Suction sheet, suction element, and suction processing apparatus using the same

Abstract

An adsorbent sheet of the present invention comprises: a porous metal complex comprising a metal and an organic ligand and having a water adsorption ratio of 30% by mass or more at 25°C under a relative pressure of 0.5; and a non-fibrillated fiber and a fibrillated fiber. The adsorbent sheet is excellent in the property of supporting the porous metal complex and the flexibility / processability of the sheet, and can exert sufficient adsorption performance.

Description

Technical Field

[0001] The present invention relates to an adsorption sheet, an adsorption element, and an adsorption treatment apparatus that efficiently separate and recover or adsorb and remove substances to be adsorbed such as moisture, organic solvents, and malodorous components.

Background Art

[0002] Porous materials such as activated carbon, silica gel, and zeolite are used in various applications such as deodorization, purification of air and water, and separation and purification of gases, and have become indispensable materials in modern life. In recent years, a new porous material called a porous metal complex (MOF) or a porous coordination polymer (PCP), which is self-assembled by combining metal ions that can take various coordination forms and a bridging ligand having two or more coordination sites, has been discovered. These porous metal complexes have characteristics such as a high specific surface area, a sharp pore distribution, and high structural designability, which are not found in conventional porous materials such as activated carbon, silica gel, and zeolite, and have attracted attention.

[0003] As such a porous metal complex, for example, Patent Document 1 discloses that a specific dicarboxylic acid metal complex is suitable as a gas storage material, particularly a gas storage material mainly composed of methane. Patent Document 2 discloses a porous metal complex synthesized from copper ions and trimesic acids, and an adsorbent is disclosed as an example of its use. Further, Patent Document 3 discloses that a porous metal complex obtained from metal chromium or a chromium salt and trimesic acids is excellent particularly as a water vapor adsorbent.

[0004] Thus, porous metal complexes have the potential as adsorbents for various gases. When used as an adsorbent, it is preferable to form the porous metal complex existing as a powder into an adsorption element suitable for use so that it can contact the working fluid with less pressure loss. For this purpose, it is important to establish a technology for forming a sheet.

[0005] Therefore, Patent Document 4 discloses an adsorption sheet containing a porous metal complex as a sheet containing a porous metal complex, a heat-resistant fiber, a clay mineral fiber having self-binding properties, and an organic binder.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, the adsorption sheet disclosed in Patent Document 4 requires clay mineral fibers, and accordingly, the content ratio of heat-resistant fibers is reduced. As a result, the sheet itself lacks firmness, and there are problems such as no steps during honeycomb processing when making a filter, for example.

[0008] Therefore, an object of the present invention is to provide an adsorption sheet, an adsorption element, and an adsorption / desorption treatment apparatus using the same, which are excellent in the loading property of a porous metal complex, the flexibility and processability of a sheet, and have sufficient adsorption performance.

Means for Solving the Problems

[0009] As a result of intensive studies to solve the above problems, the present inventors have finally completed the present invention. That is, the present invention has the following configuration. [1] An adsorption sheet characterized by containing a porous metal complex having a metal and an organic ligand and having a water adsorption rate of 30% by mass or more at 25°C and a relative pressure of 0.5, non-fibrillated fibers, and fibrillated fibers. [2] The adsorption sheet according to the above [1], characterized by containing an organic binder having a dissolution temperature in water of 65°C to 100°C. [3] The adsorption sheet according to the above [1] or [2], characterized in that the specific tensile elongation is 5%·m / g or more. [4] The adsorption sheet according to any one of the above [1] to [3], characterized by containing 60 to 85% by mass of the porous metal complex. [5] An adsorption element characterized by including the adsorption sheet according to any one of the above [1] to [4]. [6] An adsorption / desorption treatment apparatus comprising the adsorption element according to the above [5], an adsorption means for introducing and adsorbing an adsorption target substance to the adsorption element, and a desorption means for desorbing the adsorption target substance adsorbed by the adsorption element, and continuously performing adsorption and desorption of the adsorption target substance. [Advantages of the Invention]

[0010] According to the above configuration, an adsorption sheet excellent in the loading property of the porous metal complex, the flexibility and processability of the sheet, and having sufficient adsorption performance can be provided. [Brief Description of the Drawings]

[0011]

Figure 1

Figure 2

Figure 3

[0012] Hereinafter, the present invention will be described in detail. The adsorption sheet of the present invention contains a porous metal complex having a metal and an organic ligand, and having a water adsorption rate of 30% by mass or more at 25°C and a relative pressure of 0.5, unfibrillated fibers, and fibrillated fibers. Here, the pressure at the state where the progress of adsorption seems to stop under a constant pressure (the number of adsorbed molecules = the number of desorbed molecules) is called the adsorption equilibrium pressure, and the relative pressure is defined as the ratio of the adsorption equilibrium pressure to the saturated vapor pressure.

[0013] Since the adsorption sheet of the present invention contains a porous metal complex, high adsorption performance can be obtained. Moreover, since this porous metal complex is characterized in that the water adsorption rate at 25°C and a relative pressure of 0.5 is 30% by mass or more, the sheet itself can retain a large amount of water, and high flexibility during sheet processing can be obtained. Furthermore, since the flexibility can be sufficiently exhibited by the porous metal complex, it is possible to reduce the organic binder that has been conventionally used for imparting flexibility. As a result, the ratio of the side chains of the organic binder adsorbed in the pores of the adsorbent (pore blockage) can be reduced, and sufficient adsorption performance can be obtained. If the water adsorption rate is less than 30% by mass, the flexibility will be lacking.

[0014] Furthermore, the adsorption sheet of the present invention contains unfibrillated fibers and fibrillated fibers. By containing unfibrillated fibers, for example, even when step processing is performed, it is possible to maintain the step shape by itself, and the processability is excellent. In addition, by containing fibrillated fibers, the porous metal complex particles can be efficiently retained, not only having excellent loadability, but also reducing the organic binder that has been conventionally used for imparting loadability. As a result, pore blockage can be reduced, and sufficient adsorption performance can be obtained.

[0015] Furthermore, the adsorption sheet of the present invention may contain an organic binder with a high melting point and a dissolution temperature in water of 65°C to 100°C. By using an organic binder with a high melting point and a dissolution temperature in water of 65°C to 100°C, it is possible to reduce pore blockage and obtain excellent adsorption performance. If the dissolution temperature in water is less than 65°C, the adsorption performance will be insufficient due to pore blockage, and if it is higher than 100°C, the loadability will be lacking due to insufficient adhesion.

