Gel containing polymer of urea derivative

Abstract

To provide a gel that includes a liquid selected from ether-based, ester-based, nitrile-based, sulfonyl-based liquids, and silicone.SOLUTION: The present invention provides a gel containing a polymer as a gelling agent, wherein the polymer has a presence ratio of structural units represented by formula (1) in a molar ratio of 0.05 to 0.95 relative to the structural units constituting the entire polymer, and the gel is primarily composed of at least one liquid selected from ether-based, ester-based, nitrile-based, sulfonyl-based liquids, and silicone. (In formula (1), X1 is -O- or -NH-, R1 is a C2-12 alkylene or phenylene group, R2 is a C8-30 straight-chain, branched, or cyclic hydrocarbon group, the hydrocarbon group may include -O- or an unsaturated bond, and a fluorine atom may be present on a carbon atom that is at least two positions away from -NHCONH-).SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a gel containing a gelling agent and a liquid, and more particularly to a gel containing a polymer of a urea derivative as a gelling agent and at least one liquid selected from ethers, esters, nitriles, sulfonyls, and silicones (hereinafter sometimes referred to as functional liquid) as a main component of the gel liquid. Because the gel of the present invention has excellent flexibility and high mechanical strength, it is expected to be widely used as a material for artificial organs such as artificial cartilage, artificial skin, and artificial breasts; coating agents such as coating agents for catheters, guide wires, etc., coating agents for the circuits of blood purification filters, and coating agents for the drive parts of artificial joints; materials for medical devices such as cell culture sheets; gel bodies used in cosmetic packs, bandages, base materials for fragrances, toiletries, etc.; raw materials for cosmetics; raw materials for adhesive layers of films for protecting FPD screens; paints such as ship bottom paints to prevent the adhesion of shellfish such as barnacles; vibration-proof materials for absorbing automobile vibrations; raw materials for electrolytes in lithium ion secondary batteries; energy-related materials such as actuator materials and piezoelectric elements; and printing materials. [Background technology]

[0002] Patent Document 1 discloses a technique for an aqueous gel that is excellent in flexibility and mechanical strength without having a structure in which two types of polymers are mutually compounded. Patent Document 1 also discloses an organic solvent-based gel in part, in the examples, in which the liquid contains cyclohexanone. However, the technique does not specifically disclose gels that contain functional liquids such as ether-based liquids, ester-based liquids, nitrile-based liquids, sulfonyl-based liquids, and silicones. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2016-210912 A Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention discloses a technology relating to a gel material containing a functional liquid selected from ethers, esters, nitriles, sulfonyls, and silicones. [Means for solving the problem]

[0005] As a result of intensive research, the present inventors have found that a polymer having a urea skeleton with a specific structure in its side chain has a gelling ability with respect to a functional liquid selected from ethers, esters, nitriles, sulfonyls, and silicones, and have completed the present invention. That is, the present invention is as follows.

[0006] [1] A gel comprising a polymer as a gelling agent, the polymer having a molar ratio of a constituent unit represented by formula (1) of 0.05 to 0.95 relative to the constituent units constituting the entire polymer, and the gel liquid containing at least one liquid selected from ethers, esters, nitriles, sulfonyls, and silicones as a main component. TIFF2025029422000002.tif1579(in formula (1), 1 is -O- or -NH-, and R 1 is an alkylene or phenylene having 2 to 12 carbon atoms, and R 2 is a straight chain hydrocarbon group having 8 to 30 carbon atoms, a branched hydrocarbon group having 8 to 30 carbon atoms, or a cyclic hydrocarbon group having 8 to 30 carbon atoms, which may contain -O- or an unsaturated bond, and in this hydrocarbon group, hydrogen on a carbon atom two or more away from -NHCONH- may be replaced with fluorine.

[0007] [2] The gel according to [1], wherein the polymer in the gel is a polymer in which the abundance ratio of the constitutional unit represented by formula (1) according to [1] is 0.05 to 0.7, in terms of molar ratio, relative to the constitutional units constituting the entire polymer.

[0008] [3] [3] The gel according to [2], wherein the polymer in the gel is a polymer having a structure in which constitutional units represented by formula (1) according to [1] are continuously bonded.

[0009] [4] The gel according to [3], wherein the polymer in the gel is a polymer having at least one selected from a structural unit derived from a (meth)acrylic acid ester and a structural unit derived from a polyether, in addition to the structural unit represented by formula (1) according to [1].

[0010] [5] The gel according to [4], further comprising an ionic substance.

[0011] [6] The gel according to [3], wherein the polymer in the gel is a polymer having at least one silicone-derived structural unit in addition to the structural unit represented by formula (1) according to [1].

[0012] [7] A polymer having structural units represented by formula (1) and formula (3), or a polymer having structural units represented by formula (1) and formula (4). TIFF2025029422000003.tif1579(in formula (1), 1 is -O- or -NH-, and R 1 is an alkylene or phenylene having 2 to 12 carbon atoms, and R 2 is a straight chain hydrocarbon group having 8 to 30 carbon atoms, a branched hydrocarbon group having 8 to 30 carbon atoms, or a cyclic hydrocarbon group having 8 to 30 carbon atoms, which may contain -O- or an unsaturated bond, and in this hydrocarbon group, hydrogen on a carbon atom two or more away from -NHCONH- may be replaced with fluorine. TIFF2025029422000004.tif46153 (In formula (3) and formula (4), m is independently an integer of 1 to 150.) Effect of the Invention

[0013] According to the present invention, a gel material containing a functional liquid selected from ethers, esters, nitriles, sulfonyls, and silicones can be easily produced. [Brief description of the drawings]

[0014] [Figure 1] FIG. 1 is a photograph of a sample bottle containing the gel 1 obtained in [Example 1]. [Diagram 2] 2 is a photograph of a sample bottle containing the liquid obtained in [Comparative Example 1]. This liquid was obtained by carrying out a gelation operation in the same manner as in Example 1 using the polymer r1 obtained in Comparative Synthesis Example 1 as a gelling agent, but no gel was obtained, and the liquid was obtained in a state in which it maintained fluidity. [Diagram 3] 3 is a photograph of a sample bottle containing the solid and liquid obtained in [Comparative Example 2]. The solid and liquid were obtained by using polymer r2 obtained in the same manner as in Synthesis Example 1 of JP 2022-159191 A as a gelling agent and performing a gelling operation in the same manner as in Example 1, but no gel was obtained. The solid and liquid were obtained in a separated state. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Hereinafter, the embodiments of the present invention will be described in detail, but the following description is an example (representative example) of the embodiment of the present invention, and the present invention is not limited to these contents. In addition, the embodiments of the present invention can be appropriately combined.

