Aqueous radio wave absorption material, and adhesive

Abstract

Provided is an aqueous radio wave absorption material that comprises a deliquescent salt at a ratio of at least 20 wt% in a total of 100 wt% of water plus deliquescent salt. Deliquescence of this deliquescent salt results in ion dissociation.

Description

Water-based electromagnetic wave absorbing materials and adhesive materials

[0001] This relates to water-based radio wave absorbing materials and adhesive materials.

[0002] It is known that water blocks radio waves, making underwater radio communication impossible, and attempts have been made to use water as a radio wave control material (see, for example, Patent Documents 1 and 2).

[0003] However, water freezes at temperatures below 0°C, which can change the physical properties of the material and cause volume expansion due to freezing, potentially damaging the material itself or surrounding components. In response to this, for example, Patent Document 2 adds alcohols to prevent freezing, but the addition of alcohols poses a flammability problem. Furthermore, the technology of Patent Document 2 inevitably causes continuous changes in performance because alcohols and water dissipate into the atmosphere, resulting in a problem of reduced radio wave absorption performance, particularly as the water content decreases.

[0004] JP 2018-189250 A JP 2009-259905 A

[0005] The present invention aims to provide a water-based electromagnetic wave absorbing material that has a low freezing temperature, low flammability, and excellent electromagnetic wave absorbing performance. Another object of the present invention is to provide a pressure-sensitive adhesive material that can achieve excellent adhesiveness, has low flammability, and is easily releasable after use.

[0006] The present inventors have conducted research to achieve the above object and have found that by using a deliquescent salt, it is possible to lower the freezing temperature, further reduce flammability, and achieve excellent radio wave absorption performance, which has led to the completion of the present invention.

[0007] That is, according to the present invention, the following water-based electromagnetic wave absorbing materials, adhesive materials, and composite materials are provided. [1] A water-based electromagnetic wave absorbing material containing a deliquescent salt in a proportion of 20% by weight or more relative to a total of 100% by weight of water and the deliquescent salt, and the deliquescent salt is deliquescent and dissociates into ions. [2] The water-based electromagnetic wave absorbing material according to [1], in which the content of an organic compound having a flash point is less than 10 parts by weight relative to a total of 100 parts by weight of the water and the deliquescent salt. [3] The water-based electromagnetic wave absorbing material in which the deliquescent salt contains, as a main component, CaCl ２ , LiCl, LiBr, MgCl ２ , ZnCl ２ , Li(FSO ２ ) ２ N, Li(CF ３ SO ２ ) ２ N, Na(FSO ２ ) ２The water-based electromagnetic wave absorbing material according to [1] or [2] contains at least one selected from N and organic ammonium halides. [4] The water-based electromagnetic wave absorbing material according to any one of [1] to [3], in which the deliquescent salt is composited with a matrix material. [5] The water-based electromagnetic wave absorbing material according to [4], in which the deliquescent salt is dispersed in the matrix material. [6] The water-based electromagnetic wave absorbing material according to [4] or [5], in which the matrix material is a polymer material. [7] The water-based electromagnetic wave absorbing material according to any one of [4] to [6], in which the content ratio of the matrix material is 8 parts by weight or more per 100 parts by weight of the total of the water and the deliquescent salt. [8] The water-based electromagnetic wave absorbing material according to any one of [4] to [7], further containing a polymerizable monomer and / or a crosslinkable monomer. [9] The water-based electromagnetic wave absorbing material according to any one of [4] to [8], in which the matrix material is crosslinked.

[10] The water-based electromagnetic wave absorbing material according to any one of [1] to [9], having a viscosity of 50,000 cp or more at 25°C.

[11] The water-based electromagnetic wave absorbing material according to any one of claims [1] to

[10] , further comprising an outer casing.

[12] The water-based electromagnetic wave absorbing material according to

[11] , wherein the outer casing is a rubber material or a chlorine-containing polymer.

[13] The water-based electromagnetic wave absorbing material according to

[11] or

[12] , wherein the water content of the outer casing is 5% by weight or less.

[14] An adhesive material comprising a deliquescent salt composited with a polymer material, wherein the content of the deliquescent salt in the adhesive material is 20% by weight or more relative to a total of 100% by weight of water and the deliquescent salt, and the deliquescent salt has deliquesced and undergone ionic dissociation.

[15] A composite material formed by bonding together two or more materials via the adhesive material according to

[14] .

[16] A composite material formed by bonding together two or more materials via the adhesive material according to

[14] or

[15] .

[17] An electrochemical device bonded via the adhesive material according to any one of

[14] to

[16] .

[0008] According to the present invention, it is possible to provide a water-based electromagnetic wave absorbing material that has a low freezing temperature, low flammability, and excellent electromagnetic wave absorbing performance. Also, according to the present invention, it is possible to provide an adhesive material that can achieve excellent adhesiveness, has low flammability, and is easily peelable after use, and a composite material that uses such an adhesive material.

[0009] FIG. 1 is a graph showing the transmittance of the crosslinked sheet of Example 4-4 in the range of 115 to 1500 THz.

[0010] The water-based radio wave absorbing material of the present invention contains a deliquescent salt in a proportion of 20% by weight or more out of a total of 100% by weight of water and the deliquescent salt, and the deliquescent salt is deliquescent and dissociates into ions. The water-based radio wave absorbing material of the present invention contains a deliquescent salt in a proportion of 20% by weight or more out of a total of 100% by weight of water and the deliquescent salt. Since the deliquescent salt exhibits deliquescent properties with respect to water, by incorporating water, the water-based radio wave absorbing material can exhibit the excellent radio wave absorbing performance inherent to water. Furthermore, the action of the deliquescent salt in the water-based radio wave absorbing material of the present invention can lower the freezing temperature and further reduce flammability. In addition, because the water-based radio wave absorbing material of the present invention contains a deliquescent salt, it can obtain moisture from the atmosphere and recover its performance even if the moisture content decreases for some reason. The water-based radio wave absorbing material of the present invention has excellent reflection, absorption, and shielding properties, particularly for radio waves in the GHz to THz bands.

[0011] In recent years, with the advent of the 5G and 6G era, there has been a demand for materials that can control radio waves. Materials known to absorb and block radio waves include conductive carbon materials and magnetic ceramic materials, while metals are known to reflect and block radio waves. However, these materials are all opaque, hard, and / or rigid, and also heavy. Therefore, although it is possible to improve their properties by forming them into extremely thin layers, fibers, or fine particles such as powder, there are limitations to the degree of improvement and the shapes that can be realized. Therefore, flexible, transparent, and lightweight materials are needed to control radio waves.

[0012] On the other hand, although attempts have been made to use water as a radio wave control material, there is a problem that water freezes at low temperatures below 0° C. In the above-mentioned Patent Document 2, alcohols are added to prevent freezing, but the addition of alcohols creates a flammability problem. Furthermore, in the technology of Patent Document 2, since alcohols and water dissipate into the atmosphere, continuous changes in performance are unavoidable, and there is a problem that radio wave absorption performance deteriorates particularly when the water content decreases.

[0013] In response to this, the present inventors have conducted extensive research and found that by using a deliquescent salt and setting its content at 20% by weight or more relative to a total of 100% by weight of water and the deliquescent salt, it is possible to realize the excellent radio wave absorbing performance of water while solving the problem of flammability that occurs when organic compounds having a flash point, such as alcohols, are used, and the freezing temperature can be lowered. In particular, the present inventors have found that using a salt compound that does not exhibit deliquescent properties instead of alcohols causes the problem of water dissipating into the atmosphere, resulting in a decrease in radio wave absorbing performance, and that even if a deliquescent salt is used, if the amount used is small, the effect of lowering the freezing temperature is insufficient. In response to this, the present invention has found that these problems can be solved by using a deliquescent salt and setting its content at 20% by weight or more relative to a total of 100% by weight of water and the deliquescent salt. Furthermore, since the water-based radio wave absorbing material of the present invention contains a deliquescent salt, it releases a certain amount of moisture when the humidity level drops, but absorbs moisture when the humidity level rises. This makes it possible to effectively prevent the occurrence of problems such as insufficient moisture content and an inability to exhibit radio wave absorbing performance.

[0014] Furthermore, in order to improve radio wave shielding performance, a structure called a λ / 4 type may be used. In a λ / 4 type structure, radio wave shielding performance is achieved by the phase difference between incident radio waves and reflected radio waves. For example, JP 2022-165989 A is an example of a polymer material having radio wave shielding properties that utilizes a λ / 4 type structure. According to the technology of JP 2022-165989 A, since it is a technology that utilizes a polymer material, it is thought that it can be lightweight and achieve excellent flexibility. However, when a λ / 4 type structure such as the technology of JP 2022-165989 A is adopted, in order to achieve high radio wave shielding performance, it is necessary to make it into a sheet shape, and there are restrictions on its shape. Furthermore, when a λ / 4 type structure is adopted, absorption is achieved by shifting the phase of the reflected wave by half a wavelength relative to the incident wave and canceling them out, which exhibits frequency specificity, and therefore while it exhibits high absorption performance for the target frequency, it is unable to absorb other frequencies.Furthermore, it is basically designed for radio waves incident from a vertical direction, and its absorption performance deteriorates for radio waves incident from an oblique direction.In other words, an aqueous radio wave absorbing material using a λ / 4 type structure cannot achieve radio wave shielding properties over a wide frequency range or shielding properties for radio waves from a wide angle.In addition, with an aqueous radio wave absorbing material using a λ / 4 type structure, the wavelengths that can be absorbed change depending on the thickness, and therefore the absorption performance varies depending on the thickness during production, which presents a problem that it is difficult to obtain an aqueous radio wave absorbing material that exhibits good shielding properties for desired wavelengths. In particular, when using a λ / 4 type structure to achieve absorption characteristics for frequency bands of gigahertz or higher, the thickness of the water-based radio wave absorbing material needs to be about several hundred μm, so this problem becomes more pronounced, and furthermore, if the material is scratched or soiled with dust during use, the thickness may change and the absorption performance may decrease. In addition, a conductive layer is required to achieve a λ / 4 type structure, and since a metal foil or the like is used to form the conductive layer, transparency cannot be guaranteed in most cases.

[0015] In contrast, according to the present invention, by using a deliquescent salt, the water incorporated in the deliquescent salt itself exhibits excellent radio wave absorption and blocking properties, resulting in a material with excellent transparency and light weight. Moreover, since the λ / 4 structure is not used, reduction in radio wave absorption performance due to thickness fluctuations can be suppressed. Furthermore, the water-based radio wave absorbing material of the present invention can control radio waves by absorbing or reflecting them, and can be used, for example, to reflect and change the direction of radio waves, to block unwanted radio waves, and to suppress electromagnetic noise. Specifically, the water-based radio wave absorbing material of the present invention does not use radio wave interference, but rather the material itself absorbs radio waves, so that even when radio waves are incident at an oblique angle, the attenuation does not decrease but rather increases.

[0016] In the present invention, radio waves are a concept that includes electromagnetic waves. ３ Hz to 10 １６ In the present invention, the water-based radio wave absorbing material absorbs or attenuates radio waves or electromagnetic waves by absorbing them (by transmitting or attenuating them through absorption), by reflecting them, or by a combination of these modes.

[0017] The aqueous radio wave absorbing material of the present invention can preferably reflect and / or absorb radio waves with a frequency of 1 GHz to 300 THz, more preferably 5.6 GHz to 250 THz, and even more preferably 10 GHz to 200 THz. 300 THz is in the infrared region, and the radio wave absorbing material of the present invention is also excellent in reflecting and absorbing heat rays.

[0018] In the water-based radio wave absorbing material of the present invention, the content of the deliquescent salt is 20% by weight or more, preferably 25% by weight or more, more preferably 30% by weight or more, and even more preferably 35% by weight or more, based on 100% by weight of the total of water and deliquescent salt, and the upper limit is preferably 90% by weight or less, more preferably 85% by weight or less, even more preferably 80% by weight or less, still more preferably 75% by weight or less, still more preferably 70% by weight or less, and particularly preferably 65% ​​by weight or less. If the content of the deliquescent salt is too low, the freezing temperature cannot be made low, making it difficult to use under low temperature conditions.

[0019] In the present invention, the deliquescence phenomenon refers to a phenomenon in which a substance absorbs moisture from the air and spontaneously becomes an aqueous solution, and in the present invention, the deliquescent salt refers to a salt compound having such a property. Specifically, the deliquescent salt refers to a salt compound that absorbs moisture from the air, undergoes ionic dissociation, and becomes an aqueous solution. In the present invention, the deliquescent salt may be a salt compound that exhibits deliquescence at 80% RH, but is preferably a salt compound that exhibits deliquescence at 25°C and 80% RH, and more preferably a salt compound that exhibits deliquescence at 25°C and 50% RH.