[0016] The porous metal complex according to the present invention is a porous material composed of a compound having a metal ion and an organic ligand. There is no particular limitation on the form of the porous metal complex that can be used, and a powdery or granular one can be used. Preferably, it is a porous metal complex with an average particle diameter of 0.1 μm to 200 μm, more preferably 1 to 100 μm, and most preferably 1 to 80 μm. If the average particle diameter is less than 0.1 μm, it will cause a low yield during the formation of the adsorption sheet. Also, if the average particle diameter exceeds 200 μm, it will be difficult to sufficiently support the porous metal complex on the adsorption sheet, and there may be a large amount of dropout of the porous metal complex. The average particle diameter can be measured, for example, using a scanning electron microscope.

[0017] The BET specific surface area of the porous metal complex by the 77K nitrogen adsorption method is not particularly limited, but for example, it is preferably 500 m 2 / g or more. If the BET specific surface area is less than 500 m 2 / g, it may be difficult to obtain sufficient adsorption performance. The BET specific surface area is more preferably 1000 m 2 / g or more. The upper limit of the BET specific surface area is not particularly limited, but it is preferably 6000 m 2 / g or less. This is because if it exceeds this range, the disadvantage that the production of the porous metal complex becomes very difficult will occur. The BET specific surface area can be measured, for example, by the method described in the examples in the following section.

[0018] The metal ions constituting the porous metal complex are not particularly limited, and examples thereof include typical metal elements such as aluminum ions, and transition metal elements such as titanium ions, zirconium ions, iron ions, and copper ions. On the other hand, examples of the compound having a ligand include fumaric acid, 2-aminoterephthalic acid, 1,4-naphthalenedicarboxylic acid, terephthalic acid, and trimesic acid. Specific examples of the porous metal complex include a porous metal complex composed of aluminum ions and terephthalic acid (manufactured by BASF, Basolite A100), a porous metal complex composed of copper ions and trimesic acid (manufactured by BASF, Basolite C300), a porous metal complex composed of iron ions and trimesic acid (manufactured by BASF, Basolite F300), a porous metal complex composed of titanium ions and terephthalic acid, a porous metal complex composed of zirconium ions and terephthalic acid, a porous metal complex composed of zirconium ions and fumaric acid, a porous metal complex composed of zirconium ions and 2-aminoterephthalic acid, a porous metal complex composed of titanium ions and 2-aminoterephthalic acid, and the like. Even for these porous metal complexes, although the BET specific surface area varies depending on the synthesis method and purity, in order to impart flexibility to the adsorption sheet, the water adsorption rate at 25 ° C. and a relative pressure of 0.5 is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more. When it is less than 30% by mass, it is necessary to increase the content of the organic binder in order to impart sufficient flexibility to the adsorption sheet. When the content of the organic binder is large, a large proportion of the side chains of the organic binder adsorbs in the pores of the adsorbent, and as a result, sufficient adsorption performance cannot be exhibited.

[0019] The content of the porous metal complex in the adsorption sheet of the present invention is preferably 60% by mass to 85% by mass, more preferably 65% by weight to 80% by mass. When the content is less than 60% by mass, it may be difficult to obtain sufficient adsorption performance. On the other hand, when the content exceeds 85% by mass, it becomes difficult to sufficiently support the porous metal complex on the adsorption sheet, and the amount of dropout increases. In addition, the sheet strength may be significantly reduced.

[0020] The fiber diameter of the non-fibrillated fiber is preferably 5 μm or more, more preferably 5 μm to 30 μm. Also, the fiber length is preferably 1 mm to 10 mm, more preferably 2 mm to 8 mm. If the fiber diameter of the thick fiber is less than 5 μm and the fiber length is less than 1 mm, the strength of the sheet decreases, it becomes difficult to maintain the stepped shape by itself after the step processing, and it becomes impossible to process it into an adsorption element such as a honeycomb shape in the post-processing. Also, if the fiber diameter of the non-fibrillated fiber exceeds 30 μm and the fiber length exceeds 10 mm, it becomes inflexible and difficult to process. Furthermore, fibers having different fiber diameters may be mixed.

[0021] Examples of the non-fibrillated fiber include inorganic fibers such as glass fiber, ceramic fiber, and rock wool fiber; synthetic fibers such as aramid fiber, meta-aramid fiber, polybenzimidazole fiber, polyether ketone fiber, polyethylene terephthalate fiber, and nylon fiber; semi-synthetic fibers such as acetate fiber and triacetate fiber; rayon fiber; regenerated fibers such as cupra fiber; and plant fibers such as cotton, hemp, and fibers mainly composed of wood. One or more of these can be used.

[0022] Examples of the fibrillated fiber include the fibrillated fibers of the above-described fibers, and pulp. One or more of these can be used. The method of fibrillation is not particularly limited, and a normal beating method can be adopted. As a typical example, a method of fibrillating using a beater or a refiner such as a beating machine can be mentioned. Also, when measuring the Canadian Standard Freeness (CSF) according to JIS P 8121-2, the fibrillated fiber is preferably 50 ml or more and less than 800 ml.

[0023] In the adsorption sheet of the present invention, the total content of non-fibrillated fibers and fibrillated fibers is preferably 5% by mass to 25% by mass, more preferably 10% by weight to 25% by mass. If the content is less than 5% by mass, it becomes difficult to sufficiently support the porous metal complex on the adsorption sheet, the amount of detachment increases, and the strength of the sheet may be significantly reduced. On the other hand, if the content exceeds 25% by mass, it may be difficult to obtain sufficient adsorption performance.

[0024] The adsorption sheet in the present invention contains an organic binder. This is because it improves the flexibility and strength of the adsorption sheet. The organic binder is not particularly limited as long as it can bond the porous metal complex and the fiber. For example, polyvinyl alcohol-based polymers, polyacrylonitrile-based polymers, polyethylene-based polymers, polyester-based polymers, polyphenylene ether-based polymers, etc. can be used. From the viewpoint of handleability, polyvinyl alcohol-based polymers are preferred. The usage mode of the organic binder is not particularly limited, but using a fibrous one is preferred because the adsorption sheet can be easily produced. The content rate of the organic binder in the adsorption sheet is preferably 3% by mass to 15% by mass, more preferably 4% by mass to 12% by mass. If it is less than 3% by mass, the supportability of the porous metal complex and the flexibility of the sheet are insufficient, and if it exceeds 15% by mass, the porous metal complex tends to be covered by the organic binder, making it difficult to obtain sufficient adsorption performance.