[0016] The gel of the present invention is characterized in that it contains a gelling agent and a liquid, and contains as the gelling agent a polymer composed of structural units including a structural unit represented by formula (1). The structural units represented by formula (1) exhibit strong interactions between each other, and thus can act as a gelling agent for a functional liquid selected from ethers, esters, nitriles, sulfonyls, and silicones. That is, the gel of the present invention is formed by hydrogen bonding between the urea moieties of the polymer used as a gelling agent in the present invention, or with oxygen atoms derived from acryloyl groups, to form "intermolecular crosslinks". It is common technical knowledge for those skilled in the art that the crosslinked structure forming the gel can also be generated by hydrogen bonding, and if necessary, the column "2.1 Crosslinking Methods" in Chapter 1, Basics, Definition and Classification of Gels, Section 1, What is a Gel? -In place of an introduction- on pages 4-5 of "Gel Handbook" by Yoshihito Nagata and Kanji Kajiwara (editors in chief), published by NTS Co., Ltd. on November 28, 1997, may be referred to.

[0017] The gelling agent used in the present invention is R 2 The above-mentioned "intermolecular cross-linking" is further strengthened by the substituent of formula (1). In addition, the structural units other than the structural unit represented by formula (1) have affinity for functional liquids. Due to these characteristics, the gelling agent used in the present invention has high gelling ability for functional liquids.

[0018] TIFF2025029422000005.tif1579(in formula (1), 1 is -O- or -NH-, and R 1 is an alkylene or phenylene having 2 to 12 carbon atoms, and R 2 is a straight chain hydrocarbon group having 8 to 30 carbon atoms, a branched hydrocarbon group having 8 to 30 carbon atoms, or a cyclic hydrocarbon group having 8 to 30 carbon atoms, which may contain -O- or an unsaturated bond, and in this hydrocarbon group, hydrogen on a carbon atom two or more away from -NHCONH- may be replaced with fluorine.

[0019] In the constitutional unit represented by formula (1), R 2 When the chain length of the hydrocarbon group of R is long, it exhibits gelling ability with functional liquids such as polyether and silicone. 2 R is preferably a hydrocarbon group having 8 or more carbon atoms, and more preferably a hydrocarbon group having 10 or more carbon atoms. In addition, since the production cost decreases when the carbon number is small, R 2 is preferably a hydrocarbon group having 30 or less carbon atoms. Furthermore, since R has a high gelling ability,2 is preferably a straight-chain hydrocarbon group.

[0020] When the hydrocarbon group contains -O-, in consideration of the stability of the compound, CH3-O-CH2-O- in which two oxygen atoms are not adjacent is preferred to CH3-OO-CH2- in which two oxygen atoms are adjacent.

[0021] To obtain the desired gelling performance, R 2 The hydrogen on the carbon of the hydrocarbon group may be replaced by fluorine. The replacement position is the hydrogen on the carbon that is two or more carbons away from -NHCONH-.

[0022] Suitable examples of the constitutional unit represented by formula (1) include structures represented by the following formulas (1-1) to (1-27). TIFF2025029422000006.tif12497

[0023] TIFF2025029422000007.tif172121

[0024] TIFF2025029422000008.tif149121

[0025] TIFF2025029422000009.tif151123

[0026] In the gelling agent used in the present invention, multiple types of constitutional units represented by formula (1) in the polymer may be selected in order to exhibit the desired gelling ability.

[0027] In order to develop the desired gelling ability, the polymer, which is the gelling agent used in the present invention, preferably has a structural unit other than the structural unit represented by formula (1) (hereinafter, sometimes referred to as structural unit B). There is no particular limitation on such structural unit B, and structures derived from known monomers and polymers can be used. In this case, in order to gel a functional liquid selected from ethers, esters, nitriles, sulfonyls, and silicones, it is preferable to select a structural unit B having a structure that is highly compatible with these liquids. For example, when at least one liquid selected from ethers, esters, nitriles, and sulfonyls is used, such structural unit B is preferably a structure containing an ether bond or an ester bond. Also, for example, when silicone is used as the liquid, such structural unit B is preferably a structure derived from silicone.

[0028] As such structural unit B, it is preferable to select a structural unit represented by the following formula (2). TIFF2025029422000010.tif1487 (in formula (2), R 3 is hydrogen or methyl, and R 10 is a group selected from the structures represented by the following formulas (20) to (24), pyridyl, or -CN.

[0029] TIFF2025029422000011.tif124126 (in formulas (20) to (24), 11 is -O-, -NH-, or -NR 11 - and R 11 is hydrogen, linear alkyl having 1 to 30 carbon atoms, branched alkyl having 3 to 8 carbon atoms, cyclic alkyl having 3 to 8 carbon atoms, or phenyl, and the non-adjacent -CH2- in the alkyl is -O-, -NMe-, or -NMe2 + -, -CH2- of alkyl may be replaced by -CO-, hydrogens on non-adjacent carbons of alkyl may be replaced by -OH or -N(CH3)2, -CH3 of alkyl may be replaced by -CO2H, -CO2 - , -SO3 -, or -SO3K may be substituted, R 12 is -H, -CH3, -OCH3, -OH, -CO2H, -OCOCH3, -N(CH3)2, or -SO3Na, Me is methyl, n is an integer from 4 to 140, and * represents a bonding site.

[0030] As the other structural unit B, it is also preferable to select a structural unit represented by the following formula (3) or (4). TIFF2025029422000012.tif46153 (In formula (3) and formula (4), m is independently an integer of 1 to 150.)

[0031] In the gelling agent used in the present invention, the abundance ratio of the constitutional unit represented by formula (1) and the constitutional unit B can be determined from the viewpoint of exhibiting gelling ability for a functional liquid selected from ethers, esters, nitriles, sulfonyls, and silicones, and the abundance ratio of the constitutional unit represented by formula (1) is, in molar ratio, 0.05 to 0.95, preferably 0.1 to 0.9, more preferably 0.1 to 0.7, and even more preferably 0.1 to 0.6, relative to the constitutional units constituting the entire polymer.

[0032] As described above, in order to exhibit gelling ability for functional liquids selected from ethers, esters, nitriles, sulfonyls, and silicones, the polymer used as a gelling agent in the present invention preferably has a structural unit B that is compatible with these liquids. In this case, the molar ratio of the structural unit B to the structural units constituting the entire polymer is 0.05 to 0.95, preferably 0.1 to 0.9, more preferably 0.3 to 0.9, and even more preferably 0.4 to 0.9.

[0033] In the gel of the present invention, from the viewpoint of obtaining a gel having excellent flexibility and high mechanical strength at the same time, or from the viewpoint of reducing the amount of gelling agent, it is preferable that the constitutional units represented by formula (1) are continuously bonded in the structure of the gelling agent, i.e., the gelling agent used in the present invention is preferably a block copolymer in which the constitutional units represented by formula (1) constitute blocks.

[0034] In order to adjust the gelling ability, in the gelling agent used in the present invention, the constitutional unit represented by formula (1) may be a constitutional unit represented by multiple types of formula (1). For the same reason, the constitutional unit B may be a constitutional unit B of multiple types.

