonded by coordination bonds. However, coordination bonds are prone to bond exchange reactions, such as acid hydrolysis, resulting in poor water resistance, making it difficult to impart water vapor adsorption properties to metal-organic structures. In the present invention, by reacting the coordination or bonding sites of a crosslinking agent with the metal ions or organic ligands of a metal-organic structure, a composite structure is created in which a crosslinked structure is introduced into the metal-organic structure. This makes it possible to improve the water resistance of the metal-organic structure and exhibit water vapor adsorption properties.

[0012] The composite of the present invention can be made water-resistant by crosslinking the metal-organic structure with a crosslinking agent, and exhibits water vapor adsorption properties that were difficult to achieve with the metal-organic structure alone. However, the introduction of the crosslinked structure may reduce the crystallinity derived from the metal-organic structure. In the composite of the present invention, by adjusting the degree of crystallinity of the composite, it is possible to efficiently adsorb not only water vapor but also nitrogen gas and other substances. For example, although it depends on the type and content of the metal-organic structure and crosslinking agent used, as can be seen from comparing Examples 1 and 5 described later, in composites of the same composition, nitrogen gas adsorption is significantly improved when the degree of crystallinity is high. Furthermore, as will be clear from comparing Example 14 or Example 16 described later with Comparative Example 2, by including the composite in the coating film, gas separation does not decrease even under wet conditions, and gas separation can be performed efficiently.

[0013] (Metal-organic structure) The metal-organic structure used in the composite of the present invention is a metal-organic structure comprising a metal ion having a coordination site and an organic ligand coordinated to the metal ion, and conventionally known metal-organic structures can be used. The metal ions in the metal-organic structure can be any ion capable of forming a coordinate bond with an organic ligand, but are not limited to these. Examples of metal ions include Li, Na, K, Rb, Be, Mg, Ca, Sr, Ba, Sc, Y, Ti, Ar, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi, and at least one of these can be selected.

[0014] It is important that the organic ligand is a compound that can form a coordinate bond with a metal ion and also has a functional group that serves as a reaction site for the crosslinking reaction with the crosslinking agent described later. Examples of such functional groups include hydroxyl groups, methyl groups, imidazole groups, pyridyl groups, carboxyl groups, sulfonic acid groups, and amide groups, with hydroxyl groups, methyl groups, and imidazole groups being particularly preferred. Examples of such organic ligands include cyclodextrin compounds. Cyclodextrin compounds have a cyclic structure that can encapsulate guest molecules, allowing for efficient gas adsorption. Examples of cyclodextrin compounds include α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, with α-cyclodextrin and γ-cyclodextrin being particularly suitable.

[0015] Furthermore, as organic ligands, compounds having an imidazole skeleton such as imidazole, 2-methylimidazole, and 2-formylimidazole, and monocyclic or polycyclic aromatic compounds having at least two carboxyl groups such as terephthalic acid and trimesic acid can also be used. Although these compounds cannot themselves encapsulate guest molecules like the organic compounds having the cyclic structure described above, they can form metal-organic structures having a cyclic or cage-like structure that can encapsulate guest molecules by coordinating with metal ions.

[0016] The following are examples of specific metal-organic structures that can be suitably used in the composite of the present invention. Metal-organic structures in which the metal ion is an alkali metal ion and the organic ligand is a cyclodextrin compound, particularly metal-organic structures in which the metal ion is a potassium ion and the organic ligand is α-cyclodextrin or γ-cyclodextrin (α-CDMOF or γ-CDMOF), and metal-organic structures in which the metal ion is a zinc ion and the organic ligand is a compound having an imidazole skeleton, particularly metal-organic structures in which the organic ligand is 2-methylimidazole (ZIF-8), can be suitably used. In the present invention, among the above metal-organic structures, CDMOF can be particularly suitably used.

[0017] In metal-organic structures (CDMOFs) where the organic ligand is cyclodextrin and the metal ion is potassium ion, it is preferable that the metal-organic structure has cyclodextrin bonded in a range of 0.05 to 0.80 moles per mole of potassium ion. Furthermore, in metal-organic structures (ZIF-8) composed of compounds having an imidazole skeleton as an organic ligand, it is preferable that the metal-organic structure has 0.5 to 50 moles of 2-methylimidazole bonded to 1 mole of zinc ions.

[0018] (Method for producing metal-organic structure) The metal-organic structure used in the composite of the present invention is not limited to this, but can be manufactured by the following method. In other words, a first aqueous solution containing a metal ion and an organic compound that is an organic ligand capable of coordinating to the metal ion is prepared, and then a second solution containing an organic solvent is added to this first aqueous solution to generate a metal-organic structure in which the organic ligand is coordinated to the metal ion. In the first aqueous solution, the metal compound supplying the metal ions is not limited to these, but examples include metal hydroxides, inorganic halide salts such as chloride salts, inorganic acid salts such as nitrates, and organic acid salts such as acetates. Specifically, when the metal ions are alkali metal ions such as potassium ions, it is preferable to use alkali metal hydroxides, and when the metal ions are Zn ions or Fe ions, it is preferable to use inorganic acid salts.