[0025] The water dissolution temperature of the organic binder is preferably 65°C to 100°C, more preferably 70°C to 100°C. If the water dissolution temperature is less than 65°C, the proportion of the binder side chain entering the pores of the porous metal complex increases, and as a result, the adsorption performance may be insufficient. Also, if it is higher than 100°C, there is a problem such as lack of supportability due to insufficient adhesion.

[0026] The water dissolution temperature of the organic binder can be measured by a conventional method. For example, 100 ml of pure water is placed in a beaker and stirred, heated in an oil bath until the water temperature reaches 50 °C, 0.5 g of the organic binder is added thereto, the water temperature is raised at a rate of 2 °C / min, and the temperature at which the binder begins to dissolve and becomes translucent is measured visually. There is such a method.

[0027] The adsorption sheet of the present invention exhibits loadability by fibrillated fibers even when the content of the organic binder is small, and exhibits the flexibility of the adsorption sheet due to the high water adsorption rate of the porous metal complex. As a result, it is possible to achieve sufficient adsorption performance because the amount of the organic binder can be reduced and the high adsorption performance of the porous metal complex itself.

[0028] As an index of flexibility, the adsorption sheet of the present invention preferably has a specific tensile elongation of 5%·m / g or more. If it is less than 5%·m / g, the sheet lacks flexibility and cracks may occur during honeycomb processing (step processing).

[0029] The adsorption sheet of the present invention may contain one or more kinds of porous metal complexes, and may further contain a porous material other than the porous metal complex. The porous material contained in the adsorption sheet of the present invention is not particularly limited, and examples thereof include activated carbon, zeolite, silica gel, activated alumina, aluminophosphate, silicoaluminophosphate, and organic polymer porous bodies such as styrene-divinylbenzene copolymer. Preferably, they are activated carbon, zeolite, silica gel, and activated alumina that can be obtained at low cost.

[0030] The thickness of the adsorption sheet of the present invention is preferably 0.1 mm to 0.9 mm, more preferably 0.1 mm to 0.7 mm. If the thickness is less than 0.1 mm, the sheet strength will be significantly reduced, and it may be difficult to process it into an adsorption element such as a honeycomb shape in post-processing. On the other hand, if the thickness is greater than 0.9 mm, the pressure loss of the adsorption element tends to increase when the adsorption sheet is processed into a honeycomb shape or the like.

[0031] The basis weight of the adsorption sheet of the present invention is 25 g / m 2 ~200 g / m 2 is preferable. More preferably, it is 40 g / m 2 ~150 g / m 2 is. If the basis weight is less than 25 g / m 2 , the thickness of the sheet becomes thin, and the sheet strength may be significantly reduced, and it may be difficult to process into an adsorption element such as a honeycomb shape in post-processing. Further, if the basis weight exceeds 200 g / m 2 , the thickness of the sheet becomes too large, and the pressure loss of the adsorption element when processed into a honeycomb shape or the like may increase.

[0032] The method for manufacturing the adsorption sheet of the present invention is not particularly limited, and conventionally known processing methods can be used. Preferably, a wet sheet forming method obtained by dispersing a porous metal complex, a fiber, and an organic binder in water, an organic solvent, or a mixture thereof, followed by forming, dewatering, and drying, can be mentioned.

[0033] Here, the porous metal complex is preferably mixed with the above sheet constituent materials in a state having solvent molecules in its pores and subjected to a sheet forming step. If the porous metal complex does not have solvent molecules in its pores, there is a risk that the organic binder constituting the adsorption sheet will be adsorbed into the pores. In this case, even if the solvent removal treatment described later is carried out after sheet formation, it is difficult to remove the organic binder captured in the pores of the porous metal complex, resulting in inferior adsorption performance of the adsorption sheet. That is, in the present invention, by adsorbing solvent molecules in the pores of the porous metal complex, adsorption of an organic binder or the like into the pores in the sheet forming step is prevented, and after the sheet forming step, the solvent molecules are removed from the pores by the solvent removal treatment described later, thereby ensuring the adsorption performance of the adsorption sheet. Usually, solvent molecules are adsorbed in the pores of the porous metal complex at the stage of synthesizing the porous metal complex. However, if the porous metal complex does not have solvent molecules in its pores or the adsorption amount of the solvent molecules is insufficient, an organic solvent can be adsorbed in the pores by the method described in the examples below. Here, the solvent molecules refer to water and general organic solvent molecules.

[0034] When manufacturing the adsorption sheet of the present invention, after the sheeting step, a solvent removal treatment step for removing the solvent contained in the adsorption sheet is carried out. As described above, it is preferable that the porous metal complex is sheeted in a state where solvent molecules are present in its pores. In this case, it is difficult to obtain sufficient adsorption performance due to the solvent molecules in the pores of the porous metal complex. Therefore, in order to exhibit the adsorption performance, the solvent removal treatment is carried out after the sheeting step. The timing of the solvent removal treatment is not particularly limited as long as it is after the sheeting step.

[0035] The conditions for the solvent removal treatment are not particularly defined, but the temperature is preferably 50°C to 300°C. If it is less than 50°C, there is a risk that the removal of the solvent will be incomplete, and it may be difficult to obtain sufficient adsorption performance. On the other hand, if it exceeds 300°C, there is a risk that the pore structure of the porous metal complex will be damaged, and in this case, it will also be difficult to obtain sufficient adsorption performance. More preferably, it is 80°C to 200°C. Also, the solvent removal treatment can remove the solvent more efficiently by being carried out under reduced pressure. At this time, the pressure is not particularly limited and may be appropriately adjusted according to the physical properties and blending amount of the porous metal complex. For example, 10 3 Pa to 10 -5 Pa is preferable, and 10 -1 Pa to 10 -5 Pa is more preferable. The solvent removal treatment time is not particularly limited either, but for example, it is preferably 1 hour to 100 hours, more preferably 3 hours to 48 hours, and even more preferably 3 hours to 24 hours. Incidentally, the most preferable conditions for the solvent removal treatment are 80°C to 200°C, 3 hours to 24 hours under vacuum conditions.

[0036] The adsorption sheet of the present invention may be used in a flat plate shape, or may be appropriately subjected to pleating, honeycomb processing, corrugating, etc. to obtain a desired shape. Fig. 1 shows a fragmentary sheet obtained by corrugating the adsorption sheet 1 as an example of the processing of the adsorption sheet of the present invention. In particular, pleating, honeycomb processing, and corrugating require a step of bending the sheet during processing. At this time, the flexibility of the sheet is exhibited by sufficiently adsorbing moisture into the porous metal complex before processing. The method of adsorbing moisture into the porous metal complex is not particularly defined, but methods such as using a humidified room or processing while blowing steam are simple and preferable.