[0020] In the present invention, whether or not a deliquescence phenomenon occurs can be determined by whether or not a salt compound that does not contain water absorbs moisture from the air, increases in weight, and exhibits fluidity when exposed to the conditions of use. If the occurrence of fluidity is difficult to determine, it can also be determined by whether or not ionic dissociation has occurred, which can be determined by whether or not ionic conductivity can be confirmed by AC impedance measurement. Such determination can be made under the conditions of use of the deliquescent salt, and it is convenient to perform the determination under conditions of, for example, 25°C and 50% RH. If the ionic conductivity in AC impedance measurement is 10 －８ If the ion dissociation rate is 10 S / cm or more, it can be considered that ion dissociated salt is present, and more preferably 10 －５ S / cm or more, more preferably 10 －４ S / cm or more, most preferably 10 －３The high ionic conductivity is particularly useful when used as an electrolyte membrane for an electrochemical device.

[0021] The deliquescent salt may be any salt compound that exhibits deliquescent properties, and is not particularly limited. Examples of the deliquescent salt include LiCl, CsCl, and CaCl. ２ , MgCl ２ , ZnCl ２ Salts of chlorine with alkali metals, salts of chlorine with alkaline earth metals, such as LiBr, MgBr ２ Salts of bromine with alkali metals, salts of bromine with alkaline earth metals, etc.; salts of acetic acid with alkali metals, salts of acetic acid with alkaline earth metals; Li(CF ３ SO ２ ) ２ N, Na(CF ３ SO ２ ) ２ N etc. (CF ３ SO ２ ) ２ N － and alkali metal salts (CF ３ SO ２ ) ２ N － and alkaline earth metal salts; Li(FSO ２ ) ２ N, Na(FSO ２ ) ２ N, K (FSO ２ ) ２ N etc. (FSO ２ ) ２ N － and alkali metal salts (FSO ２ ) ２ N － and alkaline earth metal salts; NH ４ Examples of suitable deliquescent salts include inorganic ammonium halides such as Cl; and organic ammonium halides such as choline chloride. The deliquescent salt may contain water of hydration. After deliquescent salts have been deliquesced, the water of hydration is counted as the weight of the water portion. The deliquescent salts may be used singly or in combination of two or more. In particular, by combining two or more deliquescent salts, the water content can be suitably adjusted. In this case, it is desirable to use a combination of deliquescent salts having the same anion or cation species.

[0022] The deliquescent salt preferably has a molecular weight of 10,000 or less, more preferably 40 to 5000, and even more preferably 50 to 1000. The deliquescent salt is preferably a solid at room temperature (25°C) in the absence of moisture, and preferably has a melting point of 100°C or higher, more preferably 150 to 800°C.

[0023] As the deliquescent salt, CaCl is used from the viewpoint of lowering the freezing temperature. ２ , LiCl, LiBr, MgCl ２ , ZnCl ２ , Li(FSO ２ ) ２ N, Li(CF ３ SO ２ ) ２ N, Na(FSO ２ ) ２ N, and organic ammonium halides are preferred. In the present invention, CaCl ２ , LiCl, LiBr, MgCl ２ , ZnCl ２ , Li(FSO ２ ) ２ N, Li(CF ３ SO ２ ) ２ N, Na(FSO ２ ) ２ It is preferable that the deliquescent salt contains at least one selected from N and organic ammonium halides as a main component, and when two or more deliquescent salts are contained, it is preferable that the deliquescent salt contains at least one selected from these in the largest amount. ２ , LiCl, and LiBr are more preferred, and LiCl and LiBr are even more preferred.

[0024] The water-based radio wave absorbing material of the present invention contains 20% by weight or more of the deliquescent salt in a total of 100% by weight of the water and the deliquescent salt, and its preparation method is not particularly limited, but the deliquescent salt may be left standing in an environment of a desired humidity to cause deliquescence, so that the ratio of the deliquescent salt to the total of the water and the deliquescent salt becomes a desired value, or after causing deliquescence, water or the deliquescent salt may be additionally added to adjust the water content. Alternatively, the water-based radio wave absorbing material may be prepared by mixing a desired amount of the deliquescent salt with a desired amount of water.

[0025] In order to further enhance low flammability, the water-based radio wave absorption material of the present invention preferably contains an organic compound having a flash point in an amount of less than 10 parts by weight, more preferably 7 parts by weight or less, even more preferably 5 parts by weight or less, and even more preferably 3 parts by weight or less, relative to 100 parts by weight of the total of water and deliquescent salt, and it is particularly preferable that the water-based radio wave absorption material does not substantially contain an organic compound having a flash point.

[0026] From the viewpoint of processability, the viscosity of the aqueous radio wave absorbing material of the present invention at 25°C is preferably 50,000 cp or more, more preferably 80,000 cp or more, and even more preferably 100,000 cp or more. There is no particular upper limit, but the viscosity is preferably 10,000,000 cp or less, and even more preferably 1,000,000 cp or less.

[0027] Furthermore, the water-based radio wave absorbing material of the present invention may be one in which the deliquescent salt is composited with a matrix material, and more specifically, it is preferable that the deliquescent salt is composited by being dispersed in a matrix material. Examples of the matrix material include polymer materials such as plastics and rubber, and inorganic materials such as ceramics and glass. When the deliquescent salt is dispersed in a matrix material, the reflectance can be reduced compared to when the water-based radio wave absorbing material is used alone.

[0028] As the matrix material, a polymer material is preferred from the viewpoints that the processability can be improved by increasing the viscosity and that liquid leakage can be effectively suppressed, and further, a polymer material that is compatible with the aqueous electromagnetic wave absorbing material of the present invention is preferred from the viewpoint that the freezing temperature can be further lowered. Furthermore, the polymer material may be either transparent or opaque to visible light, but if it is transparent, visibility is ensured even with the aqueous electromagnetic wave absorbing material interposed therebetween, and therefore, a high transparency is preferred, since this broadens the applicable applications.

[0029] From the viewpoints of processability and suppression of liquid leakage, the content of the polymer material in the water-based radio wave absorbing material of the present invention is preferably 1 part by weight or more, more preferably 3 parts by weight or more, and even more preferably 8 parts by weight or more, relative to 100 parts by weight of the total of water and deliquescent salt. Furthermore, since a relatively large content of the polymer material can reduce radio wave reflection, from the viewpoint of reducing radio wave reflection, the content of the polymer material is preferably 10 parts by weight or more, more preferably 15 parts by weight or more, and even more preferably 20 parts by weight or more, relative to 100 parts by weight of the total of water and deliquescent salt. Note that the upper limit of the content of the polymer material is not particularly limited, but is preferably 900 parts by weight or less, more preferably 400 parts by weight or less, and even more preferably 100 parts by weight or less, relative to 100 parts by weight of the total of water and deliquescent salt.

[0030] The weight average molecular weight (Mw) of the polymer material is not particularly limited, but is preferably 10,000 or more, more preferably 100,000 or more, even more preferably 200,000 or more, and still more preferably 300,000 or more, and although the upper limit is not particularly limited, is 10 million or less. The weight average molecular weight (Mw) of the polymer material can be a value determined by GPC measurement in terms of standard polystyrene.

[0031] The polymer material is not particularly limited as long as it can be compounded with the water-based radio wave absorbing material of the present invention, and known resin materials and rubber materials can be used. The compatible polymer material is not particularly limited as long as it is compatible with water and deliquescent salts, but polymers having polar groups are preferred, and in particular, polymers having -OH, -NH, N ＋ Polymers having an ethylene oxide chain structure are preferred due to their high affinity, and examples thereof include acrylic acid polymers, acrylamide polymers, cationic group-containing polymers having cationic groups in the polymer chain, polyvinyl alcohol polymers, and polymers having a sugar skeleton. Specific examples thereof include polyacrylic acid, polyacrylamide, poly-N,N-dimethylacrylamide, poly-N,N-diethylacrylamide, poly-N-isopropylacrylamide, poly-N-methoxymethylacrylamide, (meth)acrylate polymers having an ethylene oxide chain in the side chain (the end of the ethylene oxide chain may be hydrogen or an alkyl group), polyethyleneimine, polydiallyldimethylammonium, polyvinyl alcohol, polyglycerin, carboxymethyl cellulose, and natural water-soluble polymers.

[0032] In the present invention, it is preferable to use, as the polymer material, a cationic group-containing polymer having cationic groups in the polymer chain (hereinafter referred to as a "cationic group-containing polymer" as appropriate). Such a cationic group-containing polymer itself has excellent radio wave absorption properties, and therefore, by using a cationic group-containing polymer, it is possible to further improve radio wave absorption properties.

[0033] The cationic group-containing polymer is not particularly limited as long as it is a polymer having a cationic group in the polymer chain, and may be a polymer having a cationic group in the main chain of the polymer, or a polymer having a cationic group in the side chain of the polymer, or further may be a polymer having a cationic group in the main chain and the side chain of the polymer.

[0034] The cationic group contained in the cationic group-containing polymer used in the present invention is not particularly limited, but examples thereof include cationic groups containing a nitrogen atom, a phosphorus atom, a sulfur atom, or an oxygen atom as the central atom. Among these, cationic groups containing a nitrogen atom as the central atom are preferred from the viewpoint of radio wave absorption performance. Preferred cationic structures are the following structures (I) or (II), and specific examples include ammonium, iminium, imidazolium, and pyridinium. Furthermore, it is preferred that the substituent of the cationic group has two or more groups bonded thereto. Furthermore, the cationic group-containing polymer used in the present invention may have an anionic group in addition to the cationic group in the polymer chain, and may have, for example, a betaine structure.

[0035] The cationic group-containing polymer used in the present invention preferably has polar atoms other than the cationic groups in addition to the cationic groups. The presence of such polar atoms can neutralize the positive charge of the cations and improve the dissociation of the anions, thereby further improving the radio wave absorption performance and also improving transparency and flexibility. Examples of such polar atoms include oxygen atoms and nitrogen atoms. Examples of groups having such polar atoms include, but are not limited to, ether bonds, ketone groups, carboxyl groups, hydroxyl groups, amine groups, amide bonds, urethane bonds, and urea bonds. Note that the imidazolium structure has another nitrogen atom in addition to the cationic nitrogen atom in the imidazolium ring, and such another nitrogen atom can also be considered a polar atom other than the cationic group.

[0036] Examples of cationic group-containing polymers include addition polymers of vinyl compounds, polyethers, polyethyleneimines, and polyoxazolines, as cationic group-containing polymers having cationic groups in their side chains. Examples of cationic group-containing polymers having cationic groups in their main chains include ionenes, epichlorohydrin-amine condensates, and polyamidepolyamine epichlorohydrin. These may have any other substituents, or may have some hydrogen atoms substituted with halogen atoms such as fluorine. Furthermore, the cationic group-containing polymer may be a polymer in which, in addition to a structural unit having a cationic group, a structural unit derived from a monomer not having a cationic group is copolymerized, and the pH may be adjusted by introducing a structural unit derived from an acidic monomer or a structural unit derived from a basic monomer.

[0037] The cationic group-containing polymer used in the present invention has a cationic group in the polymer chain. The counter anion for such a cationic group is not particularly limited, and examples thereof include imides such as fluorosulfonylimide, bistrifluoromethylsulfonylimide, and bispentafluoroethylsulfonylimide; halogens such as chlorides and bromides; carboxylic acids such as tetrafluoroboric acid, hexafluorophosphoric acid, dicyanoamide, tetracyanoborate, and acetic acid, carbonic acid, alkylcarbonic acid, triflate, perchloric acid, nitric acid, sulfuric acid, alkylsulfuric acid, sulfonic acid, phosphoric acid, and alkylphosphoric acid; and the like.

[0038] The cationic group-containing polymer used in the present invention is not particularly limited, but examples of polymers having cationic groups on their side chains include cationic group-containing polyethers (A) containing a repeating unit represented by the following general formula (1):

[0039] (In the above general formula (1), A ＋ represents a nitrogen-containing cationic group. － represents an anion.)

[0040] A ＋Examples of the nitrogen-containing cationic group represented by the formula (I) include an amino group, a nitrogen-containing cationic aromatic group, and a nitrogen-containing cationic aliphatic group.

[0041] A ＋ As the nitrogen-containing cationic aromatic group as the nitrogen-containing cationic aromatic group, a group containing a cationic nitrogen-containing aromatic heterocycle is preferred. The nitrogen-containing aromatic heterocycle in the cationic nitrogen-containing aromatic heterocycle in the group containing a cationic nitrogen-containing aromatic heterocycle may have a nitrogen atom in the ring and have aromaticity, and may have heteroatoms other than nitrogen atoms such as oxygen atoms and sulfur atoms, and some of the atoms constituting the heterocycle may be substituted with substituents. In addition, it may have a polycyclic structure in which two or more rings are condensed. Examples of such nitrogen-containing aromatic heterocyclic structures include five-membered heterocyclic rings such as an imidazole ring, a pyrrole ring, a thiazole ring, an oxazole ring, a pyrazole ring, and an isoxazole ring; six-membered heterocyclic rings such as a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, and a triazine ring; and fused heterocyclic rings such as a quinoline ring, an isoquinoline ring, a quinoxaline ring, a quinazoline ring, a cinnoline ring, a purine ring, an indole ring, an isoindole ring, a benzimidazole ring, a benzoxazole ring, and a benzisoxazole ring. Among these, five-membered and six-membered heterocyclic rings are preferred, and an imidazole ring is more preferred.