[0019] In the first aqueous solution described above, the amount of organic ligand per mole of metal ion is preferably in the range of 0.05 to 50 moles, more preferably in the range of 0.1 to 40 moles, and more preferably in the range of 0.125 to 30 moles. When the metal ion is an alkali metal ion, the amount of organic ligand per mole of metal ion is preferably in the range of 0.05 to 5 moles, and particularly preferably in the range of 0.125 to 0.80 moles. When the metal ion is a potassium ion and the organic ligand is a cyclodextrin compound, as described above, it is preferably in the range of 0.05 to 0.80 moles, and particularly preferably in the range of 0.125 to 0.375 moles when the organic ligand is α-cyclodextrin, and in the range of 0.125 to 0.750 moles when the organic ligand is γ-cyclodextrin.

[0020] The amount of water in the first aqueous solution is preferably in the range of 50 to 5000 moles per mole of metal ions, and when the metal ions are alkali metal ions, the amount of water is preferably in the range of 80 to 200 moles per mole of metal ions, and particularly preferably in the range of 100 to 150 moles. The molar ratio of organic ligand to water (organic ligand:water) is preferably in the range of 1:50 to 1:2000, and in particular, when the organic ligand is a cyclodextrin compound, it is desirable that it be in the range of 1:100 to 1:1300.

[0021] The second solution added to the first aqueous solution prepared as described above is preferably a solution capable of lowering the pH of the first aqueous solution, and it is preferable to use an organic solvent capable of deprotonating the coordination bond site of the organic ligand. When the organic ligand is deprotonated, a coordination bond is formed with the metal ion, thereby generating a metal-organic structure. Examples of such organic solvents include at least one solvent selected from alcohol-based solvents such as methanol, ethanol, 1-propanol, and 1-butanol; ketone-based solvents such as acetone; and aprotic solvents such as NN-dimethylformamide. Among these, alcohol-based solvents are preferred, and methanol can be used particularly favorably. The organic solvent is preferably added in an amount of 3 to 1000 moles, particularly 5 to 500 moles, per mole of metal ions. In particular, when the metal ion is a potassium ion and the organic ligand is an α-cyclodextrin, the organic solvent is preferably added in an amount of 10 to 400 moles, preferably 50 to 300 moles, and more preferably 100 to 200 moles, per mole of potassium ions. When the metal ion is a γ-cyclodextrin, the organic solvent is preferably added in an amount of 3 to 100 moles, preferably 5 to 50 moles, and more preferably 10 to 30 moles, per mole of potassium ions.

[0022] When adding the second solution to the first aqueous solution, it is preferable to add the second solution over a period of 1 to 20 minutes, preferably 10 to 15 minutes, while stirring the first aqueous solution. If the entire amount of the second solution is added at once, turbidity may occur, and the desired metal-organic structure may not be obtained. However, by adding the second solution over the above-mentioned period, nuclei can be formed, allowing the crystal structure to grow, and making it easier to obtain the desired metal-organic structure. The method of addition is not limited to this, but examples include adding at a constant rate using a dropping funnel, adding a fixed amount at regular intervals, and adding by gradually changing the amount added. After the addition of the second solution is complete, it is preferable to stir the mixed solution at room temperature for 5 to 50 hours, preferably 10 to 30 hours. The resulting metal-organic structure can be isolated by filtration or the like, washed with an organic solvent such as methanol if necessary, and then dried to remove the organic solvent and water, thereby obtaining a powder of the metal-organic structure.

[0023] (Crosslinking agent) The crosslinking agent that can be used in the composite of the present invention has coordination sites or binding sites, and it is important that these coordination sites or binding sites are capable of chemically or physically bonding to the metal ions or organic ligands of the metal-organic structure. In this specification, chemical bonding refers to ether bonding and ester bonding, and physical bonding refers to ionic bonding, van der Waals bonding and hydrogen bonding. The crosslinking agent is a compound having at least two reactive crosslinking groups that can crosslink with metal ions or functional groups of organic ligands in a metal-organic structure, and a crosslinking agent having at least two of any of hydroxyl groups, epoxy groups, amino groups, or carboxyl groups in its molecule can be suitably used. Furthermore, the crosslinking agent of the present invention preferably has a glass transition temperature of less than 70°C.

[0024] Examples of crosslinking agents having at least two hydroxyl groups include cellulose derivatives such as cellulose acetate, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, and carboxymethylcellulose, as well as polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, polyglycerin, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl alcohol, diethanolamine, tridiethanolamine, polypropylene glycol, polyvinyl alcohol, pentaerythritol, sorbitol, sorbitan, glucose, mannitol, mannitane, sucrose, and glucose. Among these, cellulose acetate with an oxidation degree of 53-56% and an acetylation degree of 38-40% is preferred.