[0035] A gel containing a polymer having a structural unit represented by formula (1) as a gelling agent used in the present invention has a characteristic that it changes from a gel state to a solution state when heated, in a state in which it does not contain a crosslinkable group that forms a crosslinked structure by a covalent bond or an ionic bond. Therefore, it can be preferably used for applications to articles that utilize such a phase change. On the other hand, in order to prevent such a phase change, a reactive site that can be crosslinked by heat or light may be introduced into a part of the structural unit of the gelling agent used in the present invention.

[0036] The polymer that becomes the gelling agent can be produced by a known method. In this case, the structural unit of the structure represented by formula (1) can be derived by using an acrylic monomer having -NCO or a protected -NCO as its precursor. Examples of such monomers include 2-isocyanatoethyl acrylate (Karenz (registered trademark) AOI), 2-[(3,5-dimethylpyrazolyl)carbamoyl]ethyl acrylate, and 2-(O-(1'methylpropylideneamino)carboxyamino)ethyl acrylate. "Karenz" is a trade name of a product manufactured by Resonac Corporation.

[0037] The method of obtaining a precursor by polymerization using the above-mentioned acrylic monomer having -NCO or protected -NCO, and then converting it into the structure represented by formula (1) is preferred as a method for producing the polymer used in the present invention because of its ease of production. In this case, it is preferable to use an acrylic monomer having a protected -NCO as a raw material in order to avoid gelation during the polymerization stage.

[0038] The conversion of a precursor having a protected NCO group to a polymer having a structure represented by formula (1) can be carried out according to a known method. That is, the precursor can be obtained by reacting with a commercially available or known compound having -NH2. Examples of commercially available or known compounds having -NH2 include alkylamines having 8 or more carbon atoms and aniline derivatives substituted with alkyl or alkoxy. The amount of these compounds having -NH2 added during the reaction is 0.8 or more in molar ratio to the -NCO equivalent in the polymer. Since the compound having -NH2 reacts quantitatively with the -NCO equivalent, this range is consistent with the technology of the present invention. Similarly, the upper limit of the amount of the compound having -NH2 used is preferably 2.0 or less in the above molar ratio, more preferably 1.5 or less, and most preferably 1.2 or less, in order to easily purify the polymer. In the above calculation, the molar ratio of the -NCO equivalent contained in the polymer can be calculated from the amount of the polymer used, the ratio of the -NCO equivalent present in the polymer, and the molecular weight of the structural unit containing the -NCO equivalent. The ratio of -NCO equivalents in the polymer is as follows: 1 It can be calculated from measurements such as H-NMR.

[0039] The reaction temperature during conversion to the structure represented by the above formula (1) is preferably 80°C or higher in order to rapidly proceed with the reaction. It is also preferably 120°C or lower in order to prevent decomposition of the polymer. 100°C is the most preferred reaction temperature. The higher the temperature, the shorter the conversion time. To ensure a sufficient conversion rate, the reaction time at 100°C is preferably 30 minutes or more, and to prevent decomposition of the polymer, it is preferably 2 hours or less. One hour is the most preferred reaction time.

[0040] The solvent that can be used in the conversion to the structure represented by formula (1) is a solvent that has no or low reactivity with the precursor polymer. In this case, a solvent that dissolves both the precursor polymer and the polymer used in the present invention is preferable. Examples of such solvents include hydrocarbon solvents such as toluene and xylene, ester solvents such as n-propyl acetate, butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and γ-butyrolactone, ether solvents such as tetrahydrofuran (THF), 1,4-dioxane, anisole, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, and dipropylene glycol dimethyl ether, dimethylformamide, diethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, ethyl methyl carbonate, and diethyl carbonate.

[0041] As the monomer that provides the structural unit B in the polymer that serves as the gelling agent, a known (meth)acrylic acid derivative can be used. Examples of such known compounds include alkyl (meth)acrylates having 1 to 8 carbon atoms, propargyl (meth)acrylate, allyl (meth)acrylate, cyclohexyl (meth)acrylate, 1-adamantyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, oxotetrahydrofuran-3-yl (meth)acrylate, ethylene glycol monoacetoacetate mono(meth)acrylate, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl) (meth)acrylate, 2-hydroxyethyl (Meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-(trimethoxysilyl)propyl (meth)acrylate, 3-(triethoxysilyl)propyl (meth)acrylate, 3-(tris(trimethylsilyloxy)silyl)propyl (meth)acrylate, 3-(dimethoxy(methyl)silyl)propyl (meth)acrylate, 3-(diethoxy(methyl)silyl)propyl (meth)acrylate, 3-sulfopropyl potassium (meth)acrylate, 3-((2-((meth)acryloyloxy)ethyl)dimethylammonio)propane-1-sulfonic acid, (meth)acrylic acid, (meth)acrylamide, N-(hydroxymethyl)acrylamide, and the like. In the text, "(meth)acrylic" means acrylic or methacrylic, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryloyloxy" means acryloyloxy or methacryloyloxy.

[0042] Known styrene derivatives can be used as the monomer that provides the structural unit B in the polymer that serves as the gelling agent. Examples of such known compounds include styrene, α-methylstyrene, styrene in which hydrogen on the benzene ring is replaced by 1 to 3 methyl groups, 2- and 4-acetoxystyrene, 4-methoxystyrene, 4-carboxystyrene, trimethoxy(4-vinylphenyl)silane, and sodium 4-vinylbenzenesulfonate.

[0043] As the monomer that provides the structural unit B in the polymer that serves as the gelling agent, acrylonitrile, vinylpyridine, N-vinylpyrrolidinone, and 1-vinylimidazole can also be suitably used.

[0044] As monomers that provide these structural units B, particularly when gelling a functional liquid selected from ethers, esters, nitriles, and sulfonyls, it is preferable to select methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl) (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-(trimethoxysilyl)propyl (meth)acrylate, 3-(triethoxysilyl)propyl (meth)acrylate, 3-(tris(trimethylsilyloxy)silyl)propyl (meth)acrylate, (meth)acrylic acid, (meth)acrylamide, N-(hydroxymethyl)acrylamide, styrene, and α-methylstyrene. In order to obtain the desired properties, these monomers may be used alone or in combination of two or more.

[0045] When gelling silicone in the gel of the present invention, the monomer that gives the structural unit B in the polymer that serves as the gelling agent can be suitably used, such as Silaplane (registered trademark) FM-0711, Silaplane (registered trademark) FM-0721, and Silaplane (registered trademark) FM-0725. "Silaplane" is a trade name manufactured by JNC Corporation.