[0042] The substituent of the nitrogen-containing aromatic heterocycle is not particularly limited, and examples thereof include alkyl groups, cycloalkyl groups, alkenyl groups such as vinyl groups, aryl groups such as phenyl groups, arylalkyl groups, alkylaryl groups, alkoxyl groups, alkoxyalkyl groups, aryloxy groups, alkanol groups, hydroxyl groups, carbonyl groups, alkoxycarbonyl groups, amino groups, imino groups, nitrile groups, alkylsilyl groups, halogen atoms, etc. The number of carbon atoms in these substituents is preferably 0 to 12, more preferably 1 to 8, and even more preferably 1 to 6.

[0043] A ＋ The nitrogen-containing cationic aliphatic group as may be linear or branched, and may have a non-aromatic ring structure.

[0044] A＋ Specific examples of the nitrogen-containing cationic group represented by the formula (I) include an ammonium group; mono-substituted ammonium groups containing a cationic nitrogen atom, such as a methylammonium group, a butylammonium group, a cyclohexylammonium group, an anilinium group, a benzylammonium group, or an ethanolammonium group; di-substituted ammonium groups containing a cationic nitrogen atom, such as a dimethylammonium group, a diethylammonium group, a dibutylammonium group, or a nonylphenylammonium group; trimethylammonium group, triethylammonium group, n-butyldimethylammonium group, stearyldimethylammonium group, tributylammonium group, trivinylammonium group, triethanolammonium group, N,N-dimethylethanolammonium group, tri(2-ethoxyethyl)ammonium group, and heterocyclic groups containing a cationic nitrogen atom, such as a piperidinium group, a 1-methylpyrrolidinium group, a 1-butylpyrrolidinium group, an imidazolium group, a 1-methylimidazolium group, a 1-ethylimidazolium group, a 1-butyl-imidazolium group, a benzimidazolium group, a pyrrolium group, a 1-methylpyrrolium group, an oxazolium group, a benzoxazolium group, a pyrazolium group, an isoxazolium group, a pyridinium group, a 2,6-dimethylpyridinium group, a pyrazinium group, a pyrimidinium group, a pyridazinium group, a triazinium group, an N,N-dimethylanilinium group, a quinolinium group, an isoquinolinium group, an indolinium group, a quinoxalium group, and an isoquinoxalium group. Among these, a trisubstituted ammonium group containing a cationic nitrogen atom and a heterocyclic group containing a cationic nitrogen atom are preferred.

[0045] In the above general formula (1), X － The anion represented by A ＋ X is a counter anion of a nitrogen-containing cationic group represented by the formula: － For example, the monovalent anion is F － , Cl － ,Br － , I － Halide ions such as (FSO ２ )２ N － , (CF ３ SO ２ ) ２ N － , (CF ３ CF ２ SO ２ ) ２ N － sulfonylimide ions such as CH ３ COO － , C3H7COO － , C.F. ３ COO － , PhCOO － (Ph represents a phenyl group), and other carboxylate ions; CH ３ SO ３ － , C.F. ３ SO ３ － sulfonate ions such as OH － , B.F. ４ － , P.F. ６ － , ClO ４ － , B(CN) ４ － , SCN － , (NC) ２ N － X － The anion may be a polyvalent anion, or may be a polyanion having two or more monovalent anionic groups in the molecule. For example, the polyvalent anion may be a sulfate ion (SO ４ ２－ ) and carbonate ions (CO ３ ２－ For example, examples of polyanions having two or more monovalent anionic groups in the molecule include: － O ３ SCF2CF2CF2SO ３ － , － O ３ SCF2CF2SO ３ － , C.F. ３ SO ２ N － SO ２CF2CF2OCF2CF2OCF2CF2SO ２ N － SO ２ CF ３ Among them, from the viewpoint of radio wave absorption, sulfonylimide ions, carboxylate ions, BF ４ － is preferred, and sulfonylimide ion, CH ３ COO － , B.F. ４ － is more preferred.

[0046] In the cationic group-containing polyether (A) used in the present invention, the units represented by the general formula (1) are each independent, and two or more types of units represented by the general formula (1) may be present in the cationic group-containing polyether (A). For example, in the entire repeating units represented by the general formula (1) in the cationic group-containing polyether (A), ＋ All of the nitrogen-containing cationic groups represented by the general formula (1) may be the same kind of nitrogen-containing cationic group, or different kinds of nitrogen-containing cationic groups may be mixed. － All of the anions represented by the formula (I) may be the same kind of anion, or different kinds of anions may be mixed.

[0047] Examples of the repeating unit represented by the above general formula (1) include a repeating unit represented by the following general formula (2): The repeating unit represented by the following general formula (2) is an oxirane unit containing an imidazolium structure. (In the above general formula (2), R １ ~R ４ each independently represents a hydrogen atom or a substituent, R ２ and R ３ may be bonded to each other. － represents an anion.)

[0048] In the above general formula (2), R １ ~R ４R each independently represents a hydrogen atom or a substituent. Examples of the substituent include the same as those described above as the substituent of the nitrogen-containing aromatic heterocycle. １ ~R ４ The substituent as R may be linear or branched, and may have a ring structure. １ ~R ４ The substituent as is preferably linear.

[0049] In the above general formula (2), R １ is not particularly limited as long as it is a hydrogen atom or a substituent, but is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrocarbon group, even more preferably an alkyl group or an alkenyl group, particularly preferably an alkyl group or a vinyl group, and most preferably an alkyl group. １ The number of carbon atoms in the alkyl group is preferably 0 to 12, more preferably 0 to 8, even more preferably 1 to 6, still more preferably 1 to 4, particularly preferably 1 to 3, and most preferably 1 or 2.

[0050] In the above general formula (2), R ２ ~R ４ are each independently a hydrogen atom or a substituent and are not particularly limited, but are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or a vinyl group, even more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. ２ ~R ４ The number of carbon atoms in each of the groups is preferably 0 to 8, more preferably 0 to 6, even more preferably 0 to 4, still more preferably 0 to 3, particularly preferably 0 to 2, and most preferably 0 to 1.

[0051] In the above general formula (2), R ２ ~R ４ Among R, it is preferable that 1 to 3 represent a hydrogen atom, and more preferable that 2 to 3 represent a hydrogen atom. ２ ~R ４Preferably, 0 to 2 of these represent a substituent such as a hydrocarbon group, and more preferably, 0 to 1 of these represent a substituent such as a hydrocarbon group.

[0052] X in the above general formula (2) － The anion represented by the formula (1) is X － The preferred embodiments are also the same as those of the anion represented by the formula:

[0053] The repeating unit represented by the general formula (2) above preferably contains an imidazolium group, a 1-methylimidazolium group, a 1-butylimidazolium group, a 1-hexylimidazolium group, or a 1-vinylimidazolium group, and more preferably contains a 1-methylimidazolium group.

[0054] The cationic group-containing polyether (A) used in the present invention may contain a repeating unit other than the repeating unit represented by the general formula (1). The repeating unit other than the repeating unit represented by the general formula (1) is not particularly limited as long as it is derived from a monomer copolymerizable with the monomer that gives the repeating unit represented by the general formula (1), and examples thereof include alkylene oxide monomer units such as ethylene oxide units, propylene oxide units, 1,2-butylene oxide units, and 1,2-octylene oxide units; aromatic oxirane monomer units such as styrene oxide units; epihalohydrin monomer units such as epichlorohydrin units, epibromohydrin units, and epiiodohydrin units; alkenyl group-containing oxirane monomer units such as allyl glycidyl ether units; aromatic ether group-containing oxirane monomer units such as phenyl glycidyl ether units; and (meth)acryloyl group-containing oxirane monomer units such as glycidyl acrylate units and glycidyl methacrylate units. Among these, alkylene oxide monomer units, epihalohydrin monomer units, and (meth)acryloyl group-containing oxirane monomer units are preferred, and ethylene oxide units, propylene oxide units, epichlorohydrin units, and glycidyl methacrylate units are more preferred. The cationic group-containing polyether (A) used in the present invention may contain one type of repeating unit other than the repeating unit represented by the general formula (1) alone, or may contain two or more types.

[0055] The cationic group-containing polyether (A) used in the present invention may contain two or more types of repeating units. In this case, the distribution pattern of the multiple repeating units is not particularly limited, but it is preferable that the repeating units have a random distribution.

[0056] The chain structure of the cationic group-containing polyether (A) used in the present invention is not particularly limited, and may be a linear chain structure or a chain structure having branches such as grafts or radial branches.

[0057] The terminal group of the cationic group-containing polyether (A) used in the present invention is not particularly limited and may be any monovalent group. Specific examples of the terminal group include a hydrogen atom, a halogen group, an alkyl group, a haloalkyl group, a hydroxyl group, and an azide group. The terminal group may be a nitrogen-containing cationic group (A) possessed by the repeating unit represented by general formula (1). ＋ ) and anion (X － ) may be a group consisting of

[0058] The content of the repeating units represented by the general formula (1) in the cationic group-containing polyether (A) used in the present invention is not particularly limited, but the average number per molecule is preferably 1 to 100,000, more preferably 3 to 50,000, even more preferably 10 to 30,000, and particularly preferably 30 to 10,000.

[0059] The weight average molecular weight (Mw) of the cationic group-containing polyether (A) used in the present invention is not particularly limited, but is preferably 750 to 2,000,000, more preferably 2,000 to 1,500,000, even more preferably 4,000 to 1,000,000, and particularly preferably 10,000 to 500,000.

[0060] The molecular weight distribution (Mw / Mn) of the cationic group-containing polyether (A) used in the present invention is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 2.0, and even more preferably 1.0 to 1.5.

[0061] The weight average molecular weight and molecular weight distribution of the cationic group-containing polyether (A) can be determined by the method described in the Examples below. The molecular weight distribution of the cationic group-containing polyether (A) can be treated as being unchanged from the molecular weight distribution of the base polymer (polyether having no cationic groups) before the introduction of cationic groups.

[0062] The proportion of the repeating units represented by the general formula (1) in the cationic group-containing polyether (A) used in the present invention is not particularly limited, but is preferably 5 to 100 mol %, more preferably 10 to 100 mol %, based on the total repeating units of the cationic group-containing polyether (A).

[0063] The method for synthesizing the cationic group-containing polyether (A) used in the present invention is not particularly limited, and any synthesis method can be used as long as it can produce the target polyether compound. As an example of the synthesis method, first, a base polymer (a polyether having no cationic groups) is obtained by the following method (α) or (β).

[0064] (α) A method for obtaining a base polymer by ring-opening polymerization of a monomer containing an oxirane monomer, which includes at least an epihalohydrin such as epichlorohydrin, epibromohydrin, or epiiodohydrin, in the presence of a catalyst disclosed in JP 2010-53217 A, which catalyst comprises an onium salt of a compound containing an atom of Group 15 or 16 of the periodic table and a trialkylaluminum in which all of the alkyl groups contained are linear alkyl groups.

[0065] (β) A method of obtaining a base polymer by ring-opening polymerization of a monomer containing an oxirane monomer, which includes at least an epihalohydrin such as epichlorohydrin, epibromohydrin, or epiiodohydrin, in the presence of a catalyst prepared by reacting triisobutylaluminum with phosphoric acid and triethylamine, as disclosed in JP-B-46-27534.

[0066] Then, by reacting the halogen groups constituting the epihalohydrin monomer units of the base polymer obtained by the above method (α) or (β) with an onium-converting agent containing a nitrogen-containing cationic group (onium-converting reaction), at least a part of the halogen groups constituting the epihalohydrin monomer units of the base polymer is converted into onium halide groups containing a nitrogen-containing cationic group, thereby forming an anion (X －) is a halide ion. If necessary, the obtained polyether compound containing onium halide structural units can be mixed with an anion (X ) other than a halide ion. － ) with a salt of a metal cation to carry out an anion exchange reaction, thereby converting the halide ion constituting the onium halide group containing the nitrogen-containing cationic group into an anion other than the halide ion (X － ) can be converted to

[0067] The onium-containing agent containing a nitrogen-containing cationic group used in the reaction of the base polymer with the onium-containing agent containing a nitrogen-containing cationic group is a compound represented by the general formula (1) ＋ For example, by using an imidazole compound corresponding to the imidazolium structure in general formula (2) as the onium forming agent, it is possible to form the repeating unit represented by general formula (2).