[0025] Examples of crosslinking agents having at least two epoxy groups (epoxy crosslinking agents) include polyhydric alcohol glycidyl ethers such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, sorbitol polyglycidyl ether, 1,6-hexanediol glycidyl ether, bisphenol A glycidyl ether, glycerin triglycidyl ether, polyglycerol polyglycidyl ether, and trimethylolpropane polyglycidyl ether. Note that some or all of the epoxy groups in the epoxy crosslinking agent may be ring-opened and exist as hydroxyl groups. Examples of crosslinking agents having at least two amino groups (amine-based crosslinking agents) include polyamines such as polyallylamine and polyethyleneimine, and amino compounds such as ethylenediamine, hexamethylenediamine, and triethyldiamine. The amine-based crosslinking agent is preferably a polyamine with a weight-average molecular weight in the range of 1,000 to 25,000 or a number-average molecular weight in the range of 50,000 to 150,000. Polyallylamine is preferably a polymer having a primary amine in its side chain. Polyethyleneimine is preferably amine-valued at 18 mmol / g·solid. Examples of crosslinking agents having at least two carboxyl groups include polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, and adipic acid. Among the crosslinking agents mentioned above, polyhydric alcohol glycidyl ether, polyamine, or cellulose acetate can be suitably used. Furthermore, the aforementioned organic ligands can also be used as crosslinking agents, but it is preferable that the crosslinking agent and the organic ligand are different.

[0026] (Method of manufacturing the composite) The composite of the present invention is formed by introducing a crosslinked structure through chemical or physical bonding of the coordination site or binding site of the crosslinking agent to the metal ions or organic ligands of the metal-organic structure. The composite can be produced by dissolving the crosslinking agent in an organic solvent capable of dissolving the crosslinking agent, such as ethanol or acetone, and then adding and mixing the metal-organic structure to the solution to allow the two to react. Preferably, the organic solvent is added to the solution containing the crosslinking agent and the metal-organic structure in a mass ratio of 1:1 to 1:250, with the content of the metal-organic structure being 1.

[0027] The ratio of the metal-organic structure to the crosslinking agent can be appropriately changed depending on the type of metal-organic structure and crosslinking agent used, or the desired amount of water vapor adsorption and other gas adsorption performance, and is not limited thereto. However, when using CD-MOF as the metal-organic structure, it is preferable to add the crosslinking agent in a mass ratio of 1:30 to 1:70 for polyhydric alcohol glycidyl ethers, 1:0.1 to 1:2 for amine-based crosslinking agents such as polyallylamine, and 1:0.01 to 1:4 for cellulose acetate, with the metal-organic structure being 1. Similarly, when using ZIF-8 as the metal-organic structure, it is preferable to add the crosslinking agent in a mass ratio of 1:30 to 1:70 for polyhydric alcohol glycidyl ethers, 1:0.1 to 1:2 for amine-based crosslinking agents such as polyallylamine, and 1:0.01 to 1:4 for cellulose acetate, with the metal-organic structure being 1.

[0028] The reaction conditions for the metal-organic structure and the crosslinking agent cannot be generalized, as they depend on the type and ratio of the metal-organic structure and crosslinking agent used. However, it is preferable to react at a temperature of 20 to 140°C, particularly 20 to 70°C, for 1 to 4500 minutes, and especially for 10 to 120 minutes. As mentioned above, increasing the crystallinity of the composite tends to improve the adsorption of nitrogen gas, etc., without impairing water vapor adsorption; therefore, low temperature and short reaction time are preferable.

[0029] After the crosslinking reaction is complete, the resulting solid product can be filtered, washed, and dried to obtain a solid composite. The resulting solid product can be molded into any shape, such as tablets, pellets, or granules. Furthermore, since the composite of the present invention can form a coating film on its own, a solid product-containing solution or dispersion can be prepared by stirring and mixing the solution after the crosslinking reaction is complete, and then drying this to form a coating film containing the composite of the present invention. The drying conditions for the coating film can be appropriately changed depending on the type and amount ratio of the organic solvent, metal-organic structure, and crosslinking agent used, but a range of 20 to 140°C for 10 to 1440 minutes is preferred.

[0030] In the present invention, the above coating film can also be formed on a substrate in the form of a laminate. Conventional known substrates consisting of resins such as thermoplastic resins and thermosetting resins, or fibers such as paper and nonwoven fabrics can be used as the substrate. The substrate may also be a molded product such as a film, sheet, or container, or this coating can be pre-applied to a pre-molded product for forming a container. The laminate can also be used as a gas separation membrane or a gas selective membrane. [Examples]

[0031] To further explain the present invention, the inventors will now describe some examples they have provided.

[0032] (Measurement method) [Thermogravimetric Analysis Evaluation] Thermogravimetric analysis of metal-organic structures under a nitrogen atmosphere was performed using a Hitachi High-Tech Science TG / DTA7220, with a heating rate of 5°C / min and measurement temperatures ranging from 30°C to 900°C. Furthermore, the presence or absence of residual metal-organic structures was evaluated based on the thermogravimetric change measured by thermogravimetric analysis.