[0046] In the polymerization using these monomers, there are no limitations on the polymerization initiator, radical stabilizer (polymerization inhibitor), solvent, etc., and conditions for known polymerization methods can be used. The polymerization initiator may be a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, depending on the polymerization method of these monomers.Preferred thermal radical polymerization initiators include peroxide-based polymerization initiators such as benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, di-t-butyl peroxide (DTBPO), t-butyl peroxydiisobutyrate, and lauroyl peroxide, and azo-based polymerization initiators such as 2,2'-azobis(2-methylpropionate)dimethyl (MAIB), azobisisobutyronitrile (AIBN), and azobiscyclohexanecarbonitrile (ACN). Commercially available peroxide polymerization initiators include benzoyl peroxide, which is available from various companies, as well as products manufactured by Tokyo Chemical Industry Co., Ltd. under the trade name "Dicumyl Peroxide," and products manufactured by NOF Corp. under the trade names "Percumyl D, Niper BMT, Perhexa 25Z." Azo polymerization initiators include AIBN, which is available from various companies, as well as products manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. under the trade names "V-40, V-50, V-59, V-65, V-70, V-501, V-601." In general, azo polymerization initiators can be suitably used for both thermal radical polymerization and photoradical polymerization.

[0047] The photoradical polymerization initiator is not particularly limited, and known ones can be used, such as 4-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(4-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, benzyl dimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate mixture, and benzophenone / methyltriethanolamine mixture. Commercially available products include those sold under the trade names "Darocur Series 1173, 4265" and "Irgacure Series 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850, 2959" manufactured by BASF Japan Ltd.

[0048] As described above, the gelling agent used in the present invention is preferably a block copolymer having a constitutional unit represented by formula (1). In this case, for block copolymerization, a precision polymerization method, which is a known polymerization method such as ATRP (atom transfer radical polymerization) polymerization, NMP (nitroxide-mediated radical polymerization) polymerization, or RAFT (reversible addition-fragmentation chain transfer) polymerization, can be used. Examples of such known techniques include the methods described in Precision Radical Polymerization Guidebook (Merck), Organic Chemistry Information, Vol. 56, 2016 (FUJIFILM Wako Pure Chemical Industries, Ltd.), and Radical Polymerization Handbook, NTS Publishing, 2010. The method for producing the block copolymer used in the present invention will also be described in detail in the following examples.

[0049] The block copolymer used in the present invention may be produced, for example, by separately producing a homopolymer consisting of the structural unit represented by formula (1) and another homopolymer other than the structural unit and linking them together. Examples of such a production method include the method described in Radical Polymerization Handbook, NTS Publishing, 2010, etc.

[0050] A gelling agent having a structural unit B represented by formula (3) or formula (4) can also be obtained by using a polymerization initiator containing the structural unit B. In this case, the gelling agent becomes a block copolymer having a structural unit represented by formula (1). In this case, when a functional liquid selected from ethers, esters, nitriles, and sulfonyls is used in the gel of the present invention, a polymerization initiator that gives the structural unit B in the polymer that becomes the gelling agent can be VPE-0201 (a polymeric azo polymerization initiator containing a polyethylene glycol unit). In addition, when silicone is used as a liquid in the gel of the present invention, a polymerization initiator that gives the structural unit B in the polymer that becomes the gelling agent can be VPS-1001 and VPS-1001N (a polymeric azo polymerization initiator containing a polydimethylsiloxane unit). These polymerization initiators are products under the trade names of FUJIFILM Wako Pure Chemical Industries, Ltd.

[0051] In the present invention, the structural unit B represented by formula (3) or formula (4) is further divided into a structural unit (hereinafter, sometimes referred to as structural unit B'), and the molar ratio between the structural unit represented by formula (1) is calculated. That is, the structural unit B' in formula (3) or formula (4) is (CH2CH2O), m or (O-Si(CH3)2-) m The calculation of the molar ratio of the constituent units by this method will be described in detail in the Examples.

[0052] In order to obtain the desired characteristics, there is no particular restriction on the average molecular weight or the dispersion value of the polymer that is the gelling agent used in the present invention. However, in order to obtain a gel that is excellent in flexibility and has high mechanical strength at the same time, the weight average molecular weight (Mw) of the polymer used in the present invention is preferably 1000 or more, more preferably 5000 or more. For the same reason, MW is preferably 1,000,000 or less, more preferably 500,000 or less. The most preferred range is 10,000 to 100,000.

[0053] The dispersion value of the average molecular weight, for example, Mw / Mn, which is the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn), generally approaches 1 when the above-mentioned precision polymerization method is carried out. If polymerization is carried out under conditions that give a value approaching 1, a proper block copolymer is obtained. However, since the block copolymer used in the present invention has a large interaction between polymer chains, Mw / Mn tends to increase. Therefore, from the viewpoint of the quality of the block copolymer, Mw / Mn is preferably 1 to 10, and more preferably 1 to 5.

[0054] The functional liquid selected from ethers, esters, nitriles, sulfonyls, and silicones used in the gel of the present invention is not particularly limited as long as it is in a liquid state in the environment in which the gel of the present invention is used. Examples of such ether liquids include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxytetraethylene glycol, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, 1,4-dioxane, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butanol, diethylene glycol monohexyl ether, dipropylene glycol methyl ether, and ethylene glycol monotertiary butyl ether.

[0055] The ester-based liquids used in the gels of the present invention include ethylene carbonate, vinylene carbonate, bis(2,2,2-trifluoroethyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, ethyl methyl carbonate, dimethyl 2,5-dioxahexanedioate, diethyl 2,5-dioxahexanedioate, 4-fluoro-1,3-dioxolan-2-one, 2,2,2-trifluoroethyl methyl carbonate, propylene carbonate, 4-vinyl-1,3-dioxolan-2-one, 4-chloro-1,3-dioxolan-2-one, Examples of the lactate derivatives include 4-(trifluoromethyl)-1,3-dioxolan-2-one, glycerol 1,2-carbonate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, methoxybutyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, γ-butyrolactone, trihexyl borate, and 2,4,6-trimethoxyboroxine.

[0056] Nitrile liquids useful in the gel of the present invention include 3-ethoxypropionitrile, 3-methoxypropionitrile, 2-cyanoethanol, ethylene glycol bis(propionitrile) ether, and the like.

[0057] Sulfonyl liquids useful in the gels of the present invention include 1,4-butane sultone, dimethyl sulfite, dipropyl sulfone, 1,3-propane sultone, 1,3,2-dioxathiolane 2-oxide, 3-methyl sulfolane, isopropyl methyl sulfone, 1,1,1-trifluoro-N,N-dimethylmethanesulfonamide, and the like.

[0058] The functional liquids selected from the ether, ester, nitrile, and sulfonyl types may be used in combination. In this case, the mixture may be of the same type or different types.

[0059] The silicone used in the gel of the present invention can be any silicone of any shape, such as linear silicone, branched silicone, and cyclic silicone.In addition, the substituent on Si in the silicone is not limited, and can be any silicone having a substituent such as alkyl, fluorine-substituted alkyl, phenyl, polyether, alkyl with unsaturated bond, and alkyl with hydroxyl group.The silicone can be used in a mixture.