[0068] The method for reacting the base polymer with the onium-forming agent is not particularly limited, but a method of mixing the base polymer with the onium-forming agent is preferred. The method for mixing the base polymer with the onium-forming agent is also not particularly limited, but examples include a method of adding the onium-forming agent to a solution containing the base polymer and mixing them, a method of adding the base polymer to a solution containing the onium-forming agent and mixing them, and a method of preparing the onium-forming agent and the base polymer as separate solutions and mixing the two solutions.

[0069] In the reaction between the base polymer and the onium-forming agent, an inert solvent is preferably used, and may be either nonpolar or polar. Examples of nonpolar solvents include aromatic hydrocarbons such as benzene and toluene; linear saturated hydrocarbons such as n-pentane and n-hexane; and alicyclic saturated hydrocarbons such as cyclopentane and cyclohexane. Examples of polar solvents include ethers such as tetrahydrofuran, anisole, and diethyl ether; esters such as ethyl acetate and ethyl benzoate; ketones such as acetone, 2-butanone, and acetophenone; aprotic polar solvents such as acetonitrile, dimethylformamide, dimethylacetamide, and dimethyl sulfoxide; and protic polar solvents such as ethanol, methanol, and water. Mixtures of these solvents are also preferably used. The amount of solvent used is not particularly limited, but is preferably used so that the base polymer concentration is 1 to 50% by mass, and more preferably 3 to 40% by mass.

[0070] The amount of onium-forming agent used when reacting the base polymer with the onium-forming agent is not particularly limited and may be determined depending on the content of the repeating unit represented by general formula (1) in the target polyether compound, etc. Specifically, the amount of onium-forming agent used is usually in the range of 0.01 to 100 mol, preferably 0.02 to 50 mol, more preferably 0.03 to 10 mol, and even more preferably 0.05 to 2 mol, per mol of epichlorohydrin units in the base polymer used.

[0071] The pressure when reacting the base polymer with the onium-containing agent is not particularly limited, but is usually 1 to 500 atm, preferably 1 to 100 atm, and particularly preferably 1 to 50 atm. The temperature during the reaction is also not particularly limited, but is usually 0 to 200°C, preferably 20 to 170°C, and more preferably 40 to 150°C. The reaction time is usually 1 minute to 1,000 hours, preferably 3 minutes to 800 hours, more preferably 5 minutes to 500 hours, and even more preferably 30 minutes to 200 hours.

[0072] A polyether compound containing an onium halide structural unit and an anion other than a halide ion (X － The method for carrying out the anion exchange reaction by reacting a salt of a metal cation with a polyether compound containing an onium halide structural unit and an anion other than a halide ion (X － ) and a salt of a metal cation are mixed and reacted.

[0073] The conditions for carrying out the anion exchange reaction are not particularly limited, and include the steps of: reacting a polyether compound containing an onium halide structural unit with an anion other than a halide ion (X － Alternatively, the reaction may be carried out in the presence of other compounds such as an organic solvent. The amount of the salt used is not particularly limited, but is usually 0.01 to 100 mol, preferably 0.02 to 50 mol, and more preferably 0.03 to 10 mol, per mol of onium halide structural units of the onium halide structural unit-containing polyether compound used.

[0074] An anion other than a halide ion (X － The salt of lithium fluoride (Li(FSO2)2N) with a metal cation is not particularly limited, and examples thereof include lithium (bisfluorosulfonyl)imide (Li(FSO2)2N), lithium bis(trifluoromethylsulfonyl)imide (Li(CF3SO2)2N), lithium (bispentafluoroethylsulfonyl)imide (Li(CF3CF2SO2)2N), sodium acetate (CH3COONa), silver acetate (CH3COOAg), lithium butyrate (C3H7COOLi), lithium trifluoroacetate (CF3COOLi), lithium benzoate (PhCOOLi), potassium tetracyanoborate (KB(CN) ４ ), lithium thiocyanate (LiSCN), lithium (biscyano)imide (Li(NC) ２N), lithium methylsulfonate (LiCH3SO3), lithium trifluoromethylsulfonate (LiCF3SO3), potassium hydroxide (KOH), lithium perchlorate (LiClO4), etc. In the case of salts of polyvalent anions and metal cations, silver sulfate (Ag ２ SO ４ ２－ ), sodium carbonate (Na ２ CO ３ ２－ For example, examples of salts of polyanions having two or more monovalent anionic groups in the molecule and metal cations include LiO ３ SCF2CF2CF2SO ３ Li, LiO ３ SCF2CF2SO ３ Li, Li ２ (CF ３ SO ２ NSO ２ CF2CF2OCF2CF2OCF2CF2SO ２ NSO ２ CF ３ ), among others.

[0075] The pressure during the anion exchange reaction is usually 1 to 500 atm, preferably 1 to 100 atm, and particularly preferably 1 to 50 atm. The reaction temperature is usually −30 to 200° C., preferably −15 to 180° C., and more preferably 0 to 150° C. The reaction time is usually 1 minute to 1,000 hours, preferably 3 minutes to 100 hours, more preferably 5 minutes to 10 hours, and even more preferably 5 minutes to 3 hours.

[0076] After the anion exchange reaction is completed, metal cations, halide ions, and salts thereof can be removed by washing with water or membrane separation using a semipermeable membrane, and the mixture containing the cationic group-containing polyether (A) can be recovered. Alternatively, the mixture containing the cationic group-containing polyether (A) can be recovered by extracting the cationic group-containing polyether (A) using a solvent such as methanol. Furthermore, the desired cationic group-containing polyether (A) can be recovered by a conventional method, such as drying under reduced pressure.

[0077] Further, the cationic group-containing polymer used in the present invention also includes a side-chain ammonium group-containing polymer (B) containing a repeating unit represented by the following general formula (3), which is a polymer having a cationic group on the side chain of the polymer. (In the above general formula (3), Z is a divalent linking group, and R ５ ~R ７ each independently represents a hydrogen atom or a substituent, R ５ ~R ７ may be bonded to each other. － represents an anion.)

[0078] Z is a divalent linking group, and is preferably an alkylene group which may contain a heteroatom. Examples of heteroatoms include an oxygen atom, a nitrogen atom, and a sulfur atom. Examples of groups containing a heteroatom include an amide group (-CO-NH-), an ester group (-COO-), an ether group (-O-), and a thioether group (-S-). Among these, Z is preferably an alkylene group containing an amide group, such as -CO-NH-(CH ２ ) ｐ A group represented by - (where p is an integer of 1 to 5, and preferably n=3) is more preferred.

[0079] R ５ ~R ７ are each independently a hydrogen atom or a substituent and are not particularly limited, but are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or a vinyl group, even more preferably a hydrogen atom or an alkyl group, and particularly preferably an alkyl group. ５ ~R ７ The number of carbon atoms in each of the groups is preferably 1 to 8, more preferably 1 to 3, even more preferably 1 to 4, and particularly preferably 1. In other words, it is preferably a methyl group.

[0080] In the above general formula (3), X － The anion represented by the formula (1) is not particularly limited, but examples thereof include the same anions as those represented by the formula (1) above.

[0081] The side-chain ammonium group-containing polymer (B) may also contain a repeating unit other than the repeating unit represented by general formula (3). The repeating unit other than the repeating unit represented by general formula (3) is not particularly limited as long as it is derived from a monomer copolymerizable with the monomer that gives the repeating unit represented by general formula (3), and examples thereof include units derived from unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and unsaturated carboxylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, and n-butyl methacrylate.

[0082] In the side-chain ammonium group-containing polymer (B) used in the present invention, the units represented by the above general formula (3) are each independent, and two or more types of units represented by the general formula (3) may be present in the side-chain ammonium group-containing polymer (B). When the side-chain ammonium group-containing polymer (B) used in the present invention contains two or more types of repeating units, the distribution pattern of the multiple repeating units is not particularly limited, but it is preferable that they have a random distribution.

[0083] Specific examples of the side chain ammonium group-containing polymer (B) used in the present invention include poly{[3-(methacryloylamino)propyl]trimethylammonium chloride}, poly[(3-acrylamidopropyl)trimethylammonium chloride], poly{[2-(methacryloyloxy)ethyl]trimethylammonium chloride}, poly{[2-(acryloyloxy)ethyl]trimethylammonium chloride}, poly[2-dimethylaminoethyl methacrylate ethyl sulfate], poly[vinylbenzyltrimethylammonium chloride], poly[N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride], poly[2-methacryloyloxyethyl phosphorylcholine], poly[2-(N-3-sulfopropyl-N,N-dimethylammonium)ethyl methacrylate], and the like. Among these, poly[(3-acrylamidopropyl)trimethylammonium chloride] is preferred.

[0084] The weight average molecular weight (Mw) of the side chain ammonium group-containing polymer (B) used in the present invention is not particularly limited, but is preferably 750 to 2,000,000, more preferably 1,000 to 1,500,000, even more preferably 2,000 to 1,000,000, and particularly preferably 4,000 to 500,000. The weight average molecular weight of the side chain ammonium group-containing polymer (B) can be determined using GPC in terms of standard polystyrene.

[0085] Further, the cationic group-containing polymer used in the present invention also includes a polymer (C) having a side chain cyclic ammonium group, which is a polymer having a cationic group on its side chain and which contains a repeating unit represented by the following general formula (4-1) or the following general formula (4-2): (In the above general formula (4-1) and general formula (4-2), R ８ , R ９ each independently represents a hydrogen atom or a substituent, R ８ , R ９ In addition, in the general formula (4-1) and the general formula (4-2), X － represents an anion.)

[0086] R ８ , R ９ are each independently a hydrogen atom or a substituent and are not particularly limited, but are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or a vinyl group, even more preferably a hydrogen atom or an alkyl group, and particularly preferably an alkyl group. ８ , R ９ The number of carbon atoms in each of the groups is preferably 1 to 8, more preferably 1 to 3, even more preferably 1 to 4, and particularly preferably 1. In other words, it is preferably a methyl group.

[0087] In the above general formula (4-1) and general formula (4-2), X － The anion represented by the formula (1) is not particularly limited, but examples thereof include the same anions as those represented by the formula (1) above.

[0088] The side chain cyclic ammonium group-containing polymer (C) may also contain a repeating unit other than the repeating units represented by general formula (4-1) or (4-2). The repeating unit other than the repeating unit represented by general formula (4) may be a unit derived from a monomer copolymerizable with the monomer that gives the repeating unit represented by general formula (4-1) or (4-2), and is not particularly limited. Examples of such a monomer include N-vinylpyrrolidone, acrylamide, (meth)acrylic acid, (meth)acrylate salts, and (meth)acrylates having an ethylene oxide unit.

[0089] In the side chain cyclic ammonium group-containing polymer (C) used in the present invention, the units represented by the above general formula (4) are each independent, and two or more types of units represented by the general formula (4) may be present in the side chain cyclic ammonium group-containing polymer (C). When the side chain cyclic ammonium group-containing polymer (C) used in the present invention contains two or more types of repeating units, the distribution pattern of the multiple repeating units is not particularly limited, but it is preferable that they have a random distribution.

[0090] A specific example of the polymer (C) containing a cyclic ammonium group in a side chain used in the present invention is preferably poly(diallyldimethylammonium chloride).

[0091] The weight average molecular weight (Mw) of the side chain cyclic ammonium group-containing polymer (C) used in the present invention is not particularly limited, but is preferably 750 to 2,000,000, more preferably 2,000 to 1,500,000, even more preferably 4,000 to 1,000,000, and particularly preferably 10,000 to 500,000. The weight average molecular weight of the side chain cyclic ammonium group-containing polymer (C) can be determined using GPC in terms of standard polystyrene.

[0092] Further, the cationic group-containing polymer used in the present invention includes a main chain ammonium group-containing polymer (D) containing a repeating unit represented by the following general formula (5), which is a polymer having a cationic group in the main chain of the polymer. (In the above general formula (5), R １０ , R １１ each independently represents a hydrogen atom or a substituent, R １０ , R １１ may be bonded to each other. － represents an anion.)

[0093] R １０ , R １１ are each independently a hydrogen atom or a substituent and are not particularly limited, but are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or a vinyl group, even more preferably a hydrogen atom or an alkyl group, and particularly preferably an alkyl group. １０ , R １１ The number of carbon atoms in each of the groups is preferably 1 to 8, more preferably 1 to 3, even more preferably 1 to 4, and particularly preferably 1. In other words, it is preferably a methyl group.

[0094] In the above general formula (5), X － The anion represented by the formula (1) is not particularly limited, but examples thereof include the same anions as those represented by the formula (1) above.

[0095] The main chain ammonium group-containing polymer (D) can be obtained by reacting a secondary amine with epihalohydrin to form the repeating unit represented by general formula (5).

[0096] Secondary amines are compounds in which two hydrocarbon groups and one hydrogen atom are bonded to one nitrogen atom, and compounds in which a nitrogen atom is bonded to one hydrogen atom in a heterocycle. Examples of such secondary amines include aliphatic secondary amines, aromatic secondary amines, alicyclic secondary amines, and heterocyclic secondary amines, and two or more of these may be used in combination.