[0037] The adsorption element of the present invention is characterized by including the adsorption sheet of the present invention. The type of the adsorption element of the present invention is not particularly limited, and any conventionally known type can be adopted and appropriately selected according to the use and purpose. In addition, although there is no particular limitation on the shape of the adsorption sheet provided in the adsorption element of the present invention, for example, those obtained by processing the adsorption sheet into a flat plate shape, a pleated shape, a honeycomb shape, etc. can be used. For example, the adsorption sheet processed into a pleated shape can increase the contact area with the gas to be treated in the use as an AC / DC type adsorption element, and the adsorption sheet processed into a honeycomb shape can increase the contact area with the gas to be treated in the use as a parallel flow type adsorption element, respectively, to simultaneously improve the removal efficiency of the adsorption target substance and reduce the pressure loss of the adsorption element. The parallel flow type adsorption element is superior to the AC / DC type adsorption element in terms of preventing clogging by mist and dust, reducing pressure loss, and reducing weight. Therefore, the adsorption sheet provided in the adsorption element is preferably in a honeycomb shape.

[0038] Fig. 2 shows a diagram of an adsorption rotor 2 obtained by winding the adsorption sheet of the present invention into a rotor shape as an example of the adsorption element of the present invention. The adsorption sheet provided in the adsorption rotor 2 is in a honeycomb shape.

[0039] The adsorption sheet of the present invention and the adsorption element provided therewith can be widely used indoors, in vehicles, for wallpapers, furniture, interior materials, resin molded bodies, electrical equipment, etc., for the purpose of reducing malodorous components, etc., or for separating and recovering organic solvents in the air discharged from factories, etc., or for humidity control and desiccant purposes.

[0040] In addition, an adsorption / desorption treatment apparatus including the adsorption element of the present invention, an adsorption means for introducing an adsorption target substance into the adsorption element for adsorption, and a desorption means for desorbing the adsorption target substance adsorbed by the adsorption element is also included in the scope of the present invention. As the adsorption means, a pipe or the like for introducing air or gas containing an adsorption target substance such as a malodorous substance such as an organic solvent or moisture can be considered. As a method for desorbing the adsorption target substance, there are a method of heating and a method of reducing the pressure of the system, and as the desorption means, a pipe for introducing heated gas, a heater, a decompressor, etc. can be considered. From the viewpoint of desorption efficiency and economy, a means for introducing heated air is desirable.

[0041] Fig. 3 shows a desiccant air conditioning system 11 as an example of the adsorption / desorption treatment apparatus of the present invention. The desiccant air conditioning system 11 includes an adsorption type rotor 2, a motor 3, a heat source 8 such as a heater, a fan 9, and a dehumidification / humidification region partitioning member 10. In the desiccant air conditioning system 11, when high humidity gas 4 containing moisture as an adsorption target substance is introduced, the moisture is adsorbed by the adsorption type rotor 2 and discharged as dehumidified gas 5. When low humidity gas 6 heated by the heat source 8 is introduced, the moisture adsorbed by the adsorption rotor 2 is desorbed and discharged as humidified gas 7. The adsorption / desorption treatment apparatus of the present invention can be applied to both a desiccant air conditioning system for factories and a desiccant air conditioning system for households.

Example

[0042] Hereinafter, the present invention will be more specifically described by way of examples. It should be noted that the following examples are not of a nature to limit the present invention, and any design changes made in accordance with the gist of the foregoing and following descriptions are all included in the technical scope of the present invention. First, the measurement methods and evaluation methods of the characteristic values obtained in the examples and comparative examples are shown below.

[0043] [Water adsorption rate] Collect about 100 mg of the porous metal complex (before water or organic solvent treatment), vacuum dry it at 120 °C for 12 hours, and then weigh it. Using a high-precision gas / vapor adsorption measurement device (BELSORP-max, manufactured by BEL Japan, Inc.), measure the water vapor adsorption amount at 25 °C at 40 points while gradually increasing the relative pressure in the range of 0.02 to 0.95 to create an adsorption isotherm. At this time, set the target relative pressures to 0.001, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and further set the allowable capacity for increasing and decreasing the adsorption amount to 30 cm 2 / g at a relative pressure of 0 to 0.3, 50 cm 2 / g at a relative pressure of 0.3 to 0.5, and 30 cm 2 / g at a relative pressure of 0.5 and above, and create an adsorption isotherm. Then, calculate the water adsorption rate [%] from the water adsorption amount [g] per 1 g of the porous metal complex at a relative pressure of 0.5 using the following formula (i). Water adsorption rate [%] = water adsorption amount [g] per 1 g of adsorbent × 100 ··· (i)

[0044] [BET specific surface area] Collect about 100 mg of the porous metal complex (before water or organic solvent treatment), vacuum dry it at 120 °C for 12 hours, and then weigh it. Using an automatic specific surface area measurement device (Gemini 2375, manufactured by Micromeritics), measure the nitrogen gas adsorption amount at the boiling point of liquid nitrogen (-195.8 °C) at 40 points while gradually increasing the relative pressure in the range of 0.02 to 0.95 to create an adsorption isotherm. Using the analysis software (GEMINI-PCW version 1.01) attached to the automatic specific surface area measurement device, set the surface area analysis range to 0.01 to 0.15 under BET conditions to obtain the BET specific surface area [m 2 / g].

[0045] [Supportability] A 10 cm × 10 cm test piece cut from the adsorption sheet sample is fixed so that the 10 cm × 10 cm flat surface is perpendicular to the experimental table, and a sphere (material: aluminum) with a diameter of 2.4 cm and a mass of 20 g is made to collide 10 times perpendicularly to the 10 cm × 10 cm flat surface of the test piece. The sphere is rolled at a speed of 10 cm / s. As a result, when the amount of the porous metal complex that has fallen off is less than 0.1 mg, it is marked as ○ (good), when it is more than 10 mg, it is marked as × (bad), and when it is between 0.1 mg and 10 mg, it is marked as △ (acceptable).

[0046] [Flexibility] In the examples and comparative examples, regarding flexibility, it is observed whether the adsorption sheet cracks during honeycomb processing (step processing). A 10 cm × 10 cm test piece cut from the adsorption sheet sample is dried at 120°C for 1 hour, and then left standing in an atmosphere of 22°C and 40% RH for 1 hour. Holding both ends of the thus conditioned test piece, it is bent at 90 degrees. At this time, those without cracks in the sheet are evaluated as ○ (good), those with cracks are evaluated as △ (difficult but possible), and those with cracks are evaluated as × (bad).