[0060] The gel of the present invention is characterized by including a gelling agent and a liquid, and including at least one liquid selected from ethers, esters, nitriles, sulfonyls, and silicones as a main component of the gel liquid. The gel liquid of the present invention includes a functional liquid selected from ethers, esters, nitriles, sulfonyls, and silicones as a main component, and may include other liquids. The gel liquid of the present invention includes a functional liquid selected from ethers, esters, nitriles, sulfonyls, and silicones as a main component of the gel liquid in an amount of 50 to 100% by weight, preferably 70 to 100% by weight, more preferably 80 to 100% by weight, even more preferably 90 to 100% by weight, and particularly preferably 100% by weight. Examples of liquids other than the functional liquid selected from ethers, esters, nitriles, sulfonyls, and silicones include hydrocarbon liquids and halogenated hydrocarbon liquids.

[0061] The gel of the present invention can be prepared by mixing a gelling agent with a functional liquid selected from ethers, esters, nitriles, sulfonyls, and silicones, heating the mixture to obtain a homogeneous liquid, and then cooling. The heating temperature can be set arbitrarily without any particular limitation. As described above, the gelling agent exhibits gelling ability by exhibiting a strong interaction between the structural units represented by formula (1). The disappearance and occurrence temperatures of this interaction can be estimated by thermal analysis of the gelling agent. The gel of the present invention can be obtained by mixing the gelling agent with a liquid and heating to a temperature exceeding the analyzed melting peak.

[0062] The gel of the present invention can be prepared by mixing the gelling agent used in the present invention and a functional liquid selected from ethers, esters, nitriles, sulfonyls, and silicones. When mixing, a solvent that is more volatile than these liquids may be used. That is, the gel of the present invention can be obtained by dissolving the gelling agent and the functional liquid selected from ethers, esters, nitriles, sulfonyls, and silicones in a solvent and distilling off the solvent.

[0063] Such solvents include ethanol, 1-propanol, 2-propanol, n-butanol, 2-butanol, Acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl isopropyl ketone, cyclopentanone, cyclohexanone, Ethyl acetate, isopropyl acetate, Diethyl ether, THF, methyl tertiary butyl ether, toluene, etc.

[0064] The method for removing the solvent is not particularly limited, but a heat treatment is preferable, and the temperature conditions are not particularly limited.

[0065] When the gel of the present invention is used as an electrolyte material in a battery, for example, an ionic substance can be added to the gel. There is no limitation on the ionic substance that can be used in this case, and it can be selected from known ionic substances. Examples of such ionic substances include inorganic salts such as lithium hexafluorophosphate and organic salts of lithium bis(trifluoromethanesulfonyl)imide. Such ionic substances can be dissolved in ether-based, ester-based, nitrile-based, and sulfonyl-based solvents, and then a gelling agent can be added to make the gel of the present invention.

[0066] The gel of the present invention may contain additives other than the ionic substances used in batteries, such as crosslinkers, surfactants, emulsifiers, coupling agents, antioxidants, radical stabilizers (polymerization inhibitors), antistatic agents, and hydrolysis stabilizers.

[0067] Adding a crosslinking agent to the gel of the present invention can prevent thermal phase transition and mechanical deterioration of the gel. As such an additive, known low molecular weight or polymer compounds can be used. In this case, it is preferable to use a polymer having a structural unit represented by formula (1) in which -NCO or a protected -NCO moiety is partially left as the gelling agent used in the present invention, and to use a compound having multiple functional groups such as amine, alcohol, and thiol as the crosslinking agent. By making such a selection, a material that crosslinks by heating can be most easily produced. In this case, suitable examples of such a crosslinking agent include various alkylene type diamines, polyamines, diaminobenzenes, polyols, alkylenedithiols, and polythiol compounds. Among these crosslinking agents, various alkylene type diamines, polyamines, and diaminobenzenes are more preferable because the crosslinking reaction proceeds quickly. The amino group of such an amine compound may be protected with a group that is eliminated by heat, such as t-butoxycarbonyl.

[0068] Other crosslinking agents include polyfunctional isocyanate compounds. For example, toluene diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate. In this case, the polyfunctional isocyanate compound may have -NCO protected. In order to crosslink with these polyfunctional isocyanate compounds, it is preferable to use a polymer having a functional group such as phenol or alcohol introduced therein as the gelling agent used in the present invention.

[0069] In order to suppress deterioration of gelation and obtain the desired effect, the amount of the crosslinking agent is preferably 30% by weight or less, more preferably 1 to 20% by weight, and most preferably 2 to 10% by weight, based on the weight of the gelling agent used in the present invention.

[0070] The surfactant added to the gel of the present invention is used to improve wettability, leveling, and coating properties on the substrate. As the surfactant, a silicone surfactant, an acrylic surfactant, a fluorine surfactant, etc. are used. Specifically, BYK-342, BYK-350, BYK-352, BYK-354, BYK-356, BYK-381, BYK-392, BYK-394, BYK-3441, BYK-3440, and BYK-3550 (all trade names: manufactured by BYK Japan Co., Ltd.) can be mentioned. As an example of a leveling agent, commercially available silicone-based surface conditioners can be used, such as BYK-UV3500, BYK-UV-3570 (both trade names: manufactured by BYK Japan Co., Ltd.), and TEGO Examples of suitable terpolymers include Rad2100, 2200N, 2250, 2500, 2600, and 2700 (all trade names: manufactured by Evonik Degussa Japan Co., Ltd.), X-22-2445, X-22-2455, X-22-2457, X-22-2458, X-22-2459, X-22-1602, X-22-1603, X-22-1615, X-22-1616, X-22-1618, X-22-1619, X-22-2404, X-22-2474, X-22-174DX, X-22-8201, X-22-2426, X-22-164A, and X-22-164C (all trade names: manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants added to the gel of the present invention is preferably 0.01 to 5% by weight, more preferably 0.05 to 1% by weight, based on the weight of the polymer used in the present invention.

[0071] In order to improve adhesion to the substrate, the gel of the present invention may contain a coupling agent. Examples of silane coupling agents include vinyltrialkoxysilane, 3-isocyanatepropyltriethoxysilane, N-(2-aminoethyl)3-aminopropyltrialkoxysilane, N-(1,3-dimethylbutylidene)-3-(trialkoxysilyl)-1-propanamine, 3-glycidoxypropyltrialkoxysilane, 3-chlorotrialkoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-methacryloxypropyltrialkoxysilane. In addition, dialkoxymethylsilanes in which one of the alkoxy (three) in the above alkoxysilanes is replaced with methyl can also be used as silane coupling agents. These silane coupling agents may be used alone or in combination of two or more. These silane coupling agents may also be commercially available. The amount of these coupling agents added to the gel of the present invention is preferably 0.1 to 5% by weight, more preferably 0.5 to 1% by weight, based on the weight of the gelling agent used in the present invention.