[0097] Examples of the aliphatic secondary amine include dimethylamine, diethylamine, diisopropylamine, dibutylamine, methylethylamine, methylpropylamine, methylbutylamine, methyloctylamine, methyllaurylamine, and dibenzylamine.

[0098] Examples of aromatic secondary amines include N-alkylanilines such as N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, N-pentylaniline, N-hexylaniline, N-octylaniline, N-decylaniline, N-laurylaniline, and N-benzylaniline; N-methyltoluidine, N-ethyltoluidine, N-propyltoluidine, N-butyltoluidine, N-pentyltoluidine, N-hexyltoluidine, and N-octyltoluidine; toluidine, N-decyl toluidine, N-lauryl toluidine, N-benzyl toluidine, and other N-alkyl toluidines; N-methyl naphthylamine, N-ethyl naphthylamine, N-propyl naphthylamine, N-butyl naphthylamine, N-pentyl naphthylamine, N-hexyl naphthylamine, N-octyl naphthylamine, N-decyl naphthylamine, N-lauryl naphthylamine, N-benzyl naphthylamine, and other N-alkyl naphthylamines; and the like.

[0099] Examples of alicyclic secondary amines include N-alkylcyclohexylamines such as N-methylcyclohexylamine, N-ethylcyclohexylamine, N-propylcyclohexylamine, N-butylcyclohexylamine, N-hexylcyclohexylamine, N-octylcyclohexylamine, N-decylcyclohexylamine, and N-laurylcyclohexylamine; N-alkylcyclooctylamines such as N-methylcyclooctylamine, N-ethylcyclooctylamine, N-propylcyclooctylamine, N-butylcyclooctylamine, N-hexylcyclooctylamine, N-octylcyclooctylamine, N-decylcyclooctylamine, and N-laurylcyclooctylamine; and dicycloalkylamines such as dicyclohexylamine and dicyclooctylamine.

[0100] Examples of the heterocyclic secondary amine include piperidine, pyrrolidine, 2-methylpiperidine, and 4-methylpiperidine.

[0101] As the secondary amine, an aliphatic secondary amine is preferred, and dimethylamine and diethylamine are preferred, with dimethylamine being particularly preferred.

[0102] Examples of epihalohydrins include epichlorohydrin, epibromohydrin, methylepichlorohydrin, methylepibromohydrin, etc. Among these, epichlorohydrin is particularly preferred.

[0103] The main chain ammonium group-containing polymer (D) may also be one obtained by reacting an amine other than a secondary amine with a secondary amine and an epihalohydrin. Examples of the amine other than a secondary amine include compounds having two or more amino groups, such as ethylenediamine, propylenediamine, diethylenetriamine, hexylenediamine, triethylenetetramine, tetraethylenepentamine, isophoronediamine, piperazine, diphenylmethanediamine, hydrazine, and hydrazides such as adipic acid dihydrazide. Among these, ethylenediamine is preferably used.

[0104] The main chain ammonium group-containing polymer (D) can be produced, for example, by mixing and stirring a secondary amine, an epihalohydrin, and, if necessary, an amine other than the secondary amine, under heating conditions, and then subjecting the mixture to addition polymerization by a known, commonly used method.

[0105] The weight average molecular weight (Mw) of the main chain ammonium group-containing polymer (D) used in the present invention is not particularly limited, but is preferably 750 to 2,000,000, more preferably 2,000 to 1,500,000, even more preferably 4,000 to 1,000,000, and particularly preferably 10,000 to 500,000. The weight average molecular weight of the main chain ammonium group-containing polymer (D) can be determined using GPC in terms of standard polystyrene.

[0106] Furthermore, when the aqueous radio wave absorbing material of the present invention contains a matrix material such as a polymer material, it may be a crosslinked material (three-dimensionally crosslinked material) obtained by crosslinking (three-dimensionally crosslinking) the matrix material such as a polymer material. In this case, a polymerizable monomer and / or a crosslinkable monomer may be coexisted with the matrix material such as a polymer material, and the crosslinked material (three-dimensionally crosslinked material) may be obtained by crosslinking (three-dimensionally crosslinking) the polymerizable monomer and / or the crosslinkable monomer. Examples of the crosslinking method include ultraviolet irradiation, visible light irradiation, heating, electron beam irradiation, and radiation irradiation. Urethane reaction, epoxy reaction, reaction of an oxazoline group, dimerization reaction of cinnamic acid, etc., reaction of an azetidinium ring, etc. may also be used.

[0107] The shape of the water-based electromagnetic wave absorbing material of the present invention is not particularly limited, but is preferably, for example, in the form of a sheet or plate. In this case, the water-based electromagnetic wave absorbing material formed into a sheet or plate may be used as a single layer, or multiple layers may be stacked. Using multiple layers stacked together increases the number of reflections, thereby adjusting the electromagnetic wave absorption performance. When multiple layers are stacked, the water-based electromagnetic wave absorbing materials of the present invention may be stacked on top of each other, or two or more water-based electromagnetic wave absorbing materials of the present invention may be sandwiched between sheets or plates different from the water-based electromagnetic wave absorbing materials of the present invention. The water-based electromagnetic wave absorbing material may be a gradient material whose composition changes stepwise. The water-based electromagnetic wave absorbing material of the present invention can also be used as a bulk material (i.e., a mass), and may be given any shape like clay work, or may be used to fill gaps like putty. Furthermore, the water-based electromagnetic wave absorbing material of the present invention may be a foam or may be in the form of a capsule with an outer shell. The capsule size may be on the order of cm to nm.

[0108] For example, when the water-based electromagnetic wave absorbing material of the present invention is formed into a sheet or plate, the forming method is not particularly limited, and the water-based electromagnetic wave absorbing material may be formed into a sheet or plate by being held by a sheet- or plate-like support, for example, by sandwiching the material between a pair of supports.

[0109] Alternatively, when the water-based radio wave absorbing material of the present invention is made into a sheet or plate shape, or a bulk body, it may be injected into a desired site in a fluid liquid state, and a matrix material such as a polymer material may be crosslinked in situ to make the material into a sheet or plate shape, or a bulk body.

[0110] Furthermore, when the water-based electromagnetic wave absorbing material of the present invention is formed into a sheet or plate, the surface of the sheet or plate water-based electromagnetic wave absorbing material may be roughened or grooves may be cut into the surface for the purpose of scattering electromagnetic waves on the sheet or plate surface. In this case, since visible light also tends to be scattered, from the viewpoint of ensuring visibility, a surface material (for example, a surface material made from methyl methacrylate) may be provided that conforms to the roughened surface or the grooved surface, so that the surface material covers the irregularities of the roughened surface or the grooved surface of the water-based electromagnetic wave absorbing material of the present invention, while the surface of the surface material makes the physical surface smooth.

[0111] Furthermore, the water-based electromagnetic wave absorbing material of the present invention preferably has an outer casing. For example, when the water-based electromagnetic wave absorbing material of the present invention is in the form of a sheet or plate, it is preferable to use a pair of sheet- or plate-shaped outer casings as the outer casings, and sandwich the material between the pair of outer casings. By having an outer casing, it is possible to increase the reflection attenuation and reduce reflected electromagnetic waves.

[0112] Furthermore, by providing an exterior, the water content in the water-based electromagnetic wave absorbing material of the present invention can be controlled. In this case, the effect of preventing the dissipation of water is also achieved, but this is preferable in that fluctuations in electromagnetic wave absorbing ability can be reduced. Therefore, it is not necessarily necessary to cover the entire surface with an exterior or to seal it. Therefore, a configuration with some holes may be acceptable, and even if part of the exterior is torn during use, the electromagnetic wave absorbing ability can be suitably maintained by providing the exterior.

[0113] The moisture content of the exterior is preferably 5% by weight or less; if the moisture content is too high, interaction with radio waves or electromagnetic waves may occur, potentially affecting the radio wave absorption characteristics. The moisture permeability of the exterior is preferably 0 to 50, more preferably 0.01 to 30, and even more preferably 0.1 to 10. The lower the moisture permeability, the smaller the fluctuations in moisture content in the atmosphere (e.g., seasonal fluctuations). Furthermore, since the aqueous radio wave absorbing material of the present invention absorbs radio waves and converts them into heat, a relatively high moisture permeability of the exterior can allow moisture to escape and absorb the heat of vaporization, thereby preventing overheating when the temperature becomes high.

[0114] The exterior is preferably made of an organic material such as plastic or rubber, or an inorganic material such as glass or ceramic. The outermost layer of the exterior is preferably water-repellent. Water repellency can be determined by dripping water onto the surface of the exterior and observing whether or not the water penetrates into the interior. Alternatively, if the method of dripping water is unable to determine whether or not the water penetrates, the exterior can be immersed in water and the weight increase determined by whether or not the rate of weight increase is 1% by weight or less.

[0115] From the viewpoints of suppressing fluctuations in the water content of the water-based electromagnetic wave absorbing material, dimensional stability, and low flammability, it is preferable to use inorganic materials such as glass and ceramics as the exterior. Furthermore, from the viewpoint of the resistance to breakage of the water-based electromagnetic wave absorbing material, it is preferable to use organic materials. In particular, from the viewpoint of the degree of freedom in shape, it is preferable to use resin materials. From the viewpoint of the degree of freedom in shape and the degree of freedom in deformation of the water-based electromagnetic wave absorbing material, it is preferable to use rubber materials. Among resin materials, from the viewpoint of low flammability, chlorinated resins such as vinyl chloride resin, vinylidene chloride resin, and chlorinated vinyl chloride, polyimide resins, fluororesins, and polycarbonate resins are preferable, and from the viewpoint of low moisture permeability, vinylidene chloride resins and polyolefin resins are preferable. Among polyolefin resins, cycloolefin resins are particularly preferable. Furthermore, among rubber materials, from the viewpoint of low flammability, silicone rubbers, fluororubbers, and urethane rubbers are preferable, and from the viewpoint of low moisture permeability, fluororubbers and butyl rubbers are preferable.

[0116] In order to reduce moisture permeability, it is also preferable to provide a thin layer of an inorganic material on the exterior. Such a thin layer of an inorganic material can be formed by, for example, vapor deposition of aluminum, aluminum oxide, titanium oxide, zinc oxide, etc. Among these, metal oxides are preferred from the viewpoint of radio wave absorption performance.

[0117] Furthermore, since scratches on the surface of the water-based electromagnetic wave absorbing material can affect the electromagnetic wave absorbing performance, the pencil hardness of the outermost layer of the exterior is preferably H or higher, which makes it easier to maintain the electromagnetic wave absorbing performance over a long period of time. The pencil hardness of the outermost layer of the exterior is more preferably 2H or higher, even more preferably 3H or higher, and even more preferably 4H or higher. Furthermore, the preferred coverage of the exterior is 30% or higher, more preferably 40% or higher, and even more preferably 50% or higher, of the entire aqueous electromagnetic wave absorbing material, with the upper limit being preferably 100% or lower, more preferably 95% or lower, and even more preferably 90% or lower.

[0118] Furthermore, when the water-based electromagnetic wave absorbing material of the present invention is composited with a polymer material as a matrix material, it has flexibility, and therefore, by utilizing this flexibility, it can be applied to various uses, and in addition, it may be reinforced by various methods when used.

[0119] As a method of reinforcing the water-based electromagnetic wave absorbing material of the present invention, for example, a frame material may be placed around the material, and examples of the frame material include metal, wood, resin, rubber, and glass.

[0120] Examples of reinforcing methods include integrating a sheet-shaped, plate-shaped, or bulk-shaped aqueous radio wave absorbing material with a fiber material, and mixing a fiber material with a cationic group-containing polymer to form an aqueous radio wave absorbing material. Examples of fiber materials include glass fiber, natural fiber, synthetic fiber, carbon fiber, carbon nanotube, ceramic fiber, and PTFE, and millifiber, microfiber, and nanofiber can be used without limitation. The fiber material may be a single fiber, a twisted yarn, or a coil, and may be a woven fabric or a nonwoven fabric.

[0121] Further, as a reinforcing method, a method of mixing a filler can be mentioned. Examples of fillers include particulate fillers, whiskers, fibrous substances, conductive substances, magnetic substances, metals, carbon materials, ceramics, nanofibers, microfibers, dyes, pigments, foaming agents, hollow particles, etc., and their particle sizes are not particularly limited, but are preferably 1 mm or less, more preferably 100 μm or less, and even more preferably 50 μm or less. In particular, when the water-based radio wave absorbing material is to be made to maintain its transparency, it is preferable to use a transparent filler. From the viewpoint of diffusing the heat generated when absorbing radio waves and making it less likely to ignite, a filler with high thermal conductivity is preferred. Examples of fillers with high thermal conductivity include, but are not limited to, alumina (20-30), sapphire (42), graphite (100-250), silicon carbide (200), boron nitride (30-50), aluminum nitride (150-250), silicon nitride (27), and magnesium oxide (45-60) (the numbers in parentheses represent thermal conductivity [W / m·K]). The preferred lower limit of the amount of filler added is preferably 1 part by weight or more, more preferably 5 parts by weight or more, and even more preferably 10 parts by weight or more, per 100 parts by weight of the aqueous electromagnetic wave absorbing material. The preferred upper limit of the amount added is preferably 900 parts by weight or less, more preferably 800 parts by weight or less, and even more preferably 400 parts by weight or less, per 100 parts by weight of the aqueous electromagnetic wave absorbing material.