[0033] [Gas adsorption / desorption evaluation] The adsorption and desorption of metal-organic structures and composites was evaluated using a multi-point method with a BELSORP MAX II measuring device from Microtrac-Bel, under liquid nitrogen temperature and measurement pressures ranging from 0 to 100 kPa. The adsorption isotherms of nitrogen gas were measured to assess the nitrogen gas adsorption performance. The adsorption performance of carbon dioxide gas was evaluated by measuring the carbon dioxide gas adsorption isotherm using a BELSORP MAX II model manufactured by Microtrac-Bel at 298K under measurement pressures ranging from 0 to 100kPa using a multi-point method. Furthermore, water vapor was measured using a BELSORP MAX II model manufactured by Microtrac Bel, employing a multi-point method to determine the water vapor adsorption isotherm at a measurement pressure of 0 to 2.90 kPa under a temperature of 298 K. This allowed for evaluation of the water vapor adsorption performance and water resistance.

[0034] [Crystal structure] The crystal structure of the metal-organic structure was evaluated using powder X-ray diffraction (PXRD) with Rigaku's SmartLab. The degree of crystallinity in the composite was calculated using the following equation (1) based on the scattering intensities of the amorphous and crystalline phases at temperatures from 5°C to 40°C, after background correction using the Voigt function for the obtained evaluation results. (Crystallization) = (Scattering intensity from crystalline phase) / (Scattering intensity from crystalline phase + scattering intensity from amorphous phase) (Scattering intensity) ... (1)

[0035] [Gas permeability evaluation] The gas permeability of the coating film was evaluated using a flow-type gas and water vapor transmission rate analyzer (as specified in ISO 15105-2:2003) manufactured by GTR Tech Co., Ltd., under conditions of 35°C, 0% RH, and 20% RH, using the isobaric measurement method.

[0036] <Preparation of the complex> (Example 1) Pure water was added to a 150 ml container, then potassium hydroxide was added to the container and dissolved at room temperature. γ-cyclodextrin was then added and dissolved at room temperature. The pH of the resulting solution was 13.98. Next, methanol was added dropwise to this solution over approximately 15 minutes while stirring with a stirring bar. After the addition, the solution was stirred for 24 hours to obtain a suspension containing the solid product. The pH of the solution after methanol addition was 13.85. The solid product was filtered from the obtained suspension, and the isolated solid product was washed with methanol. After washing, the solid product was dried overnight at 50°C to obtain metal-organic structure A. The molar ratio of each component was potassium ion:γ-cyclodextrin:water:methanol = 1.00:0.12:20.37:2.86.

[0037] Next, a stirring bar and ethanol were added to a 140 ml container (mayonnaise bottle), and ethylene glycol diglycidyl ether was dissolved at room temperature. Then, while stirring the solution, metal-organic structure A was added to form a mixed solution. After preparing the mixed solution, it was left to stand in a 65°C incubator for 72 hours to obtain a suspension containing the solid product. The solid product was filtered off from the obtained suspension, and the isolated solid product was washed with ethanol. After washing, the solid product was dried at 50°C for 4 hours to obtain complex B containing the metal-organic structure. The weight ratio of each component in the mixed solution was set to metal-organic structure A:ethylene glycol diglycidyl ether:ethanol = 1:32.63:197.25.

[0038] Based on gas adsorption / desorption evaluation, the resulting composite B had a maximum nitrogen gas adsorption capacity of 5.63 cm³. 3 / g, maximum CO2 gas adsorption capacity is 2.92cm³ 3 / g, maximum water vapor adsorption capacity is 472.1cm³ 3 It was found to have water vapor adsorption capacity and was a water-resistant material. PXRD measurements revealed peaks originating from metal-organic structure A, as well as a halo pattern, in the obtained composite B. The crystallinity was 5.7. From the thermogravimetric analysis evaluation, it was confirmed that the decrease peak of the obtained composite B shifted to a higher temperature compared to the metal-organic framework A, and it was a composite having a crosslinked structure.

[0039] (Example 2) A composite C was obtained in the same manner as in Example 1, except that ethylene glycol diglycidyl ether was used as sorbitol polyglycidyl ether and the weight ratio of each component in the mixed solution was metal-organic framework A:sorbitol polyglycidyl ether:ethanol = 1:51.52:197.25. From the gas adsorption / desorption evaluation of the obtained composite C, the maximum nitrogen gas adsorption amount was 8.23 cm 3 / g, the maximum CO2 gas adsorption amount was 0.65 cm 3 / g, and the maximum water vapor adsorption amount was 449.49 cm 3 / g. It was found to exhibit water vapor adsorption ability and was a material having water resistance. From the PXRD measurement, peaks derived from the metal-organic framework A and other halo patterns were confirmed for the obtained composite C. The crystallinity was 56.7. From the thermogravimetric analysis evaluation, it was confirmed that the decrease peak of the obtained composite C shifted to a higher temperature compared to the metal-organic framework A, and it was a composite having a crosslinked structure.