[0072] There is no limitation on the antioxidant that can be used in the present invention. For example, nitroso compounds such as 3,5-di(t-butyl)-4-hydroxytoluene (BHT), hydroquinone, methylene blue, diphenylpicric hydrazide (DPPH), phenothiazine, N,N-dimethyl-4-nitrosoaniline, o-hydroxybenzophenone, and benzothiazine derivatives such as 2H-1,3-benzothiazine-2,4-(3H)dione. Other examples include Adeka STAB AO-20, AO-30, AO-40, AO-50, AO-60, and AO-80 sold by ADEKA CORPORATION, Sumilizer BHT, Sumilizer BBM-S, and Sumilizer GA-80 sold by Sumitomo Chemical Co., Ltd., and Irganox 1076, Irganox 1010, Irganox 3114, and Irganox 245 (all trade names) sold by BASF Japan Co., Ltd. These antioxidants may be used alone or in combination of two or more. These antioxidants may be commercially available products.

[0073] The gel of the present invention may contain an ultraviolet absorbing agent, a light stabilizer (radical scavenger), an antioxidant, etc. Examples of ultraviolet absorbing agents include TINUVIN PS, TINUVIN P, TINUVIN 99-2, TINUVIN 109, TINUVIN 213, TINUVIN 234, TINUVIN 326, TINUVIN 328, TINUVIN 329, TINUVIN 384-2, TINUVIN 571, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479, TINUVIN 5236, Adeka STAB LA-32, Adeka STAB LA-34, Adeka STAB LA-36, Adeka STAB LA-31, Adeka STAB 1413, and Adeka STAB LA-51. "Tinuvin" is a trade name of BASF Japan Ltd., and "Adeka STAB" is a trade name of ADEKA Corporation. These ultraviolet absorbents may be used alone or in combination of two or more. These ultraviolet absorbents may also be commercially available products.

[0074] Examples of light stabilizers include TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 622, TINUVIN 770, TINUVIN 765, TINUVIN 780, TINUVIN 905, TINUVIN 5100, TINUVIN 5050, 5060, TINUVIN 5151, KIMASSORB 119FL, KIMASSORB 944FL, KIMASSORB 944LD, and ADK STAB. Examples of the light stabilizer include LA-52, Adeka STAB LA-57, Adeka STAB LA-62, Adeka STAB LA-67, Adeka STAB LA-63P, Adeka STAB LA-68LD, Adeka STAB LA-77, Adeka STAB LA-82, Adeka STAB LA-87, Cytec's trade name: Cyasorb UV-3346, and Goodrich's trade name: Goodlight UV-3034. "Kimasorb" is a trade name of BASF Japan Ltd. These light stabilizers may be used alone or in combination of two or more. These light stabilizers may also be commercially available products.

[0075] The amount of these antioxidants, ultraviolet absorbers, and light stabilizers added to the gel of the present invention is preferably 0.01 to 5% by weight, more preferably 0.05 to 1% by weight, based on the weight of the gelling agent used in the present invention.

[0076] It is also suitable to add a hydrolysis stabilizer to the gel of the present invention in order to suppress hydrolysis of polyacrylic acid esters and the like and to prevent deterioration over time or due to the environment. Examples of such hydrolysis stabilizers include Carbodilite (registered trademark) manufactured by Nisshinbo Chemical Inc., Carbodista (registered trademark) manufactured by Teijin Limited, and Stavaxol (registered trademark) manufactured by Lanxess KK.

[0077] The gel of the present invention can be formed by coating on a substrate, or by pouring between substrates or into a container, etc. Methods for coating on a substrate include coating using a dispenser, spin coating, roll coating, caten coating, flow coating, printing, microgravure coating, gravure coating, wire bar coating, dip coating, spray coating, meniscus coating, and inkjet coating.

[0078] When it is desired to improve the adhesion of the gel of the present invention to a substrate or other member, the gel may contain an adhesive that bonds the gel of the present invention to the substrate. The bond formed during adhesion may be either a non-covalent bond or a covalent bond. The adhesive may be performed by the gelling agent used in the present invention or may be contained in the functional liquid. The adhesive may be formed on the substrate before the gel of the present invention is applied or injected. Examples of such adhesives include the above-mentioned silane coupling agents and compounds having one or more isocyanate groups or blocked isocyanate groups. EXAMPLES

[0079] The present invention will be described in more detail below with reference to Synthesis Examples, Examples and Comparative Examples, although the present invention is not limited to the following Examples.

[0080] <Measurement of weight average molecular weight (Mw) and dispersion value (Mw / Mn) of polymer> Analysis was performed by GPC measurement. The equipment used was a high-performance liquid chromatograph system manufactured by Shimadzu Corporation. The column used was two Agilent Technologies PLgel 5μm MIXED-D2 columns connected in series, and THF was used as the solvent. The standard reagent (standard polystyrene) for the average molecular weight was STANDARD SM-105 manufactured by Resonaq Corporation.

[0081] <Confirmation of the copolymer's structural unit ratio and polymer structure> Nuclear magnetic resonance spectrum (500MHz, manufactured by JASCO Corporation) 1 The measurement solvent was CDCl3, and tetramethylsilane was used as the standard substance.

[0082] <Monomers, polymerization initiators, RAFT reagents, ether-based liquids, silicones, alkylamines and solvents> The following commercially available products were used: Monomers: 2-isocyanatoethyl acrylate, methyl acrylate, 2-hydroxyethyl acrylate (all manufactured by Tokyo Chemical Industry Co., Ltd.) Thermal radical polymerization initiator: 2,2'-azobis(2-methylpropionate)dimethyl (V-601), silicone-based polymeric azo polymerization initiator VPS-1001N (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., polymeric azo polymerization initiator containing polydimethylsiloxane units), polyethylene glycol-based polymeric azo polymerization initiator VPE-0201 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., polymeric azo polymerization initiator containing polyethylene glycol units) RAFT reagent: 4-cyano-4-[[(dodecylthio)carbonothioyl]thio]pentanoic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Ether liquid: dimethoxytetraethylene glycol (Tokyo Chemical Industry Co., Ltd.) Silicone: Polydimethylsiloxane, code number DMS-V05 (manufactured by Gelest Co., Ltd.) Solvent: Anisole, n-heptane, acetonitrile (all Fujifilm Wako Pure Chemical Industries, Ltd.) Alkylamine: n-dodecylamine, n-hexadecylamine, n-octylamine, n-hexylamine (all manufactured by Tokyo Chemical Industry Co., Ltd.)

[0083] The monomer, 2-[(3,5-dimethylpyrazolyl)carbamoyl]ethyl acrylate, was synthesized from the above-mentioned 2-isocyanatoethyl acrylate as a raw material according to Japanese Patent No. 4879557 (JP Patent Publication No. 2006-151967). The compound structure is 1 This was confirmed by H-NMR.