[0122] When the water-based electromagnetic wave absorbing material of the present invention is formed into a sheet or plate, the thickness thereof is preferably 10 μm to 3 cm, more preferably 50 μm to 2 cm, and even more preferably 100 μm to 1.5 cm. When the water-based electromagnetic wave absorbing material of the present invention is formed into a sheet or plate, the basis weight at the thickest part is preferably 100 μg / cm from the viewpoint of sufficiently enhancing the electromagnetic wave absorbing performance. ２ It is preferable that the concentration is 500 μg / cm or more. ２ More preferably, it is 1000 μg / cm or more. ２ It is more preferable that the density is 5 g / cm or more, and although the conditions are not particularly limited, it is preferably 5 g / cm ２ The following is the result.

[0123] Furthermore, the water-based electromagnetic wave absorbing material of the present invention may contain other electromagnetic wave absorbing materials for the purpose of further improving or adjusting the electromagnetic wave absorbing performance, such as carbon materials such as graphite, metals, conductive polymers, conductive ceramics, and magnetic materials.

[0124] Furthermore, the water-based electromagnetic wave absorbing material of the present invention may be provided with a conductive layer. The conductive layer may be formed, for example, from ITO, PEDOT, copper, silver, or gold. The conductive layer may be solid or intermittent, and examples thereof include striped, mesh, and repeating patterns. A λ / 4 structure may be realized by utilizing the conductive layer. By appropriately patterning the conductive layer, the amount and angle of reflection and refraction of electromagnetic waves can also be controlled.

[0125] The water-based radio wave absorbing material of the present invention can be made into a sheet or plate shape and used in the form of, for example, a partition, a screen, a wall material (wall, wallpaper), a curtain, a window, an apron, a hat, glasses, clothes, a coat, etc.

[0126] The water-based microwave absorbing material of the present invention has heat-shielding properties due to its ability to block infrared light, and therefore, when used in the windows of buildings or vehicles, for example, it can suppress temperature increases inside the building or vehicle. Furthermore, when placed on the top surface of a solar cell, it can block heat rays without blocking visible light necessary for power generation. Solar cells can be heated to approximately 80°C by solar radiation, and this temperature increase reduces power generation efficiency. Furthermore, high device temperatures also shorten the device's lifespan. Use of the water-based microwave absorbing material of the present invention can improve the efficiency and extend the lifespan of solar cells. Furthermore, when placed on top of a plant, for example, it can block heat rays and suppress temperature increases without blocking solar radiation for photosynthesis, thereby improving the plant's growth environment.

[0127] Furthermore, when the aqueous radio wave absorbing material of the present invention is used as a curtain, it is preferable to use a material having high flexibility and low flammability as the above-mentioned exterior, and specific examples thereof include vinyl chloride resin, vinylidene chloride resin, chlorinated vinyl chloride resin, fluororubber, silicone rubber, urethane, polycarbonate, etc.

[0128] Alternatively, the water-based electromagnetic wave absorbing material of the present invention can be made into a bulk body (=lump) and placed indoors as a decorative object to absorb electromagnetic waves, or can be placed near an electric circuit, as a housing for an electric circuit product, or in a predetermined space inside the case of an electronic device to absorb unnecessary electromagnetic waves. Furthermore, the water-based electromagnetic wave absorbing material of the present invention can also be used as a sealing material for various electric and electronic parts.

[0129] Furthermore, the water-based electromagnetic wave absorbing material of the present invention may be used with another radio wave reflector disposed on the outside, thereby increasing the degree of freedom in designing reflection and absorption. Specific examples of the other radio wave reflector include a metal plate, a carbon-containing plate, a metal mesh, and glass or plastic with a conductive layer. In this case, the angles of the water-based electromagnetic wave absorbing material of the present invention and the other radio wave reflector can be made variable manually or automatically, thereby further increasing the degree of freedom in designing reflection and absorption. Furthermore, when the water-based electromagnetic wave absorbing material of the present invention is composited with a polymer material as a matrix material, its excellent flexibility allows it to be manually or automatically bent to a desired curvature before use.

[0130] The adhesive material of the present invention is also an adhesive material in which a deliquescent salt is complexed with a polymer material, the content of the deliquescent salt in the adhesive material is 20% by weight or more based on 100% by weight of the total of water and the deliquescent salt, and the deliquescent salt is deliquesced and dissociated into ions.

[0131] The adhesive material of the present invention contains a polymer material and a deliquescent salt, and since the content of the deliquescent salt is within the above-mentioned specific range, it can achieve excellent adhesiveness, has low flammability, and can be easily peeled off after use.

[0132] Well-known examples of adhesives and bonding agents include acrylic adhesives, SIS adhesives, and polyvinyl butyral. However, while these adhesives provide good adhesion and function well during use, they are difficult to disassemble after use or require many steps for disassembly. Therefore, there has been a demand for adhesives that can be easily separated after use while achieving sufficient bonding strength. In contrast, the adhesive material of the present invention can achieve excellent adhesive properties and strength, and can also be easily peeled after use; more specifically, it can be easily peeled using water.

[0133] In particular, composite materials such as laminated glass are difficult to disassemble into their original components, making them difficult to recycle. In contrast, when adhesives and pressure-sensitive adhesives such as the acrylic pressure-sensitive adhesives, SIS pressure-sensitive adhesives, and polyvinyl butyral are physically removed, the substrate is destroyed or the adhesive remains, making clean removal difficult. While the use of organic solvents is conceivable for removing acrylic pressure-sensitive adhesives, these methods are undesirable in terms of the working environment due to their flammability and adverse effects on the human body. Furthermore, organic solvents and hydrofluoric acid are used to remove polyvinyl butyral used in laminated glass for automobiles, which are also undesirable. In particular, when the substrate to be combined is an organic material such as plastic, the removal procedure using organic solvents may damage the substrate. In contrast, the adhesive material of the present invention can achieve excellent adhesiveness and strength and can be easily removed after use, effectively solving these problems and making it suitable for such applications.

[0134] In addition, although the above-mentioned pressure-sensitive adhesives and adhesives such as polyvinyl butyral can strengthen the bond between the substrate materials, they have the problem that once peeling occurs for some reason, they do not re-adhere. In contrast, the pressure-sensitive adhesive material of the present invention has sufficient bonding strength when in use, and even if unintentional peeling occurs, it will re-adhere upon re-contact, so it has the advantage of being less likely to lose its bond in applications where repeated deformation or vibration occurs.

[0135] Since the adhesive material of the present invention contains a deliquescent salt and water, it also has excellent radio wave absorption properties. Therefore, in addition to the method using water, it can also be easily peeled in a short time by irradiating it with microwaves (2.45 GHz) from a microwave oven or the like, generating high-temperature steam to spread the interface. In particular, since the adhesive material of the present invention has low flammability, it can suppress combustion or ignition even when exposed to microwaves, even when high heat is generated. Furthermore, the adhesive material of the present invention can be suitably used as a sticker to be attached to items that are easily damaged by peeling forces, such as clothing and furniture. It can be peeled off without damaging the clothing or furniture by wetting it with water, rather than by mechanical peeling. In this case, it is also preferable to provide a waterproof layer on the edge during use before peeling.

[0136] Examples of adhesives that can be peeled off with water include classic glues made from natural water-soluble polymers. However, glues made from such natural water-soluble polymers achieve their adhesive properties by hardening during adhesion, and because they are inflexible, they have the problem of peeling off when subjected to mechanical strain. Furthermore, although a peeled glue can be reapplied by wetting it with water, it is difficult to achieve a clean finish. Furthermore, while it is possible to keep natural water-soluble polymers wet for long periods of time, because they are naturally derived, there are problems with mold and bacteria growing, which can lead to poor appearance, and there is also the problem of the water-soluble polymer itself decomposing.

[0137] The polymer material to be contained in the adhesive material of the present invention is not particularly limited, and the same materials as the water-based radio wave absorbing material described above can be used in the same manner.

[0138] In addition, in the adhesive material of the present invention, the content of the deliquescent salt is 20% by weight or more based on 100% by weight of the total of water and the deliquescent salt, and the same deliquescent salt as in the above-mentioned water-based radio wave absorbing material can be used in the same manner. Furthermore, the preferred range of the content of the deliquescent salt in the adhesive material of the present invention is the same as that in the above-mentioned water-based radio wave absorbing material.

[0139] The adhesive material of the present invention may contain components other than the polymer material, the deliquescent salt, and water, and may contain salts other than the deliquescent salts, such as sodium chloride, potassium chloride, etc. Furthermore, the adhesive material of the present invention may contain a surfactant, an anionic polymer, an amphoteric polymer, etc., and may further have its pH adjusted by adjusting the type of monomer used or by using a buffer material.

[0140] Furthermore, the adhesive material of the present invention may be reinforced with a fiber material. Examples of the fiber material include glass fiber, natural fiber, synthetic fiber, carbon fiber, carbon nanotube, ceramic fiber, and PTFE. Milli-fiber, micro-fiber, and nano-fiber can be used without limitation. The fiber material may be a single fiber, a twisted yarn, a coil, a woven fabric, or a non-woven fabric.

[0141] The adhesive material of the present invention can be suitably used as a pressure-sensitive adhesive. In this case, the pressure-sensitive adhesive material of the present invention may be gelled and used as a pressure-sensitive adhesive in the form of a molded article. Pressure-sensitive adhesives using such pressure-sensitive adhesive materials of the present invention can be suitably used as pressure-sensitive adhesives for composite materials obtained by bonding various materials together. For example, a composite material may be obtained by contacting the pressure-sensitive adhesive material of the present invention with a first material and a second material to bond them together, or by polymerizing and / or crosslinking the pressure-sensitive adhesive material of the present invention in contact with the first material and the second material to bond the first material and the second material together to form a composite. Alternatively, the pressure-sensitive adhesive material of the present invention may be crosslinked and gelled or physically gelled in advance to form a sheet-like or layer-like molded article, which may then be interposed between the first material and the second material to form a composite. When a composite material is obtained, a continuous 0.2 cm thick sheet may be used. ２ The adhesive can be bonded by joining the surfaces of the above areas together. When forming a composite by bonding, it may be applied in a solid manner or in a dotted manner. When the adhesive material of the present invention is not used in an airtight exterior but is used in a state where it is in contact with the outside air, an increase in the humidity in the atmosphere increases the amount of moisture in the adhesive material, which reduces the adhesiveness and makes the adhesive material more likely to leak out. Therefore, it is preferable that the adhesive material is cross-linked gelled or physically gelled.

[0142] Taking advantage of its properties, the pressure-sensitive adhesive material of the present invention can be suitably used as a pressure-sensitive adhesive for, for example, radio wave shields, curtains, stickers, badges, cushioning materials, vibration-proofing materials, fire-resistant and flame-retardant materials, electrochemical devices, etc. In particular, when the pressure-sensitive adhesive material of the present invention is used as a pressure-sensitive adhesive for electrochemical devices, it can also function as an electrolyte membrane because it exhibits ion conduction.

[0143] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. Note that "parts" are by mass unless otherwise specified.

[0144] Experimental Example 1 (Evaluation of deliquescence) The salt compounds shown in Table 1 were prepared as salt compounds, and 400 mg of each was weighed out and placed on a plastic dish with a diameter of 2.5 cm. These were used as measurement samples, and their appearance was observed. The test was conducted in Kawasaki City, Kanagawa Prefecture, and started in August 2022. Five days after the start of the test, the samples were visually observed to determine whether they had become a flowable liquid. For those that had become a flowable liquid, AC impedance measurements were performed, and samples whose ionic conductivity was confirmed were determined to have deliquesced under the conditions. The conditions used were August 2022 (temperature 22°C, 77% RH).

[0145] The measurement samples were then moved to an indoor environment with open air and no humidity control, and changes over a long period of time were observed. When the humidity decreased in November 2022, some salt compounds were unable to retain moisture and became dry solids, as shown in Table 1. For samples that were in a fluid liquid state under the conditions of November 2022 (temperature 19°C, 42% RH), AC impedance measurements were performed, and samples that showed confirmed ionic conductivity were determined to have deliquesced under those conditions.

[0146] Furthermore, when the humidity further decreased in January 2023, some of the salt compounds were unable to retain moisture and became dry solids, as shown in Table 1. For those that were in a fluid liquid state under the conditions of January 2023 (temperature 14°C, 25% RH), AC impedance measurements were performed, and those that showed confirmed ionic conductivity were determined to have deliquesced under those conditions.