[0047] [Specific tensile elongation] A 15 mm × 100 mm test piece cut from the adsorption sheet sample is dried at 120°C for 1 hour, and its weight is measured. Then, the dried sample is left standing in an atmosphere of 22°C and 40% RH for 1 hour, and the maximum point elongation [%] is measured with a tensile / compression testing machine (TENSILON RTG - 1310, manufactured by A&D). The distance between the chucks is 50 mm, and the tensile speed is 15 mm / min. From the obtained data, the specific tensile elongation is calculated by the following formula (ii). Specific tensile elongation [%·m / g] = Maximum point elongation [%] / Sample width [m] / Basis weight of adsorption sheet [g / m 2 ···(ii)

[0048] [Pore retention rate] Collect about 100 mg of the adsorption sheet sample, vacuum dry it at 120 °C for 12 hours, and then weigh it. Using an automatic specific surface area measurement device (Gemini 2375, manufactured by Micromeritics), measure the nitrogen gas adsorption amount at the boiling point of liquid nitrogen (-195.8 °C) at 40 points while gradually increasing the relative pressure in the range of 0.02 to 0.95, and create the adsorption isotherm of the sample. Using the analysis software (GEMINI-PCW version 1.01) attached to the automatic specific surface area measurement device, set the surface area analysis range to 0.01 to 0.15 under BET conditions, and determine the BET specific surface area [m 2 / g]. Then, based on the BET specific surface area [m 2 / g] of the porous metal complex, calculate the pore retention rate using the following formula (iii). Pore retention rate [%] = {BET specific surface area of the adsorption sheet [m 2 / g] × 100 / (porous metal complex content in the adsorption sheet)} / (BET specific surface area of the porous metal complex sample [m 2 / g]) × 100 ··· (iii) The higher the pore retention rate, the more it indicates that the pores of the porous metal complex are not filled (not blocked) by a binder or the like, and the adsorption performance is improved.

[0049] [Sheet performance (water vapor adsorption amount)] Collect about 100 mg of the porous metal complex (before treatment with water or organic solvent), vacuum dry it at 120 °C for 12 hours, and then weigh it. Using a high-precision gas / vapor adsorption amount measurement device (BELSORP-max, manufactured by BEL Japan, Inc.), measure the water vapor adsorption amount at 25 °C at 40 points while gradually increasing the relative pressure in the range of 0.02 to 0.95, and create the adsorption isotherm. Then, determine the water vapor adsorption amount [ml] per 1 g of the porous metal complex at a relative pressure of 0.95. As an evaluation of the sheet performance, evaluate that a water vapor adsorption amount of 410 ml / g or more is ○ (good), greater than 400 ml / g and less than 410 ml / g is △ (fair), and 400 ml / g or less is × (poor).

[0050] [Workability] In the examples and comparative examples, as workability, observe whether the stepped shape can be maintained by itself after the stepped processing. The suction sheet sample is made to be 30 cm in width and 30 cm in length, and passed through a corrugating machine that can theoretically produce corrugated paper with a width of 30 cm and a length of 21.4 cm. Then, after leaving the corrugated suction sheet standing in an atmosphere of 22°C and 40% RH for 24 hours, the recovery rate of the length is evaluated as ○ (good) if it is less than 20%, △ (acceptable) if it is from 20% to less than 50%, and × (poor) if it is from 50% to 100%.

[0051] [Water dissolution temperature] Regarding the organic binders used in the examples and comparative examples, when the water dissolution temperature was actually measured by the following measurement method, it was the same as the catalog value except for the organic binder of Example 8. The catalog value of the organic binder of Example 8 is <99°C, but the actual measured value was 95°C. 4 mL of pure water and 0.02 g of the organic binder were placed in a 6 ml glass bottle. The glass bottle was placed in a water bath heated in 5°C increments from 50°C for 10 minutes. The organic binder in the bottle was stirred with a spatula every 2 minutes. The temperature at which the binder first started to dissolve and became translucent was measured visually.