[0040] (Example 3) A composite D was obtained in the same manner as in Example 1, except that ethylene glycol diglycidyl ether was used as 1,6-hexanediol diglycidyl ether and the weight ratio of each component in the mixed solution was metal-organic framework A:1,6-hexanediol diglycidyl ether:ethanol = 1:43.19:197.26. From the gas adsorption / desorption evaluation of the obtained composite D, the maximum nitrogen gas adsorption amount was 14.64 cm 3 / g, the maximum CO2 gas adsorption amount was 5.46 cm 3 / g, and the maximum water vapor adsorption amount was 332.00 cm 3 / g. It was found to exhibit water vapor adsorption ability and was a material having water resistance. PXRD measurements revealed peaks originating from metal-organic structure A, as well as a halo pattern, in the obtained composite D. The crystallinity was 46.3. Thermogravimetric analysis confirmed that the decrease peak of the obtained composite D shifted to higher temperatures compared to the metal-organic structure A, indicating that it was a composite with a cross-linking structure.

[0041] (Example 4) Composite E was obtained in the same manner as in Example 1, except that ethylene glycol diglycidyl ether was replaced with bisphenol A diglycidyl ether, and the weight ratio of each component in the mixed solution was set to metal-organic structure A:bisphenol A diglycidyl ether:ethanol = 1:63.84:197.25. Based on gas adsorption / desorption evaluation, the resulting composite E had a maximum nitrogen gas adsorption capacity of 16.93 cm³. 3 / g, maximum CO2 gas adsorption capacity is 4.93cm³ 3 / g, maximum water vapor adsorption capacity is 274.67cm³ 3 It was found to have water vapor adsorption capacity and was a water-resistant material. PXRD measurements revealed peaks originating from metal-organic structure A, as well as a halo pattern, in the obtained composite E. The crystallinity was 36.0. Thermogravimetric analysis confirmed that the decrease peak of the obtained composite E shifted to higher temperatures compared to the metal-organic structure A, indicating that it was a composite with a cross-linking structure.

[0042] (Example 5) Composite F was obtained in the same manner as in Example 1, except that the weight ratio of each component was set to metal-organic structure A:ethylene glycol diglycidyl ether:ethanol = 1:32.66:197.25, and after preparing the mixed solution, the mixed solution was stirred in a 65°C bath for 60 minutes to obtain a suspension containing a solid product. Based on gas adsorption / desorption evaluation, the resulting composite F had a maximum nitrogen gas adsorption capacity of 105.57 cm³. 3 / g, maximum CO2 gas adsorption capacity is 2.11cm³ 3 / g, maximum water vapor adsorption capacity is 342.11cm³ 3It was found to have water vapor adsorption capacity and was a water-resistant material. PXRD measurements revealed peaks originating from metal-organic structure A, as well as a halo pattern, in the obtained composite F. The crystallinity was 17.1. Thermogravimetric analysis confirmed that the decrease peak of the obtained composite F shifted to higher temperatures compared to the metal-organic structure A, indicating that it was a composite with a cross-linking structure.

[0043] (Example 6) A stirring bar and ethanol were added to a 70 ml container (mayonnaise bottle), and polyallylamine (average molecular weight: 5000) having a primary amine in its side chain was dissolved at room temperature. Next, metal-organic structure A was added to the solution while stirring to form a mixed solution. After preparing the mixed solution, it was stirred at room temperature for 24 hours to obtain a suspension containing a solid product. The solid product was filtered off from the obtained suspension, and the isolated solid product was washed with ethanol. After washing, the solid product was dried at 60°C for 4 hours to obtain complex G containing a metal-organic structure. The weight ratio of each component in the mixed solution was set to metal-organic structure A:polyallylamine:ethanol = 1:1.00:5.00. Based on gas adsorption / desorption evaluation, the resulting composite G had a maximum nitrogen gas adsorption capacity of 56.62 cm³. 3 / g, maximum CO2 gas adsorption capacity is 5.98cm³ 3 / g, maximum water vapor adsorption capacity is 359.01cm³ 3 It was found to have water vapor adsorption capacity and was a water-resistant material. PXRD measurements revealed peaks originating from metal-organic structure A, as well as a halo pattern, in the obtained composite G. The crystallinity was 76.5. Thermogravimetric analysis revealed that the decrease peaks in the obtained complex G were consistent with the decrease peaks in the metal-organic structure A and polyallylamine, indicating that the complex had a cross-linking structure.