[0084] [Synthesis Example 1] Polymer 1 (X of formula (1) 1 -O-, R 1 is ethylene, R 2 nC 12 H 25 Synthesis of a block copolymer (a block made of structural units containing a structural unit of , and the other block is polymethyl acrylate)

[0085] In a Schlenk flask, 2-[(3,5-dimethylpyrazolyl)carbamoyl]ethyl acrylate; 1.2238g (5.158mmol), V-601; 5.9mg (0.026mmol), 4-cyano-4-[[(dodecylthio)carbonothioyl]thio]pentanoic acid; 13.4mg (0.0331mmol), and anisole; 3.1g were placed, and freeze-degassed three times using a vacuum pump. Then, the reaction was started in an oil bath at 75°C under a N2 atmosphere. After 45 minutes of reaction, an anisole solution of methyl acrylate (methyl acrylate; 1.89ml (20.63mmol), anisole; 1.9g) freeze-degassed in the same manner as above was added to the reaction solution using a syringe. The polymer in the reaction solution sampled at this time had an Mw of 21300 and an Mw / Mn of 1.60. The temperature of the oil bath was then raised to 80°C and the reaction was carried out for about 4 hours. The reaction solution was cooled to room temperature and used as is for the next reaction. The Mw of the polymer in the reaction solution was 80600, and the Mw / Mn was 2.48.

[0086] 1 From the H-NMR measurement, the abundance ratio (r, molar ratio, see the formula below) of the precursor block of the structural unit represented by formula (1) in the sample was 0.2. The polymerization rate of methyl acrylate was 90%. The polymerization rate of methyl acrylate was 1 The ratio of methyl acrylate monomer to polymer was determined using H-NMR.

[0087] r=A / (A+B) A: A compound derived from a precursor of the structural unit represented by formula (1) 1 Abundance ratio calculated from integral value of H B: A structural unit derived from polymethyl acrylate (structural unit B) 1 Abundance ratio calculated from integral value of H The above block abundance ratio (r, molar ratio) corresponds to the abundance ratio (molar ratio) of the structural units constituting the block composed of structural units including the structural unit represented by formula (1) relative to the structural units constituting the entire block copolymer used in the present invention.

[0088] 2.67 g of the above reaction solution was weighed out, 0.190 g (1.03 mmol) of n-dodecylamine was added, and the mixture was reacted in anisole (10 ml) at 100° C. for 2 hours. After the reaction solution was cooled to room temperature, it was reprecipitated in heptane and stirred for 1 hour. The resulting precipitate was filtered by suction, added to acetonitrile, stirred for 1 hour, and then filtered. The obtained polymer powder was vacuum dried at room temperature for 8 hours. 1 From H-NMR measurement, the conversion rate of the protected NCO moiety to urea (α, see the following formula) was approximately 1. In addition, the Mw of the synthesized polymer 1 was 52,800, and the Mw / Mn was 1.69.

[0089] α=BCP / (BCP+Pre) BCP; conversion site derived 1 Abundance ratio calculated from integral value of H Pre; Protected NCO derived 1 Abundance ratio calculated from integral value of H

[0090] [Synthesis Example 2] and [Synthesis Example 3] Polymers were produced by changing the type and amount of alkylamine added. That is, instead of n-dodecylamine, n-hexadecylamine was used in Synthesis Example 2, and n-octylamine was used in Synthesis Example 3, respectively, and polymers 2 and 3 were produced in the same manner as in Synthesis Example 1 above, except that the amounts added were changed to match the chemical equivalents. The results are shown in Table 1. Synthesis Example 1 is also shown in Table 1. In Table 1, the numbers in the Synthesis Example / Polymer column indicate both the number of the synthesis example and the number of the polymer.

[0091] [Table 1] X in formula (1) 1 -O-, R 1 A polymer comprising structural units containing a structural unit in which the structural unit is ethylene TIFF2025029422000013.tif31145

[0092] [Example 1] 100 mg of polymer 1 obtained in Synthesis Example 1 was weighed out as a gelling agent, and 900 mg of dimethoxytetraethylene glycol was added as an ether liquid, which is the liquid of the gel, and the mixture was heated to 100°C in a water bath to completely dissolve. When this mixture was cooled to room temperature, a gel (Gel 1) that had lost its fluidity was obtained. A photograph is shown in Figure 1.

[0093] [Example 2] When the gelation operation was carried out in the same manner as in Example 1 except that Polymer 2 obtained in Synthesis Example 2 was used as the gelling agent instead of Polymer 1, a gel (Gel 2) in which fluidity had disappeared was obtained.

[0094] [Example 3] A gelation operation was carried out in the same manner as in Example 1, except that Polymer 3 obtained in Synthesis Example 3 was used as a gelling agent instead of Polymer 1. As a result, the mixture maintained its fluidity, but when left at room temperature for about 1 hour, a gel (Gel 3) in which the fluidity was lost was obtained.

[0095] [Comparative Synthesis Example 1] Except for using n-hexylamine instead of n-dodecylamine and changing the amount added to match the chemical equivalent, the polymer r1 was produced in the same manner as in Synthesis Example 1. The Mw of the synthesized polymer r1 was 47300 and the Mw / Mn was 1.78.

[0096] [Comparative Example 1] The gelling operation was carried out in the same manner as in Example 1, except that the polymer r1 obtained in Comparative Synthesis Example 1 was used as the gelling agent instead of the polymer 1. However, no gel was obtained, and the liquid maintained its fluidity. The photograph is shown in FIG.

[0097] [Comparative Example 2] In the same manner as in Synthesis Example 1 of JP-A-2022-159191, X in formula (1) 1 -O-, R 1 is ethylene, R 2 nC 12 H 25 A polymer (polymer r2) consisting only of - structural units was obtained. Using this polymer, a gelation operation was carried out in the same manner as in Example 1. However, a gel was not obtained, and the solid and liquid were separated. A photograph is shown in Figure 3.

[0098] [Example 4] Polymer 4 (X of formula (1) 1 -O-, R 1 is ethylene, R 2 nC 12 H 25 - Synthesis of a block copolymer in which the block is made up of structural units containing a structural unit that is a polydimethylsiloxane, and the other block is made up of structural units containing polydimethylsiloxane.

[0099] 0.500g (2.107mmol) of 2-[(3,5-dimethylpyrazolyl)carbamoyl]ethyl acrylate and 4.0g of VPS-1001N (approximately 50% by weight) were weighed into a 50ml three-neck flask, and reacted with 3.0g of toluene as a solvent at 80°C for 4 hours in a nitrogen stream. After cooling the reaction mixture, 0.469g (2.53mmol) of n-dodecylamine was added and reacted at 100°C for 2 hours. After cooling the reaction solution to room temperature, it was reprecipitated in ethanol. After stirring for 1 hour, it was left at room temperature overnight. The resulting precipitate was filtered by suction and vacuum dried at room temperature for 8 hours. The Mw of this polymer 4 was 56800, and the Mw / Mn was 2.10.