[0052] <Example 1> Fe(NO 3 ) 3 ·9H 2 O 16.2 g (40 mmol) and trimesic acid 7.5 g (36 mmol) were dissolved in 32 ml of water and heated at 95°C for 15 hours to synthesize a porous metal complex. As a result of performing physical property evaluation on the obtained porous metal complex by nitrogen adsorption measurement and water vapor adsorption measurement, the BET specific surface area was 1575 m 2 / g, and the moisture adsorption rate was 53%. Thereafter, after immersing the synthesized porous metal complex in water for 24 hours, it was filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. This porous metal complex sample was 80 mass% (excluding solvent molecules), 8 mass% of aramid fiber as non-fibrillated fiber, 5 mass% of aramid fiber as fibrillated fiber, and 7 mass% of polyvinyl alcohol (PVA) fiber with a water dissolution temperature of 70°C (catalog value) as an organic binder, and the basis weight was 100 g / m 2Using a wet papermaking apparatus (manufactured by Toyobo Engineering Co., Ltd., the same applies hereinafter), an adsorption sheet was produced with a mass as specified. Further, a solvent removal treatment was performed at 130°C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained samples, the supportability, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0053] <Example 2> 80% by mass (excluding solvent molecules) of the porous metal complex sample obtained in the same manner as in Example 1, 10% by mass of aramid fiber as non-fibrillated fiber, 3% by mass of aramid fiber as fibrillated fiber, and 7% by mass of polyvinyl alcohol (PVA) fiber with a dissolution temperature in water of 70°C (catalog value) as an organic binder were mixed at a ratio of basis weight 100 g / m 2 Using a wet papermaking apparatus, an adsorption sheet was produced with a mass as specified. Further, a solvent removal treatment was performed at 130°C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained samples, the supportability, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0054] <Example 3> 80% by mass (excluding solvent molecules) of the porous metal complex sample obtained in the same manner as in Example 1, 8% by mass of aramid fiber as non-fibrillated fiber, 7% by mass of aramid fiber as fibrillated fiber, and 5% by mass of polyvinyl alcohol (PVA) fiber with a dissolution temperature in water of 70°C (catalog value) as an organic binder were mixed at a ratio of basis weight 100 g / m 2 Using a wet papermaking apparatus, an adsorption sheet was produced with a mass as specified. Further, a solvent removal treatment was performed at 130°C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained samples, the supportability, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0055] <Example 4> A porous metal complex sample obtained in the same manner as in Example 1 was 80% by mass (excluding solvent molecules), aramid fiber as unfibrillated fiber was 8% by mass, aramid fiber as fibrillated fiber was 9% by mass, and polyvinyl alcohol (PVA) fiber with a water dissolution temperature of 70 °C (catalog value) as an organic binder was 3% by mass, and they were mixed at a ratio to obtain a basis weight of 100 g / m 2 An adsorption sheet was prepared using a wet papermaking apparatus at a mass that would result in this. Further, a solvent removal treatment was performed at 130 °C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained sample, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0056] <Example 5> A porous metal complex sample obtained in the same manner as in Example 1 was 75% by mass (excluding solvent molecules), aramid fiber as unfibrillated fiber was 10% by mass, aramid fiber as fibrillated fiber was 6.3% by mass, and polyvinyl alcohol (PVA) fiber with a water dissolution temperature of 70 °C (catalog value) as an organic binder was 8.7% by mass, and they were mixed at a ratio to obtain a basis weight of 100 g / m 2 An adsorption sheet was prepared using a wet papermaking apparatus at a mass that would result in this. Further, a solvent removal treatment was performed at 130 °C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained sample, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0057] <Example 6> A porous metal complex sample obtained in the same manner as in Example 1 was 70% by mass (excluding solvent molecules), aramid fiber as unfibrillated fiber was 12% by mass, aramid fiber as fibrillated fiber was 7.5% by mass, and polyvinyl alcohol (PVA) fiber with a water dissolution temperature of 70 °C (catalog value) as an organic binder was 10.5% by mass, and they were mixed at a ratio to obtain a basis weight of 100 g / m 2 An adsorption sheet was prepared using a wet papermaking apparatus at a mass that would result in this. Further, a solvent removal treatment was performed at 130 °C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained sample, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0058] <Example 7> A porous metal complex sample obtained in the same manner as in Example 1 was 65% by mass (excluding solvent molecules), 14% by mass of aramid fiber as non-fibrillated fiber, 8.8% by mass of aramid fiber as fibrillated fiber, and 12.2% by mass of polyvinyl alcohol (PVA) fiber with a dissolution temperature in water of 70 °C (catalog value) as an organic binder. They were mixed at a ratio such that the basis weight was 100 g / m 2 An adsorption sheet was produced using a wet papermaking apparatus at a mass that would result in this. Further, a solvent removal treatment was performed at 130 °C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained sample, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0059] <Example 8> A porous metal complex sample obtained in the same manner as in Example 1 was 65% by mass (excluding solvent molecules), 14% by mass of aramid fiber as non-fibrillated fiber, 8.8% by mass of aramid fiber as fibrillated fiber, and 12.2% by mass of polyvinyl alcohol (PVA) fiber with a dissolution temperature in water of <99 °C (catalog value indicating that it starts to dissolve before the boiling point of water) as an organic binder. They were mixed at a ratio such that the basis weight was 100 g / m 2 An adsorption sheet was produced using a wet papermaking apparatus at a mass that would result in this. Further, a solvent removal treatment was performed at 130 °C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained sample, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0060] <Example 9> A porous metal complex sample obtained in the same manner as in Example 1 was 80% by mass (excluding solvent molecules), 8% by mass of rayon fiber as non-fibrillated fiber, 5% by mass of rayon fiber as fibrillated fiber, and 7% by mass of polyvinyl alcohol (PVA) fiber with a dissolution temperature in water of 70 °C (catalog value) as an organic binder. They were mixed at a ratio such that the basis weight was 100 g / m 2An adsorption sheet was produced using a wet papermaking apparatus with a specified mass. Further, a desolvation treatment was performed at 130 °C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained samples, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0061] <Example 10> 80% by mass (excluding solvent molecules) of the porous metal complex sample obtained in the same manner as in Example 1, 8% by mass of PET fibers as unfibrillated fibers, 5% by mass of aramid fibers as fibrillated fibers, and 7% by mass of polyvinyl alcohol (PVA) fibers with a dissolution temperature in water of 70 °C (catalog value) as an organic binder were mixed at a basis weight of 100 g / m 2 An adsorption sheet was produced using a wet papermaking apparatus with a specified mass. Further, a desolvation treatment was performed at 130 °C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained samples, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0062] <Example 11> Basolite C300 (manufactured by BASF) was used as the porous metal complex. As a result of physical property evaluation by nitrogen adsorption measurement and water vapor adsorption measurement, the BET specific surface area was 1609 m 2 / g, and the moisture adsorption rate was 43%. Thereafter, the above porous metal complex was immersed in N,N-dimethylformaldehyde for 24 hours, followed by filtration to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. 80% by mass (excluding solvent molecules) of this porous metal complex sample, 8% by mass of aramid fibers as unfibrillated fibers, 5% by mass of aramid fibers as fibrillated fibers, and 7% by mass of polyvinyl alcohol (PVA) fibers with a dissolution temperature in water of 70 °C (catalog value) as an organic binder were mixed at a basis weight of 100 g / m 2 An adsorption sheet was produced using a wet papermaking apparatus with a specified mass. Further, a desolvation treatment was performed at 130 °C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained samples, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0063] <Example 12> 3 ml (10 mmol) of tetraisopropyl orthotitanate and 2.5 g (15 mmol) of terephthalic acid were dissolved in 45 ml of N,N-dimethylformaldehyde and 5 ml of methanol, and heated at 150 °C for 15 hours to synthesize a porous metal complex. For the obtained porous metal complex, physical property evaluation was carried out by nitrogen adsorption measurement and water vapor adsorption measurement. As a result, the BET specific surface area was 1199 m 2 / g, and the water adsorption rate was 38%. Thereafter, the synthesized porous metal complex was immersed in N,N-dimethylformaldehyde for 24 hours, and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. This porous metal complex sample was 80% by mass (excluding solvent molecules), 8% by mass of aramid fiber as unfibrillated fiber, 5% by mass of aramid fiber as fibrillated fiber, and 7% by mass of polyvinyl alcohol (PVA) fiber with a water dissolution temperature of 70 °C (catalog value) as an organic binder. Mixed at a ratio of, a wet laid paper machine was used to produce an adsorption sheet with a basis weight of 100 g / m 2 and the adsorption sheet sample was obtained by performing a solvent removal treatment at 130 °C under vacuum conditions for 24 hours. For the obtained sample, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0064] <Example 13> 5.3 g (22.7 mmol) of zirconium chloride and 3.78 g (22.8 mmol) of terephthalic acid were dissolved in 500 ml of N,N-dimethylformaldehyde and heated at 120 °C for 24 hours to synthesize a porous metal complex. For the obtained porous metal complex, physical property evaluation was carried out by nitrogen adsorption measurement and water vapor adsorption measurement. As a result, the BET specific surface area was 1283 m 2 / g, and the water adsorption rate was 42%. After that, the synthesized porous metal complex was immersed in water for 24 hours, and then filtered to obtain a porous metal complex sample with solvent molecules adsorbed in the pores. This