[0044] (Example 7) Composite H was obtained in the same manner as in Example 6, except that after preparing the mixed solution, the mixed solution was stirred at room temperature for 60 minutes to obtain a suspension containing the solid product. Based on gas adsorption / desorption evaluation, the resulting composite H had a maximum nitrogen gas adsorption capacity of 167.73 cm³. 3 / g, maximum CO2 gas adsorption capacity is 19.74cm³ 3 / g, maximum water vapor adsorption capacity is 371.65cm³ 3 It was found to have water vapor adsorption capacity and was a water-resistant material. PXRD measurements revealed peaks originating from metal-organic structure A, as well as a halo pattern, in the obtained composite H. The crystallinity was 70.0. Thermogravimetric analysis revealed that the decrease peak in the obtained complex H was consistent with the decrease peaks of the metal-organic structure A and polyallylamine, indicating that the complex had a cross-linking structure.

[0045] (Example 8) Composite I was obtained in the same manner as in Example 6, except that after preparing the mixed solution, the mixed solution was stirred at room temperature for 30 minutes to obtain a suspension containing a solid product. Based on gas adsorption / desorption evaluation, the resulting composite I had a maximum nitrogen gas adsorption capacity of 160.69 cm³. 3 / g, maximum CO2 gas adsorption capacity is 17.67cm³ 3 / g, maximum water vapor adsorption capacity is 403.95cm³ 3 It was found to have water vapor adsorption capacity and was a water-resistant material. PXRD measurements revealed peaks originating from metal-organic structure A, as well as a halo pattern, in the obtained composite I. The crystallinity was 41.0. Thermogravimetric analysis revealed that the decrease peaks in the obtained complex I were consistent with the decrease peaks in the metal-organic structure A and polyallylamine, indicating that the complex had a cross-linking structure.

[0046] (Example 9) Composite J was obtained in the same manner as in Example 6, except that after preparing the mixed solution, the mixed solution was stirred at room temperature for 10 minutes to obtain a suspension containing the solid product. Based on gas adsorption / desorption evaluation, the resulting composite J had a maximum nitrogen gas adsorption capacity of 140.25 cm³. 3 / g, maximum CO2 gas adsorption capacity is 17.23cm³ 3 / g, maximum water vapor adsorption capacity is 367.12cm³ 3 It was found to have water vapor adsorption capacity and was a water-resistant material. PXRD measurements revealed peaks originating from metal-organic structure A, as well as a halo pattern, in the obtained composite J. The crystallinity was 61.0. Thermogravimetric analysis revealed that the decrease peaks in the obtained complex J were consistent with the decrease peaks in the metal-organic structure A and polyallylamine, indicating that the complex had a cross-linking structure.

[0047] (Example 10) Composite K was obtained in the same manner as in Example 6, except that polyallylamine (average molecular weight: 5000) was replaced with polyallylamine (average molecular weight: 1600) having a primary amine in its side chain, and the weight ratio of each component in the mixed solution was set to metal-organic structure A:polyallylamine (average molecular weight: 1600):ethanol = 1:1.00:3.31. Based on gas adsorption / desorption evaluation, the resulting composite K had a maximum nitrogen gas adsorption capacity of 10.42 cm³. 3 / g, maximum CO2 gas adsorption capacity is 3.22cm³ 3 / g, maximum water vapor adsorption capacity is 201.31cm³ 3 It was found to have water vapor adsorption capacity and was a water-resistant material. PXRD measurements revealed peaks originating from metal-organic structure A, as well as a halo pattern, in the obtained complex K. The crystallinity was 93.4. Thermogravimetric analysis revealed that the decrease peak in the obtained complex K was consistent with the decrease peaks of the metal-organic structure A and polyallylamine, indicating that the complex had a cross-linking structure.

[0048] (Example 11) Composite L was obtained in the same manner as in Example 6, except that polyallylamine (average molecular weight: 5000) was replaced with polyethyleneimine (average molecular weight: 100000) (amine value: 18 mmol / g·solid), and the weight ratio of each component was set to metal-organic structure A:polyethyleneimine (average molecular weight: 100000):ethanol = 1:0.35:9.00. Based on gas adsorption / desorption evaluation, the resulting composite L had a maximum nitrogen gas adsorption capacity of 13.27 cm³. 3 / g, maximum CO2 gas adsorption capacity is 1.45cm³ 3 / g, maximum water vapor adsorption capacity is 548.43cm³ 3 It was found to have water vapor adsorption capacity and was a water-resistant material. PXRD measurements revealed peaks originating from metal-organic structure A, as well as a halo pattern, in the obtained composite L. The crystallinity was 84.0. Thermogravimetric analysis revealed that the decrease peaks in the obtained composite L were consistent with the decrease peaks in the metal-organic structure A and polyethyleneimine, indicating that the composite had a cross-linked structure.