[0100] According to the catalog of Fujifilm Wako Pure Chemical Corporation, the molecular weight of the polydimethylsiloxane portion in VPS-1001N is about 10,000, so the number of structural units B' in this polymer can be calculated to be about 135. In addition, since the molecular weight of the structural unit of the structure represented by the above formula (1-3) is about 328, the number of structural units represented by formula (1) can be calculated to be about 143. Therefore, in polymer 4, the abundance ratio of the structural units represented by formula (1) to the structural units constituting the entire polymer is 0.51 in molar ratio.

[0101] [Example 5] Polymer 5 (X of formula (1) 1 -O-, R 1 is ethylene, R 2 nC 16 H 33 - Synthesis of a block copolymer in which the block is made up of structural units containing a structural unit that is a polydimethylsiloxane, and the other block is made up of structural units containing polydimethylsiloxane.

[0102] Polymer 5 was obtained in the same manner as in Example 4 above, except that n-hexadecylamine was used in the same chemical equivalent amount instead of n-dodecylamine. The Mw of this polymer 5 was 64,200, and the Mw / Mn was 2.31. Furthermore, by the same calculation as in Example 4 above, the number of structural units B' in this polymer can be calculated to be about 135. Furthermore, since the molecular weight of the structural unit of the structure represented by the above formula (1-7) is about 384, the number of structural units represented by formula (1) can be calculated to be about 141. Therefore, the abundance ratio of the structural unit represented by formula (1) was 0.51 in molar ratio.

[0103] [Example 6] Polymer 6 (X in formula (1) 1 -O-, R 1 is ethylene, R 2 nC 12 H 25 - A block copolymer in which the block is made up of structural units containing a structural unit that is a polyethylene oxide, and the other block is made up of structural units containing polyethylene oxide.

[0104] 0.8043g (3.389mmol) of 2-[(3,5-dimethylpyrazolyl)carbamoyl]ethyl acrylate and 1.0000g of VPE-0201 were weighed into a 50ml three-neck flask, and reacted with 2.5g of anisole as a solvent at 80°C for 4 hours in a nitrogen stream. After cooling the reaction mixture, 0.754g (4.07mmol) of n-dodecylamine was added and reacted at 100°C for 2 hours. After cooling the reaction solution to room temperature, it was reprecipitated in ethanol. After stirring for 1 hour, it was left at room temperature overnight. The resulting precipitate was suction filtered and vacuum dried at room temperature for 8 hours. The Mw of this polymer 6 was 19300, and the Mw / Mn was 1.60.

[0105] According to the catalog of Fujifilm Wako Pure Chemical Corporation, the molecular weight of the polyethylene oxide portion in VPE-0201 is about 2000, so the number of structural units B' in this polymer can be calculated to be about 45. In addition, since the molecular weight of the structural unit of the structure represented by the above formula (1-3) is about 328, the number of structural units represented by formula (1) can be calculated to be about 53. Therefore, in polymer 6, the abundance ratio of the structural units represented by formula (1) to the structural units constituting the entire polymer is 0.54 in molar ratio.

[0106] [Example 7] 100 mg of polymer 4 obtained in Example 4 was weighed out as a gelling agent, and 900 mg of polydimethylsiloxane (DMS-V05) was added as the silicone liquid of the gel, and the mixture was heated to 100° C. in a water bath to completely dissolve. When this mixture was cooled to room temperature, a gel (Gel 4) that had lost its fluidity was obtained.

[0107] [Example 8] As a gelling agent, 100 mg of polymer 6 obtained in Example 6 was weighed out, and 900 mg of dimethoxytetraethylene glycol was added as an ether liquid, which is the liquid of the gel, and the mixture was heated to 100° C. in a water bath to completely dissolve it. When this mixture was cooled to room temperature, a gel (Gel 5) that had lost its fluidity was obtained.

[0108] As is clear from a comparison between the examples of the present invention and the comparative examples, the polymer used as a gelling agent in the present invention has a high gelling ability with respect to functional liquids selected from ether-based liquids, ester-based liquids, nitrile-based liquids, sulfonyl-based liquids, and silicones as gel liquids. [Industrial Applicability]

[0109] According to the present invention, a gel material containing a functional liquid selected from an ether-based liquid, an ester-based liquid, a nitrile-based liquid, a sulfonyl-based liquid, and a silicone can be easily produced. Such a gel can be used as a raw material for electrolytes in lithium ion secondary batteries and for various other purposes, and is therefore extremely useful industrially.

Claims

1. A gel containing a polymer as a gelling agent, the polymer having a molar ratio of a constitutional unit represented by formula (1) of 0.05 to 0.95 relative to the constitutional units constituting the entire polymer, and the liquid of the gel containing at least one liquid selected from ethers, esters, nitriles, sulfonyls, and silicones as a main component. (In formula (1), X １ is -O- or -NH-, R １ is an alkylene or phenylene having 2 to 12 carbon atoms; R ２ is a straight chain hydrocarbon group having 8 to 30 carbon atoms, a branched hydrocarbon group having 8 to 30 carbon atoms, or a cyclic hydrocarbon group having 8 to 30 carbon atoms, which may contain -O- or an unsaturated bond, and in this hydrocarbon group, hydrogen on a carbon atom two or more away from -NHCONH- may be replaced with fluorine.

2. The gel according to claim 1, wherein the polymer in the gel is a polymer in which the abundance ratio of the constitutional unit represented by formula (1) according to claim 1 is 0.05 to 0.7 in terms of molar ratio relative to the constitutional units constituting the entire polymer.

3. 3. The gel according to claim 2, wherein the polymer in the gel is a polymer having a structure in which constitutional units represented by formula (1) according to claim 1 are consecutively bonded.

4. The gel according to claim 3, wherein the polymer in the gel is a polymer having at least one selected from a structural unit derived from a (meth)acrylic acid ester and a structural unit derived from a polyether in addition to the structural unit represented by formula (1) according to claim 1.

5. The gel of claim 4 further comprising an ionic substance.

6. The gel according to claim 3, wherein the polymer in the gel is a polymer having at least one silicone-derived structural unit in addition to the structural unit represented by formula (1) according to claim 1.

7. A polymer having structural units represented by formula (1) and formula (3), or a polymer having structural units represented by formula (1) and formula (4). (In formula (1), X １ is -O- or -NH-, R １ is an alkylene or phenylene having 2 to 12 carbon atoms; R ２ is a straight chain hydrocarbon group having 8 to 30 carbon atoms, a branched hydrocarbon group having 8 to 30 carbon atoms, or a cyclic hydrocarbon group having 8 to 30 carbon atoms, which may contain -O- or an unsaturated bond, and in this hydrocarbon group, hydrogen on a carbon atom two or more away from -NHCONH- may be replaced with fluorine. (In formula (3) and formula (4), m is independently an integer of 1 to 150.)

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