porous metal complex sample was composed of 80% by mass (excluding solvent molecules), 8% by mass of non-fibrillated aramid fibers, 5% by mass of fibrillated aramid fibers, and 7% by mass of polyvinyl alcohol (PVA) fibers with a water dissolution temperature of 70 °C (catalog value) as an organic binder, and mixed at a basis weight of 100 g / m 2 An adsorption sheet was prepared using a wet papermaking apparatus at a mass that would result in this basis weight. Further, a solvent removal treatment was performed at 130 °C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained sample, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0065] <Example 14> A porous metal complex sample obtained in the same manner as in Example 14 was composed of 80% by mass (excluding solvent molecules), 9.2% by mass of non-fibrillated aramid fibers, 5.8% by mass of fibrillated aramid fibers, and 5% by mass of polyvinyl alcohol (PVA) fibers with a water dissolution temperature of 70 °C (catalog value) as an organic binder, and mixed at a basis weight of 100 g / m 2 An adsorption sheet was prepared using a wet papermaking apparatus at a mass that would result in this basis weight. Further, a solvent removal treatment was performed at 130 °C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained sample, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0066] <Example 15> ZrOCl 2 ·8H 2 O 200 g (0.62 mol) and 72 g (0.62 mol) of fumaric acid were dissolved in 2 L of N,N-dimethylformamide and 700 mL of formic acid, and heated at 130 °C for 6 hours to synthesize a porous metal complex. As a result of physical property evaluation of the obtained porous metal complex by nitrogen adsorption measurement and water vapor adsorption measurement, the BET specific surface area was 884 m 2 / g, and the moisture adsorption rate was 33%. Thereafter, the synthesized porous metal complex was immersed in water for 24 hours, followed by filtration to obtain a porous metal complex sample with solvent molecules adsorbed in the pores. This porous metal complex sample was mixed at a ratio of 80% by mass (excluding solvent molecules), 8% by mass of aramid fiber as non-fibrillated fiber, 5% by mass of aramid fiber as fibrillated fiber, and 7% by mass of polyvinyl alcohol (PVA) fiber with a water dissolution temperature of 70 °C (catalog value) as an organic binder, and an adsorption sheet was prepared using a wet papermaking apparatus at a basis weight of 100 g / m 2 to obtain the mass. Further, a desolvation treatment was performed at 130 °C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained sample, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0067] <Example 16> 12.87 g (55.2 mmol) of zirconium chloride and 9.45 g (52.5 mmol) of 2-aminoterephthalic acid were dissolved in 600 mL of N,N-dimethylformamide and heated at 120 °C for 24 hours to synthesize a porous metal complex. As a result of physical property evaluation of the obtained porous metal complex by nitrogen adsorption measurement and water vapor adsorption measurement, the BET specific surface area was 949 m 2 / g and the moisture adsorption rate was 32%. Thereafter, the synthesized porous metal complex was immersed in water for 24 hours, followed by filtration to obtain a porous metal complex sample with solvent molecules adsorbed in the pores. This porous metal complex sample was mixed at a ratio of 80% by mass (excluding solvent molecules), 8% by mass of aramid fiber as non-fibrillated fiber, 5% by mass of aramid fiber as fibrillated fiber, and 7% by mass of polyvinyl alcohol (PVA) fiber with a water dissolution temperature of 70 °C (catalog value) as an organic binder, and an adsorption sheet was prepared using a wet papermaking apparatus at a basis weight of 100 g / m 2 to obtain the mass. Further, a desolvation treatment was performed at 130 °C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained sample, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0068] <Example 17> 3.6 mL (12.3 mmol) of tetraisopropyl orthotitanate and 3.6 g (19.9 mmol) of 2-aminoterephthalic acid were dissolved in 48 mL of N,N-dimethylformamide and 12 mL of methanol, and heated at 150 °C for 18 hours to synthesize a porous metal complex. For the obtained porous metal complex, physical property evaluation was performed by nitrogen adsorption measurement and water vapor adsorption measurement. As a result, the BET specific surface area was 1248 m 2 / g, and the water adsorption rate was 43%. Thereafter, the synthesized porous metal complex was immersed in water for 24 hours, and then filtered to obtain a porous metal complex sample in which solvent molecules were adsorbed in the pores. This porous metal complex sample was 80% by mass (excluding solvent molecules), 8% by mass of aramid fiber as non-fibrillated fiber, 5% by mass of aramid fiber as fibrillated fiber, and 7% by mass of polyvinyl alcohol (PVA) fiber with a water dissolution temperature of 70 °C (catalog value) as an organic binder. A adsorption sheet was prepared using a wet papermaking apparatus with a basis weight of 100 g / m 2 and the mass to obtain. Further, a desolvation treatment was performed at 130 °C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained sample, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0069] <Comparative Example 1> 15 g (40 mmol) of aluminum nitrate and 4.32 g (20 mmol) of 1,4-naphthalenedicarboxylic acid were dissolved in 400 mL of water, and heated at 180 °C for 24 hours to synthesize a porous metal complex. For the obtained porous metal complex, physical property evaluation was performed by nitrogen adsorption measurement and water vapor adsorption measurement. As a result, the BET specific surface area was 639 m 2 / g, and the water adsorption rate was 17%. Thereafter, the synthesized porous metal complex was immersed in water for 24 hours and then filtered to obtain a porous metal complex sample with solvent molecules adsorbed in the pores. This porous metal complex sample was mixed at a ratio of 80% by mass (excluding solvent molecules), 8% by mass of aramid fiber as fibrillated fiber, 5% by mass of aramid fiber as fibrillated fiber, and 7% by mass of polyvinyl alcohol (PVA) fiber with a water dissolution temperature of 70 °C (catalog value) as an organic binder, and a wet laid sheet was produced using a wet laying apparatus at a basis weight of 100 g / m 2 to obtain a mass. Further, a solvent removal treatment was performed at 130 °C under vacuum conditions for 24 hours to obtain an adsorbed sheet sample. For the obtained sample, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0070] <Comparative Example 2> A porous metal complex sample obtained in the same manner as in Example 1 was mixed at a ratio of 80% by mass (excluding solvent molecules), 8% by mass of aramid fiber as non-fibrillated fiber, 5% by mass of aramid fiber as fibrillated fiber, and 7% by mass of polyvinyl alcohol (PVA) fiber with a water dissolution temperature of 60 °C (catalog value) as an organic binder, and a wet laid sheet was produced using a wet laying apparatus at a basis weight of 100 g / m 2 to obtain a mass. Further, a solvent removal treatment was performed at 130 °C under vacuum conditions for 24 hours to obtain an adsorbed sheet sample. For the obtained sample, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0071] <Comparative Example 3> A porous metal complex sample obtained in the same manner as in Example 1 was mixed at a ratio of 65% by mass (excluding solvent molecules), 14% by mass of aramid fiber as non-fibrillated fiber, 8.8% by mass of aramid fiber as fibrillated fiber, and 12.2% by mass of polyvinyl alcohol (PVA) fiber with a water dissolution temperature of >100 °C (catalog value indicating that it does not dissolve after boiling water) as an organic binder, and a wet laid sheet was produced using a wet laying apparatus at a basis weight of 100 g / m 2Using a wet papermaking apparatus, an adsorption sheet was produced with a mass such that, further, a solvent removal treatment was carried out at 130 °C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained sample, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0072] <Comparative Example 4> A porous metal complex sample obtained in the same manner as in Example 1 was 80% by mass (excluding solvent molecules), 13% by mass of aramid fiber as fibrillated fiber, and 7% by mass of polyvinyl alcohol (PVA) fiber having a dissolution temperature in water of 70 °C as an organic binder, and mixed at a ratio such that the basis weight was 100 g / m 2 Using a wet papermaking apparatus, an adsorption sheet was produced with a mass such that. In this comparative example, non-fibrillated fibers were not used. The produced adsorption sheet was further subjected to a solvent removal treatment at 130 °C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained sample, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0073] <Comparative Example 5> A porous metal complex sample obtained in the same manner as in Example 1 was 80% by mass (excluding solvent molecules), 13% by mass of aramid fiber as non-fibrillated fiber, and 7% by mass of polyvinyl alcohol (PVA) fiber having a dissolution temperature in water of 70 °C (catalog value) as an organic binder, and mixed at a ratio such that the basis weight was 100 g / m 2 Using a wet papermaking apparatus, an adsorption sheet was produced with a mass such that. In this comparative example, fibrillated fibers were not used. The produced adsorption sheet was further subjected to a solvent removal treatment at 130 °C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained sample, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0074] <Comparative Example 6> A-type silica gel (manufactured by Toyota Chemical Industry Co., Ltd.) was used as the adsorbent. As a result of physical property evaluation by nitrogen adsorption measurement and water vapor adsorption measurement, the BET specific surface area was 820 m 2 / g, and the moisture adsorption rate was 25%. Thereafter, after immersing the adsorbent in water for 24 hours, it was filtered to obtain an adsorbent sample in which solvent molecules were adsorbed in the pores. This adsorbent sample was composed of 80% by mass (excluding solvent molecules), 8% by mass of non-fibrillated aramid fibers, 5% by mass of fibrillated aramid fibers, and 7% by mass of polyvinyl alcohol (PVA) fibers with a water-soluble temperature of 70 °C (catalog value) as an organic binder, and was mixed at a ratio to obtain a basis weight of 100 g / m 2 and an adsorption sheet was produced using a wet papermaking apparatus at a mass that would result in this. Further, a solvent removal treatment was performed at 130 °C under vacuum conditions for 24 hours to obtain an adsorption sheet sample. For the obtained sample, the loading property, flexibility, pore retention rate, water vapor adsorption performance, and processability were measured.