[0049] (Example 12) Composite M was obtained in the same manner as in Example 6, except that polyallylamine (average molecular weight: 5000) was replaced with cellulose acetate (degree of oxidation: 53-56%, degree of acetylation: 38-40%), and ethanol was replaced with acetone. The mixed solution was stirred at room temperature for 30 minutes, the solid product was washed with acetone, and after washing, the solid product was dried at 60°C for 6 hours. The weight ratio of each component in the mixed solution was set to metal-organic structure A:cellulose acetate:acetone = 1:0.10:9.90. Based on gas adsorption / desorption evaluation, the resulting composite M had a maximum nitrogen gas adsorption capacity of 214.32 cm³. 3 / g, maximum CO2 gas adsorption capacity is 41.24cm³ 3 / g, maximum water vapor adsorption capacity is 419.31cm³ 3 It was found to have water vapor adsorption capacity and was a water-resistant material. PXRD measurements revealed peaks originating from metal-organic structure A, as well as a halo pattern, in the obtained complex M. The crystallinity was 61.3. Thermogravimetric analysis revealed that the decrease peaks in the obtained complex M were consistent with the decrease peaks in the metal-organic structure A and cellulose acetate, indicating that the complex had a cross-linked structure.

[0050] (Example 13) Composite N was obtained in the same manner as in Example 12, except that the weight ratio of each component in the mixed solution was set to metal-organic structure A:cellulose acetate:acetone = 1:0.010:9.99. Based on gas adsorption / desorption evaluation, the resulting composite N had a maximum nitrogen gas adsorption capacity of 299.46 cm³. 3 / g, maximum CO2 gas adsorption capacity is 43.91cm³ 3 / g, maximum water vapor adsorption capacity is 427.54cm³ 3 It was found to have water vapor adsorption capacity and was a water-resistant material. PXRD measurements revealed peaks originating from metal-organic structure A, as well as a halo pattern, in the obtained complex N. The crystallinity was 45.0. Thermogravimetric analysis revealed that the decrease peaks in the obtained complex N were consistent with the decrease peaks in the metal-organic structure A and cellulose acetate, indicating that the complex had a cross-linked structure.

[0051] (Comparative Example 1) Various measurements were performed on the metal-organic structure A shown in Example 1. From the gas adsorption / desorption evaluation of the obtained metal-organic structure A, the maximum nitrogen gas adsorption capacity was 326.73 cm³. 3 / g, maximum CO2 gas adsorption capacity is 45.09cm³ 3 / g, maximum water vapor adsorption capacity is 0.00cm³ 3 The value was / g. It did not exhibit water vapor adsorption performance and was not a water-resistant material. PXRD measurements confirmed the crystallization peak of the obtained metal-organic structure A. The degree of crystallinity was 98.9.

[0052] (Example 14) In a 140 ml container (mayonnaise bottle), a stirring bar and acetone were added, and cellulose acetate (oxidation degree: 53-56%, acetylation degree: 38-40%) was dissolved at room temperature. Next, ZIF-8 (Basolite Z1200, manufactured by Sigma-Aldrich) was added to the solution while stirring, and the mixture was stirred for 10 minutes. After that, the solution was subjected to ultrasonic waves for 10 minutes. The solution was then stirred for another 10 minutes. After preparing the mixed solution, it was air-dried in a rectangular pad to obtain a coating film O. The weight ratio of each component in the mixed solution was set to ZIF-8:cellulose acetate:acetone = 1:2.00:53.86. The obtained coating film O was evaluated for gas permeability at 35°C and 0%RH, and the results were as follows: (Permeability of carbon dioxide gas) = ​​2702.74 bars, (Permeability of oxygen gas) = ​​9346.20 bars, (Permeability of nitrogen gas) = ​​663.99 bars, (Selectivity of carbon dioxide gas relative to nitrogen) = 4.07, (Selectivity of oxygen gas relative to nitrogen) = 14.08. Furthermore, gas permeability evaluation at 35°C and 20% RH yielded the following results: (Permeability of carbon dioxide gas) = ​​4.34 bars, (Permeability of oxygen gas) = ​​1.10 bars, (Permeability of nitrogen gas) = ​​1.00 bars, (Water vapor permeability) = 0 g / m³ 2 At 24 hours, the carbon dioxide gas selectivity relative to nitrogen was 4.34, and the oxygen gas selectivity relative to nitrogen was 1.10.

[0053] (Example 15) A coating film P was obtained in the same manner as in Example 14, except that the weight ratio of each component in the mixed solution was set to ZIF-8:cellulose acetate:acetone = 1:2.99:80.78. The obtained coating film P was evaluated for gas permeability at 35°C and 0%RH, and the results were as follows: (Permeability of carbon dioxide gas) = ​​726.34 bars, (Permeability of oxygen gas) = ​​258.04 bars, (Permeability of nitrogen gas) = ​​163.90 bars, (Selectivity of carbon dioxide gas relative to nitrogen) = 4.43, (Selectivity of oxygen gas relative to nitrogen) = 1.57. Furthermore, gas permeability evaluation at 35°C and 20% RH yielded the following results: (Permeability of carbon dioxide gas) = ​​2.32 bars, (Permeability of oxygen gas) = ​​0.91 bars, (Permeability of nitrogen gas) = ​​0.54 bars, (Water vapor permeability) = 0 g / m³ 2 At 24 hours, the carbon dioxide gas selectivity relative to nitrogen was 4.30, and the oxygen gas selectivity relative to nitrogen was 1.68.