[0147] Then, in August 2023, when the humidity increased, the salt compounds that had dried into solids became fluid liquids again, as shown in Table 1. Under the conditions of August 2023 (temperature 30°C, 77% RH), AC impedance measurements were performed on the fluid liquids, and those that showed confirmed ionic conductivity were determined to have deliquesced under those conditions.

[0148]

[0149] As shown in Table 1, salt compounds that deliquesced under the conditions of August 2022 (temperature 22°C, 77% RH) and August 2023 (temperature 30°C, 77% RH) can also be said to deliquesce under the condition of 80% RH, and therefore can be judged to have deliquescent properties. In addition, ZnCF4, which maintained a deliquescent state under the conditions of November 2022 (temperature 19°C, 42% RH), ３ SO ３ , K(FSO ２ ) ２ N, CaCl ２ , MgCl ２ , LiCl, LiBr, ZnCl ２ , Li(FSO ２ ) ２ N, Li(CF ３ SO ２ ) ２ N, Na(FSO ２ ) ２ N and choline chloride are considered to be particularly useful, and even under the conditions of January 2023 (temperature 14°C, 25% RH), LiCl, LiBr, ZnCl ２ , Li(FSO ２ ) ２ N, Li(CF ３ SO ２ ) ２ N, Na(FSO ２ ) ２ N and choline chloride are considered to be even more useful.

[0150] In addition, calcium chloride (CaCl) in a deliquescent state was obtained by the same procedure as above. ２10 g of deliquescent solution (calcium chloride content: 25 wt%) was collected in August 2022 (temperature 22°C, 77% RH) and placed in an 80 μm thick polyethylene zip-top bag to create two samples. One was a zip-top sealed sample, and the other was an unsealed sample. These samples were then similarly observed in November 2022 (temperature 19°C, 42% RH) and January 2023 (temperature 14°C, 25% RH). The unsealed sample lost 5 g in weight and had dried and solidified, while the sealed sample lost up to 3 g in weight but did not solidify and maintained its deliquescent state. Furthermore, when observations were continued until August 2023 (temperature 30°C, 77% RH), the weights of both the sealed and unsealed samples recovered to their initial values. These results suggest that calcium chloride (CaCl ２ ) can also be said to be able to maintain a deliquescent state even in a low humidity environment. This is thought to be because the polyethylene layer reduces the movement of moisture. The moisture permeability of the polyethylene layer used is 7 g / day / m ２ is.

[0151] On the other hand, a 25 wt% aqueous solution of sodium chloride (NaCl) was prepared, placed in an 80 μm thick polyethylene zip bag, sealed, and tested in the same manner as above. The weight continued to decrease monotonically, and by August 2023 (temperature 30°C, 77% RH), salt precipitation was observed and 6.2 g of weight had been lost, with the weight never recovering.

[0152] Experimental Example 2 (Low-Temperature Evaluation) As a salt compound, CaCl ２ , LiCl, and NaCl were prepared, and aqueous solution samples consisting of salt compounds and water with salt concentrations shown in Table 2 were prepared, placed in glass sample bottles, and placed in a low-temperature bath to check the freezing behavior. The freezing behavior was checked one hour after placing in the low-temperature bath. Water to which no salt compounds were added was also evaluated as a reference.

[0153]

[0154] The results in Table 2 show that when water is used as a radio wave absorbing material, it freezes below 0°C. When freezing occurs, the interaction with radio waves weakens, the radio wave absorbing ability decreases, and there is a possibility that the volume expansion may destroy surrounding components, as well as problems such as loss of flexibility and decrease in transparency. Furthermore, when NaCl, which is not a deliquescent salt, is used, freezing occurs at temperatures up to -20°C at 20% by weight, and at 25% by weight, it does not freeze at -20°C, but at higher concentrations it becomes impossible to dissolve, so a lower freezing temperature than this cannot be expected. In contrast, when CaCl ２ It can be seen that LiCl does not freeze even at extremely low temperatures of -65°C or below.

[0155] Experimental Example 3 (Compositing with Matrix Material) One part of methylenebisacrylamide (Sigma-Aldrich) as a crosslinking agent and one part of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxymethylpropanone (Tokyo Chemical Industry Co., Ltd.) as a photopolymerization initiator were added to 100 parts of a (3-acrylamidopropyl)trimethylammonium chloride solution (Sigma-Aldrich, 75 wt % aqueous solution) as a matrix material, and dissolved. Then, calcium chloride (CaCl ２ ) and water, calcium chloride (CaCl ２ A precursor solution was prepared by adding 20 parts of calcium chloride (CaCl), 80 parts of water, and 30 parts of the polymer component in a weight ratio of 1:1. The solution was sandwiched between two glass plates spaced 3 mm apart and irradiated with 365 nm UV light to polymerize and crosslink the polymer. This produced a transparent and flexible calcium chloride (CaCl) polymer matrix containing a crosslinked polymer (B) having a side chain ammonium group and a repeating unit represented by the following formula (6): ２ A three-dimensionally crosslinked sheet containing PEG-1444 was obtained and cut into a size required for the experiment (size: 10 mm x 10 mm x 3 mm). The obtained three-dimensional crosslinked sheet was then placed in a glass sample bottle and placed in a low-temperature bath, as in Experimental Example 2, to check its freezing behavior. Even at -65°C, the sheet maintained its transparency, and no freezing was observed.

[0156] Experimental Example 4-1 (Radio Wave Absorption Characteristics) CaCl ２ and LiCl were prepared, and an aqueous solution sample (CaCl ２ Aqueous solutions of ion-exchanged water containing no salt compounds and LiCl aqueous solutions were prepared. Ion-exchanged water containing no salt compounds was also prepared as a reference. Each sample was evaluated for its radio wave absorption performance against radio waves in the gigahertz band by the following method.

[0157] First, each sample was poured into an acrylic resin water tank having an internal space of 17 cm in length, 17 cm in width, and 3 mm in thickness to prepare a test specimen. The thickness of the acrylic plate constituting the water tank was 2 mm.

[0158] Then, using the test specimen prepared above, the return loss (dB) and transmission loss (dB) of radio waves in the gigahertz band were measured in an environment of 25°C and 50% RH. Specifically, for the test specimen prepared above, radio waves were irradiated perpendicularly to the test specimen using the free space method, and the S (Scattering) parameters (S11) and (S21) of the reflected wave and transmitted wave were measured. The measurement frequency was in the range of 5.6 to 110 GHz. The larger the return loss and transmission loss, the better the absorption performance and shielding performance. The return loss can be calculated using the following formula. Furthermore, the return loss was converted to reflectance. Return loss (dB) = 20 log |S11|

[0159] The measurement conditions were as follows: - Device configuration - Free Space Microwave Measurement System (HVSFS, MAC Systems Corporation) - Network analyzer: Keysight Technologies (Agilent Technologies), N5227N 10 MHz to 67 GHz - Wave Guide T / R Module: Keysight Technologies (Agilent Technologies), N5260-60004 67 GHz to 110 GHz - Millimeter-wave controller: Keysight Technologies (Agilent Technologies), 8510XF - Transmitting and receiving antenna (C band): HVS Technology FSS-01 with dielectric lens - Transmitting and receiving antenna (X band): HVS Technology FSS-04 with dielectric lens - Transmitting and receiving antenna (Ku-W band): HVS Technology FSS-07 with dielectric lens・Coaxial cable: Keysight Technologies (Agilent Technologies), 11500-60002 1mm Test Cable - Measurement conditions - ・Focal length: 30.5cm (based on the antenna-sample distance) ・Polarization plane: Linear polarization (Horizontal / Vertical) ・Measurement frequency: 5.6 to 110GHz

[0160] The measurement results are shown in Table 3.

[0161]

[0162] From Table 3, it can be seen that water reflects a portion of the radio waves in the gigahertz band, and absorbs most of the radio waves that penetrate without being reflected. The transmission attenuation in water is below -40 dB, which means that the radio waves are attenuated to 1 / 10,000 or less. In contrast, the deliquescent salt CaCl ２ When the material contained LiCl, it showed reflection and absorption behavior similar to that of water, and it can be said that the material has excellent radio wave absorption properties as a water-based radio wave absorption material. Compared to the case of water only, the reflectance was slightly lower and the absorption was slightly higher.

[0163] Example 4-2 CaCl prepared in the same manner as in Example 4-1 ２To 100 g of the aqueous solution, 4 g of dimethylacrylamide as a polymerizable monomer and 0.04 g of Omnirad 2959 (a photopolymerization initiator manufactured by IGM Resins) were added, and the polymerization reaction was allowed to proceed by irradiating UV light from a high-pressure mercury lamp. The viscosity of this solution was 3100 cP. The resulting polymer solution was then poured into the same acrylic resin water tank used in Example 4-1, having an internal space measuring 17 cm in length, 17 cm in width, and 3 mm in thickness, and the radio wave absorption performance for 80 GHz radio waves was evaluated in the same manner as in Example 4-1. As a result, the reflectance for 80 GHz radio waves was 23%, and this result showed that the inclusion of a polymer reduced the reflectance compared to when the polymer was not included.

[0164] Example 4-3 Three types of polymer solutions were prepared in the same manner as in Example 4-2, except that the amounts of dimethylacrylamide and Omnirad 2959 were changed as shown in Table 4. The viscosities of the resulting polymer solutions at 25°C were as shown in Table 4. These polymer solutions were dropped onto the center of a 76 x 52 cm, 1 mm thick glass slide, and another glass slide of the same size was placed on top and fixed so that the gap between the two glass slides was 1 mm. At this time, the dropped polymer solution became a roughly circular droplet with a thickness of 1 mm and a diameter of approximately 15 mm. When this glass slide was placed vertically, it was observed that the droplets of the low-viscosity solution (polymer solution 4-3-1) gradually moved downward. Solutions with a viscosity of 50,000 cP or higher (polymer solutions 4-3-2 and 4-3-3) did not move or change shape, exhibiting low fluidity and excellent shape retention. In order to achieve the radio wave absorbing function, it is more desirable that the radio wave absorbing material is present in the required location with the required thickness, and therefore it is more preferable that the mobility of the material in response to an external force is low.

[0165]

[0166] Example 4-4 CaCl prepared in the same manner as in Example 4-1 ２To 100 g of the aqueous solution, 30 g of (3-acrylamidopropyl)trimethylammonium chloride solution (Sigma-Aldrich, 75 wt % aqueous solution), 0.3 g of methylenebisacrylamide (Sigma-Aldrich), and 0.3 g of Omnirad 2959 (IGM Resins, photopolymerization initiator) were added and stirred to obtain a mixed solution. The resulting mixed solution was cast into a size of 15 cm x 15 cm x 0.3 cm and then irradiated with UV light from a high-pressure mercury lamp to obtain a crosslinked sheet. The radio wave absorption performance of the resulting crosslinked sheet for 80 GHz radio waves was evaluated in the same manner as in Example 4-1. The reflectance was 45% and the transmission attenuation was -20 dB or less (transmittance 1% or less). The radio wave absorption performance of the resulting crosslinked sheet in the 2 to 6 THz range was measured using a terahertz spectroscopy / imaging analysis platform TAS7400TS (manufactured by Advantest Corporation). Transmittance measurements were performed at normal incidence, and reflectance measurements were performed at an incident angle of 10°. The reflectance in the 2 to 6 THz range was 20% or less throughout the entire range, and the transmission attenuation in the 2 to 6 THz range was -20 dB or less (transmittance of 1% or less) throughout the entire range. Furthermore, the radio wave absorption performance of the resulting crosslinked sheet in the 115 to 1500 THz range was measured using an ultraviolet-visible-near-infrared spectrophotometer (manufactured by JASCO Corporation, V-670) with an optical path length of 10 mm. A graph showing the transmittance in the 115 to 1500 THz range is shown in Figure 1. These results confirmed that the crosslinked sheet obtained exhibited a transmittance of approximately 90% in the visible light region, and had high transparency while also possessing radio wave shielding performance over a wide range of frequencies from 15 to 1500 THz.

[0167] Example 4-5 CaCl prepared in the same manner as in Example 4-1 ２10 g of aqueous solution (viscosity: 2.9 cP), 82 g of silicone for molding, and 8 g of silicone curing agent were weighed out and placed in a plastic cup and mixed thoroughly. The mixture obtained by mixing had the characteristic that it dispersed to some extent while mixing, but gradually began to separate into two layers when mixing was stopped. The entire amount of the mixture obtained was poured into a glass petri dish and left to stand for 24 hours in an environment of 25°C, whereupon the silicone cured and the radio wave absorbing material, CaCl ２ A silicone rubber with a slight dispersion of the aqueous solution was obtained. On the other hand, more than 90% of the CaCl ２ The aqueous solution did not compound with the silicone rubber and remained in the glass petri dish in an uncomplexed state. Next, 10 g of the polymer solution prepared in the same manner as in Example 4-3, 82 g of molding silicone, and 8 g of silicone curing agent were weighed out and placed in a plastic cup and mixed thoroughly. The mixture obtained by mixing became homogeneous, and a cloudy finely dispersed solution was obtained in which the polymer solution was finely dispersed in the molding silicone. The obtained finely dispersed solution was poured into a glass petri dish to a thickness of 10 mm and left to stand for 24 hours in an environment of 25°C, whereupon the silicone cured, yielding a silicone rubber in which the polymer solution was finely dispersed as a radio wave absorbing material. The radio wave absorption performance of the obtained silicone rubber was evaluated in the same manner as in Example 4-4, and it was found to have radio wave absorption performance in the range of 2.45 GHz to 220 THz.