[0075] The measurement results for the adsorption sheet samples obtained in Examples 1 to 17 and Comparative Examples 1 to 6 are shown in Tables 1 to 5.

[0076]

Table 1

[0077]

Table 2

[0078]

Table 3

[0079]

Table 4

[0080]

Table 5

[0081] From Tables 1 to 5, it can be seen that the adsorption sheets of Examples 1 to 17 are excellent in the loadability of the porous metal complex and the flexibility and processability of the sheet, and have sufficient adsorption performance.

Industrial Applicability

[0082] According to the adsorption sheet, adsorption element, and adsorption / desorption treatment apparatus of the present invention, it becomes possible to efficiently separate and recover or adsorb and remove adsorption target substances such as moisture, organic solvents, and malodorous components. Therefore, it can be expected to greatly contribute to the industrial world.

Explanation of Symbols

[0083] 1: Adsorption sheet, 2: Adsorption rotor, 3: Motor, 4: High-humidity gas, 5: Gas after dehumidification, 6: Low-humidity gas, 7: Gas after humidification, 8: Heat source, 9: Fan 10: Dehumidification / humidification region partitioning member, 11: Desiccant air conditioning system

Claims

1. A porous metal complex having a metal and an organic ligand, and having a water adsorption rate of 30% by mass or more at 25°C and a relative pressure of 0.5, non-fibrillated fibers and fibrillated fibers, wherein the non-fibrillated fibers include fibers having a fiber diameter of 5 μm or more and 30 μm or less, wherein the non-fibrillated fibers include fibers having a fiber length of 1 mm or more and 10 mm or less, wherein the fibrillated fibers are selected from one or more of fibrillated aramid fibers, meta-aramid fibers, polybenzimidazole fibers, polyether ketone fibers, polyethylene terephthalate fibers, and nylon fibers, and an adsorption sheet for a desiccant air conditioning system.

2. The adsorption sheet according to claim 1, comprising an organic binder having a dissolution temperature in water of 65°C to 100°C.

3. The adsorption sheet according to claim 1 or 2, having a specific tensile elongation of 5% m / g or more.

4. The adsorption sheet according to any one of claims 1 to 3, containing 60 to 85% by mass of the porous metal complex.

5. An adsorption element comprising the adsorption sheet according to any one of claims 1 to 4.

6. The adsorption element according to claim 5, adsorption means for introducing and adsorbing an adsorption target substance to the adsorption element, desorption means for desorbing the adsorption target substance adsorbed by the adsorption element, and continuously performing adsorption and desorption of the adsorption target substance, and an adsorption / desorption treatment apparatus.

Images