[0054] (Example 16) A coating film Q was obtained in the same manner as in Example 14, except that the weight ratio of each component in the mixed solution was set to metal-organic structure A:cellulose acetate:acetone = 1:3.00:80.91. The obtained coating film Q was evaluated for gas permeability at 35°C and 0%RH, and the results were as follows: (Permeability of carbon dioxide gas) = ​​2794.50 bars, (Permeability of oxygen gas) = ​​12287.56 bars, (Permeability of nitrogen gas) = ​​901.69 bars, (Selectivity of carbon dioxide gas relative to nitrogen) = 3.10, (Selectivity of oxygen gas relative to nitrogen) = 13.63. Furthermore, gas permeability evaluation at 35°C and 20% RH yielded the following results: (Permeability of carbon dioxide gas) = ​​6331.47 bars, (Permeability of oxygen gas) = ​​24424.36 bars, (Permeability of nitrogen gas) = ​​1730.11 bars, (Water vapor permeability) = 0 g / m³ 2 At 24 hours, the carbon dioxide gas selectivity relative to nitrogen was 3.68, and the oxygen gas selectivity relative to nitrogen was 14.11.

[0055] (Example 17) The coating film R was obtained in the same manner as in Example 14, except that the weight ratio of each component in the mixed solution was set to metal-organic structure A:cellulose acetate:acetone = 1:5.96:160.96. The obtained coating film R was evaluated for gas permeability at 35°C and 0%RH, and the results were as follows: (Permeability of carbon dioxide gas) = ​​1495.66 bars, (Permeability of oxygen gas) = ​​1754.51 bars, (Permeability of nitrogen gas) = ​​1643.27 bars, (Selectivity of carbon dioxide gas relative to nitrogen) = 0.91, (Selectivity of oxygen gas relative to nitrogen) = 1.07. Furthermore, gas permeability evaluation at 35°C and 20% RH yielded the following results: (Permeability of carbon dioxide gas) = ​​366.77 bars, (Permeability of oxygen gas) = ​​426.38 bars, (Permeability of nitrogen gas) = ​​396.77 bars, (Water vapor permeability) = 0 g / m³ 2 At 24 hours, the carbon dioxide gas selectivity relative to nitrogen was 0.92, and the oxygen gas selectivity relative to nitrogen was 1.07.

[0056] (Comparative Example 2) A stirring bar and acetone were added to a 140 ml container (mayonnaise bottle), and cellulose acetate was dissolved at room temperature. Then, the solution was subjected to ultrasonic waves for 10 minutes. After that, the solution was stirred for 10 minutes. After preparing the mixed solution, it was air-dried in a rectangular pad to obtain the coating film S. The weight ratio of each component in the mixed solution was set to cellulose acetate:acetone = 1:27.00. The obtained coating film S was evaluated for gas permeability at 35°C and 0%RH, and the results were as follows: (Permeability of carbon dioxide gas) = ​​3941.84 bars, (Permeability of oxygen gas) = ​​14906.25 bars, (Permeability of nitrogen gas) = ​​1005.00 bars, (Selectivity of carbon dioxide gas relative to nitrogen) = 3.92, (Selectivity of oxygen gas relative to nitrogen) = 14.83. Furthermore, gas permeability evaluation at 35°C and 20% RH yielded the following results: (Permeability of carbon dioxide gas) = ​​3070.56 bars, (Permeability of oxygen gas) = ​​12166.05 bars, (Permeability of nitrogen gas) = ​​806.15 bars, (Water vapor permeability) = 0 g / m³ 2 • At 24 hours, the carbon dioxide gas selectivity relative to nitrogen was 3.81, and the oxygen gas selectivity relative to nitrogen was 15.09. [Industrial applicability]

[0057] The composite material of the present invention is water-resistant and has water vapor adsorption capacity, making it suitable for use as a water vapor adsorption material. It can also be formed as a laminate by creating a coating film on a substrate. Furthermore, as is clear from the results of the above examples, the composite material of the present invention has gas selectivity, and therefore can also be used as a gas separation membrane or a gas selectivity membrane.

Claims

1. A composite containing a metal-organic structure and a crosslinking agent, The aforementioned metal-organic structure is a metal-organic structure comprising a metal ion and an organic ligand coordinated to the metal ion, A composite having water vapor adsorption properties, characterized in that the crosslinking agent is bound to the metal ions or organic ligands of the metal-organic structure.

2. The composite according to claim 1, wherein the crosslinking agent has at least one of a hydroxyl group, an epoxy group, an amino group, and a carboxyl group.

3. The composite according to claim 1, wherein the crosslinking agent is any one of a polyhydric alcohol glycidyl ether, a polyamine, or cellulose acetate.

4. The complex according to claim 1 or 2, wherein the organic ligand is a cyclodextrin.

5. A coating film characterized by containing the composite described in claim 1.

6. A laminate characterized by comprising the coating film described in claim 5.