[0168] Example 4-6 A 17 cm square, 100 μm thick soft PVC sheet (water content 1 wt % or less) was attached to both sides of the crosslinked sheet produced in Experimental Example 4-4, and the edges were glued together to obtain a radio wave absorber with a flexible exterior. The obtained radio wave absorber with an exterior was transparent and flexible, and could be easily wrapped around a 1 cm diameter pipe without damage or curling. The radio wave absorption performance of the obtained radio wave absorber was evaluated in the same manner as in Example 4-4, and it was found to have radio wave absorption performance in the range of 2.45 GHz to 220 THz. Furthermore, when the intensity of the reflected radio wave at 80 GHz of the crosslinked sheet of Example 4-4 was taken as 100%, the relative intensity of the reflected radio wave of the radio wave absorber with an exterior produced in this example was 55%. This result demonstrates that the inclusion of an exterior can reduce reflected radio waves. Furthermore, when the crosslinked sheet prepared in Experimental Example 4-4 was immersed in water, fluctuations in the refractive index were observed in the water, which suggested that salt was eluting into the water. On the other hand, when the radio wave absorber with an exterior prepared in this example was immersed in water, no change occurred in the water, confirming that no salt was eluted into the water. Furthermore, since no salt was eluted into the water, it can be said that it is suitable for outdoor installation. In particular, by taking advantage of the property of no salt elution, it can be used, for example, as a curtain. Furthermore, when a large area is required, it is preferable to use a fiber-reinforced exterior material to prevent it from breaking under its own weight. Furthermore, it is thought that a similar radio wave absorber can be constructed using a flexible exterior material other than polyvinyl chloride resin, such as silicone rubber. In this example, a radio wave absorber with an exterior obtained in the same manner as above, except for a size suitable for a curtain, was hung as a curtain at the entrance of a building for one year. It was confirmed that there was no change in color tone or appearance, and that it still exhibited good radio wave absorbing performance even after one year.

[0169] Experimental Example 5 (Adhesion Test) Solution samples having the following compositions were prepared: Sample No. 1: 80 parts of water, CaCl ２ Sample No. 2: 80 parts water, 20 parts ethanol, 4 parts polyacrylamide (Mn = 40,000) ２20 parts of cellulose acetate, 4 parts of polyacrylamide (Mn=6,000,000) Sample No. 3: Precursor solution prepared in Experimental Example 3 Sample No. 4: 80 parts of water, CaCl ２ 20 copies

[0170] Sample No. 1 was a viscous but fluid solution (viscosity: 41 cP), Sample No. 2 was a highly viscous solution with low fluidity (viscosity: 674,000 cP), and Sample No. 3 was a highly fluid solution (viscosity: 1.5 cP). Two glass slides (7.5 cm x 2.5 cm x 110 μm) were prepared. A few drops of each solution sample were placed on one of the slides 1.5 cm from the edge. The other slide was then placed on top of the first slide, offset lengthwise, so that the overlapping length was 3 cm (overlapping area: 3 cm x 2.5 cm), and pressed down sufficiently to prevent the solution from leaking out from the edge. This was used as a test specimen. Sample No. 3 was then subjected to a three-dimensional crosslinking operation by further irradiating it with 365 nm UV light.

[0171] Then, one of the resulting glass slides was held, while the other glass slide was left unheld and held horizontally (with the glass surface perpendicular to the ground) for 10 seconds. As a result, for the test pieces of Samples 1 to 3, the glass slide on the free side remained in its original position without tilting. From this result, it can be said that the two glass slides were sufficiently bonded at the 3 cm overlapping portion and had excellent adhesive properties. On the other hand, for the test piece of Sample 4, the glass slide on the free side fell off the moment it was placed in a horizontal position.

[0172] Furthermore, when the test pieces of Samples No. 1 to 3 subjected to the above test were completely submerged in a water tank and left to stand for about 4 hours, each sample spontaneously peeled off and separated into two glass slides. This indicates that the samples can be peeled off without requiring mechanical force and function as pressure-sensitive adhesives with excellent recyclability.

[0173] Experimental Example 6 (Combustion Test) A combustion test was conducted on Samples No. 1 to 3 prepared in Experimental Example 5 above. Sample No. 3 was prepared by irradiating 365 nm UV light to perform a three-dimensional crosslinking process. For comparison, a combustion test was also conducted on an acrylic transparent double-sided adhesive sheet (manufactured by Daiso Co., Ltd.) and a polyurethane transparent double-sided adhesive sheet (manufactured by Daiso Co., Ltd.). The combustion test was conducted by measuring 100 mg of the liquid sample and cutting out a 100 mg piece of the sheet sample. Each sample was placed on a stainless steel plate and exposed to a lighter flame for 5 seconds to check the combustion behavior. The results are shown in Table 5.

[0174]

[0175] From the results in Table 5, it can be confirmed that the water-based radio wave absorbing material and adhesive material of the present invention also have excellent flame resistance.

[0176] Experimental Example 7 (Manufacturing of Manganese Battery) Manganese oxide (MnO) was used as an electrode active material. ２ 100 parts of acetylene black as a conductive additive, 10 parts of PTFE powder (polytetrafluoroethylene powder) as a binder and reinforcing material, 1 part of polyacrylamide (Mn: 6,000,000), 1 part of zinc chloride (ZnCl) as an electrolyte, which is a deliquescent salt ２ 2 parts of zinc chloride and 8 parts of water as a solvent were weighed into a mortar and mixed thoroughly to obtain a clay-like positive electrode mixture. In the obtained positive electrode mixture, zinc chloride dissolved in water to form an aqueous solution, and polyacrylamide dissolved in the solution. The obtained positive electrode mixture was rolled out thinly with a roller to obtain a 1 mm thick sheet. This was cut into 10 mm squares and placed on a 1 mm thick, 10 mm square platinum sheet to form a positive electrode sheet.

[0177] A solution was obtained by adding and dissolving 1 part of methylenebisacrylamide (manufactured by Sigma-Aldrich) as a crosslinking agent and 1 part of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxymethylpropanone (manufactured by Tokyo Chemical Industry Co., Ltd.) as a photopolymerization initiator to 100 parts of (3-acrylamidopropyl)trimethylammonium chloride solution (manufactured by Sigma-Aldrich, 75 wt % aqueous solution). Then, zinc chloride (ZnCl ２ ) and water, zinc chloride (ZnCl ２ A precursor solution was prepared by adding 20 parts by weight of (3-acrylamidopropyl)trimethylammonium chloride (ZnCl), 80 parts by weight of water, and 30 parts by weight of a polymer component (a polymer component obtained by polymerizing (3-acrylamidopropyl)trimethylammonium chloride contained in the solution prepared above). The solution was sandwiched between two glass plates spaced 100 μm apart, and irradiated with 365 nm UV light to polymerize and crosslink the polymer, thereby obtaining a transparent and flexible zinc chloride (ZnCl ２ )-containing three-dimensionally crosslinked electrolyte film was obtained (ionic conductivity at 25°C: 2.7 × 10 －３ S / cm). The obtained electrolyte film was cut into a 12 mm square and placed on the positive electrode sheet prepared above to obtain an electrolyte / positive electrode laminate.

[0178] A 100 μm-thick, 11 mm square zinc plate was then placed on the electrolyte film of the electrolyte / cathode laminate obtained above as the negative electrode, and gently pressed down to adhere the layers together, yielding a manganese battery. Battery evaluation of the resulting manganese battery revealed that it functioned as a battery with an electromotive force of approximately 1.5 V. Because the adhesive material of the present invention has ionic conductivity, it can be used as an electrolyte for electrochemical devices. Furthermore, despite the absence of an exterior coating to prevent drying, the use of a deliquescent salt makes it less susceptible to moisture loss and easier to maintain functionality. Furthermore, the polymer composite significantly reduces the risk of electrolyte seeping out of the device. When disposing of the battery, the individual layers can be easily separated by immersing the battery in water, making it highly recyclable.

[0179] Experimental Example 8 (Fabrication of an Electrochromic Device) A solution was obtained by dissolving 3 mg of Poly(Fe-btpyb) Purple (Tokyo Chemical Industry Co., Ltd.), a dye for electrochromic devices, in 1 mL of methanol. The obtained solution was then spray-coated onto the conductive surface of a 5 cm square ITO-PET film and allowed to stand for a while to evaporate the methanol, thereby obtaining a purple electrochromic electrode. The amount of coating was set to an amount that allowed the view on the other side to be seen, since a relatively thick coating would impair transparency. Next, an electrolyte film (ionic conductivity at 25°C: 9.0 x 10) was prepared in the same manner as in Example 7, except that the electrolyte salt was changed to LiCl. －３ The resulting electrochromic device was obtained by cutting a 6 cm square piece of ITO-PET film (S / cm) into a 6 cm square and laminating it on the electrochromic electrode. Furthermore, a 5 cm square ITO-PET film was laminated on top of this as a counter electrode. In the resulting electrochromic device, the layers were well adhered to each other, and no additional external restraints were required.

[0180] When a voltage of 3 V was applied to the electrochromic electrodes of the resulting electrochromic device, the purple color gradually faded and decolorization was observed. Next, when the polarity of the power supply was reversed and a voltage of -3 V was applied, coloration was observed again. This behavior could be repeated, confirming that the device functions as an electrochromic device. Although this electrochromic device does not have an exterior to prevent drying, the use of deliquescent salt makes it less likely to lose moisture and easier to maintain its functionality. Furthermore, because the deliquescent salt is complexed with a polymer, it is extremely unlikely for the electrolyte to seep out of the device. When disposing of the device, the individual layers can be easily separated by immersing the device in water, making it highly recyclable.

Claims

1. A water-based radio wave absorbing material containing a deliquescent salt in a proportion of 20% by weight or more out of a total of 100% by weight of water and the deliquescent salt, in which the deliquescent salt has deliquesced and undergoes ionic dissociation.

2. The water-based radio wave absorbing material according to claim 1, wherein the content of the organic compound having a flash point is less than 10 parts by weight per 100 parts by weight of the total of the water and the deliquescent salt.

3. The deliquescent salt contains CaCl as a main component. ２ , LiCl, LiBr, MgCl ２ , ZnCl ２ , Li(FSO ２ ) ２ N, Li(CF ３ SO ２ ) ２ N, Na(FSO ２ ) ２ 3. The water-based radio wave absorbing material according to claim 1, further comprising at least one selected from the group consisting of N and organic ammonium halides.

4. The water-based radio wave absorbing material according to any one of claims 1 to 3, wherein the deliquescent salt is composited with a matrix material.

5. The water-based radio wave absorbing material according to claim 4, wherein said deliquescent salt is dispersed in said matrix material.

6. The water-based radio wave absorbing material according to claim 4 or 5, wherein the matrix material is a polymer material.

7. The water-based radio wave absorbing material according to any one of claims 4 to 6, wherein the content of said matrix material is 8 parts by weight or more relative to 100 parts by weight of the total of said water and said deliquescent salt.

8. The water-based radio wave absorbing material according to any one of claims 4 to 7, further comprising a polymerizable monomer and / or a crosslinkable monomer.

9. The water-based radio wave absorbing material according to claim 4, wherein the matrix material is crosslinked.

10. The water-based radio wave absorbing material according to any one of claims 1 to 9, which has a viscosity of 50,000 cp or more at 25°C.

11. The water-based electromagnetic wave absorbing material according to any one of claims 1 to 10, further comprising an outer casing.

12. The water-based radio wave absorbing material according to claim 11, wherein the outer covering is made of a rubber material or a chlorine-containing polymer.

13. The water-based radio wave absorbing material according to claim 11 or 12, wherein the water content of the outer packaging is 5% by weight or less.

14. An adhesive material comprising a deliquescent salt complexed with a polymer material, wherein the content of the deliquescent salt in the adhesive material is 20% by weight or more out of a total of 100% by weight of water and the deliquescent salt, and the deliquescent salt has deliquesced and undergoes ionic dissociation.

15. The adhesive material according to claim 14, wherein the polymer material has a three-dimensional crosslinked structure.

16. A composite material formed by bonding together via the adhesive material according to claim 14 or 15.

17. An electrochemical device bonded via the adhesive material according to claim 14 or 15.

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